*m B tm m is o f aom v w m w a jx x u v z subs m u m *
rta m a m a w am x m a /s zm m x o f m sm nm cfm m
m m VAiums m o m m m m im a m s

H&tord

hm

Jacobs

A D IE S IS

Sufeaiiisd to t o Stool t o Admmood
Stadias
of
State M s m s i t r of Agri^mlta® and
AppU&d Science in $artoX ftalfUlmat of
to

v & q x ix m m M

to

to

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ProQuest Number: 10008557

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and
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IHSIilSSlSHiSSSSS-

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B&oisajpti JL&@

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A n p s t It, 1931, in hsvrytfcarg, O hio.
M a fflM M * B tb lie S to d l ©f B e w w ta g , Ohio.
^ ^ p B S J sfc w g M i#* S to o l, l$h?*

Graduated frets

Bottling Green Stats U n iversity, Boding Green, Ohio,

» Bachelor of Seianee in G ta is try , 1953.
Michigan S tate U n iversity, East Lansing, Michigan, 1953-1958.
SlWfMBP' CUT &OX@ZIO@ 3JB UIP^SIIIa ©

a w rfm m m l K M ilt ly i
$ a t o * it y , X953.

* i/S # )*

Stadrat A iw latant, flw lln g QmMn Stats

Graduate A ssistant, Michigan sta te U niversity, X953-1958*
Ittsmuld Foundation F ello e, i&cfcigan Stats U niversity,
Sumer 1957Itesonto O hteical Ganpaay N & lcv, ^Lchipa State U n iversity,
Spring X$$6*
iiosaazrii C te is t, Kojspsrs Gberaiaal S o., ? m i» l:enn(^Xmsia,
! »

•

f t w r f w i^ sad honor B o aietlM ) tawdosn Classical Society
•Bob Society o f tbe S ip * X i.
OhwaicsX Uourm l Club o f Boding Green Stats U n iversity.
QtedeaX FeXXcw, BosOing Green State U niversity.
*A. $ « y o f t o AXkylation of Mydratropon itr ile w ith Aisyl U iU e s ,11 dissertation enbsltteci in p a rtia l
flolfiX X nm t o f t o re<^dreeo$ts fo r t o dspee o f Master of
Science, M ieM pn State U n iversity, 3955.
H ith Gordon L . SSoeraer, BA Study o f t o A lkyi& tlcn o f
Ky^rntroronitmXe w ith AsqI H alides,» J . Org. ciura.,
S y H tt# ( M .
With B to rt I). Stoeiss, " t o BeeaXfarim tion o f Thiiranos v ith
frie tly X fto » |M te ,« J . Org. t o n .,
XTO-X800 (1958).

iv

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I I

♦ 3 GB3I — 9 R«K)-GH8KJH-CHa + (CH3)3SI

Krn GH3, CjHe, i*C 3% ,

A ll e ffo rts to iso la te tlx© l*<lkaxy**2^•’’diiodopropanes fla ile d .
t o reaction of 2*alkcKym@thyl th iiranes w ith o r^ n o lith ta com­
pounds resulted la the formation of a lk y l a lly l ethers and lith iu m
merc&ptidas.

/

S

\

RH}-CBaM3H«*CHa + KLd -— «* R-O-CHj j i * a + HSLi
H - CH9, Cj)HSa

a-CaE,, n -C ^ j R n -G ^ , C6H5

A desulfUriaation was also dbserved ha the reaction of trie th y l
jhosphite w ith the th iira n e s.

/

S

\

R-CH-*CHa + (C*H50 )3P ■— » JKJK»CHa + (G ^O ^FS
R • GH3OCH3J Oj^Bg£X/Hgj i —
G-jEpOQBjgj n—
C3H7OCHaj a^G^H^OGH^
0 ^ 0 % , CHjjCl, CH3, H, CeHQ, {G $ s0 ),£ B .
t o reaction of trie th y l phosphite w ith several l-a3JccKy-2-Tiier~
captopropanes was also investigated and found to re su lt in the
production of a lk y l propyl ethers and trie th y l thicnophosphats.
SB
IM)-CHa-CH-CH3 + (CaHs0 )3P — s* R-0-CHa~CHa-CH3 + (C ^O ^P S
R - CH3, C^i5, n ^ K y

▼iii

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m m s o f ocm m m
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i. i m

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.............

1

. . . . . . . . ...............................

6

A* Matfcode o f ¥ r*fftm tlc a ..
........ . . .........
.......... . . . . . . . . . . . . .......... . . . . .
8 . ae»ction m otom tom
0 , Properties m iI Beeebione of ttfcylene S u lfid e a ....
1# Bing cleavage by priUmxy end oecandery am in os...
2* Bing eleawftga fey rsercaptoma.... . . . . . . . . . . . . . . . . .
3* King cle&mge by aleobol® .
. .............
U* King eleamge by acids................
5* tin g cleavage by aeid halide® and related cost*
p o m tis ...................
6# King clewmga by litfeiara aluminas!iy d rld a .. . . . . .
?. ting clasmge with crganom etalllcs
........ «...
8 . King cleavage w ith halogens
............... . . . . . . .
...........
Cleamgs v llfe meifeyl Iodide
10. A lkyl&tion m o tio n s . . .......... . . . . . . . ..................... .
XX, S ffeo t o f cs&diaing agents on alken®s u lfid e s ...
12# BUedllaasaui reactions................ ......

....... . .........

n x . a F in m L

6
1?
26
JO
32

3h
3$

36
38

39
ItO
til
1*2
U3

hk

i&

Prejmmtictt o f B tiylen * S u lfid e, (T h tira n o ).. . . . . . . . . . . . .
P re p a a tia * of Projyiena S u lfid e, (2-Metfcyl fh iX reae). . . .
Preparation o f leobutylm e S u lfid e, (2,2-m rnetfcyl

U5
1*6

Preparation
Preparation
Preparation
ire ja ra tio n

&8
U?
$0
$1

* T e |e ra ta .© n

of
of
of
of
or

Preparation
Preparation
Preparation
F rep ratio n
Preparation
Preparation
Preparation

of
of
of
of
of
of
of

- iU U L J k e . m i u

Styrene S u lfid e, (2^Xbaajyl IM ira n s ) ........
................
(braXetm n* S u lfid e
SKJI&oronettyX Ifc iira n a ...................
IMo^ctdaXdofcy&e I'le U y l& c e ta l.
i*wwusay*«wi5sjpro^y^>"oj^oropop8iie. . . . . . .
l,2 -Ip o ^ 3 ,na®tfc€i^rpr©pa*i©..... . . . . . . . . . . .
2<4£ebbo!symei^yX Thlirane
................
X~8ttofl«y-2<-lydr^^
........
l,2^po*y*3*»etJMi^rpM|ane................
MtteOKyawtfeyX Thiinm e
...............
lHRropoay^2“lydra!<y«»3,"eiaororropftn©
X,2HBjxny^3^px?poK3r|SPop8iie • • • • • • . . . . . . . . . .
B-FropcaQnBstbrl T iiiir a n e ............................
*%

w» M i |M Mu j ^Tt

n ■!Irma f it Md i m m . im i i * r ■■ i in » f i* l M M . i A M M k A M k d . M i J k

ac

53
5U
56
58
59
60
61
61

M L B OF COMtERXS * Q m M m sti
feQ pm ft&m o f
. ...
Frapiration of X,2*Epo^>HUio|Topcsxy|sWFaad. . . . .......... . . .
Frejm raticn of 2~I®0ja^pcKys»thg?l fh ifra a o .
........ .
Proparaticn o f lH B ata^2~h^cdr*3*cfcloyo]^Fan#
.
Fraparatlan of l #2Hlpc«Qn3^twiS3rF^^
.......... .
Preparation of 2*Batoa^M>thjrl m & iiw a e ........... .....
FrojmmtloKi of Xj2*lpc^3^m eQQrpro£m a8 .............
Frogaratloa of 2~fhm ss$m f&?l fh iiiw n o *. . . . . . . . . . . . . . . . .
Fraps-ration of
®t^XwaSaop?o|«no.............. .
Frojas-nfitXcsi of f 1
HPf T M W j f f f f i yli fh iln u is .
Frep&swtion of XwS ti^ tM o X w3woliXorop8!iop8aiti.w’2 • * • • * • • • • • •
fm p m M m o f X-l^ltM oX^2,3^pCKyppom R«
..........
Aitasspfcad Frap&saticn of 2~KthylthlolJs®tr$& Thiinm a........
FTop&rahicn of l*P ro y^lth io l^2,3 -opoxjrp^opsmo
..........
Attempted Fropfcratioaa of
IM ir& n © ...
Ee®pwr*tia& of AwdX«$» S & w t^ X a cw tal.....
.
Fropajwtion of Glyuidftldeh^vie D io t^X aco tal
.
frw p m tifln o f l*3itthea^2~propanol.
.......................
Trepanation of lH fotho^2^rm opropem o.
........ .
Bp0T30*ii.iloo o f X^etlxai3r^estoroat^iTO i!#a8.■ « • • * • • .» • ....
Frapamtion o f 1 -E th o x y ^ n ^ p a a c l.....................
Irw ja m tia i o f XH Stfco^Z^s^opropna
........
Froi»m tloa of l~Etfeos^2«!aareftpfc©prof*»e..... . . . . . . . . . . .
FraparatAaa of 3~& thc«^o|»»oX -l .........................................
Preparation of 3 *Btfc«^X^3?osjo|TO|»3a8
... .
fm p m ^ L m o f 3 ^ ^ o ^ X « ^ fm p to p ro p o a o .. . . . . . . . . . . . . . .
Fr®pw»ttcn o f X*Stttcasr^-^S«3W &*****.......... ...............
Frspumticn of l~1ita$c% ?^*pevpam l. .............. ..............
F w ip istX m of X-X«oFro|^tsgr-2“pspoi»nol.
............
of a a tg frX itfc ta ....
............................ .
iYOptolBtlOBi Of
$tM*™
..............~............ ........... *.~..........
Furific& ticsi of Gcw &poI& I fsdsttori Ffcoaptoite.**. . . . . . . . .
Attamptad Condaimtiaas of AXkaaa Sulfidoa w ith HsOoaXc
and Aoatcaoatic is t w r a .................... ...........................
Iteaction of 2^1kcetynatiiyl TbU sw m w ith P ip e rid in e .....
lieaolion of 2«AXk<a^sst%X Thiirane w ith Morjdaellno..» ...
inaction o f 2-Ethos^a®th$l tfciim na w ith Id e t^ la n h ie ....
Hawstim o f B^Srepc&ynathsrl ftd in a a w ith hiot^Xauidao...
Reaction of X ^ th c ^ ^ ^ ® ^ P te ^ 3^F is^d iao p p o |m 0 w ith
m #tbg& Phosphite... . . . . . . . . . . . ................. .....................
Beaetiosi of X"4f«tlKngr<‘V N m i^ 3 'W ^ ^
w ith
M M f X F iK fc jM t© .......
...........
Heaction o f l-B th 0 8 ^ n a 0 fm |to “3*Fipe3Pi^inoFTOpan® w ith
T rie th y l Fho»s4dt®..
....................... ................... .
Reaction o f l-Stha^2«^aarcm rto"3-,aiorTholiaopapopan® w ith
Trlothsrl Phosphite.............................................................

1

m U OF GCUMTS « Continued
Reaction o f
Reaction of
Reaction o f
Aluminum

Page

2-HethraQnaeti.yl TfciLraoe w ith Brom ine..
9h
2-$thcw pi»ttip. B&trene w ith Bromine.. . . . . . . . 9$
B-Hethca^metfoyl Biiin&ne w ith Lithium
Hydi^e-~Pr©parfctIc«i of l-Hethaxy-2-m eraarto.............

96

React!on of a^theaqymeihyi Tblirane w ith Lithium Aluminum
L ^ ild « --F ire p ra iim o f l^ itfc«a^ 2,n3«poft|^o|rop»ae.. . . 97
m »oU m o f 2-FropeocyMethyl fhUmwae w ith Lithium Alumi­
num Ii^ rid e --F r© F a i» tim of l-F ro jxa s^ -ta eri» p te Ifc fK iu .* .
...........
97
Ks&otloo o f 2-i&tcm3fK®tfcg$. fh iira n e w ith Lithium Aluminum
hyidrida—Fpepamticsi o f i^ tc a g r2 -*« a im p to p p o p w .... 98
fia&etien of l^l&cx^2-m ere*rtopropanes w ith 2 ,ij-d in itro fth l

98

Attempts to Besot I^ lk c a ? r,>2-R)oifmptoprop«o0 w ith
S ^ tro p h tla lic A n h y d rid e ......................
Attempts to Beset l^lko^2-m rca|^ppopB iM W w ith
3»$HE>ixkitrobenso3d ClderLd® * , . . . . . ..............
Attempts to Prepr® the Mexmrtoaoet&ldei^de M n itro -

99

100
100

Reaction of l,2-Ep<sqr3*,T»8ihc«3r^
w ith Lithium
Aluminum l^drlde^Bpapm ticsft o f l-S to th a s ^ -p ro p n c l.
Reaction o f l*2^p<3^3-«tbcsQT^peh® w ith Lithium Alumi­
num tiy& eU k**^M pum M m o f l-B th axy-2-p *o p n cl. . . . . . .
Baactioa. cf l,2«d fya^3»p o p c*yp D p n * w ith Lithium
Alantnm l^ydrldte--fir®pm tioa of W fopeasy-2-propeaol.
Inaction of X*2-%^^3*iso'ppo|«3a3r|mjpu© w ith Lithium
Aluminum
o f l-Iaopropcay«2-p*o»
pnoX • # « • * « . . . « # • . • • * • • • • • « • • • • • « • • • • * « • » • • • • • • • • • • * . «
Eaeetim o f l 92H£poa^3«tutoK^popm0 w ith Lithium
Aluminal® L ^ iid s **l^ p m tio » . o f l-B u to s y -2 -rro p a o l..
iieaeticn o f 2^1kescysi®tfcorl fh lta a e s w ith Methyl Io d id e ..
Reaction of BHButcoqyiaB&fyl TzxLtmm w ith B u iy llitiiiu ia .. . .
ta o tla a c i 2«iutc§!$®©thfX Thiiw ae w ith Pha^yHithiam .. .
Raaotiesa of 2-l«ofrope®^?ietl^i fM im n© w ith fiu ty llltb liim
Reaction of 2*Xtot*wpc*awetfyl Bdimss® w ith Phenyllith iu m ..............
Reaction o f 2~^p®st&®®UtyI TM im ne w ith B u ty llith iu m ...
Bm eticn of 2*fropeaeys»tfcyl Ufeiim m w ith P h ^ lH tM a m ..
Reaction of 2^1tocaqp*ttyl ThUzm a w ith i& ty llith la ® ....
Bm stLm of 2*£ttocayaatk9L 1hiX2*me w ith P h a ^ llltM a m .. .
Reaction o f 2K #th o ® y»t% l U dim aa w ith B u ty llith iu m ...
Reaction cf 2-?SattoQrmatS^l Ihlixane w ith rh a n y H lth to ..
Reaction of a-Ghlorcmetispi Thiinane w ith T rie th y l
Xhoajfcii©.. . . . . . .........

x ii

101
102
103
103
loh
10L
106
1C?
108
108
XD9
109
110
HD
lit
H I
Ill

mays o f gow m m - a m u m rn

i-ag©

Reaction of a^fetfcgrl Tfetixwsis w ith M e th y l P h o sp h ite.... 112
Reaction o f th U m m
SAilfid©) w ith M e th y l
.............................................

J h o s p h its

Reaction of 2-Eth®sysiatiyl Tfciixsne w ith M e th y l
Phosphite.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction of 2-Frop(aqpet2y l Thlimn® w ith M e th y l
P h o s p h ite ...................... .
Reaction of 2-Iscpropax^isyWyi Udixsns w ith T ris th y l
Phosphite
...........
Boaotim of
Qdlsane w ith M e th y l
f t o j f c ii a . . .. . * .
......................
Reaction o f 2—FljSQOEgygwtlyl tfajim ae w ith IrX e tty l

Ih o s iM ts ......

...........................

113

HU
11U
ll£
1XS

m

fa c tio n o f Gytlobmmm S ulfide w ith M e th y l fh©epfcit©.. 1X6
Reaction o f 2-Fhw jyl M im s w ith M e th y lF h o sih ite.. . *
116
Reaction of 2 , 2-B istha^ia»tiiyl Ttoiim is w ith M e th y l
1
^. o e i M t e . . P
Ih
.*^.P. ^.P. .^P..r .^P. .^P. .^P. . .^P.^P. . . .^P.^P. . .^P. ^.P^.P^.P^.p.^P.^P.^P. W
. ^P
. ^P
. ^P
. ^P
. . ^P
. ^.p^.P^.P H ?£
Reaction o f l-fiath cag K t^ ^
w ith M e th y l
117
Phosphite........................... .............. ...............
Reaction o f lHSthcsEyH3f,,csnfleapt©^
with friefehyl
J to ip M to ..................
.................
118
Reaction o f XHftportSwrHiHss^^
w ith frie h h v l
P h osph ite................... ..... ....................... ............................... 118
Attempted Reactions o f SMixeaasw ith Ir im r y A lc c h o ls .,. 119
i? . sascossxai ajsb m

m

m

. ...............................

f.

121
16U
169

w it *

im ? o f m & m

m m m

m gs

X* fie ld s o f

M i x n m . .. . .....................

225

I I . A n ly tio k l Sfctft fo r 2^2S£«i$3a®tl$i Thiiranoa.. . . . . . .............126
I B . XS«auti of <ay©34fl Ettosre.................

12?

XV* 2CML&I of

128

? . laflaenc® o f Matan&ft s iti Hq3a m ti© o f Haactants m
. r f „ ...........
.

TflLaffelft f l f

133

in . Asaalyfcioal Bate fo r tb® l^lte«w^*^roaptopro|»ao@ . . . . . . . 11*2
V II. Ccwpwlsasi of tb® Ragrsioal Iropsrfcles of tbs Klkcagr**#*"
Obtained
tbs X4A3&t Hodaction of Glyoldyl
Mtkmm m& bgr tbs AXk&lisi© £a&tign*d aond®wtl<m of
iro^rXsoas Oistd© u lib Alcobola.... . . . . . * » # . . . « • • « • . . . . . . . . . 11*9
f i l l . Yields o f trJuaotl^lm lfcm iaa lodM® frosa I^ccsaposltion of
tbs 2<iU&e«3Wt$$l
h y stetfcyl lodMo*.#. . . . . . . . . . 151
I f # Iw o B u ria a tia a of IM irasisa

b^

2dv

fr M J ^ i Fboepbit®. . . . . . . . 156

X

i*

m mm mm

t o structural

h ^m m cpe&ic o to rs and eyolto sulftoes

to tm p tm lh l® fee t o f m M toKntoritaggr Msoetotod tri.tfc t o la tte r
oa sp« »i»*

t o s , tlx® mm® m ±m m , epceside o r alksaa ce&d®, Xe&g

u ltli toe t^oXiid ethers, baecsasss tMijsma©, ©j&aulfidlQ or
applied to tho eerraspcsidtog suitor eofipouiids*
ife# toast

fa aiao frsQusii&tar u*wd to describe to©

e&igtotto cyclic sulfides.
Hast iMWKtcXatssr®

aislsw iijg s ^ te a ©ras&cgrsd to to© p^ssjost study

to to s t nannf1? t^ 1Gi’- ^ ir ^ i, Abatoaeto to *»b1lofc to© beto r o o r s u ito r &ta&

to toes® c^edi.8 sulfides to

tmsber css® «xr^ <xs2potuad© are ffMMtd
A

m dm&mtixm of a tMXsww# For miagiL®» t o eospound Ccfa^K&^KSMfca
to m£m m & to &® fr*piMB$i»g&SiBft. toXtosm®.
j > m .ill ■Jjn |Sfr JfitiS

of. mu

juifcittidtwfinVJnirt

j

ti

mk

*»titeeiuuy*-«44-

ukdt

i&Ik-jw.

to

stofSLer a lip h a tic

«k ^ 0 — ■^.,— -=.

15*]^ ®Ls#£ISK3©

SSt©

mi.

#

4*

—

OS?

--— - -

a

0

Q$l&*b**CMm to referred to m isetattfU n® s u lfid e .
s

$to

to iti& lX y ttisSsrtolsiBS to re lve d a study* o f to©

re a c tio n o f a X lfto tto © toyl« © maMMm n ito la b ile a? a c tiv e fydrogen
eaapMMte such s#» d to to i s ttla m to m d e to y l aoetcaoetato.

to

cQodenr

m U m o f ®pmM®& i& to t o a c tiv e w toyton© e m p ^m ls, aceto& eeiic
e s te r (1 ,2 ) and nRXonto © star <2*J#I&#S) to s becotis a valuable s g m to tto
to o l, «K$ to o f tp ito gpaam l
to Bjgfljy M
to to

im

cw n i l # t *

t o a lk ^ la tio a product®,

I ) tb@M^toe® are o f coM iclM ^ble

to te re s t in

a
and Alaaan&er (6 ) M
«&&f!fcgk eailfidea

m m tim m i

pw taaO ^r peportod to a i sissjiiia

-saito

cpmeacstato in tto presence c£

m m m i t a y « f to t not n ito etogft i t a t i w etogft aeato&cetoto.

It w

«*®ectoKl 11111% by if iB if selection o f paasiiaat ocaiSitim s. alksr*

X&tien could

usto® stog&east a tlfM e e and distisyl aalonate

t o m M m e i.

o r ito ^ l. s to to tm to to *

kawm or, In to e j* « N n t s to # 1i t was fesaast th a t

liaan toffiftjffit to® ^ryiairMjl^iwtg &ffiayyfoy $$§$*§ ^rta'fy

f tH8 l.igh

toatototew aeitegrto# l i t i i o r no *a% X&tiea M f n i «
PKtoteto la

toe oases

Ailbftl'ftft

Ito afcjor

a pdl^sw ie a iifM © . A fte r

im

addAtooiisi. isudatiens la rsanticei »^#l# *m$ ^^8^-m a^^.i
fS flu ^ ttl %0

$ |g t

i f fflftBHafyfl gp.M ,««* ^a>j»

w r w ^ i^ ^ ^ r iw r a & jg tie it t o il*
ay*.& ItfDfiC W ff

’tunagtw^ffl & p !I(S ^ o f

toe ppapnsaltoa is # etostotojf «#

in jto ttto to i toifnssias*

A atiyyfly o f to e litw i^ ix w o f ^to^taae
to s t *|M to y^FFW^!* tafasasBSi^i #wft
fyiiiiiaai*!. ffltt.li%,y astotototoil

ayyi siSJElxlis xwaetisS
gg& %\^f Sjyi&hMis of » » *

im^dma^ (7 ,8 ) <sa3ty a re la tiv e ly fto

lep eris ana to to itosKl toaM ag i& to to® fss^paa&tett o f atones® BiXfide®
\?$mj) m sw&wmFt w u o %na pwestieo® c®r s^xsnciee s&si* ystFSjOaa aaciao*'*
^ k f 4! \

u f a U i l t o A A t n iflft

y t N U t t ' j j K A ^ irtulMb.rife

t id io paapatobaye toon
toa to tfi
ii'g rtiff*iiffi'ia

m&lk

of

*te jf^

n i i i n rii-*i»>«l irU mum

nt.<A A M i B n n r I'frtS w t i t r i i

ib iM - u u

tom tod ( 7 ,8 ), aO^r a s jip s rfic i^ i
p®a®%is8ia o f

oiOT?®8poas3.lag salfbp

^ # *1 %

uC!^pG«£«SHP \¥}M < fj *

1M& a ito a tic n , m drnbt, is

la paH to toe fa c t to n t eH ^ eae

spe n et as peadiiy aosesaibie ?nop iwb stoble as t t o lr a^gan
aaaalesiiMil tto y

a *®sfe wuslsep tnslaQoir tcsisunls «g»if»
M&$lmm m&£M® p^^^^dses tsitid n a £m hm m a f t e

3

tm m m M m <21*12) , m m i& m wfoemd a t io» totapamta© imlasa a
eto ilissar «Mfe a*

m3SU », m aliqft rmsm ptm, or ass a lly l

®#lfid# ( 13, Ik ), 1» added to lt«
fftdfl# SS

Tba i«(ly»M £attlai of

bjjf

sul*

ftl lgy.*U^ ifa-Snoml add®,

outsi salt©* sa»d & , ip sW to «sd aoetic add (11, 125.
%$& tN*3ijgfo
of

aBferg©

o f tfe® riag^oposaiaig

odd®®,

t ® tbe

of

t$s® tatfe-tift $#!>cK$B®t* tawiiaiitiii fltatedal tresaitEtlGB® as® ©beesvad (!&)•

1E$mi lltassattirs sa&rob

zwaalad that

f tda# rsaodjl® tfee

tfce aik**** sal**

apcxsid® 1b skke^t ctf th a lr reactlcs®®

msm% Us! «*»«*

1, *i^ wm>0 s^$- wwb wed vttfc botb ( 16, 17,18),

M i ^ as sauf casta® am b® d M

In ufcsteti the opposite is tsuo (16,17,18) .

th# iM ttiftls ti tte t tfea s®a®ttoai prodaoia dbt&iBSd tsxm an
i&th a g$ra& ra&gss^
afB lo^ te 1$# awe swoI&se id th

bo
t^m ,

by feeiael
ignite sslsl9®dla.@.

tt& * applies espallgr to n td A ^ (16, 17,IB ) s w a m a id th ih© d ro c tlo i
$ f rSB^oiwd^g of

2y eabatttated thllrB&se*

®S HOffe |®|3C2Pt*d
lug

1SS SXf^fta&aB altfc tto iB'teSt of @Et0Bi**

ipssfjp^

as$setitist©d t&lisausee, and of

t b# ISSsaStef® da^figg with ^a&atiGBs of a&eb eotaps&Bdff a ith
t m w i m o l^ p b ills m ganlft*
to dbtftin smpc®ad® p w ^ lB g anfflolaot o M iilit j to p@mit a
gto ^’ of tb d r naadi<m« idtb ife irlr eteasg sesiolBophllic |oag®Bta, tba
of tbe fdlowlBg %tsas of compom^, E « n a*<^ilA?4i sB

h

/ \
O f tit® fSjfltiwffi# (§>#3£i) awSlS&ln

«tnKpmdflf« «n^r tons® &is r M t g t o
e ^a w ^w id in s isallks*

pEwpBa^tiSxsaa o f t h-tliffiffi51
w e m ic R o f m spends In to t o

W s lM li. tkiocaasiat^s (flk .1 9 .2 0 ). c r

m o ira a (21,22^23) m m

«A-

I • 0#S*1
IE * CB®# GjgH®*

l**^'3(1^»

▼ jBjgBF^w’Tsmjgi K3HP"
f iWty "Ua^

34tl3S ©3? HD
-

f ’liSSS

In

msm

©Xttep nat^hsxl# ansi W 9

tWBMP'dl
foy

etatiX® a t rooes tisspsa?0.tw3P® £&& swspaX

€a ttm © ti*sr liasst# tte t&laatlMBi* t M tiw ta ff- m m v^&y w eptEM.®
and 2^|»oly pyLpM^yM spsn a iP M p m p&tfmin&mea «§r a is tiijy a tx m ,
u i u i aft

fhiitfa n.1 r t j S ^ ^a.

n ^ ^-n* aMid>ii»tMkiI

t tA ^■■^■— i

m m a t ?®w lo i p a a iw t® ,
w

iltl iftlltfii rifrnH't ■ilffir M k J a

*^4^ 4*MitttS tC*.!*

JLJg -~i-—

»

taOy m d ta g l* s w $ » o f t o s a to tte U m M

p?®pTOi# «nft «&too#± It «ssM fce tbtad&ai a® t o

p $ 3» ris © d la a f«*r <tegn a | 2 a r t e i « i t o
© to r 1$&lxtKMNt»

J t JL d J L *8 j| "* «i<-jlA*,*8 ■■-*—

0to a § ® .

it
£ l*ia , c*& r t o

®mM Is® eta©!©© In t o i r rm oU cas

H im m c to ftx tli© m p H .
Tim ms^m%» m&m%&& &sr a srfca# ©£ t o i r lato& oiicm n it t atewr

tMtona©

is x z te iM

XitMsua aluatani fegrirtd*,

tt& m & l

jtopkit®, swti$rl

t o t o * |tMRsyl iitfa te % ba%a llt b t e , mom$&£? msSxm said p $ m *y

la addition* m m m X

raacticas

gS

^Ljcidyl ethers,

m zondm y m&rc&ytG ethera and m aavM ry m rm p to mzina a tiw s ms®
Iw asb tp b ed .
Sera* cmpataMs tetm&oiox® prajmnsd
■^Ith w ism xr j j l

ndtey

reaction of sti^Lsa© w H M m

(23)

(2b) fc&v© reoeivsd

isc&aloal apjCktcablc^ a * sta rtin g

£<«*

p^ssst!© ® ,

aff ^BHl# ts s tii# aids* asidic&siEKitsSi a*y* ‘vnlcandjsaiicn accelerators •
fha

}^

q

Whsnnfely jfouad IndttStrtaX nffi% In

the aediflaftt&aB o f seel fib e rs (2£„2&) and as sywfefeafcic polyiaers (27).
A tlfflftly ss® jfesp

ifo®

r t ffc systssi m®

|a^4a»iiaiwi. th is ygny* in a im part (20) fre*9 |jb9 Stanfeaftl %#®®TOh SewMteils®#
d e a lin g s ib li t i m Sjpsd&ssi® ®df
nkt ***$

r

T his ptpM f p o in ts

ctjf tfe* tt4 ifnftfi# rin g systsn in perrftitting easy argfs® to

SbHttS

ttewanfrjir,

fhqt nfrflrj tXSt fiMpteSS1 fftttdy Concerning

%hf» ^bi^"*0p9iaing reastifja® oef tfei&wftyi|fflfa sb®
®esfsssi^. o f tb® proposed
reagents in tfa* #|Sii®3iSilS' ISoIng®*

by ^

l& c i th at

jyfyojy iyd attftok by nttc3aoptdJLic

6

II*

BJOTHIOAL

A . a s to d s o f Enafam bicii
An to fe ito a |swic«i®2y, m®%m& w lS M m m y Bn otoidsred t o
ioQJEW im tofpo® o f ths $to&sss aside#*

m vsw of t M # r®3al&c»ship,

I t is petops m rp ils in g to H as t o t «n appselafele tim Is ts m X
topsed to lta & iig t o dUm&my <& s to le a e csdld® before t o f ir s t
ssiocisssfdl s t o o ls of mm*w®i® sttig&aae m U ld * w
c ta rlea A* M s

(2£f30) ttam t d iS e rtM t o

reposted*

m p em tto n of sto les®

aa&de In 18S9* b at I t m s sst u n til 2£2C t o t t o f ir s t a s tb m tic
y rn ^ m M m o f etiylsn e «0£id© m s m p t« S % 3fcre«3L M s p to (X1S1 2 ).

I t sSmSd# ibcmrow# bn FfflTt’4 ,raftCf1‘ bbet HUpeger #?r^ fcomasg 3s im

m ),

m& J&etaMEL 3s m $ (32)# rep asto t o fswpsjasto* of derivatives s i

s tb ito s wiXHsle b**i to m b west t o is to «tlsp?cwa th e ir d e la e (35)♦
f f io r to t o roporfcs by M s g is e (lX tf12) a tto fts to prsimm
s to lm s s u lfM a , by proeetae# sig& tar to to s s mfSLcyed t o t o

of

ppo&teed &

ms fir s t thought

to m a noseessno #ux*l®e# m b m s n o ts filly & s ta tu re os ^ o ta ^x s s s
-dSt

**•■ ^

u * J U U * MittaauiMtfJt Utli

JtH S Jl9 *Hl

S l V f St

^KUM* Mid

U

ik A'i It Wi*^ SL-imm

Mh

Jfc_.

.,— .--

O-

j3 jB l a k A l u M j l

fftf&fc (0«bUS)®# SUft Mg?haa» iMrilaMmlfty m SsBt CTSt*j»i»l« l (33) ,
as M l ss t o

y t t f 1#23 Is t o

period <m o rg m lc o te lirtry » t o

Shea

o f t o e o to e itfc tiv e books (33) o f t o t
to te w s b appears# "eth yle ne s a lfia e ,

d % ^ % , com epaadixig to e to to e «sdde# is a n » re s ta y s o t m p b l® o f
s e d s to i*

I t $M u s u a lly I ts i^ S y m rito to s h a re obtained*

and < **# # )»

d is u lfid e ."

?

R e s p ite t o

n e g a tiv e a t t it u d e w t o i* jm m & M , e o a c a r to g t o

s ta b ility of stoles® •B lfldes, I f ms In t o period a£20-l#23 t o t t o
t o t a ls ! B t o p t o t o

M s ( M

s iim

( 1 1 ,1 2 ,3 U ,3 5 ,3 6 ) p M i s M

t o fts a lte of t o t r studies cm t o $§mtosis of mmoms&c etol®**®,
pm$®%mm9 t o butylena

fixr «bs©rto t o t slltaaa sulfides

ware fto e d , la low yields, tost a»

e to tim of sodium sulfide

allowed to reset wlt&t e ith e r iSa®

90ft 301(1)

s
H ^S

e * b, a% ,
1 • balogoa

l td # fS ftJtel

©p ditM o**

M

.

♦

2&&a9

g^ ;3

s$no# hssu tifilis s d fesr Touts

la rkin © (37) to tspsmtezn

towstosylethylene sttifids, t o fey OMixigMvfc (38) fo r t o systoM s
Of tJK to to leth ylen e

S U lIM #.

Atoa?tadbsB,tel3f fcmffsau ms&rs atawwri before a *n»«wwri «***§ aora
jM tfood fojp rihfg^»!>i!ftg» sptsulfldes appeared Is fhs litesm tar®#
la l$3l* Batoaster t o

J a to l ( W ) to s r to d in p e tto £«u®, a t o ils

iro p o m tlm o f t o t o salfSd©# t tm

s % im e c&ides.

t o la tte r were

coKHftoed lu te t o oom sptoJag m & iw ecm pcto* By t o acticm of
tosous tiiieu raa a t roost temperature.
.0 V

S

/
\
ii
C % * € ftg ♦ t y K H f f i #

&«
to a

s

/ \
GBg— 0 %

0
ii

b^K H & g

U to p ro to *** mm la te r « l i M

By Galvenor m& Ms associates ( 21),

t o jaor® te to O y *T Btom&ll to . to m a to ( 22) j i t M il be slabctosd
eai in s o rt M M X in & au b o ^an t amotion o f tb i* th esis.
la a second p a te n t, issued t o years in t o , Vwitom x? t o

(1$) described tbs

JSekal

of amxidss into sMmilfides by tbs

action of p o to s ta tb to y s » te in a^iacst® solution a t roc® topom tore,
✓ °\
GEa—GBa ♦ S8GH

,

xS

♦ ISOGtt

fM s saeetid faaaaaai - iam@$dur$ M e *&**«» been earbandsd b r Sx&dsr ft**** m #
oo rU b ora to rs (11*), by M s s t o

Ktsfc ( I# ) , t o

remains as one o f t o

meat © cnrenieat la b o rs t^ fy pjoomstems ft^ iM h io fo r tb s synthesis* in
§ to y ie ld s , o f t o

s im to elafX a s u lfid e s *

to be < jiito p M H | p M M

to

re a c tio n has ppm m

to r® *u® m s tro n g ly p o la r groups, such

as the csstfOKyl, alpm to tb® sps&td© Mug ( 21) .
tWeNpww
t™
t* fiv
e^IF veers
fte r th
ttW w(p#
f ir s»PF'^tP rS
T ert bv
-aFPPFW
ICTWW*P a
|WF»
PFFV
*W■E
'TST lWriifl*i>iMfci»
I'PF'WFFiyWTW^PI ary?
l.uil.l■.! .fftftlraafl
Ww
(3$), an ad d itio n al g to t o p p tp to lre p ro to n 1® fear obtaining ep taa lfid s s see d a a to M by C oltof (]&)« to o rd in g to th is n e to d , etigrlene
ware obtained by tre a tin g
taC SM d eo latio n s.

w ith seek

t o weak a llm li *to d » t o foraatic© of peltom s,

ubiab e a rlie r isn&ere bad fo to . to be t o smjor product w ith eonsesr*
tested a lk a li,

C o ltof ( it l) o ls ito q p M to iM m yield s o f to ' woncsasrle

etlflssse atiU & ls ceald be eb tato d by t o dehydcmoMortotlen of

9

CX 3B
1

*

N

*~ *s * CKsr^Eg *

1% l i lipnHWtgii th a t jawfflci^BSili

QC* ♦

*

m i

sa^t i ! Mnssbcftsbs bs used to

nm itealiae t fes fc$tlr©g®n ©biersEdo fowsd and s t i l l

tbs jft of

tbs re la tio n Msefe**© i» Urn m m p ox ? .$ to ?#5, to obtain jtdfb yield s

hflffid

(2)2)^ i t about ib is sw#y period, ©bssswsd th a t

Wmi wm^Amm$ pewfffixmm ©f c^xLOis®®^®' w
’Wirtflh*!rttltftl

‘HtiJbt fitIlift M-Ukt. •AlL

M,Mt

^Urin .^B

&$awi ftft iw
tfc giuk jft|jdBalk -*- A .

31&ft ©€®sj

*|

JIbBi Aa

tab

w ith ©thgft tafenu o lfida (a lip id wl&ofc. decomposes on banting, releasing
w i» t

be seosSdsswd to bo s ta s ia solfh?) fo r' about te n b a m h tbs
fteOp^te

MblktttaWBTi Hii'Blta Mfli

1/fISMB ftltCfSf3^

($

.BB

J ^ t UMABCt w W

%»Wa*tllS«!u'4S l ■*.--■&

wm

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w a a p ta a , and sobs® $t&g& ss£U$d@* In ad d itio n, i t was found th a t m
p td J s jt t t r t iit t feg5$ggd i #^*b s lE y lte e was pMftWflf w e r syrib ss a t 3S&0 ess*
-»■.A. f --• —
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msaatt ftisg^ysn®
ms W
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w ith tto diissat stMitican o f

d iit e to m «Oi£ta« m s o tx r iid oo t b j W f» w sm i M s assooiatm (3$ ) ,
tsfoft mowtsici tb& t essalofeoisstos is not cw sw l^d in to its a ilfId s vM n

te te d to EEO° i4.tE Mttesslar mtlim? In fym c, w wfeen te ts d Sja ssiltcm
m tbs stmgs l# ) “630o M^is w M t t e t is m p i n s as m i& ly si*

t a s f i t « p p « tb s t tb s d ii^ s t o a ts ly tio method o f ^ n tlis s is ,
so In p o rts ix t w ith s tlfls n o oM dst osiwioi be ®api.cysd fo r tb s T rspam tlcn
i f s th ^ tm ssU M ss*

A p re a e te e o f ttO X m m im m & o rig in , and doubtless capable o f

«**»

wsM8 mperted $m l$h$> by t o t e and Sigo&ago (27)# to y

s y tto to e d frn a e iw p ia a e t^ tb iira n e by th e to rs ® ! d e ty te fc te o f
l #t^ to © $ y e e i? o !*

oyais

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m jm

<% ^«ca% H9B *

jy *

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In tb s m s ye a r, s t o w r * M m

and Tmmefcaae (& l) described

th e re s u lts o f tb s l# ii8 ? s s tl$ p tl£ n c® ib® coasreansicKi o f stS^flUana *aytdee
M o e tty to ® t o f i t o h r t o e e t o a o f tM o m ® , aU aO i too^yam tea
t M o^w foagriiid# and mntSst®®*
© tbyte© m drfm t o

$boy fom td t he r@BsM.cii between

t o tM o-reagsnts* g e n e ra lly to be a K o to n d c , and

fw g K to n i © astern! co stin g , in to e s* fo r t o
fodwd as the $®3©a? fito tke b *

mmomrfLa s u lfid e to bo

I t m o a t e to e rv e d t o t as t o xm etotm

l^oosstlad, the %U o f tb s

muf tte

o f po lyn ario

increased#
am<4

(39)

©aside, ftfi

-Stated th a t 0€$Sp0t383d.8 U fa*

*.w* p*o$ylan© o?»i .de y y gt good y ie ld s Of

to© oowtaposmmg ^K lX e m M xm mzm trsa te d w ith m Uw rea o r pom sai*®
A&.

a.,

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M s ttM to s ls ta (21) war® usable to isoO&te

pmt* c f th e $9<^cMerlc 2 H ^ d r£ n ^ a a t^ l tfo tjfflfte in pw ptra'M ona u tilis in g
g ly o te X *

A t o il s r a ltu a tte m e to w e d in attem pts to pmp&m

2»*pbei36fl t'biiiaaLim fro p sty®*®0® ostSd®*
to f^ n tu r e , a c id ity t o

Shrssi c a re fu l c o n tro l o f th e

m m M ,m to e re su lte d t o y in t o

production

n

of

m ta rlftl* atcflottjr* mm and ObsdsarlaiR (Ii3 ) bears

fltte o e a M m lsc& » tl**g a a m le S -ih s o /l th iim iQ bgr fiffig&qylag * a o d tfl*

c& iiai of the |@ M l proeotee of Ct&raKtor and eo*«©i?fefa*« <21) # which
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mmm$ «

/la id a? the m a il/ pol/sseris# at/?©**® enl£i4© wm
k% pMaofc* the

thiim ae la etSIX uatauftia*

1?t# yfttttiPO of the pMlaet pN$$*0©$ fX*CBi th® swotloo of OH elth#*1
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taat^yjfty ^ t Hl gtyQg^ y # o f th®

m attested h r ike wossfe o f Bodforss (h b ), who fewari

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^yaataMj*, asld# f r t

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# a o liw *

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t l mi roaeM® oom irliig ite o o/olobasgaaa cxide
m tb * w fe H le watisata^ i t me cfessswd that

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m m (21 ). Opsa
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any <xsspe5ti$>d w ith a© spsdUla

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t o n t o d ito & e to L itd m i& r® m s ttaod*

t t is m im w ii^r t o t no

.egwSHo Stf&ftd* ftesm tioa M l cfcaamd to n tm r*a&&UAH& tydrosyifcisl*

w

to tbs $m$

e-owiiiions*

M 3$S»3* BoaslwsiX t o AoAttnMm {22} xvportod t o resu lts o f tola?

toestipfta of t o to^ofwMd«a of Sibyl*0* odds* iafco olofin
tt&f&dtes by t o 4 o tto o f A ^iM tti t& tcum »

to ar

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t o tm m tio n o f p ^ ^ X a tit i»X fid# frm proiylsm aside a coisiQtembXg

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t e m a$&0# by adding 2*5 M to

p» ooflft of sold {h^»oKto«io* stdJteic* sostic*

bssssaie

« r 5^o 3a® »m lfo n l.-5 to t o a i M i as/Sattca of tt& m xm ., te rm s s d

to ;srt$ld of

mXflde by £C$* m m m sqptol&r ^m tbiisy of

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it t M l* t o m jo r prasteb m@ imm&
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to b©t o

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stotos {$)*
A second m tafeto feature o f to# tld im ti# rin g eystaa to its to**

a b ility to « d * t w ito toe M&ltar a tm to toe t r i - or to to aem to o t s ta te ,
thss* alii- A ttm pts to
<nd.de.tlon; o f to# cyclic
stog*

ssad

salfoaos by to# d ire c t
to ts yssalted only to yuptore of tbs
( 3$) ctsfiwyod to st too

of

st&ytone su lfid e w tto cm em tm tod n itr ic acid produced MG
afyt products rwflttXtisig £$<tM ipeactioa o f’ to to laatsrtol w ith nor® etoylsns
st& fM s* but no w&Sm&M « * m M tm m s toototsd.
CuXv«mor and .ton assoototss {3$
lytoogan percsdils# mat

11cm recsntay,

to re reported to st nsitosy aqueous
interact© s ite ©toylen© salftoe®

to give is lta ld s o r «ilf«m® to t instead, produce# a v a rie ty o f sub­
stances resu ltin g f j » rin g etosmgs*

A tm unstable mlSmm «£ toe tetm m ryletlylsn® sulfide clues
to ® to n described (63L»£St) but to y m m not prepared by direct c&idatos of toe m rasp to iag cyclic sulfide.
la g s m ra l, to e a to n e mOMOm e ra c o lo rle s s , v o la tile lip id s

a lto a strong g to lc -lik e odor, to y are ra te r insoluble t o quit©
a to te l® w ite © w a n o rp n ie s t o t o s .
m to e o t t o to d , m

t o to m -a s y le tty lm © s u lfid e s ,

oe ygttelltea s o lid s , possessing r a t o r bigb s a lt­

in g potato end to d to b® m e s to le t t a t o simple ©tefla s u lfid e s ,
M ito respect to t o
a ftjo rlto r o f
I t o lf , t o

s iy s ta a l te to s te y o f c y c lic s u lfid e s , t o
to e to n w a d e d o u t on eteyloa® s u lfid e

a re r a t o r re c to s tu d ie s ,

Tkm u ltra v io le t spectra of

e te y ta c s u lfid e m s f ir s t reported la 1^58 <43), t o
m s d e to to to in 199D <€*)#

to

d ip o le am ent

t o r e c to work by t o is ( 63) m t o

v io le t spectra of' «t&yteRe* propyim e t o

u ltr a -

a yslo to e a e s u lfid e s bote in

s o lu tio n t o in t o .
gat to s s in d ic a te t o t a s in # ® b to in t o reg io n
o f 2400 1 (38160 m *
system* i
m m

) m y h& t o t o t e r t e tic o f t o

p a ra lle l study on t o

te iira n e sla g

ttm ra s p to la g e p c to ss wmm&M t o t

M p t o m m tra ra sp w m t in t o region m m 2300 I .

t o infrared sptofim of sHytene sulfide bus received considerable
co trato , sines t o in it ia l to e by to sp sra t o Bapra (6 £ ), t o d etrain ed

bote t o It e n sjtoram of t o lip id t o t o infrarad spectrum of t o
m\m r* B ectoly, Q atote, S to i t o ItoSagtea (66) detobed tee infra­
red spectra®! of lip id s ttg ta * sulfide, t o otorasd teat certain of
t o bands repeated e a rlie r by M m & m t o inpra (66) wsra not

29

to x a o ts rls ilo « f wcfwxasilc sfebgdsno s u lfid e, M i x & to r m m d»« to
iw o fli o f polysjarisad s a lfto aad/or o to r

A t to o t t o

M t to o # fto g s m t o Cava (6?) ratoostlg& tsd t o infrarad spaotxum
or t o vapor t o t o M e n qpoetam o f t o liip id , w itb t o re s u lt t o t
t o l r obimrmtions eonftra to w * ©f Gtatteie t o bis oo-sorkers (6 6 ).

HAtoa t o past IW , m&m t o Porter (63) ha** rae&sured t o
Infrared spectrum af trto g d tM to o e and to e reported tba pdneigmX
OTOf PJWWTWO

Ifc addition to stoytag t o tatm m d dpectrun. Gutfarle and bis
ooB toxnior® (66) d stsrato d t o m por p m m m t o various tow *© *
dyoaaiie

fx$p stb^sis- su lfid e*

gptsd tba
of

^unoer ( 69) Wft alao invest!**

jsopextles of
data# bfoft

sulfide, a«^ frcsa heats

ffjitiafead j£g b w t of fom allcQ .

Tim dipole M *m t of stolen® su lfid e im bam detensined by
CMOtbard affld (Mnmkwm ($&$*

tia» StS&StgSXOS Cd? ethvieiJS m lfidg* &rej

m$M to e bam mmmmi m tba basis of t o ir s&erssMv©
spectra (1 0 )*
mamm t o

4m m p < H ) I mm reeto S y ompsmd t o boats of sen*

M otion o f at^ d m a mM®$ tiS&m&Mtam mad ©tbylane oalfftdo to r e la iia i
to tba sixain w m & m o f t o i r rin g systo o .

to m tip ttlm e concerto n iib t o rtog opening reactions of cyclic
m M M rn Imm r to L to in t o to a x m tia i t o t to s s cmapcands re s to le
t o o ex^ p to to g osypsa toifsstos Is nasr raspaeis (K6A?#18).
Bomnnmp, I s ©cntmst to t o epeadto, very fr©cp®ntiy t o in itia l

30

protob® of tin g f im im am not

»o*l«t «tf to s «

as such, du» to f& r to r w

ppotatii wttb opOic snlfid© or because of

p g ly M fto tto of t o tOkena *tm d * (16,17,18)*
M t o m & s m m m rtm , m *to g g * 19 m to to Sftlatat** oteroao*
lo g ic a l ordsr* aa i t apftsarsi t o t a m m usef&L discussion weald bo
m rn m im i t m . m $& rn fmrtatoisig to %ha w a tM m s o f a fm rtto U r
v m m & i*itb ftU tm sulfides w i grouped feog*tor«

1# fto g Glmmg® by B to r y and Sseoiwl&sy Asdaas

UiFf® and IXiotilftl (23) lam 4 a M M In $ato& form, tbe propmUcn
o f B ^ fe s tits jiio a pw diatft o f &Jt! f ^ s< E a«'8B and it® bcesclogs, by t o

of ftbydUNMi or

jwtlffta/f with prfmarr end secondary

6UBKSIS0®,. fiv jUAWesjiv v** 2X1 wmO P*M§wSIIGw vm ft 000 8 X000 ® OftpftO jwl GT jJGmf&lFSJug

tb o jpH o f tb a 'fH iO tlia i mla$t®r<*,
to

jr t a i y a t t t tf m

eapedU&XXy

as ftsaaol*

Tb** sbratig biSBdtetttesy o f

product to s m t w ith a d d itio n a l s u lfid e m s noted,

tb s wels a a tlc o f sal f j j da to amtes mao gm & tm than eno*

A « 3 i# t sm dlfleatlm o f to # peoootoe Im m om hfy bam m&eywd by
m o tfk m m a M .

J t o t o (72) # im

t o pmpsmt l m of ■mrlcws lHsabstltsit@a

mmmplmm to n s t^ to n ariLfids and m x im s m im compounds.

fries* to t o report by »•!¥• and ItaO M (23), B slsp to (11,3£) bad
atHm^tod t o p w a m tlm o f amtofelaibis by t o action o f abacus assacaia
00 © tly lto s u lfid e ,

to w s r , bo

able to iso la te cnly solid pcOyraw®

to s fe asislASiMRl U til® or- m aitrogan, Sadieatiag t o t t o reaction
Ksapsly produced pojymerlc s u lfid e .

31

t a M l y*Nm la te r , Snyder and fcis associate* (lit) described the
M u lte o f to d ie s carried out « itfe to y to e , propylene* le to ty le n e
t o o y to to a n * sulfietea and a v a rie ty of isrtaawy and eeetow fy to n e s *
®m m m m m w w m m m m m b a t to p to M re a m a r 100% ., t * r periods

■of 10 to 5$ bears w lt t a t t o te w & t of catalyst* or solvents*

33a

t t o s t o to t o fsadings o f Sag** t o to o la i (2 3 ), t o y observed m
b on efiuial a ffe c ts t o o to to * o r alto n a® chloride m s added, or to o
tb * «MySt««tt dSlim t& m o f •fefenii' *n*tw» u yt ti«ESL®md«
> CW3 < ♦
©

B^SI M
l""l”» B^f»( > 0—■<; < )*SE

Gsajr ^noawal1* ring ftsslou t o observed 'ty Snyfler t o eo-vortes. m
.all instances, « r c or less of t o initially fcrto
t o t oa to font p l y w r , a l t o a # , t o t o of excess t o n e mpfressed

tb ts ssftst&sit*

Ns
An tostov® imroati^ati® by t o ifcssian toaiei Bms (13),
mtmwmi id tb t o m to o t of attyU o* w lfM o v itb ton es, bm re I t m o c le a rly d a a to to to t o t t o
m m m M o tio n e to itio n s p t o t o y ^ployed (23,2b) in producing

t t t o t o t o t o fto te o s to a * ifa ito to o not iatapNMftbto, t o to y
frs c p to ly t o e to e to a b l® as t o y b to to favor t o to e reaction
mmm above, m m il as w O fto p caym rlsstiau

Moreover, i t m e

32

m m m & t o t t o n frm i& y vm p m d

au lfld a ras a d M to a

•d fc ito i o f t o m 6m in m im U is m * ® to »% and a lls t o to stand a t

mm

t o jt o t o a t m m i w boom* t o t o e to to ® ooamraicii c f t o

to fM a to pdl^aarlc s a to ia a ceoarrad*

In ffeot, t o m o t t o of

a t o t o t adXfto mlih alcoholic Mjatty^uuriai m » moammto d as a stalked
fo r t o

tgm M M biv® d a to tto ile n o f a to to a s o lft o .

to o rm tte t® nsmXd aj^ear to efflar an « & *to atlaa

t o to m

for t o

fa ilu re of

B t o ft o to to la ta nay aa d ^ kto X t a n t o reaction of ©ttyXim© 8o l0d «
<*iMt

etr aXooMLlO

(21,.3§)

*

$g$ t if f o tk o r k@nd.# feyfft (73) obBapmd th a t
oaxwslad oat In a
baaaoiia.

«wwif»m # 1^ . an
em «f“

tb s raaotxcna

hmnb

atkgdL stfcw or

«»« alsaoat coai'iletoXy antrrBaaod.

A® a ro a a ltj tbs sngsnt o f asdnoHdeOL JjM3ntsd w s aubatantlolXf ia r
o ra ^a d *

thl* p s t o t o wmm&& ton
to p M g m

by Sofatofca t o dpoanri { l h ) t

m m $tem t& m a ^ t g t e t o t o

ototan®

to fto *
Z* mn% t o M g i tgr mm&ptetm
Bmmml p ito ta t o t to n g m ato m t o im e tlo a of opiealfM oa

* tth mmmptwm* & s iw ia im to t ito ® d in X$i£> to top® t o M aytag
(ti») d a s to to t o t o t o H * o f & n it o r of ccssixtos « to to d by to tin g
a s&xtur© t o p t o o f an aXIgrl w a r t e i wXtk « d tto e to to ® or pro*yl«»®
m a tu * , in m t o r i m tfsm b a t 3&0**20Oo0 . t o l l a l l of t o a u lfto imd

33

t e M g Qonrctesv (75) m rs anabls to a£f®ct reaction
t e a r t e s to a o t e i t i w , M tb © ite r iscbutylsns o r cyclctoea© suXfto *

Baactlm s <SM «ooor» h e m m t, t e a catalyst such aa g«H ta

g t t a t e « r to m t e l t o r t o (i m * i m %M i t e r or auwtic adbd c a s te s )
iflspi snfXcyvda
A
/, \
> S**M1 <

m*
<sr

Mg£

&S in t e nm ^M m « f it e m

it
ttte M M ffii
, (

s u lfito w ith jr t e r y t e g a c o te y emkm$

t e t o t e ! j t o t e i i^ssu.ltiug fro® rin g £lsslca ste ad % it e t e tte e n c y
to react t e t e r * giving r t e to $rto«b® containing racar® te n cm thio~
wW^93P ^S$9Gtp#
J k ilk lt iih M t

<i[ If 11 Mh

II
*HS-<J«<W8K ♦
ii

l i l t
> C«**€ < -H i M ^ K H H S -M W
V /
i i
i i
*

habar iwaelc by UuXifsnor

H < mXlsboratc®® (15) on tbs raaeticn

bssts^sin stsis^Ussii yt»i.ria&iaiy fia^

suUTajd® o r priasay mrmptaniJj

M tote te t te tm® thiols 4© act rteily bringto u t ring ctoragi.
Ufa &3l

CVtSldhSEiEfiBl®

:Hdfa anri afehyl $agtrQ&ttaii» tb®

roaobmis m t t o t e in « t o t e t t o £m six t o r i a t 120ea . and.
ra c c re te u m te ip d *

t e t o r t i salts of t e m raaptan* m m

tm xM u m did occur in t e

sofpaote sm nar, but in mch

in s ta te oemldsmbl® t o p t e a m te & a l m s fom ed.
g alfid a cw ararte $roiyX®B® t e

Fotaaten iydrogsn

cyoXcbwam saHldas In to t e corres­

ponding d ith ie U t e w ith 2-cM w cH S tto t&Ubranft p te a te te te o g ty o iro l.

3U

1® M a g ' a b to fla g ilm im

of to to to ly ls tly X o a ® m ilfid® la

th&ft I» r# t o * »0 t o b m wjmoossafux <as).

'IHaift t o Wooto**! (tt) to®
t o t a a m a m * ®m%

cat ataUar rmoticafi on

mtuam m&

«ait« «f a ii^ t i a

t o m m m m o f p *® « s ta lg t a t o m & m ® w ith 2 -n -ta y l thltrm iw

te l hmm m ® w m to | * t o % am£L m sm t «c l#2<ntoarajtootaxi* alm g
ttUkh conatombl© quantities of p S p to s aMwHal (6 3 ).
J - Blag s ia ra tp tar A t o lls
to

jwopstotaa, o f

t o t o t u t o mvo&ptmm mm first

tfm d M t W t o t o * s t® r« t t o

Zim & m <?5>-

By o&plcyiBg b m

t r i*

£3aoxl4» as «taly©t, to y *w o *b l# to iaelat® m i l assouata o f t o

*8Pttipl8M fToxst t&o fm otioa of isobutyl®*© stlfid© with jrissssy
ea tu m to

L iit o & m rm & bim oeoarrad bstaresn

isilfM ® Had ss^sdasy o le to ta * or botsisaa jr im fy &X«ofccl» t o o tto r
Ittto U n o or syoXtoswi®
to iis e l*

m

3JS4s *

Ife ndstoXs lo»@r to n butyl W 9

Oaaa a p la * |K ^ w ri« tl€ a i o f t o toJdd® m s cfessrto.

O tttonor t o

his a^so clato (15') a to studied t o ogtoag of a lto ©

tfoM M m W *fltoag'l,
,top«tof t o fato tot at toimsy topsmtur^^

t o mUtkSm -mm ffci*2y o M t e to smtol mtar t o alctoUu taa
s e lf id© t o w t o war® t o t o la a soalod tub® fo r
t a w a t 100%## a jaissto© o f ctaRagft products r t o l t o 9 hat tendivMml
eestpotos w «*t t o

® a te t o m e cto itic sis# to o ia t®

o ta a c l 0 m ajmlogms rw a lts , t o a#d n s t o t o t H t a l ata cta ro s

war© act dstssrol&Ad#

35

k* Bing G U m g * by At&de
Althoigii 4S M » mmmx

m rn^m r n yritfm m am rn of

dnfUfc id iid e a * SBiitabie n e s te i of th® conooatmtion ean re a d t in
the imtmM&a. o f aiagiUi acMMMKtn addition prex&tde* For *saus£ile,

m o ^ to (Xi»32»3h,35,36) tm M m % m&Lwrn f l a m
Ig fe tfll& w le add P
**rdwtaww4e

M

and emcoateated

a^lo s^ tfcsm lM o l in 33# yield . Coiofefcw M
t * ytaSU! 2^vo rn >m B m m .cl.

bMxm d

it*8 » rh (W ) * t * * M * to ia d a te ta g * quantities o f M jm o p ve& m *
t& id a IfeMi t t * m s M m of «»s©8ti eataefertnetad tydroctilori.'.: ad d w ith
pso^fensiS' silfM ® #
ti& m m r, tm im and Heath (15) have extended th® reaction.

Vbm an «

*

of soneenteatiad l$ d r© # ta tc a d d m s esq&qyed w ith eyolo-

w 7 f f )id® m i

tfellsto®# the 2^faXorcthi©Xs wasp®

to n ad in aedemete to good y td d e *
a t redfii

su n re m its were obtained by w l& a g

m<j tdma the waot&on srfaetaip© ®&s k©r& tm ii dsead

by ©cnMn&en# ehaking*

Fdytasrs m w feuded in jasper ame«nt8 when the

f d le d n g eendttlaaa m m asj&cgrad, (a ) reaction carded out a t r a f t e
testim sm te^* (Is) m m re n e tl*. sstote^ m@ not torax#O y hm ogm tern,
end (« ) tNM Ling hyssrofsn ohto& le gte in to the e d ild e .
lloostmrd m d Mead© (76) hew* prtsdteeed substantial am snts at
g ^ ^ w d t e e t h io l by tsm d n g w tt^O m msifld® w ith dry hydrogen
flff r
Hen M m

(5?) h®@ i^eesgiay sham th at in the reaction of hydro-

obXoric a d d w ith gye&dMBMKft s u lfid e , the 2-*caaoro^iohoinn®tkioX
which is produced, assist® m U m d^ M tha tm m c«aifi®*m tl«*a.

36

UtaH m m m m o f feei&Sug
« lte d r M M m

&e®tie ad d was aliened to react

m &m ®, O & m m t o

|le M « o f

fci® co^orlsaro e to to d loir

a o to te , alcag m tk largo aaaoasita o f

feAfffeiaa** v»iiitiw MfttarSale
Sfcm aft { n ) to# amown t o t t o to o tle * o f acetic a d d w itii

p ^ t e o ittM d * gtvaa a 15$ | W

In

of to & » to itim

otodoto to to a aSasteo of

A |y foer%|y

h$|4

and

titiotl&sr

a p)l^®668PSslOg laftSJOBOO on o loClii
Bdeidna end Ha^a

product, m a il

oo"' act, asosrta^calf'
(1$)#

{$&) Josne re&ceted t in t n itr ic

obeL**

dined OthdSIB' WdffldO to ttse a d 40 BD^,eQM®*00<ak »»“* M^«S«>CBaiIM0HwH3m
>

$» nt**g GleasBgo tp AoM ^31444 ^yid

i 5f%3^ |j 0 # a patent ^n ato d to
f l.yy%

41

d w # 0®i*

Oo^pcoxids

and Basafosd ( 7 6 )

tbB OGWWdOB o f OtS^laB® e**^Piste f n-frA 2«,ol&OrO®tlf&

tM o to la ta fc@r t o action of tee%& cfeloriaa* la additioa, t o efotosls
o f tm o tto y o tla ^ l to o a e to ta f t a o tt^ te o m lttd * t o acetic tosydrkle
i^ d ^ in a yiRft d^sorHsod#
SeswO. fW <m la te , ftiid* to Wtonttd (76) reported to t treat-

M ttt of mtog&tm mHS$M nttfc c ito m o a ^ l citold© or brtod® resulted
la t o I n a t o

o f S H ttta ito itfl t*ii©chlor©&atot@ t o

^stocaoetate

fOM^ONStlOOy^f*

Id a (» > la» tto n to 2Hodeofcl§& tfcto cto to Aran t o reaction
o f m tytotft a O fld e u lifc ao etyl IndU e*

3?

Q v&m m , Vmtom t o Im m (35) tort ytporto tot qytlafcessoa

MftffoSfr *a& m&stfk cft&todt mdlly £em &*©tta©q^Xoli«8QrX tfcSmeetats
to M # & & & •

V m w tem m&m,® t o

tfeiiw a*® to ©

msmfeod «$*Xb® toU gr with aott^X e&Lcs&a© to torn & <^er©rr©sgrl tfcto*
ao tto te t o a 4S4M Afopf«i9l th to © «teto vtqpcK&trfty.
a to ttm

t o to to t®

of t o p r t o to m s t*ot d s t t o t o .

t o t o t t o i (57) t o to rn t o t t o tototo&c&i of setose**®
ap ttM A wit h

oMiWjj,#® m m lts to t in* £caaaa,M.<*i of taaasas** astfaflf

tNflS jgJ|g«®^ ^

SlOStBtSS#

Stowt { f t ) t o W
with

tot t o xm cttm of prosgftease «ul£M®

M

a tM U i* peotoum m&toUmt yinMa of ^-eiOerojrojp. to o *
f t

« is lw # aii|i*gHJ%*5S*^*€i% to /c #

ox- o% k;m

SiltSSMI of tM.MC«tiy£5*

w w w r

■VT*lw■HTwIww wlW

r*P***

T i P ^ W ' W W P ^ ^ l f illww h i s

^e ^ m p » * n m u w w u

fw

ptff

w v hhm *. p- i w

0
4>< j%*t o P *to o r© i»*e0i
*■■11 ■■■- p»i e im^

1#02*a %t,jfr
i»» >#..■ ^w1

^

gppiw s*
B M 194 to o a s to t o to a f© to to m o t to ® r t o t o w ith p?o$$to*s
s u lfid e %t o «$©«*» «©a%& ctt& toto* to t a®y«3ftJ«a®»» gtot® to g® asseto®

of H «!&CK«£**fg& thStow m to (35)*

to to to to s tortstX pttofc o f t o tm aU m of ;*o$f9jn * to fto t
ttltfe » to r l ctotttoft t o m'M mfr o csp to * t o d a to M in 1550 V
to to to

S to p (17) .

t o ® fm i» m m t o

t

to

p to e t t o t o

o f sto ^ X to X etoa w ith \v v g fa m to fto ® m s

a to a to t * 2*©£&©r©^farX th lto to to *
to to N K A * t o w t o l t o

to c p m tito tir® aaam t f**css

M a ito U

t o t o # s to a to 2 t o p #

Ht t o t o t t o of t o i s t o

M km &m * v ^ W ^ m m a m s t o a c tty l

th ito to t® to to c to to a l asaomt.

3a

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rn m m oitfe aoefcic

la t o

Ito to ® of a t o l mmt% of jp M a s i i*s a to im m M&m &* mm
m$m product voa&ttftg f t o to # r o to ta w

fc to to bo 2-ooo^rltoo*

p ro fitto

mtmlrn (5? ) i» ii

t o t ^ te to a w * a ilfid e and metie

fto a o a t o d te a iM * o f
M i tt* to te ti» (1$) m m to b to to IM a t* aay aoao-

^ to e s r t o

to la to & tte a p r to to f t a t o w ^ ctta# of cOofia salftd®e v itb t o
M tto ia g M&§m mmpmm&rn bmm&l mrnat&M, s ta y l chloric!® , 3 ,5 ^ 1 *
s i t t o t o f t (M m M ® , ta s tito ^ te a to t toaf& do t o pHo&hsso ooXfoagft

w«W% 3P8K38SS®w*jjr# JmtjII \jQf/ IpMI *w!wMw3#wS3 vs3© prOfAXa*SlGa Ca & saJwMlsr
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iqq,

#teitS9B

ram

p ro ^ ts io sitiSUIas* For eaasples

0 0 ^ * 0 1 ♦ CEs~ *r% ****** ^ B ^ iig ^ - O C la
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a t t (tS ) f& rat t o t o t o t o to a o ilm of

# 3 to » ® ig to fe * ixi 19&+ t o

rs&goat me

£mm$ to * t o t q p lt* *#© ctogr with t^sXdmme aul£34e» jmc%g/lM» s a lfid o

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to to a m * tim in g mwaadue? «mpilsaa® to mob to ta l® # ,
to ®bm% ?$$ y ie ld , W ih m im Um tlm dt t o pmsmm o f t o toaaerto
Uitoto«

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a i%

to contrast to to m

m

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ga3*-a!K;iia

*%«*« t o ta ts * (68) to to that

i i t o t o i «r 2-n -h e ^ /l tM to m h r M toto® toaSiam If M if t i ^
* m
^l"

to y

l fm m rn m « f to®- « & a « M cm M riM fcU A * t o * m m # large

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to

sst

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^ to lS lto ®y to® M m . m, MMmm
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m®

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to® r m M m o f ® t o ^ » m &&Um w ith Q x ig ito m p l s has
m to d y b«wi H r iM

fey S m rM X and M® associate® (16)*

to® a c ilm

$®s$js®mtoj8i brossto# m ^ W m m m mOJtm produced figraCLtoaaom

of

to ®T$ yto l*t# t o t o t t e i t o t t o CW #ato rm g to s *to y « a to o t» su ito r
to w M

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uator© o f t o s a lto r © ctototog m t e ia l to untetossi* Vton butyl ragiestm i

urns u to , c y e lto s » ® m s obtained to 12$ y ie ld , anti

us# dyMtawS is $% yis&d.

Be&otim o f ctpCLotaBoano w lfid o

Him feaaasa s#MPSita ehXos&a# w d « $s mm rvodaeUm of 33$ cjolo-

iM a o * 18# b m w l mrm pt&n m d $% ImwtfL d taalfid® .
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(!£ } foosd m at

wm%am$» did m t f m t

mad i^ L -H t b te

m m rrtsm a m pm sM m with *lkm sulfM®®,

tNKt ta tH m d offsotod a

mcrtlco* giwiag rts® to <&af$s»

smr? # 3 % i « r «»yl m«sr8&$rtaj. $br wmsssjt#* rh a s ^ llim to w ith «ydo*
Im bs^ snXSido 0 m <50# o f tlilo jism o l ard *3# of cyolohaKsa©. Lik«»ls©,
mOJOdto v ttb b n % m ts te rta ilU d Is mm te x m tim o f &?$
qt&tibm m m mad &$% & f 1+atfm udtoUit*

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wills wr©§f!l4W m d vtfegriUna *m3I$6o» tfc©#3&$1 or asyllitfcta ooritpasad

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«&££#« w ith M a x im *m& h m d m tmm bean mpar^md vm m Hty by sto m rt
mud CoKtftM < & )•

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&p « m K M *^3$$3?# # $ i -«$bm$4« to j**gA x* t o s a lta M p p t o
m & tm m ©f t o t o & U t o f t d M M m M U M *

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s*W?*«Xl ® £$to is mm of i? f e r ^ » t o M J U to bgr ms&<m aecawftugr
im uM m ® mtsh- m p& $m m $m Um *

Sto&rfc t o Q tots (S3,) £mm\ t o t xlilmSm t o ferosato vcttixi
todlist pveftftm* wlfi^ my JtoHy« U to adaptions wro carried

10;

out ia

dtelfioas

$mm& ^«w» ottatot m
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m M to

a c id .

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(15) t o

» p < w to t o t t o t o r t o m * J$d re$ » pspesdd® aop paomagmat® wcaM
t o

t*itfc iA ttton o m&M&m to fe w aolfogidOB or soKeoes*

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toforto to toargo datotetetta wtifo ts m lto ?fcoe-

jtocma ocnpnto (15)# to * «w
#

at atdimxy tespom**

%taXto»rso t o tjre$g te» to J & to y t t o v te o is l& p td s o ltb

u to fl to ife ta OS) t o « to to b oMcotostor (a$). to^oss « M b
Halt® t o te a d to m o t optotoeto^r «&& otfcg&ro sulfid© ta t t o
itooto© of to p txrtw U mm w&m m (15)* B
ts
fe
^
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sonlttte Jnotu&y

premia© toK««ao to o to & to mitfe to « *® t o t e tod® t o io d te (35).

cC 'm $$rnrn S u lfid e
( m im r n )
S

s \
Gha-"OEa
A solution containing 97 g . (1*0 sade) of potassium tbiocyanata

«ita»c0.vod in an equal quantity of* water m s rl&ced in a 350 n&. th rsenecked fla s k fitte d w ith a toK axseter, mechanical s tirre r and a
d elivery tube, A constant stream o f ethylene oxide m s passed through
the s tirre d rm ettcn m betee, kepi a t -1C to -5 ° , u n til I t had
70 g* in weights which r e tir e d fiv e hours. A fte r an ad d itio nal three

hours o f s tirrin g * a t the m m tempera!are* the transparent reaction
mixture had bepn to separate in to two layers.

Afew

drops of thiopfeend

m m added to s ta b ilis e the ethylene su lfid e (13) and the mixture m s

set aside o ve m i# ii a t 0-5°^ •

t o liq u id im te ria l m s decanted from

the precipitated potassium cyaaats end the o ily top la y e r, which bad
increased on standing, m s separated and washed three times w ith U5 m l,
portions o f a 20$ solution of sodium e&Lcride. An ad d itio nal few drops
o f thlophenol wars added to t o crude ©tfcylena su lfid e and i t m s dried
am p anhydrous calcium o fc lo rto .

Fractionation a t atmospheric p astu re

to o n # a 2x30 cm. column packed w ith 3/16 inch glass helices gave 25.2
g. (0.h2 ad ® )* a hSt% y ie ld * c f etlyl® ae su lfid e b o ilin g a t 51*-55°
(7i*7 te a .),

t o reported b o ilin g point is 55-56° (?60 mra.), (7 3 ).

Ii6

t o etly le n e su lfid e prepared in th is manner ramlned transparent fo r
fiv e to s ix days to n stared a t 0 °0 .
Indent o f uj® 1 4 ^ 9 6 .

tbs su lfid e bad a re fra ctive

Haynolds (I;?) m rarts o£S XJj8?8.

Frepsimfclon of Prot^LsiM Sulfida
(2-HethyX IM to n e )

s

✓ \

In to a 2 -1 . tote-necked flas k provided w ith a sealed s t im r ,
dropping fum iel end p a ra lle l side-arm fitte d w ith a nsflux condenser
end to ra o w te r, m s charged 1$2 g. (2 X ado s) of thiourea, 700 ml.
o f m te r and 60 a l. (2 X equivalents) of concentrated s u lfh rlc acid,
t o fla s k m s placed in an IceHaatfc and cooled to 10°C * A 116 g.
(2*6 M ie s ) quantity o f propylene ceeida m s added drcpvise to the vigor­
ously s tirre d reaction m ixture, in three bears. Following an additional
fifte e n minutes of s tirrin g , the reaction mixture was allowed to warm
to room temperature and neutralised by alcwiy adding 212 g . (2.0 moles)
o f sodium carbonate dissolved in 900 m l. of m te r.

t o oU layer m s

separated mid the aqueous phase m s extracted three times w ith ISO rsCL.
portions o f n-pontane. A fte r standing overnight, additional o il bad
separated from the aqueous phase and the peatane extraction m s repeated.
Use o rig in a l o il and pantos extracts m ro ccofclnad and dried over
anhydrous sodium s u lfa te ,

t o pastas*© m s removed and the residual

liq u id m o fractionated a t atmospheric pressure through a 2x30 cm.
Odum packed w ith 3A 6 inch glass helices,

to

propylene su lfid e

hi

d is tille d a t 73*(M?U° (737

1.1*732.

The b o ilin g point as

reported by Bordwail and Andersen (22) is 72-75°. A 752, 107 g. (0.72
aw&e), y ie ld ear obtained.
Irepamtica of lacbutyieaa Sulfide

(2,2-Ltoti^l fhlixane)
S

/ \

I
CM»
A solution containing 57 g* ( 1 .0 mole) of potaeoimn thio<^»m te
dissolved in 100 ad* o f water m s placed in a 50C m l. three-necked
fla s k ®«pippsd w ith a mechanical s tirre r, dropping fUnnal and p a ra lle l
sMemrm p w id e d w ith a rad u x condenser and tbemsoawtar.

To the

vif& rcasly s tirre d solution m s added dropdss, 72 g. (1 .0 a d « ) of
re d is tille d iscbutyXaa© aside.

'She temperature m s maintained a t 25 to

30° throughout the a c t io n of the ©pajdde, which r e tir e d three hours.
The- reaction mixture m s than s tirre d fo r an. ad d itio nal three hoars.
Estsm al codUng m s required

Urn© to tin s , in order to keep the

reaction temperature balosr |G°G. fb® lower aqueens 1ayer m s raaaored
by raaaas o f a p&pst and. the a s lfid e layer m s s tirre d again, fo r fiv e
hours, w ith a fresh solution o f potaasta® thiocyam te containing $0 g.
o f the s a lt in ICO s i. o f m te r.

The liq u id m aterial m s decanted

£ rm the potassium oyaa&to p recip itate and separated in to two portions.

The arsons fb&es m a extracted three tins® w ith $0 ®0L. portions o f
e th er.

The ether extracts ware combined w ith the organic pirns© and

dried o w aafcydrewe caletusi chloride. the ether m s rssacrea end the
crude su lfid e w s fractionated through a 2*30 era. Fenske-type column
pac&id w ith glass h elices. A 71 g. (0 .S1 sole) g eaatity of iacbutylane
su lfid e d is tillin g a t 03.$ -% ° <?iil n u ), Jq 1 .1*6UC m s collected.
*WL» oorreapoaded to m to% y ie ld based on the tadde.
and Z ieg ler (H i) report thane constants ass

Snyder, Sterna*

b . p. 8U-86° and aj^ X4*$iX.

three ad d itio nal preparaticme o f th is su lfid e gave yield s in the range

Prepftmtion o f Styrene S ulfide
(2«*!heKgrl fbiiran© )

u

/

$

\

jj

411 apparatus m s cleaned, rinsed w ith mmor&un p re s id e solution
and dried before mss.
la a 500 s£L* 4ta*s*u»eked flask equipped w ith a sealed s tirr e r ,

r e f t e oondsmer and tb®rac®a®bsr m s placed a s&xtmre containing 60 g*
(0*50 m ie ) of re d is tille d styrene cs&de, 50 g. (0.52 rata®) of potassium
tbioeyanate, 100 ml. of diorama and 100 m l. of m te r.

The rafostare m s

s tirre d a t 60'° fo r csss hour, allowed to cool to room temperature and
poured in to a m ixture o f 200 g. of crushed ice and h00 rai. of m te r.
9fa* crude su lfid e m s extracted w ith three 100 s i. portions of ether
and the ccsMned ether extracts were washed twice w ith lgo ml. p ertim s
of water' and dried erar anhydrous potassium oasfeeaate.

the ether m s

U9

rmmsA la s fta ia a n d the vm M m l icOsatim ms filte re d through a
Sintered glass f i lt e r .

the unreacied styrene oo&cia m s removed by

d is tilla tio n a t 1 m . pressure tteougi a 2x20 cm. colusm packed w ith
3A 6 IXMdi #sss h elices. f t ® the b « je m ta r» of tb® d is tilla te
reached 50° the rem itting llq a ld m® transferred to a short~p>th d ie *
t lllfittc n apparatus end fractionated under reduced pressure. A 31 g*
CO.23 table) cgasm&ity o f Shphaoyl tfcUraae b o ilin g a t 28*30° (0 .1 a n .),
20

tip 1.6035 m e co llected.
compound @mt

Sts reported physical constants fo r th is

b .p . g5**28° (0.01 tea.), u^° 1.6015 <U3).

The yie ld of

product m s U5$, based on tbs m ide used. A second preparation gave a
U7J6 y id d .

the mOfM® m s stared a t 0cC.
l^epamtlcm of G yolctasm Sulfide
(? ™1M&bleyoXo(k,X,G )heptam )

A U9

g. (0*50 mfi&e) e n t i t y of ayelohaasan® es&d© m s -added in on©

portion to a solution of 121 g. (1.25 moles) o f potassium thiocyanate
dLme&radi in 100 ad* of m te r and TS b l* of 95% ethanol, contained in
a 1 *1 . two-«©cked Ifrufc e^ipped w ith a sasclanic&l s tirre r and re flu x
condenser. A fte r aHowiag the reaction mixture to stand fo r about four
hoars, an ad d itio n al h$ g* <0.50 w l® ) of' cyolofcexaa© aside m s added
and the resu ltin g solution m s s tirre d vigorously fo r th irty -® is hours,
th e aupenmtant la y e r and the a^aeais phase war© decanted from the

5b

precipitated potassium cyamte in to * 1-1« separatory funnel.

The

psfcmMxm cyambe was mimed w ith 1m $0 aO.. porticos of ether, and

to s e were added to t o sepamtcwy ite n s l end used to extract the cycletessmm s u lfid e *

t o ether e x to c i m s washed twice w ith SO iriU porticos

o f saturated aodtai chloride sciatica end dried w a r anhydrous t o t a
awXfiaie.

t o e to r was ressoved m t o steam bath and t o residual

lip i d mm d is tille d under reduced pressure through a 20 inch Tigreux
cofcuat.

t o to n tm M m d is tille d a t ?ch?2° (20 m .)f ^

1.5310*

t o y ie ld o f product was 6?$. B y e ic a l constants reported by van to S la n
(111) fo r eyolefcaxeo® s u lfite are*

b . p. 71.5-73° (21 m .) t 69-71°

(19 mu)p djjj* 1«5306HL*5311«

Irefm m iicia of t-Chloromethed fillr a a s
( Z h to p lto c to ty tirin }

s

/ \
Ol-OBg-CH—QEj|

A 1 -1 . to te e a e c M flas k epipped w ith a sealed s tirr e r , droning
J to a s l, toaw sestar t o r e f t a ccodasmar was charged w ith 3d g. (0 .5
mole) of thiourea, 175 ad*
eotesfttsatsd s u lfb rlc a d d .

w ater, t o

15 aflL. (0 .5 e p lm la n t) of

The mixture was cooled to 0 to 5 °£ .

^art

of t o thiourea was Insoluble t o a r to e ® e to itic o a , but i t dissolved
as t o reaction proceeded.

To t o s tirre d solution, kept a t 5°# was

added U6 g« (0 .5 mole) o f eptd&crobydria, la an hour t o a h a lf,
t o reaction mixture m e s tirre d m additional quarter o f an h a ir,
allowed to m m to room tm p sm tem t o

oareffclly neutralised w ith

51

53 £* (0*5 ml®) of t o t e caartxamts dissolved in 250 ml. of m ta r.
Tli® t o ta & m m m sapar&to and t o s^ioogs phase m s esttoaeiad w ith
t o 50 A * portions o f n«*p®ntoo. A fte r sevoml boor® of standing*
a d d itito l o il M
m® repeated*

aejaaatad to n t o supaous piaso t o

t o wgM&o to w tilm t o

t o QKtractica

panto© © tto s i® m m c to in a d ,

dried «wsr aafcydrms t o t e m U ato , t o t o pm to© m s rmcved J& mcno*
t o em m ntotad nm te© m s

d is tille d to y ie ld pure

f « ^ w o it o y l tfe ttn k tt b o ilin g a t h?^B° (23 m .), o^° 1 .527U* An 85#3$
yield # 145*9 g« (©*1$ n o te ), m s s ta te d .

t o reported vwOaea am i

b .p . TO-Sl0 { H it am .), ag° 1.S280, (3 5 ).
to p w tia n o f T M o g ^ia s M a l^d e Biefcfcyl&eetfti
to to m )
/ v
CB-OE—Oli
0#%-O
In a 500 r& . ttaw rtooeketil fla s k fitte d w ith & sealed s tir r e r , n a fta
o s M ir t o

dropping t e t o « t placed a s o ln tic a protaxed from 91.0

g . (1 .0 n e la ) o f p o to w te to o o y& m ie t o

lo o a£L. o f m te r*

To t o

v l^ tm s ly s t& rto ftt& ftoton m s n d to U46 g* (1 ,0 mole) o f g ly c te te k y d ©
« to to lA o to l t o

20 » !• o f a tfe to L , o w a t o

tte s d s tirrin g * t o
3s y « rs , t o

to

Cn con-

s o lu tio n b%mm to b ld , v lth separation o f t o

to p to te © nos© to 30°0.

m t& s x * fo r tm tg M fo ** to r s *
to n t o

hour p e rio d .

to

to

t o li^ id

re a ctio n m s a lia se d to
la y e rs were decanted

t o l l amount o f s o lid present, w tu m te d w ith s o d te ch lo rid e

52

mad extracted terae tteea m m WO sSl. pertecns o f m p o staa.

in te r n w

Tbs

n m m bgr dtetlX X attea through & beelre t a l i Figreux

©©lam* fte m ute m rife * ia » pteoetf *a a 300 sSU teonieoked fXagk
m p ip p i m m & nuteMo&X s tirr e r end re flu x eourieiaaar# and treated
* it e ft teeah m
fiftlt In W

tn

of potesnta teteeywm te ooat&iiiiag 5$ g* o f tee

f t l. o f water*

fb® resu ltin g utetera m i s tirre d vigorously

fa r tees^jrtea*' ^oars atasd m>tik®d up ftt described sbere. fte penteno
eseteftote wars dried mm? « a ^ «
r aftered i& 3 M & *

^

sodium a& te te mad tea peataae m s

eonsataftted residue m e d is tille d under reduced

pressure through & te30 oa* Fansgce-tyr* cotaum. A y ie ld of 6?$ of
pure 2#2n^etiX33iyr.iQti^l thiiwuaa M JU fig ftt 80° <10 m ,) M

1*1*615

m i obtained.

R y o ta *! constants Ad reported by Wxigbt (90) fo r te le

m teid U l a re i

b*p» % ° O k aa«), m|0 1 *14613*

ire p « s ftti« o f X H M ia a r'M Q te N A ^

m

teft balol^drlja m i iWfftrad by rm cting ssstesnol m tb epiel*Lcro*
hpdrSii is tfat presence o f an ©aid catalyst. I ty p ic a l pmvrnmbLm
fUdUMtt
te & 2*1* t i m

iM

& **& eQiiPted w ith ft sealed s tirre r*

to p p in g te a m n d jm m li&L *& **« *» fitte d w ith a va&aa condenser
aad te e rftc w te r, m » pteoed 28S g. (9*& w la s ) o f laeteaacl mm 6.7 sal.
o f m csritm ted a u ita ic ao id .

Urn s tirre d ©entente of tee fla s k ware

heated to r $ f t a and 277*5 $* (3*C moles) of ©pioidcrteyariia ware added

53

droprise In ti#o hours* The resu ltin g solution. m s s tirre d and ra fto e d
fo r m s M H A cm l four hours, and m l mW® orswaighi. A 30 g* (0.35
m%&) quantity

bsatow* carbonate w s added and the r-iiJCture m s stirre d

fo r f «

t a r e , filte re d and “t o m m m m istim e! m s vmm&d by d is t il-

Xetl«$w

ffa» rm itim %ms fmoticsm ted under reduced pressure. A 232 g.

(1»9 m &m ) qjjum iity <tf m terh al to ttin g a t 68-70° (11-33 w u ),

1.14i50

ms c©ll«tsd» X ib m tea m M m Hot
sm s

b* p . 76*5° (80 » . } * «$* 140*22, (11 2). A 62 J $ y ie ld m s

M s& m ® based m epicKLorelQelrin * A second preparation gave a 675

y ie ld *
%

the fo lla & n g s&rer&ewfeal sicdificaticn, the yie ld

wm te im e e d to 60#*

f t * rads m tlc o f nathand to opiohXcrcberdrlzi

m # xeised fs w 3»1 to M l end the am otion t o p & t o s m s Eatntainad
a t 25-30° a M le the ej&eidUm$sydid» w

being added.

the am otion nix**

to te m s s tirre d an ad d itio nal fifte e n hm m a t room temperature and
a fte r nrntm X im tic® o f the ad d catalyst and filtr a tio n , the excess
methanol m s WKsrad under swtaesd pressure,

A
A sedation o f 231 g . (1*66 ssal®®} o f l^ th o K y ^ i^ ro ^ y -B -c K lo ro p o p a e in tee lite r s o f abmitote stoap ms. Skmtgri in to a 3-1* th re e ssidw if fla s k s q p ifp tf triLth a nmlMUtkaX s tirre r., a d d itio n flask: fo r

m m

to

pmXUBL trn & w m fitte d w ith * y a fta o to w a r t o

to to to a r *

f t * O M k m e mp*JGrfesd la m ic<H »tk t o

12Q g* (3*0

® » to ) «? fto S y f t o a t o t o t a l if t o t o e m m added in m i l porticos.
In m e bcur* t o la lasMJig t o to ^ m iu r® of t o reaction e iis to s a t
0*$®C* AFfcesp «a t o iiic m l liv e t a r s o f s tirrin g a t 5 °, t o rsaeilco
i M i r t mm eat aside

A .900 sal* <*janfcifcy

en l t o a to r lay© * m e s e $ M tid *

t o aqueous layer m e extracted

to e e tim e idtfe ?$ a i. porticos o f e to r .
te n

cn the eleeeHbatSst

to sar m e added,

t o cctoaed © to r to c iic o s

tb® &&t&r «**•* jm jm d ,

ffiaa ra si^ ie

m e d is tille d tta u g b a 2s&t m * o d taa packed w ith 3/16 took &Lasa
ta le a s *

ft*

1J£19*

d is tille d a t liOHi^0 (2&-2S an»)f
t t * *fto A » ie reported to te d a t S3*?0 (85 an*}* n|^

1*U€12, (112)*

Fear p s p t t o s p r# yield s off 0 1 .6 ^ W , 83$, and

8 1 *^ taead o» t o I^ 1 li€ ^ 2 wl3ydw y^3*a^aro^p0aj© used.
•g
4»i^ M
B
B
esH
a^i tw
_S M p ^ m p p n M

Ww H P lJtr*|ra«n

W U

•flrm i P ^ * w "WSBP

'

t o toigtafc

mei Bollard me 80S (132)«
w

•w*

« R » ‘W

•*' ™ f r ^

^

f

*

ItoeMNKfeto of M l@ tosg®*tto^ t o ta l®
/ \

t o to ta l® me p w p ta f ta a t o cam aptol&g octal® and a lto ?
m $m m f ^ s s t e to o o p u ta or- to r o m *

to n entotriag p to to s n

to a e p u ta , t o proaaste® of Sampler, S t a r t t o to g ta (Ik ) ms
t o l i t o * t o le i d t i (M m rea t o t o t o dstoopad by B t o t o l t o
A s to to (22) m s M X c to *
U&oepmaie M ls t o

A % p to I p ^ p a m ti® u tilis in g p etassto

Xtoa $0© A# te e s -ta ta flask prcarldad witb a sealed stirrer,
to ffln g I M

t o ta fc lte t o r t a Ix&tiiiig * t o t e condenser to .

to r t a t o r , mm s te a l n g* (l.o to * ) of p o ta to toocpwata t o
TO *&* «f t o r .

to to® n&mm&p to r ta ao teiai, kept at 20- 30°,

m® to a d d n to a t* SI g, (1*0 ® m ) of
t o n g an t a r t o

to r n $sa#to»*

t o ta b id solution wm s to re d

t o an a d d itia s a l t o ta r® t o s a t aside ova to g b it*
ly s t o m s separated t o

to

to

ta o ( t a »

a rp & ie $m m m » ta s te d a® described

s ta a t a b a IM S m&mm a a te ta off p a ta to a to o c p to * ( fif t y ®mm
o f to

S ilt in 300 4 U o f m t o ) , t o

fiv e t a r s ,

to to

p t a i agrsto

mm AfjftfP atttSFi*^%NI ap* tbs f^p p p isiyar pmi ipie*4pfH* *ri-fejh ^*p ffirat
jupfy*

tbrm 25 s i* porticB* of etissr* ffip

aH$g®* dff#rptp|jfl| fttyl

ytffipf %j@
gp&dried OPST p^foyftppp

aii# tb# at$3@r mm wm&mi . $ls canttk produot sea
mmdtm .j4,nVt.r^<!fl*pj %m®l0Ur&* ttelMsSl ft

CBS* FeKSkS*#art>®

wfeimMim iM.<ntote^. feritak lAA

elass .MLAcas. ®h® mior fractdoa distilled

a t & .5 -& 0 (35*17 »»#)*

1 *^ 1 * t o piapamticaia gws y ito a off

ffPefPPMRfWVnlt

JWHWWWWlF'WW

W<S*.i(*W,r

p ^ P WPWIP

w«spw 1w

93$, t o 9 % b a to an t o 1 ,
to n t o

-•— ^r* '^•W* — —W

•! .W*BIw 1 W M P P * W P * P “

a to .

m wm &m o f «& to x w s w p o to to t o a c rrm p to ljig

to ta l® ms aooo^aitoi- idtfe t t a %

t o feAlosdag p r t a t a ms

mipAoyad*

to a 1 -1 . to ta s a d to flask to& W ** *&ti* a sealed sfetrmr, t o t e
atom iser, tap fte ® t o t o t o tta m to a r mews ita e d ?5 g. (l.o to o )
off tto w e a to . 30 s&* off a .to te i® aaid s o te im (1.0 a*. of acid

%

In

A * of to e r ).

I# $*%$P and

t o to w e d coto sto o f t o fla s k were cooled

M IM S m n p u td ie 88 g# (1*0 nola) of l*2*epaQr"34*

3S6^bC8QT$8top8llfl t o to e d d ro jto e 3» t o to r s *
a fte r t o epotoe M

k quarter o f asi hoar

b to to e d * t o to o tlc n to a w ® t o allowed to

m m to m i -to to to e to eatotoy twtoiOtod with 106 «, (1 *0

to e ) of l i t e

to to m ts d ls to to In

«&* or m ta r.

t o aqueous

a ra fto to t o a to e to d t o i* t o ® nX* p a tte rn o f « to r«

f it o t o

k £ t o e tto ls ii m m m U hm m a t o t t o m l o n t o separated t# m t o

state aod

etbsr

m i wsaated.

tt£8$S WXP& ^oratotoisd $&$& tbs ©rgpssto la y e r

eiber

dried orer anhydretis

SBftf&ta# A fte r r#$ew&l o f tbs etbsr* the resides was d is tille d
sjsdar r s^efld ppesiBtosi tfaroagh a 2x60 oa* e to R pMSiM i'd w ith 3/16
$jass M lM K *
to

t o m $m tm z U m d is tille d a t 6C° (16 rasa*), d j? \*k 7 9 l

■m m t®pssM to & $f% y ie ld * A second p ^ p m iim gave s ta lla r

namftt#* to to n l analyst® *fcr

o a & to a to t
b,

fw to follswiag results*

c* t& £ $ $ u§ t * # i s# 30*7? .

m to t

0 * 116.301 h, 7 *9Ub

jo<£&«
im m m U m <s€

OH
t o M lo ^ d li WM to a to d by t o d iffe re n t aatoada, cm u iilis ta g
aabjsrcimus s ta to e to e rld s t o
t o t o a lt o *
m Um of to

t o © to r coventrated t o t e ie to d a®

t o » to g tto a e to a a ic to to d * was a t o , a sligfct t o i f i p ? w «ta« t t a t o t o by ¥s» 2^1,

(2 ) m s m^Lqy&d

57

to M

to

a

la n ra a i Sa /t o d , A tgrs&MX SQ«ato»is

-& a 3*1* toswwsksd ftofc pptoto with a ssalssi stops®*,

t o ^ & g Jtaato .t o p to la X

to d in g & y a fta coadmssr sad

t o m t o t o , wm® $ & to 5 *&* «C «n l9d m s atom ic d&orid© sod XJjDlt
g• < a to m ) o f M p tim * a to t o *

t o re flu x ocadsnssr sad dropjtng

f&nasul m m p ro tis ta t n it& as&dwm ahlo&ld® tutbas * t o m o t t o fiM k
m® i§&o®a la Amto-fc&tb IdtoXXy At 2C°c,

i $$$ g.

(£x ades)

qu&siilfcy of to to « a s i$ M a w n added topsls® oarer a period of tiro
to w *

t o m to-b& tfo m s mpa&«©d ty/ a t o to g ata& s t o t o reaction

sdsitePS- m # wSssssd. fo r as <bcw* A fte r
•*-w* iA-ui

ssixlaisstlissd, if|t& aB
ff¥?ifaw
>

bgp muosito. Mi^tyiJiEM,
a

the

atlmicCLms reTOred

edaowbyatsd resls&ie m s

ftdiJTO |ACted Ultfo 3/1& ^nnti

ms

t&raugb

b josllcss, to gSsfs a £5-3$

fie ld « t f t o t o to tta g a t 71**755° (13"Xi; i® i.},

1*14£5* & aeeto

p?#ptoto p » a $*«!$ ytod* as litemtoe toaos for X-^ttor^,w

4pt»*®^3*ol&o^

b* p. 0*>tlo (IS m u), 71° (2 sn«), (2 ),

*§s 14370 ( n z ) .
It o

o « m *tm to s u lte te to d m s m floywZ m t o oataO^at, a

w itfto tto of to to to

mptmm

fcg
r ®as»m
»*a»iaaiato«>to Bsllto (H2)

t o a t o , t o w » X to In a t o to tm s a In jd to * A ty p ic a l propam-Awawiftwww♦

m

a 2-1*

mm

p a t o t o g . (0*0 to s s ) o f
t o t o t o l M * to d ( d* X*0U)«

to ta ** as detoto atom, mm

e tte O . t o

6*5 ®&* o f ooaom-

fo t o iflg caw to r a te m d to a tto n

58

m a added to p s to * 372 %, (luC nolog) of @|^oKlo3e*ol^driii> la. t o and
m h O f kmm,>

t o m *U o a i a i p i i t p

t o iis lly i w

m $m m x to tin g mm r m ^ r n to t n la M

A n a l #ta©B0 o f t o

to j& °, b it

t o to p e ra te ® duriag t o

a ftd itia u

t o reaction iaix&ire m s

to ta e d t o an n d d tto a a t o r to * # t o eXXoto %& qqoX to m m
tm m ftu v **

A lto siding «kmmni im stim asxtoat® * (30 g.)« t o »o3j»-

t t o mm i t o t o t o mmm3L bm m t o to n t o t o t * w e m i^ t,
m o t& m

to

m i fU te o d t o t o mo&m e tto c a m s

in maae ttwottgb & 30 cts. Tlgraux colnm .
tite

t o exude s to a c t m s d ir*

oetoKSi <&©8oa?$b$»$ .eibcw# unter j^©duo®& p*es©ujc*#.
a jjttU s d a t 72-73° (U -1 2 jmu)*

X.4^% * A 703Cj i t o m * 4MkIjmkI«
t t lt o

to

t o eottstants reported by Flcre®-

M 3 t o fo r tfeta m ieri& X axe*

b* p. 00-82° (20 m .)>

» f f 1-1070, (U 2 ).
o f t,2 ^ p ® s y -3 -e M « y i^ p ^
y
a
t o epotoe nm p e p t o A m X -® tto y « 2 *& y d ^ ^
l^ a to n g t o

p e s e ta s « f

toee-aedced £U#fc

t o M lt o

(112),

in a 3 -x .

***& * to te d #btaux# solid® z M lU m

*»a jto lla Q . to # -# * * to d ln g A x s fta e u d m w t o tonooavtar,
m m p in to t o t o o

« f t o to t ® s to p 'to 277 g. <£*c m cto) of
t o f 3 to m s m ifo rto In ®a is e -

t o 120 g* (3*0 srt&Mft) flA to s iy p to e to t o t a b^fdrc&ide m s

$9

fcdslod te i s w ll ptM f& tm ,
a to tftto d t o

to

m &m

fla s k , a t a m i© wblob

m c itlm to p o m ta ® a t 0 to £°o ,

the m c U « nigfeiu*

*3 sttewrt at Oto 5° fano
aaddlticm
Xjftfc
rah
o
u
rs* a
n
dton at ro
c
a
a
topm too fea? motto fifhossa tars. A £00 s£L votaa of vato ms

addW and to t m^mom lay®? m s sepsm tod ana o scto o to ! w ith t o IOC
a&* js o ttta s o f s to r *
hbm otiBttfasd* and t o

t o orf^tonSL o tto layor and atiser ostm ota
# tbear m s im w rad ca t o

foot- t lg w v cg&sm* ftta tiX U itlc n o f t o

sioa?Hbatfe using a two

rsoldae through a 2x30 «sa

f0ato*% p@ o tte ti p to d w ith. 3/16 temk gt&sa h o lto t g M to ®
l tf.-2-o|'#^3^li03S^opinoboilingat #
H
?
7
0(5
1m . ) , aj^ l.h ® $ l*

to

m
$£
L
«
$
jt of ttowfctol* A m®<m* sisC
ta
t?r^p&ratleti g
o
v*a
$3$ $ ia M o f t o

p r o to i,

a 15^ jtiUQd o f to o w io r ia l and
b« p+ 61® (S£ janu}*

and X'olXard (212) obtained

t o physical constants as

l«!tP2«6« t o l r zoacticn to o m s o o a a to i shctpiar

to n t o t m®& in t o f » s » t mote* Is a 2$L,

(2 ) cs& tto t o

o t o r s o lw J t, «ud ttMKt a la rg e * n t o r m tio o f ©odim iqtocK ido to
bfelnfclSMn to o te tto a T356 yia W ®f

b o ilin g

at ia>m® CM»*)*
i^ g p w tio a o f

A

to to m

tooa
a
«
p
s
u
n
dm
of^ptodbrto to M
O
tta
d
teste
a
d
ytoertod
for

tfetomo* m t b t o results town in &bl» I#

2n ad d itio n , t o follow ing p*oG®eto t o to d *

6o

m * i* n * rnw & *m m m m m p m u m m k & sm ied «&**«*■,

r e fte

ft droppfcig f t a a l t a

m m tim m m m m w m ii& l M M « ® m

mmmmafcm, m m s& ftta jog 4 U ©f t a l t a l t a 8U g. (1.10 w d m ) o f
m ® m ft.

t o m ntext* H U o o c ta t© C ^ ° m d s a in ta ita a t th is

to g to ta r® M

i 12B g . (1*00- «&©} of l,2^i?c^3««ttay|3?© pj3ft' m s

lA W - 4m p*3m 1ft mm t a r .

t o f t a l l t o s?xasid© bad been added, t o

solution m ft allowed to u s to 20° cam* an t a r and a S *lf garied.
3$mi o ttrro d im ctfQ a i mmdm %©wt feaf t a t 20-2S0 fo r an s d d ltto tts l fe a r
ta * %

p c a ta Hat© 80G a£U of m to o ew tftlta in a 2-1* sepamtory

ta n s !* mm m ta a ta w ith mwhmI
a lt Wl*

<MW

rail* porticos o f «Uxm£mm*

*«&&*» aulf& t© , tfc# ciiilerofOWa W

ypacyad

ass© mm coft©@©tr©s®» imsicsxQ f®» qsu»*!jjuwk* unoer r&®iG©o prossurw»

JKk-^±jSk

JW'tr tUt

1.1 i>n)tkiiWti ilttmX-jfa imutfr.dk iitfciat

AtaMfeatadF ^8L*Jifc

AOtotMi

Mu J }

Ti^ mlfcifift <1SlinA

iMArf** ilfcrt rw iftit1
^!

o f 2 M t a p w t ^ i to ta ft® * d is tillin g a t $0° (11 a n *),

k m

IJiTKS ms c ta lta *

t o t o r imn* off to ft a®tta was dtsetsst&sta

b & m m of t o tarn*' stold M a lta *
g m t o fte&taiiig m o lti*
¥&md*

m m m kaX analysis for G3b10^

M ta a ta t

c, 0D.3Ui H» 8*Uti S, 27.12.

0, «&.CSS fi* 8.76s S, 17.32.

t«
t o U o ^ r lii t o

m m m i lw t o sold o a ta la rta rsaeticaa o f

pK spaA -1 nltfe © p io ld o ro lf^ria g ta o r itn g to t o procedure a lre a d y
to ta ta
to © t o

fo r t o

i^ d t a ls o f 1 - M t a ^ - t y d r s ^

*

ra tio o f ppopanol-1 to o^iciilorobsR Sria m s 3*1, a 70$ ri« l©

m.

* * * d b tfc ito . 4b 83# y ia ld m i m l l t o to n tbs s a iio w s 1**1.

It e i

d is tille d a t 86-68° (13-31* s » .),
*^ % M&»

b-p.

t o rsportad ztagnto*3> constant® fo r th is ecsapoind ares

<20 an.), Ȥ* 10*378 (212).

/° \

t o ^ » id 3& tftlur ms pwsred hy ds^rtoXc^an&tica of l^roposjr*
nltfe sodiiin l$*!ra3&d® according to- t o stitod
slxm^r dsseoribse* for t o a p ito a i® of 1,2mrx»y-3m»tbc8$r?r©pane.
4 9&% y ie ld m i obtained in mob o f t o pretam tim s md®.
d iirtllX sd a t M H $ * (16HUJ m *)s

IJ & IS .

to

product

Stas nrrs’o jy i giyeidyl

a t t o is awpartsd to tecSl a t 77.7® (6£ » . ) ,

1 .10)03 (112),

« f 2HRrosngqrasttagft IM isaas
s
/ \

t o sgnBflis Itu ifid # wm prepared fre a 1^2-®p£^3-p)t^pcS3fppointo
t o * & ta * p to to i m ttdU&oasaito s r tfe io x m , ssiplegrtag t o appwsato
to

p w to ra s already described t o t o s y a to to of 2 *m to ® y M to l

tb U M S .

to

to to a s d is tlU e d a t 63° (11 a n .), n jf

X*2»6$U t o s t o a l w ® 3® m t o a($»yS3 gave t o follow ing s m a lts .
O s ito to to i
S# 23. ^ .

U,

E, 9 A 9 t 8 , 2U.2E.

fdto®

to n t o ® » : petosta th io c^ aats m s

0 , &*21s E, $>xlf
a SW 7*«Ed

63

t o mm of t M w c n ptr* a

m * cfetoto*

yi«16 b t t o css t o

X #a^ i»^ 3^ p (? o p ^ p ^ i«»® m m .
o f l» Ia o |^ r^ » ^ 2 *i^ T K ^ ^ 3 wclil cropropana
m

t o Jm&M&spmM mm prop#sd, £rm Frojanol~2 and ag&c&OtoipIr&i,
a w to te g to t o p w s to a described fo r t o fipntoc&s of l-a s to s a r^ *
% ? to g ^ 3 ^ to o p ro |to • t o » i» m tio of rropancX-2 to opioiaoro%4®1» m o ta x *

t o jp m p to te s & m yltiS M of i*c$ t o 1*2$ of
to llin g a t 8 ^ 1 ° (21H25 sea.)»

1 *1*332 •

flu mporfead oeaaatauts ar®| b* p. 8?«6T#5^ (20 s a .),

JU ffQ (x x a ).
to |» m ti€ ® i o f X .,2 ^ a ^ 3 *6 s o to 'l^ ^
0
/A

t o gto&$yX o to r mm p?©ptod % t o d o lo fto lalo g am tia i of
X-dsotoP’^ Q T S ^

i& tb to ts ® Igdroadte#

t o pro-

to u r® w f&ccM m s s te lla r to t o t <tss<srlbsd fo r l,to im r * 3 m « to Q r
ps® $to*

to

is o p p o ffi gtyd U fyl s t o r lit o in t o

to a s q s m t ^ p a m tio n

of 2*to© p?op^m tl^X tMiarsa&s dis&IXXod a t 55HSgg (1*1*4i3 m * ) , ^

X*lsOft* Uttote® mtos* wprto br iXcrm-QsaXtoo to foXXto (1X2)
to *

b* $* 68® {65 »»*)# »?? 1*UC68* t o yields to n t o ireptottcaas

is fto p d $}£•

63

Tmptmt&m dt

Thiixam

A
t o ifeitzane t o tm m d ty t o action csf aqueous petaatom tfcio-

^rnmm or M m nm m

m&aying t o

t o mtemto tOxmtfp
ft# 2 to ® to i» P ^

fa t ayiitootalag 2totfcc«yB»tol thiizan®.
it&iam i d istillo d a t

(U m u ) ,

l*fe6£L

It a t o a l mrnS^mm fo r o^H^S ®sm t im f«3lc«iag results. Oaloalatadt
o# S k.& l £# £ .0 fl a, 2tu2ii. M
4 38jl y ie ld <sf tba

i

0, Sfo*l$| ii, 8.?6| 5, 2t*.G?,

wm dbia&asd « t e potossltua thlocyaaate m »

IM Militt T
IBW
m
TiiW*fcdUh. &
M
kxk
«Mk w
E&u
*&L
(H
Jlhfajlti zasRiiiau
iB^irfcimftlB-1*^
.,rtnV
i^1-.dfc jkL
j
trni^tl ■■*--A-aaad,
mfflut
$P yi&us
asi@
&ti A
to©
thjuairea
procedure
m o-■—

wAm

fm p u M m of
m

to

ialo&ydrlii wa cfeiatod f t m

® |4d4w © igri»a* to to ta s

to

raacfctcn of bfutamca-l with

* M m t o catalyst, asecawatug to

to m tito d daoestod for to prafasatlaa of
m pm *

to m im iM l mm& la to w S aM fM to prepamiieii of l,2-@pcs*r'

3 ^ s a te y i» p iia d is tille d a t
values fo r th is cmpeoad a r il

(l> ilU ®*0#

X4&S0* U ie m ta e

b#p. 130*111 (20 saa.), ts^* I . 8I420 (3 1 2 ).

A ¥$m& of 50gfi wm cbfcatod to n t o sola smile of 1-butanol to © pim® 3 *1 , wfcazms a V S y£®3d m o m H t o to o th is ra tio

wm k*Z*

6U

Brspamiic® off

0

ft® butad # 3 rc i^ l s to r m o dbtatod i» a&aOda o f ?o«9&, to a
t o awaftas % tead^® d e lp s lro ^ o g to tto o f l^ tc a ^ 2 « l^ *m ^ 3 -^ M o ro »
ppas*

ft® apparatus t o

procedure waplcgred were sim ilar to those

described fo r t o s p ito fita of

ft© butyl

gtyu&tyl « to r boiled a t 61*68® (16 » . )# a jjf 1.1066* ft© pbysloal
m r tM to w e p fto t o m a

© to r are*

b . p. 6??.7° (20 m * ) t

XO tfO (112)«
h p p M ta a o f ftH to ta p M tty l ftiis a n a
A

.

a“lCij^i0’**O,*iri'ia’<l|i’**Cli8
t o ib & lp to m s isvpwsri £mm to ' te to a o tto of l,2<©typaqr3”*
b a to ^ p ro p w idtfe © ito r p to © $ « toooyasaai© or to o u m * aeo to iag
to t o p m t o © alraady de&cribed fo r t o aytxtoais o f 2m stfcc*yM tltfl
W & im m *

14*679*

t o M m to g to ilfl. tSaitou© d is tille d a t 8cc ( E » ,) »

SSm mb t « l a s m i:^ t o t^E^CB gave t o fcOlcwing re su lts.

O to to M t

c# S6 .?0j E, ?«ii6f s , 21.70,

wm*fa

Q$ $ S .m L, 9 * & t

8 , 21*90* A jtiU frt « f h 0 mm realised t o a p o to a ta toooyaaate m s

to M P d # t o a 90$ yield t o * t o tfetorsa astod ms used.

65

topamtta of

A
la a X**l. toao^aedksd teak e^pippad with a Fri&dxde&i ecndenaor,
aaotNnfcnl atte«®r, t o * » a t o r sad dropping taael w m * added, in <wd«r,
?5 g. (1^0 m3*) of t o a d ditolto in 100 nX. of

t o fdlcMlAgt
ii± < m m ,

ijS g. (1.0

of

m &&)

of sodium i^ydrcsride, and 105 g* (2.0 nciLea)

t o aiatojp m s stored cwsralgfct vltoit toting

«ad t o o at aspmtetal^ 70^5° t o eigkt hours* t o reaction toturo
m s ftltgrtd* m t o d feds* t o h diosaae and t o o distilled ttato yeduesd
p m iiM t e r n # a 2 *3 0 a t* Feato-typ© © e to i packad with 3/16 inch
glass to tto* A
a t XHr&9&* (3D**tt ■ **)»

of

$ & .1 S

of theoyi glyxddyl etor, distilling

1«£2B»» mm etotoned* Tn a

ppepassa*

tf*ti.j| $ 5 ® *7$ y l#ld m s m§3A*sd. fha Ittewatsir© mines fox? this
{ftS & to S to r «3?»* t# p. 137*U*©° (23 m . ) t nj? 1 .5 W * (2 ).
to fa m to o o f 2 *Ito m g m to l IM ixoae
a
/ \

t o t ldivm mm ppp&red t e n X ,2 ^ iw ~ 3 n to ® *y p r0 s s a e aad
potatosxa tto o g to t® , » tiX to a § t o preastos p w io ia fly described fo r
to

s y n to to o f

to to a a *

not Ip d d a M by t o to m m sistod*

to

c y e lis a o t3 4 s c a ild

t o 2n to ossw sto a th to u n

s ^ e fc iito a t 106° <1 » . ) , n§^ 1*5735. A yield o f 61.0?' mm obtained.

66

E ta ttM L analysis fo r

gpm tbs follow ing re s u lts .

Caloulateds

0* m * m K 6.0? | S, lj?.3X* Fotmdi 0 , 6506* fi, 6 4 6 j S# 1*.33*
ITsp&mtXcm of
7ex
M K .^ - c u .

& * 2 -1 . t e ir m e M

flask ftbiaet w iib a sealed s tirre r, dropf&ig

ItowasX «ad pmXXeX side-arm ta^pped w ith a tbsraomeier and dropping
^ i w l i m *e placed 231 g« (2 .5 moles) of consseraial eflchlarcftydrla,
XS04 c« (24i? m dta) o f re d is tille d d ta g ft ta n s (b . p. 55-56°), and
1 4 £* <0.1*3 mbXe) of w ta r*
hm m a t 25*30°, t t a i 000M

a » reaction mlsstore wm s tirre d fo r fiv e
t© 20° ms$ 320 g. <3.0 moles) of sodium

tifflteoMiito, dissolved la 200 sal* of m t«r# m s added In three oaartars
o f an t a r .

Tbs f««tgr eoXutim m s vigoemaay s tirre d fo r an ad d iticn al

fo rty im tatsf taking which a yellow o il separated.
M l tte a^pwoi®

«&«

Tbs two layers w m

u&t& two 3jU> $0L twfck&js
were cQribiaad, dried

®m r anl^droio p ta a is m hydtald© and tbs etfcsr was rmenred.

Tbs cisad®

p e s ta t m s J t a t t a a lly $&stiHsd ms&m reduced pressure through a 60
mu f ig r r o eetasa.

$ » l,2 ^ p ^ 3 ^ ® % 5 a iila o p T O |a m d is tille d a t

5 8 -® ° (S3 * » .) . . *

1 4 3 3 7 . A y ie ld o f <57.35 » » cb teirac.

liy a io a l

constants m reported by Oilman soft M XIayfc (113) fo r th is m aterial
wm* b . p . ® ° (32 ana.), o f 1 4 38 a.

67

t o fa m tto of

Jfeiinaia

tfafck

$
H-Olia-dB-^GBg

$a ft $00 a&* to o ra a c k a ti f i t o
drepfi&g to n a l t o
to

aspipjad wlifa a tw d aaieal s tirre r,

p r e lle l a t o ir a fitte d w ith a r e f t a condenser

to *s s to ii> » w « r»2sto 1$ g. (O.S£ ®ol®) of tb ia w m t o

o f n a tM M L
to ©*$°f t o

lUo n£U

t o a tte n d c to to s &* t o saacUcn n * m m m cooled
6£ g« (c*53D (MO*) of l #2^p«& y~3-di^^

added In an hra? sand a b a lf * fits reaction j&tsture
■C**^ during' ttd s fieriest

fo r an

was
w fw tsltted a t

in if hour* a fte r

it

mm allowed to m m , In to o® haters, to rom to re im te ® ,, t o rm eticn
uKbstaro wm pewred te to 300 A * o f m ta r, and 'to product m s extracted
H im tm r $D A * portions of' o i& o re to t.

to

e c to to c lto c fo m extracts

w m dated a w r to y to n s t o t o toJ& t® , filte re d t o

m i m to #

t o rm id m l Uqpldl

t o oKtorofam

d is tille d to u r reduced pressure

to o u # a 2§s30 an* e o ta a packed w ith 3/16 Inch giant bailees,

t o pep®

p t o t o d latX & M a t VJ° (IX » * ) , i f f 1*1*832. A y ie ld o f & $ was
obtained.
tiia s ttln to t

a a to tm l to Ig ratn t o Cyfti^B a*w t o ' follow ing re s u lts ,
c» £?*93| I * 10*31*1 f , 10*001 S, 22.07.

I , IOJiSs ^ 9 *& $ #* 21*96.

F c to *

c# 5?M1*

m
to
m

m % M u m d m ® m ® m % im &

tot tooatod by Todaen,

T c Z te s d

J&ata (lib). 4 # » aa. tostpstod fl&sk *$ils$ftci vdLtb * w M

«t&ie»©% topgdng f S M X

m d

pmBftl ftto-ftasi fitted tdtii ft tomasftte

t o yftfto m t e s ^ » m # t o r p a mife XQQ *&• of togsfr«Hs ©tor t o
1*0 g* at fto d sine atitartUto* t o ©tor unt ha&tod %o r&fim: t o ft
mixture ©cspoto « f 31 g* (Cu$ oaito) o f efeism®to<& t o U6 g« (0 .5 KK&e)
of

m& toast tep&s# to t o vigorcasly ©timxi aa&iticn

In ft fcfttf boas*. Us©

%®ft

for* ©a

iicwa?®*

Ajtfeftp oooXMg tbo wsismsMms i«s$ntnj?© to ro w t©stp80ftttoP©? tte d o o r n y 4**
lyft ^fflsayyrt HlffiHI tbft
«meS |j^ «tfeer

t© ti*8 ftMfft c£ tibo

fonftffti by ofoiyji*

l“©8|^5® lra^» t bftfl

^i*t4cm .

coneontsfttBl

ttet&Sgtl ft 2*3C CB9. OG&ftSft p&ckftd With 3/l6

It o #ft«i M L 1 « 4 A ytssM of 66«3K# Si g» (0.33 »©&©)* «f product
f i l i n g f t t 80*32° ( H f ® 4 , je ^

m « ftb te ln x l*

t o rsperted

cmstaats £«r ton ^orc^tonyppoiyl aulfia© are* b. p. 4P*
(1.5 a s .)* ■§* WBW (H U )t o p if t iim

o f X « E # fltb io M #3^xaiyra*o|fta©
✓ °\

O iia

A

of t o fwctoe© un«3 by Haaitseaea t o Setoftteocu

W $) S I «®?&cy««S to ©Motel to ft laaiftrto.* Xn a 300 n&. town©eked

£$m& p m t& M w itE & mmsbm&ml s tirre r, r a f t a ocnaaafier and dropping

funned wm

tu g. (0*36 note) o f potaasiiim Sgpdzooeldft d ito lte d

in 50 A * of tn to #

to to©

it M

tmm wm nddod dropdoe,

t a in * & w i fe w , 3fe f . (o .a a «®a») o f

.

A fte r etlrrS ng onotfear fcalf fe w t o m o tio n ro t oeng&eteti by Adding
of' it i$ 5 w jiw a p te ftS to feydrc*lsi& solution to t o mister© «ad

M

g td M n g i t for m M m

ttom

feoit, i t thin point, to m o tio n stbrfems

M B iM ' o f two l i^ id it e m and ft m i l aiacunt o f © olid.
i l H l t a p>©test m s « M M
dftetS *war ftnfrowircsis ftOdlMKi
*f&«» fftgdtefel ffil w s

t o dftftiroei

ftttfe to o * $C r& . pcsrtiona e£ © to r,
«*** tte atfear mb* rwaored in mono.

13*^ aador roduood jroawai® ifepcsigfe ft 2x30 cm.

fm ia rty p o o to a a sato d «ltfe 3 /M incfe $L&»s holloas* 1 y ie ld of 03$,
22 g . ( 0 J , n fla ), of pwSaei a irtU ita g « t & -630 (12-13 a n .). a*5
X A iT tl wm oollftctod*

t o raoor&d pfeyaicnl constants fo r th is eoftpoaad

b* p. 6?° (15 *» « ), 1*2* (3*5 « n .), a^2 1 *W 9 (115)*

wm

A tteM pto IrftfW fttim o f 2*-S^t^ltfelolm«tfeyl Zbiim nft
&

/ \

t o itw d ttt* t t e w»t s is d to to t o t to o r to d fey B ssto& l ate
ju m n

(tut)

fa r t o w m t o n of ste&Sta ite a s s a lf lt o .

to m s iftto d f i m
to

p n M

A 500 afu

p ip p e d «ttfe ft m ln siq aX i t i r m , dropping «

M * w m w rw im idtfe- m t e « s d m

to t t a t f t r ,

t e i to rg s d m tfe 115 adL« « f m ta r, 15 sal* <Cu5 m to lo n t) o f eom w r
fr& f^

teH ferio ftoid and .1# g« (0*$2 nolft) of tfeicu m *

t o s tirra c

70

ta a ik m m »

to M .0% ami M

tta® * m dta 0

g. (0*5 itata) of

J^pasgrp^i^^ m s a * ^ te in is o 3m am t e r and a t a lf .
m m m r n m 1 m m m m tm m starrin g , tta a M m wm m * m > m

t t e t * t a p # to m a * to »

tsBspm tars* A t tb i» point a v o ta ta te t

m tita M J 4 tad. $mm&f wtekte dtarffcfta m oors&il m Ptm llsm tioB d

m

m m U m oteteow m 0 g. {©
•£*tata) of *ed*ui m
s
b
c
s
m
tad
is
m
L
v
o
d

ta^A ^ofm tar*
M

3ta m o&taag t a ta tte was l l # t pink in oeloa*,

#i- s t m t e i iw t a 'M M o tao 3,gpmf «fc&ta wars sepem tta,

Tim

aqm m - $mm wm m & m M wm* tf* * * % ml* p o n te s <$ e tta r.

Th#

waasa$,«2 lieSW

©tab&mta c it e ssd&a&sats maNi dried ewer ttriM im iii
Tfe#

ptadtatag ’fSseoai® red **fi m m tabJsatta to mesaim d is M X ta ttta i deccs**

pEts# ssapddl^ ppdtaoimg a Klso<c tAffy ssass#

sarG^%*6«<;ii3*< 5B ^ ls
A w d ifte tA a i of tta r& m ^ m of teitss o o tt sad $ o u ft*tM a i (13$ 5
M A 500 «iU teo o m etsM rcnad**

feottswsd M e gtalfim tl wttfe * mstam itaL s tirr e r , r a f t e ooadmmm sad
stropping t o t a l m s stosod a ao & slte i&opurta to a SI* g. (1*5 actas)
of petesito ^md*i« uni $00 t&* «f mtar« 33a»s&imd altali edn~

t t e ta s eo o M to C° «ad 2CC g* (1*12 s t e ) of n ^ r a ts n a t^ l m e
wIM tepwM to It* 4a f«S5r*$w* misatse. After an s&litieml hear
of

to «

tta sotaite of a-p^ifi smrapftldo m s elteed to

tomimAtaro mA

3«

fo llc e ta g roacticsi.

71

Isa m 1*1 •
fttto l t o

fitte d m th a sealed s tir r e r , dropping

|M I3 M I M 6»*«ni holding a

and v tO m tnsntanaar,

m * l i M * X2®«4 i * (1*32 a t o ) o f
^ im p tiid e m s f i M

t o a -r r o ifl

to t o stirre d #pcad4e in Six hnare, daring

sfeissh to togtotare of to resetoi isfctore m* to stoto At 3tH^°b.

t o atsite® us# t t e s d t e &n t o i t i t o . t o hears, t o to n t o a s to
t o t o Xayws « 1 M w

t o t o m m ©emmted t o

m$mm: l&grar m i tomoto wfcbfei tom
tswo ooiltosS» dirXtd orer

wrarfaw? %*j?

s€« portions of «tor* tore

«ft4tw» mlfitflt And the other ms

.

^tiRQi

f | ifr waartafoyq m ff
SPfi^dfe^OSiiidl $^?^SNSIME^0a 1i©

jM O «f |sM*tft toteg a boiling point of 78 -79 °

X .li7l##

to

thTOttgh A
jL«x3

(13~lb *«».), n?$

t o U to m to s to M # t o i^ o r^ th io x-2,3^ p co q n ^ o ^ ^ © «*«*

b*r* I*£° (f m u ), r § X*U
?3Gcm),
I t o s t f t o f t o i i t t o * o f t ^ f ^ t id o la a t o l fh iim m
h
/ \
?**

t o M lto s g t o & t o t & M of ad st& ig a to a te t o t o synthesis
o f to im n o s m m M & xg*& « J to * t moom#*

In & $>0 issl, t i M
to ifS n g f t o s l t o

M

A M te sh ip p e d v itb a ito s u s to l s tir r e r ,

p to lo X sidis-n.'m p s to to u lth & toassasusto t o

W O* Bondasaar, ms jfls s *; an tqaeois setotlm of poSassto teicsjwarte

72

(81 g», 0*03 ad® to 85 to# o f w ater}*

to th is vigorous^ s tirre d

S to a tim , M M A t 15*25°# m® added d ro p ise , X1Q g* (0*83 mole) of

to an hoar aad a half* A fter stirrin g
toe reaction tototton ®a additional five hours, toe lo w aqueous to w
ess rew ed tgr mmm of a pApat# and set aside* toe ©rgmie le w *» *
treated again, At race* tm w eti& ra, with a fm h potassium tolocysmte
soluticn. (JjO g* in 85 s i* of eater), fee a second fle e boars* toe two
to w ® pmwnfc, sere separated and toe Arsons le w ms combined with
toe pastes* m q m w %M m sad extracted with etoer*

mmcotoiaed with

toe etoer mfcraots

toe erpato phase, dried ow r anbydrcua magnesiais

m lfa te , end stosr m e rasped la mcao. toe reaidue ms d is tille d
trader reduced pressure through a 10 into tftgreaac column to recover 9h%
o® i p smriujsig ejpcea**®*
» . ffla Metteod o f Culwnor !*■ «,■ ^

U p -*-

to toe apparatus described to w s , m s ptooed 1*2 g* (0*55 s»le) of
to to ttm smd too so# o f s&thyl alcohol*

The s tirre d fix tu re m s codied

to 1*4° and M M , there to ils 86 g* (0*50 aele) of l-p p © ^ lto io l*€ ,3 *
spesW®Pm® m a added d ro p ise to i t , ore? toe coirs® of (me to ur*
to® r m o ta i toxtora m s uttered a to ta l of £ear hours a fte r rs s c w i of
toe ic e -to to .

to * m o tto n tosstura m e torn paired in to 300 to . of

m to r end to® exude product extracted w ith toree-75 to . portions of
atoemfeaw* toe extreats were dried a w anhydrous sedliiia salto te and
toe ehlorcfons was resawed i a m caa.

i& s tilla ttc n c f toe viscous

residue under recced pressure was uuaucamstol.

73

0«

Boadiwflfr

A a y frro fjffi)

32a the ajspretns s m M & m shore, w r» $Laced 175 «&. o f water,

15 «3U (0<5 e<piw.) of aolffcric reid red kO g, (0*52 aola) of thiourea.
2ka reafcsot# swi red ed to ©°C* a»d M d th ere, while 66 g. (0*5 mdX»)
o f A«?»of9&thlQl'"g ,3res«8yprepure w»» added drepdre orer a two hour
p a io d *

f t * fla s k was kepi to the tee-featfc fo r m additional twenty

s ta te s * A t the end o f tid e t&ae the flask was fm e d w ith & ve&uBiinaia
d d t i s o lid *

the ies-hatfc ws* rerered and the flask allowed to ware

to m m Um pm toar* in the coarse o f three hours. An aqueous eo d te
maftnamftd re la tio n (53 g», 0*5 a® l* la 250 »£U of w ater) wee added orer

a th ir ty sdrsite period*

Th# so lid dissolved, aad the resulting

separated *&t© two d is tin c t layers.

The layers were separated and the

aspreus r^ s s m s retracted w ith three-50 id . porticos of ether.

The

arsenic rNtre ««** ath@r retracts wore dried w a r antodrous
^.awwMrtrtwi ani ■Ra.faa„ Bareoal d t the ether le f t a wisccas broian residue
iddch could not he distill«ud o r te th e r p u rified .
hfflgem U m o f A ereM n Jta ig rla cs tal

a ijfO K ih

l&ft^DDd. m w tm feed flta fitted with a refto ooadensar,
pretested with a saa«ta et&or&de darylng tube, were ftaed hk g* (0.??
raoie) of re*f»*F«*W

acrelotB sod Ihh g. (C.57 *»le) of atfcyl orthofornate.

A warn relation of 3 g* of aastasm nitmt* in 5t> al. of Prelate

7k

stfcttto. MS to e d t o the resulting gol&ticsn ms allowed to s tto t o
eight b a u ti t o reaction c&Kto© M i filte re d , fa » grams of sodium
© to m to rnr® to e d to t o U lto ts t o i t ms d is tille d directly
fin * t o m a im carbcemte, to r n # a 2x30 esu ctona pacto with 3A 6
M b glass beOioeao t o to n fraction d is tille d a t 120-121*° (7u7 rm .)t
X4«DCCU A y lto of TO ms realised. t o Htem tar© to te s as
reported by vm Allan (1X7) t o p i eordeia d ls to is o to l are*
t * p* m ~ m °> a |5 i- w - w w *
to p H ra tim of Olyoidaldehyde Iie tiy le e e ta l
«a%"0 ^

/©N
CaHftH-Cfi*

o # s-©
In a X**X* toas-wolcod flas k e^ir-pod w ith a mechanical s tirre r,
.ysiXssE oo$wl68306ir# and pa.mi ^<ai sddsnMEi9 prcvidod with a
t o to p p in g to n a l, P
aoetaX t o 2C0

i jiA to 60«G g. (0.1*6 saoXe) of acroloizi d ie th y l-

o f water p m m tiM to 0-« cG.

To t o vigorously

s tirre d soXutim m s added, in too® porticos, ?lj0 s&» of hypociaorous
sold solution (0 .03I4 g « M ., CisBo mol©), prepared by t o method of
W

(130) •

t o reaction misste® m s sto red t o cocXed fo r an

ad d itio nal tliir ty mi@s*i®e, t o to n to e basic w ith 60.C g. o f sodium
bicarbonate.

t o «bnm iypoot4orme acid m s destroyed w ith 5 h0L. of

1«H t o t a thicm X fate to u tim .
chloride t o

t o to & tim m s saturated w ith sodium

to sm to d three Mstm w ith ?5

portions of bsaaaa®.

t o bsassrs® to m s ts were dried «p«r toydrous sodium s a lfate t o 37 g.

75

Co<98 t e e ) o f ftM O y poHdmd s c d ta hydroxide war© added.

fha re -

aO fttftg s d te re m s s tirre d fo r th ir ty m im tea, heated to t e t e aid
ttta e d

te r *

The sodium chloride end sodium kydrcsdUJ©

lo re m t e t e m% msd Vm homam was removed by d h s tilla tte .

The

r te d m l lim pid m s fractionated under reduced pressure, through & 2x30
sm# t e t e poked w ith 3/15 Such glass h elices.
* t 60-62° (10 3*9.),

The product d is tille d

14025* A y te d of 555 m s rm lia e d .

The p p s !-

m l te s te fc s fo r $y »id ia tey d © dietfcylaeetal as reported by Ifo iS b liit,
^ A * (115) area

b . p . 60-62*° (13 ®®*), ^

1.2023.

ire p a m tim o f l - i ia tte y -2 -p o p m o l
, • a

^

^

E

,

m

In to A 5®0 s i. three-necked flaate provided w ith a sealed s tirre r*
re flu x eomdsnser end mawtnjrt. aydemr^ fitte d i*lth a tboram eter and
drotx^nK funnel. m s dbsrsed 6L. s. (2 .0 moles) o f aw*t haniol aid 3 st»
(0 .1 3 g m t.) of s o d te . A 6^.7 g. (1.2 moles) quantity of ptojylene
te d e m s -Added and the m otion* m iter© te te d u n til a constant r e f t a
tm pem ture m s dham w i*

The skcss® m t t e d m s removed, sad the

reatio&O. Itq s id m s d is tille d th ro e # a 2x2*0 cm. F®Mte9*^ps c c lim
poked m tfe 3/15 inch glass te le s ® .
XkB^O$° (?U6 Bsa.),

The pure product d is tille d a t

14*>XC. Basra end M l© (55) reposted the

follow ing rty»l<*A constats t o lm rtte q r^ -p ro p H te * b. p. 218.S-H$?°
(755 m u)» ® ff 1*2*017* T te® u p t t ®
range 63,-62*5.

preparation® @®ra yield s in the

?6

nm a-mpbfefepl m M m

P t e l« a
d telm tlv® las

m cvym aZateM fro a 6Q-8c°

wm

* • P* 71*5-?3°*

tkm reported n o tin g p o in t fo r th is

7 J W ° (9 9 ).
fmp&m Mca o f
G%<K!% <®-CK3

B
r
&» a 2$GjtfU t t n r M i Hiak Ettai with a moohanlml stirrer,
dropp-ing loans! m d p m X M l

Bolding a a rs fte am Zm m r ana

th sm m stsr, m m p3»©@d 316 $* {%<%9 M & m ) of l-sjsibca^-Farapm *3! *
Te the> s tirre d solution m s added, In two hours, 90 g. (0.33 iaole) o f
fre o lily a ia tillo d siiosptaoas trlb n'm do (b . p. 3^-*1700/? ^ m * ) *

Tfc#

rm otdcti &±Kt&r® m s s tirre d fo r an ad d itio nal two hoars and than dis**
iilld

In to WO A * of m to r.

flm o il l&gm %sm

wasted w ith

w ater r a t il tx m o f m%& mod M a d « w a n b ^ a is c a le ta ci&orid©.
flsa sand© trodoot was
w ith 3A& Ineh
t9-b 9*5° (60 n a *)t ^

throusb a

telioe® #
iJ it o .

cbi. ocOjhsh maked

2te p*od&ot bodied a t 28-29° (20-21 « . ) ,
A yUftd o f 23# was obtained. £&m eatel

s
m
ly
a
tiU
BforQ&B»0 g
a
m
ttefo
llo
w
in
gsw
w
lto
. G
a
lo
a
la
to
d
s c, 3
1
*
3
7
5
B
, 6 .0 0 3 B
r, S
»
*3
0
* fw ttit 0» 3
1
.1
7
1B
*5
*
9
7
3B
r, 5
2
.0
?
.

77

Preparation. of
C»3KK iEs^p*-GB3
m.

la ft 250 m i. one-meeked fla a k provided w ith a re fla x cotidaawr
ware jiftAtiid 60 s&* fif 95$ otbanol, 12*9 g> (0*17 a d e ) c f thiourea and
11*92 f • (0*17 mol®) o f X"^iiaa^^3?!^opropaa8.

The reaction mixture

laen areftaed fo r m rm im m , allowed to co d to room temperate© and
10 g* (0*25 mol®) o f ftodlaa

dieacOsred 1:.-. lO ; m l. o f water a m

added* A t « lU la e eolation m » re fin e d fo r twelve hours, cooled end
a e id ifie d w ith eu lfu rle acid (7 *&• o f ceasu la & ®a. of m te r).
a d d ftctetiQB wee washed w iti* three £b m l. porUcsaa of b e a e e .
o®i>inad "beaeeae nwctrnet# were dr ied ever <uihjydroas
t$$® bttEsnene w
th ro u # ft 2300

rMeved

'Ehs
The

eulfhte and

The residual *?tiy tfi was inactions.ted

Fanaks~typ® co ta a lacked w ith 3/16 lach glaaa helices*

f&® product d is tille d a t 26«2?.60 (2 0 4 am.), h3-£0.5° (1*6 » . ) , n^?
1.1402.

The 2,l*4 n l1 s ro |h w jrl ifcloethar d erivative melted a t 79-00°.

WMmtafal aatitysLs fo r Cjohia^AsS gave the follow ing re s u lts .

G ^O ftted ft

G# U * a ij II, W

ill

% K>.30| 6, U .8 0 .

Found?

a, J0.9U

1 ,1 *4 6 * s# 10.26* s , 11.92*

frepuwtlea of l-^tlice^HS-jropencl
Gahs-0«GB3-'aH-0H3
OH

la a l - l . tJawasekesf flaftk provided w ith ft sealed e U rrs r,
dropping ta n a ! tad p a ra lle l * dd#“am fitte d w ith a re flu x condenser

73

m

to m m m te r, wsm tfM Ntf

g. <30.0 ad es) «T absolute « to n o l

and 1*35 g* <©*€$ g -a t.) of ecdiusn. Tot o s tirre d s o la tia * m s added
316 g . (2*0 te le s ) o f irojylen® cadde. t o fla s k m s tested u n til &
m s observed, allowed to c o d , and the
mesas a tte n d tag then nasaov'ed jyg jg^ng.

The rem ising liffi&id m s

d is tille d t o m # a 2ssM) m * m m m tacked w ith 3/16 inch glass te lic e s .
A y ie ld o f 8C# o f l- e t o g - t - p ^ f t o l, d is tillin g a t 125-126° (735 m u ),
30^ 1*1*060, wm ctotftliMd* t o gtywlesl constantsfo r tills ccapomd as
reported by ate to o d and to a re <100} are* b . p. 130-130.3° (760 a n .),
sjjf* l.bC$S.
$^tanaM.csi o f
0

C”Ghjj—
Cii*tlligj

L
In a $DC A * tbree-roaked fX&^£ p w id ed w ith a sealed s t o w ,
re flu x eendaBUiw

j& m ila l side-®®* haidiwg a ttersaom tsr

funnel a m passed 1*1*6 g* (0.1* M ia ) o f Im U K oy-g-fseFftM l*

dropping
t o alkosy

a lte r m s to te d to 0°d* m& 2&B*k g. (0.1* tel© ) ©f re d is tille d pteeSterois tribroaid© m m added dropds© in th irty minutes.

t o reaction

ttixtoure m s allowed to %mm to room tm p sm to s , paired onto 20C g. of
t o , end t o sipsase ite m m s m p m is d and extracted twice w ith 50 sO.
portions o f bensens.

t o erpnl© layer and benzene extracts were con-

b to d , m ated mosMmtosl^ w ith m te r, 1©$ te & to carbonate, saturated
m m m e h lo rto solution and dried w®? to yd rm s sodium s u lfa te ,

t o benzene m s rmorsd and t o re s to a 1 XtoAd m s d is tille d under

79

toftto pressure through * 2a3e
m &® m *

ij*

J im

m *

l'toawHHtatotopn* stilled at U6^6.5° (28 as.),

n^0 XJtOO^« A ytto of

m to w »

©oten packed wltb 3 A 6 Inch glaaa

{318), b*

p»

21% m *

32-3ii° ( 1 M 1 w.),

obtained* Utewtesre
IM M .

Preparation ©f l«E^ce^2rfjm^ptopropaa0
C^%<H3ii|fGH-CKa
SB
t o mmrnpbm m » propped in 1*7$ yla3d, f t o t o corresponding
batode* bar t o t o

«

s a to d , according to t o procedure already

described ffer obtaining

.

t o product die-*

t ille d a t itU° (24 a n *)* n |C' IJbliOO# to e e constants are t o m m as
to n e reported t o t o product obtained in t o reduetim of S -eto n y*
msfefcgri tM Aw se w ttb liif c t e a te ta m ly&xlde.
Frepam ticn o f 3“StoasypropKw>l-l

to e e c a p to t o c fe te ito by a a e rific a tio n of t o procedure o f
M tfe t o Spun® (9 0 )*

Sa ft $W i& . to w tte c te i f t e k equipped w ith

a a e e te io a l e tir r e r , t o t e etoaaasw t o p a ra lle l s ld e -w * p ro e ito
e ith a toraom eter t o dropping te s ts !, w e p3ato 30O aflu o f dry
sylens t o

25SD 1. (3 4 ssolee) ©f t e t o y d is tille d 1 ,3 -p ro p to io l.

t o e o te te t o to te d to 90* t o «? g. (1.08 g -a t.) o f t o t e w e

to e d in —*11 p t o t o .

t o e t o addition of t o t e m s begun, ©eternal

w ,9 not mammary*

When t o t o t e bad reacted* t o reaction

ac

a

m

s

hasted to m £tex end 18? ,2 g. (1 .2 solas} o f re d is tille d

iedlde m » added drojidse Sa me ami a half hours. t o resulting
solution ms r e fta «n Additional hear, « & m d to coca, and the precipi­
ta te or s e ta * iodide ms remrod by m tm tlo o .

Has filtr a te ms

tfM U M uadv reduced p s m is three#* a 2x30 ora. ©elsum packed w ith
1 A 6 Inch glass b ailees.

m u),

lbs l-^ F tta y p p o f^ o l-l d is tille d a t 6b-6?°

1.1*171 „ 1 jpistU of S7J( ms realised. t o reported

emsteahs fo r th is eosspoaiKl ore*

b . p . 155-1430 (760

ag?° 1.1*175

(9 6 ). Aadsrsoa, |& |& . {11$}, rep o rt, b . p. 69- 70° (22 m i.), 5£-6Q°
(12 urn#}.
£2f«pttmtlcss o f l-gtbcsQr-lHtHroaoprojea®
a^%-0«vBa«CBa-€B243i*
Is a 300 i&« three-aadced fla s k p m load w ith a sealed s tirr e r ,
toflasK awmlaiser »*¥* dropping funnel, ware ptftBiri £2$*2 g. (0 *20 iao3s)

st» WmsmmMMM ppctt^pBOsos tcShrooaa®* *ne roacsic® nasg was oooLsa an
^ *ii mfc .S

lutilmAutbMkh j WHtta M l

i A HCwTTIi MfciiiiiiiiiWiB tfilifriV

m AccHsatfc and a scO aiim o f #

M d M k *vAl« # U N

m

■■tw

-*- •'-

-&

it ■>»

g# (0*66 rade) of >ethcs^ppo|wiica«l

and 121g . (0.35 ao le) o f $flFidto» was added dropulae in & h a lf hour,
t o dropping ften S l m s ratOaead by a thar»o®®t«r, and the sm eU m
adxtaw heated to 60° fee? m e and a quarter h airs. A fte r aooling, the
liqaAd phase was decanted and the apftSJne salts were washed ssrarsl
U s m w ith hansons. t o bensoae wrfaacte and organic m te rl& l were

eee&im d, washed m ceeesim ly w ith w ater, and saturated sodium bicarbon­
ate eolation and again w ith w ater. A fte r drying w

mbydrcus ao d ta

31

sa&ffct* t o bsasso® m s rm m d ana t o m lA » l liq u id m * d is tille d
un isr ssdacsd ^ s m ra to m g b a fegG ca* c to n j» to d w ltb 3/16
M l

fe flto l#

t o 3**aib€ig2rlH3romoia*opB«« d le tiila d a t S9-6C.30

(30*31 is®*)*

A y tS ld o f 7Uf m s r-aalissd.

TOlaw * * * * • aa‘ f a - “ »* b - *>• a * * * * 0 < * * » • ) .

to

lite ra tu re
ij

*«

to ja m iim o f l^ U ice ^ -^ o im ^ o p rc ^ s se

t o s to r*m w m $ ta mm obtained by t o th ia irm method, aapioylag
to

follow ijig f^potjodure. Sa a $0© s&# om»-n©ak©d flas k sq&ppsd w itb

a f t f t a ocm teSir t i s

jftm d 120 & . o f 955 o to n o l, 23.6 g. (0.31

mol#) o f thiourea sml $®«3 g* (0.31 sola) of 3~«thG ^i^m aoFrorane *
t o v a u ltin g s o to tto wm mtteami $m twanty to r s , allowed to cod
abbA 20 if* (©»*> sodLs) of
fnim added.

hmSpmtibds dissolved in 20 d . of m tST

Hftw xm cttoa ztdJEtssrs m # ssfl&sml fc 9 as

twelve

bm m » 'm m aoid *& th tfto t® s o lto lo acid ( l l u&. in 100 d . of water)
aim t o rs s s lto g 3agp«ft « w

fltputod.

t o aqueous jt o e m s m to d

to s s t o ts t o h SO d . p o sto M o f bsasms,

t o baaamie sto& cts sad

tfg u tf* Is^ss* ****** oofetaid, d e M w « r toydretta sodium su lfate and
to b im

m s awwed j& MS&&*

t o residual liq u id m s d is tille d

m $m reduced pem m m to rn # * a 2*3© 015* fanskeHsypa colmm reeked

vitfe 3A 6 to fc #M I0 b a lto s .

t o sain fm c tio a boiled a t $**£6°

(25*26 m u )* A y ie ld of liT5 m s obtained.

t o b o ilia g rc in t of

82

ptopropaao %% reported by Gragg, Alderra&a and i-»yo

( m } bo te
e
* S
8
H
S
T
0 (25m >).
f3m$mmUm off X^tosKy^~pro*smol

cm
In a 3«X*

fiM ft shipped w ith % sealed s tirre r, r o fta

and pumaiail ^td ^ n m srorided ir m a tteaonafesr and dropping
ta n a il* « ltlj a atssa aetaftln g to w ithin a £m centlm tsrs of te© s tirre r,
ware f&noed 2G3S g* (27#5 n o te ) o f 1-teatanaL and 5 g* o f sodium lsydmdd©*
to X W «m 0 end 339 g. {$ .£ wOes) of pro^ylono
fwe^Ai 'inif'

dropaiao 1st tte w hour#*

of

reaction jalap*

‘t e l mm <sm%5mM M i l a constant re flu x temperature m e observed,
W » m m U m sdjctoa m s ©oc&ed to. rcm t n p a t e « f tbs oatelyst neats® 1 -

isod *&tfe d ilat® n&ftexle a$M and tee asoesa eloobol m » removed 4a w m c ,
IW tic m tltin of th@ ooncsasstjaatod residue under reduced pressure throigte
a W O cnu ©«0as» padced u ltb 3/X6 iaeh glass bailee® afforded an 82#
yl*ad o f w ta ria l b ettin g « * m i l 0 (20 a n .), & -& 0 (ID a n ,),
*2 * 1.U .52.
M »|

IJ ilfi? ,

B » tigm lcbl conBtantB re-wrtad fo r row l^tosy-e-naop B atil

b . p. 7k*7lt.S° ( » K B .), n^° l.lilT C (ICO ).
fropam ticai of l*#tepcqr^}~ptagm &
3S**GJgHqp'
Gli

a ® reaction and mbeeouant ia o la tic n of the product were performed
in tba sane m y «mi previously described fo r the rre ja ra tlc n o f

&3

ioeaipt t o - i &OG g. (10 .C jades) o f l^proponol vare
mtfks&wt* A ¥U% y ie ld of i«jm pG »gr^«fs»Fi8^ b o ilin g a t U i8.£-3£o°

C?y* M *)»
(730

14*332 m s abtsiaaii* ilta a ta r© values*
m

b . p. 3i*S.£-

.) (l£ 4 ), «§° 1403C ( * £ ) .
IVef&m tlan of l^I^propasgr«2-p3Popaaol
i-O ^-C K JB 3-GBKJBa
O
K

t o jrvpfem tixai of l “iso|TO |!ce^^"p^i«aol wm1 carried cut by the
p rto te ® p w io ia B y desoztod fop l^m to ^2«|^T »n ca» except th at
M S* g* (2?#5 a c ta i) o f Jfr^pmpneil w e used, and tbs reaction to p e m te ® mm 75- 78° O* Beating o f t o macfcim mistur® w s continued fo r
M&gp* hour® a fte r t o addition of projyisae cedUia m e ecsarletod, A l&%
yte&d o f l^ o p ^ i^ y ^ '-p ro p ^ c a ^ d is tillin g a t 335-137° (73? -«*•)>
X
«
ls
D
6
Sm
s obtained. Litamtoe values (loo)* b. p. 1
3
7
-1
3
8
®(7
6
0
* . ) * i | ° 3L4iW .
to p m to t* o f

M g ^ to w s m s prepared ju s t p rio r to use, according to t o
fOXIsNlgtg Ttfsostes c m )*

tos©-**®c&ed flask provided

id th a tMOsd s ilrw r*. to pp in g f n to l and lo r to p m tu re to ra o M te r,
m s ;8A®*d 2C50 riL. of luabytous a to r .
v ith dsy,
in to

A fte r meepiag t o a p p m to

nitrogs®, 8*6 g« (1.23 g "» t.) of lito a s i m s cut
ptmcm, rtiam i v ltK « to r and. added to t o ra&etioa fla a k .

81*

t o w m M m O m & m $ it s © estate m m cooled to -lc °o . (Dxy Xce*® « ta * to p ) t o 30 t© i*0 t o p i o f a scOnticn ccfspeto of 60.5 g.
C0.^u siela} o f n-butyl brcnlde d im e to d In 100 &L. of dpy © to r w s
added to in s ta te t o m o t t o ,

to

m s Indicated by t o solution

bsoea&ag tu rb id , and t o m a lo d a r o f t o n-fcutyi bromide solution m e
t a n added to p iis e la t a r t y s ta te s .

t o m o t t o mixture m e aliened

to maw up to 0*10° in t o im m t o m t e t o by deoantatian through a

mmm 0mm to e plugged w ith 0am wool, d ire c tly in to t o f t a s ,
(p m ic ttB ly flashed taith day n lto g e a )* used in t o m o tio n s of
gwfcllccE^Btosyl i t o m

s iife iH m tyin tM n m .

I^ p M s tlo a of

In a 500 A c tSawe^wscSeed

provided y&tfr a dropping dsnnel,

tarm w t& ter, m m lm am l e U m a t t o r s f t a ctoenaer protected te m
to e to e {apgssnta flashed w ith dry o n w r-fta n ito g s a ), were placed
3 .5 g# £0.5 g m t*)

I t o t a swtal t o 100 A . o f imiydrcus © ta r .

f© t o e t e t o lm m im tto m m m w tm wm added, ra p id ly , approsdjaat^y
30 A . o f a a lx te ® o f 1*0 g* (C.25 etoto) o f re d is tille d brcaaetasane
in 5b A * e f d iy © ta r .
to t a t a *

t o m c t o t A xture became ta b id t o

cassaaato

t o t o i i a * e f t o braadjsnasne-etor solution m s added,

in an t o r , t o

s tirrin g wm centtoed fo r another t o boars to a lt o

@ «tosts reaction o f t o littd h ia .

t o mixture m s filte re d by decants-

t a t to m ^ i a narrow glass tab® packed w ith $asa wool,, d ire c tly into
t o a r t , (x r e v iw ly t a t o d w ith nitrogen), used in t o reactions of

8$

w ith fftMHQr&lltUbEmu th is procadure is
m m m

to g i* ® * & & % p m

o r * ■ * ! x m $ m ( 123) .

Ib rlfia & b lm of '^*»TSPoifci tr ie ih jl Phosphite
{'-'^%C )^F
o«w w © i*a m m p & * * & & * m * m m

u a $gq a&. cm *a*& 9&

m m W ® m m vW n a mdaae eendansar protected by a calciara ohlcriUI©
mm,

S m rn a &mm o f m ® m m m » m & to tfcs piosphits and

i t M i sot aside* omvuiglife*

pfacop&t© and sodium m m heated to

W **# M rfU ri to m u t» |s e m te ® s and the M e fe iy l jfc o a ffc it* *m
ta u n M in to a cloan $D® tfu flas k* A fta r repeating th» tro ati*m t
wtofc M lm

tk a w tM a a i m s d is tiU e d undea* radaoad p re so n * through

a 2x30 on* Otitesi packed w ith 3 /16 im h glass helices.

Pure trte fc iy l

ftlMftsAi® difffcSSMat $P«5®(SD «*)» 5$° (1? m*)« Scott (10$)
a M lin g p o in t o f ^-"5 8 ° (20 ms*) fo r th is compound,
Attempted CondMMti&cnn of &lka»e
wlifc M tim to and AaotoaMtte Bstsrs
I t a t f n t ftttm q?to ware jKufe to basing about too

of

m ta lo m d aootcnoofeio M $«r Say p ro iy to e and iacfcwtyioae s u lfite *
Bo*r<r?m% in a ll m m tria d no &$£&& nenonariLo atidit&cn product m s
Im B a M I and « S y the p jly w l^ tiiQ n o f th e s u lfid e m a obiaanred*
<
S
B
tofoU^Ing pwsoteww
o
s
mo
n
p
a
n
p
o
**
A* la a 500 A * te M -w K fcttd

provided w ith a M a lo ti a tir r a r ,

jpaftaet ooodtMMrand drowsing fusm el was^ pa&oea 3co r.a. * f absolute

86

S tosiol and 2*3 g* (0 .1 g#«s&«) o f a to ttic to iu n . A fte r a ll t o
t o t e i lad d lt o lt o * 21* g. (0 #15 ssto) cf m lto s ester m s added t o
to n satetoe use to te d to r e f t a .

To t o vigorously s tirre d solution

oss added d ro p to e, to g . (0 4 2 t o * ) o f m m ® * * s u lfid e ,
t t a mm ® m $M M U im oM m rs t o
MMUK#

t o t o i~

m m m t o eolation t© boccsae

t o raauiil& g mM%%m mm ra fta a d fo r one t o r and to a ecn~

o m to to to atan t SO a!#

to

ocncsKifcmtsd solution m e filte re d and

t o filt m t ft pored M o ios«m tsr#

Ho p recip itate m s fom ed. t o

w&M®m pimss m s n m tto lto mi&b d ila te >$toet&8«ic acid and washed

w ith e to r»

t o e to r tm tM m mm dried over atoSneu® t o t o sulfat©

sad to tK D iriU

to s n a te mm t o only prodact obtained.

result® sere

s lth

to to e s ti® ester and
ptNm tar®, 00^

3M 3ar

ester and iscbutsftene sulfide#

tSsen

to fk te were mjSkgfsd in t o abcve

pO^ssrlc profitless su lfid e and recovered acetosoetio

mfmSSr Wmw WWmfflm®«

B.

is a «M H U t*r» toosmeelced £ M < eqpiispid w ith a sealed

s tir r e r and t o « to * a »

adaptors,

me of

sblcb m s fitte d witfe a r e f t a

M t o t a if and i e w s l i r m ile t o © to r bold a dropping fto n e l and
M to g to s to t t o e , mi>® t f a t o S i g. <0.35 to n ) o f t o t e i^dride
t o 360 s i* o f a n M rm s s to r#

A s ta r sterna o f a *to g m m s passed

M f t o to n fc ta to 3 0 # m t t o en tirs rm e tim period.

To t o v ig o r-

o to r s tto e d e u a p w te o f t o t e S trid e mm to e d * over t o course
<tf «n* t o * t o f b o w , 56 g* <045 n to ) of d ie to l m la m te . a gray
s p n g f m ss soon fille d t o a s e ^ lito fla s k . A fte r m additional

37

ttim to® <s£

s tirrin g , 30*3 g* <©,35 w&m ) of iso-*

IttkjfiM m to fld e 'in t o ugu of toydrm s ether ms to ad dropwise over
tt

t o r p irta l* x» t®®si*mtee rise ms c to r to during this

# m M m p m M * taut t o te ja a to i of a white solid t o t o l m s obsm to# A fter tfHL t o iaobui/laj*® sulfide lad bean added, t o nitrogen
is ls t to e m s

by a p o to glass topper and t o rm eticn nd**

to n s t o t o v&th i t t t o s tm four t o a half tomm* F ifty * u of
*tif& t o t o i t o to ed t o t o to to e stirred u n til t o eto aticn of
ty te p a t o e m to * t o m m $ mm p etto to o $G© peas of t o t o
t o fSltmb® mm
t o Siyersi ts p m ta d *

bo a soramtory to n a l t o t o

t o s t a r layer m e dried <w*r anhydrous oaddto

eUtiEida# b i* aftfear im m ad emua t he ecBflanferetsd lemidiie d is tille d under
reduaod pressure# ©sly wsreeoteil
m tfifif la y e r m s wad#

m le m te m e rw$08wed«

ft*

mtth d ila te iiydroctloric a d d and astsacted

etlsaj? * BmpfflSBtdtoi o f the ebfeer le ft only a m ay natt^,
a mft&sr o il*

su lfid e m s r^otrered as a solid toOTjaric

mberiteA* A-satwsid i,f ffij; 4«h yfe4g>^

yetto o f isdbst^dUm® su lfid e to

to to .# to a r t o rn m m Iz& m M mm it s , $ m to U a r m o a ts . h ikm tim ,
& m i te m t o t o t o Saytode m

of

i& to y to e d to an e q a ito a r a ilto re

iaMbd® t o t o t o s ester gave to y polyaeepic iato tyL eas

to fld e t o w m M

to to * t o r .

t o us® of p-dloma®, n-fcatyl

e t o r , m t® tm lyd rctean as to m tits also fa ile d to p rce to the desired
w m im m M m s m to ft, t o

la ted*

t o y t o y n t o ito u ty im e su lfid e m s is o -

86

C. U %

fla s k mpXppad a * abw s, m m iSUtto

t o * • o i *M i|M r^ t9* ® to to t o 23-0 g . (o*6 g .« *t*) «e M te m c
M l w added la sebOI ite e s #

A fto «32 t o scdlm bad reacted, t o

t o £ S to t o ©oeto to *M B to p o m to s , ?&g. (0 ,6 to o ) o f d le tl^ !
imOomt© w eregdto dropw to* Boet* X?#& g« (o*2 to o ) of iacbutyloua
utoto m
oto a d .

jtfU
&
M
t In $
Q
QriU «
C

to m to of

t o i t o i o f t o w O fid * t o a p p to m to y a a U liU ta r per afcsto.
ftfM N N i uttetosg m® pwssidsd to o i^ o it t o t o iiic n p s rto . A lto
O tM tO g t o m o t t o H teta® t o @5 ta r a * t o apiam tus t o so a lto a d
t o t d to o t m m m l o f t o s t o t o to n t o reaction. fla s k m s s»d«
possible.

s&hmqjmit motowp <s£ t o s m e ito iafcsto* gave only tirnmcted

dtofegtft M&xm%® (90%) t o paSysaerlaed iscbotyto® t o f t o .
Jk

***** $M?rissd <11% a t tbs m flm : 'tm rm o tOT of ©tband1 018©

m i& m to yiw o. a ©<$jdsa»tji€s» product.
rin*ifhiff1**T y|iIifi

J L a*.

—■ ■ iuiO JSi

M

m fiitr. ii%*>'i^> iWiifi

utrnh

>wJgh.«» juJM *

S to l& r jrssaltffi to ® dblftliwd w ith ao sto o atic s s to t o
to U d a as*

p ro iyto o

to ffc to *

&« A xon w tllis fe g m S ^ m m a lto m a torfUM tods as t o ccodsn®*
log « # » * ala© « 3 « d to pm ttim t o i S f f l i t o o f s a to ic ©star by
is t o t y lw

t o it o .

S to lto y m omOmmtAm. oaw nad btooen pro&tan*

« g y ^ t o to to o s tts ootsr. 0m<& a g to to y pdtynnic t o f t o m s
ia t o t o *
m m m o f & *to q to tt9 3 > ® dton»s a ith H p to d to
t o to to fa g ^K p to to tsA proctor© resulted la t o b lg to t ylsOd
s i » t o r * s m m w m p to o t*

la a goc bCL. two*toced fla s k © to rr***

8?

KXftb a m & m M te s s r t o

£mm£L were placed 85 g* (1*0

BSto) at m m m m

to

<t». p. ioi«-aai.s7723 m ., & > i.i.s&s)
ij

t$ * U tiff 'tommmm-*

t o M & 9 s o lu tio n was co$GLod to o ° t o a

t o lt o aeOttt&fla of t o 2-^;cag©*afelgrl thiiwura, 0*5 Jade* dtoc&r@d
la t5 «0U « f to to ® , m s to e d la t o t o a t o .

t o rm c tim afcctaw*

t o JnM a t 3 ° fo r an to lt& eam l t a r , mnaed to rocsa tes^amtar® and
m s to ta a t i Jto two

t o mxtma i& p to d la t and banana® were

mmm'&d la vacuo mad t o s to s a fe ttto sM dua m s fractiom ted under

M a t o fmmsmm t o m # a 1*6 m * fi® m x cc&um.

K rai $2 g* (0*5 ad o } o f Znmthmgm&kgl feiiran® and §5 g. (1*0
a d s ) of

ttossw# Has obtained a

am N p to K H f& g ^^

o f lto to D q r£ "*

tS to ffila g a t 88-$0° (2«*3a®.)» a^C l*2t8£l*

H a a m ittl to ly a io fo r c # i*ijo s qpm t o ftiU to a g re s u lts .

O ftto iiM t

Q.$ $?«3£| H, lO O li I , 1 *m a* 1 8 .^ . Ktodt s» 5?*C1| 1, 3jd.Q3j
I# ? 4 3 l St X M o *
t o i^'droeiaorido was p *s$*ral by b to lla g dry fcydrogan cd crid a
to © an ® tos® i # e 3 » tta o f t o e « p t o *

t o derim tiv© was <**it©

JBtitoms&e but a n ^ e rM to t o t a t 130*232^*
gtnr© t o $ m m $ m to & ts t*
5*00# I# 6 *I0 | » f lk *2 0 .

J to & l

K lo to a l analysis t o

C a&m lato*

c, U8*8?| fc,

0# 88*02# I» 8.831 H, 6.28# 3, 18.30*

S s to a l adk&t&oal p t o ^ t i t o m r© m a to d m i w ife 2-tohcsQ r
a s tty l %h&imm t o js if t o t t o , 4a w lito t o m l& ra tio o f raactanfe,
to ® t o r t o t t m s o ira it to © w W .
awral# w•

t o re m its are ta b u ia to 3a

*W » & * •

(04

i3fi&s) «r

to isaii© asd 8? g. ( 1.0

Nflilo) o f i&pas&d&i® to rs * m # c$st»to»t & 90*6$ yie ld of l-eto ^S T ^ *1
b o ilin g a t 3&9-0310, (20 » » .), s jf I4«fil9<
m m M l analysfe to r O ^ j W

^

t o follow ing M 0 ft » .

0 , 60.001 E* 1 0 4 b l I# ?.00| S, 16.00.

fte ^ s

ettto teto d f

C, g?.98$ E, 10.33$ R*

7-10J S , 15*95* l!M 6 s ao6 vo& ctto ot& dttlm s t o seres&l o tto
p e? *® ® tt«a * * * lla iM

I 11 t e l e V.

*4tfc 'te iis o lia a
M a a t
ijar^ ph@©®teP®
p^0f% m s^ to r the
wm

#68fc**W^

.<*/*

-.'■^fc ArfcWl n

JkaMuuiil jhUHMMbnt'

<5®$eyiJb@d

Wfm

of 2-CLk«$®etJ^X Ifdlvane# with iljje rid la ® .
s a w ®M Mm %fUl 8W»s# Kmewss&
*>*jl "t ,#*Uh$l- Ml «£*

*4 #Hi iSSi^^

( t 1^5J c.^S

■—'*"»■

\

J ^4k.*-»*.&

‘rfKni.yfi M i A A d t W M k X ' j m u

■of tls i £& tirla& £&H®sd by tlse action o f K&^pfeoiliii® <aa
th iira i*3 $ jm m . &&&$ %hM£ of l« s s » ^ i® ^ *w rs a |^ 3 ^ r|^ c a izio iT O p m ®

35**36° ( I t $&#)* ft!!** 1.1#® .
G®tt%rx&3p 0 m Urn fe lM ta g restate.
n$ 743$ 3# 16.73. M

)

sialygfi® fo r

GalaOatois c* 50.21$ li, 8^0$

o, 50,52$ E* 3.86$ 8, f.6o$ 3, l6JdL. t o

results of o tto rmoiiesms of t o * M t o i arid isorrfeoIJse are atom in
t e le f # alm s with t o roasstto

to

ic o to t t o » d V t o x t o t m

^rlo p *d .

of $? g. (0 .5 « to ) o f t-e to s ^

to to a ® uttfc <m m&® o f anrpfaolto had a boHing point o f 66-68°

n
at

m **

An 8&*3$ g to # mm Mk&mMU S ta to a l ato y**

to

« t# $m
K» 9«*Tf % 1 M U
to

IM

$®XXm$Mg re m its *

t

(kam l&Uds

a, $2,683

Ct 5 t*# g E, §>,27| S, 1£.<$5. t o yields

w m rn m m m u rn m t o t o * &* « to r tm M m s o f 2 t o * t o t o f i

tW n » 9 t o aar^ioHsi© w e to O n to d in m m ? .

to ix a a *

BmsMm. o f

<*fth

33aJji rwwston 'wm m$w&®& m% in to #m t«b^as dessadbsd for

t o r» e to a of 2'^ vcs^ ^ tE rl to to a s s tdtb $&$at&A5m.
(pMai (G«5 t o # ) o f d to ta n v n to g l to to n s t o 170 g* ( 2*0 to e s ) « f
to l# t& B a ! da«to3*adw» ww?» topSUgrwS.

Stsbse^mi wortc-np of t o

mmMm nlastoe wsnXto In t o mmmsy of botb ©^pantos* mtonged
#»>$ in n@B3^ y ^psEntil8iM w Asamts# Cnee Again the ^rolntdoa of Eset
mm toarto m toti&gto to

tolwtog tot react!®did

<w w ,
msnm^n of ■&**iwpcieransyte^ inn&xwa©
sfith
$ & MU a « iTtifiAnff

t o fo O te to i p t o p
fm m & w

~*i m tlTii*Mi id* T m i i »\

m i p t t o t o a lt o t o t eagy^edby

<125)# fo r rs& attng

gtoto& ae* A M

>-‘
Hft\-S >A

rn U g l

t o #fcfag& g iy n id y l e to rs % itE d i«

jbBU mresiafeid £ M e fitte d n&ife a n a fte «to«iser

im to r p d ultfe 37 g» (0*5 « * • ) of to to y d is tille d d ln to teto ®
to

75 A * o f n a to - A 1

tM to W

g* (0 4 5 to # ) g a to ity of 2 n » P to * to !L

s to ly to o d # wit& togM M b a g its tla a .

s*to mo ©torto*

to

8e tempsxatur©

r@gto.cn siitiw ms reftaed

92

m® m te m tm m # tm m im w x i U a s® pm ta*7 £mms& t o

psU m bw

p H t o « * M . A f to wm m X. mt o t o * t o X q p i» w m
m m m m to

t o < u t o w <teto o n * t o d p o t t o s i^okU S ® .

ilto S a n M m «T t o to er& O .
lack

a 2300 cm* a to m packed w ith 3A 6

W U cw e ffto o d 3&,6 g. of M

it o

t o t o t o t o t o le f t

a v t o t o ^ m m ma&$m w h to o t o l t o he d is tille d a t t o a t o
f S W If *
ees 4sasfj?ied oat* asoecdlag to the above geoeafal

A tMactmi

woaedtJP® SKsewt th a t the

water m s em itted*

heat tMMt MMwMfottff ea

la *&***> tira iiM itla i.

the two jje&gsis’ts* bat *ii]ffiHi silm e^psBt

f vfe ^f4 i;a¥3-‘t i liFt!if o f t fe# nw totlcB ®hstef@# ®ost cs£ the
t h ftfW 18! W ffft £^K^W ed ©XOhEBlggeid* it

*****

!.«.»» a^faaM m i^p* QbaWVed

(S*0)#

to VSSCt

iM k d le t o t o t o t o

reported t o t « to *lU B tic s i of t o

wm&%s& in mmmmw o f t o

rm c% tm . ppottaat

t o stert& B g to a r ta ls , to ic o to g t o t t o

re ad ily s p lite ant 4^dSii^Sa@lBe»

HMtom of 1

isrepae

M. a SPO A * « r s t o
t o t o i l t o W ith a t m

< 3 to p to d e d w ith a t o m w t e r w e ll

m * f t t o H p g * wamm I»dked With 3 M t o t

g iM t t o i t o t o a w *3*K S* t t o m f f dSstmissg hm&> ew e t o t o 33-2
g# (o*g sjcOe) o f j t o f t o

pheagfelte t o 1B.?3 g. ( 0 .1 ssto)
t o re a rtim id a taw m s

heated toil i t

rm u3 m & VS0Q*

t o hoHihg poiat of trtatfyl

n

Som a fte r t a t o g m $ bm$m, %m b o ilin g m te ria l begas

be coHeot is t o dlwUXlm$ hm&. l& s ilU to mm gqXX®eto a t sseA
a* m ie t o t t o to fe ttlo ta to p s m te © r s t o t o is t o mag© tyXtkQ»
Oa

SOI «£ to e * te t8 & d is tille d a t l0 ..2 ^ .e ° (?$> wu)»

t o p i^ ia e a am toofts reported fe r s& tbyl a ll^ L

%*3Wk»

© to r a m

b . p*

C?5? as*)#

•6C/s m& abtaSziBNS# '13a> <a^,^afel ^i^ t.-\i ia

1.3773-1.3803 (332)* A yield e£
.ean residue m s fs&ciics&ted

to@ r m&isml pnmam toaig h t o p&skid cofcxsa. A lto* recorswy of
m m m t r i t o y l jtm ptsit© , a m

(in m ») -ms e ite lx to *

i

of m bari& l boiidag a t 133°

t o to ^ c to x a e to s to b ** (c ^ o ) j*H>(x* s^-ao) * i®

Xttptrtod to b o il a t 138° (ID m .) (238)* t o mjcri&gr of ztttotfal ooald
net be fto fle d by % s n d M llA & tto t o a n M
ftofc

m

la t o distiiX&tlcs

4 |OMUd» vfaleb ms readily ssttoble Is to ecssaaa orpsiQ

®0lfStlt®e
tm, /vf

•**ainlW^TW^lWM*eW*a

'WBb w

©w

* ™©lP:TWwW'IPB»i^jy

Wr

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m

a m n m r m m lm d y d m a rlM
to

t r iif t o l to s p iita ,

asom t t o t m i& N iliur ^ s t o t t o o f ir& s to i 1t o jb t o t o

l-s to ic s ^ **

m s» m O x p ti, to . t o pat to p a m tu r*

m » s lle t o to m c b X?3C>*
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m m m *-

a

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t o tosfe to m pot m lt o to M set be d is tille d to e r

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to te -e p m m mv®&&& ou t aootoS ag

to « $ to s to « & ptorn^m m i t a t o t o t o t o #

«tf

fs*m an o ^ it o t o afecfesre

t o M e th y l phe&tMi® tfanw

mm m m rn d a $3%& m
4 f X«388?* ft#
?I*3 w# (128)>

«t e ta * *03g& m m # u r n * * m

w to M o to to e fc r th is e ta * era* b*
3U|%2(U l)*

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&&

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to to to to » *

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s^3L^ing the

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d t «&iqft a lly ! e ta ? beUJtig a t d£HS6°

1«39# mm ta to a d * i& tM te e m ta s a b* *». 66*6?° vt

t y an* (1 2 3 ), ^

1«3@9£ Cl3X}« A tte s te d d ie tiia a tto o£ t o vieccns

bra®* otiU M to v t o t o t o t r HMWaa m & wm®omm£®l«
m wsM m « f

IM to a e
vith firoito®

TM m m m U m mm m w M m% tm m dSiig to t o aetfeod developed by

ta to

t o O to te (m >#

3H a m

$SL* rn m rm rn d n& ek t o ile d w ith

a < m M s t e w * m O m mmdmms? t o d v ta a g &m rol ime t o t o Kuh
0* (046 toft)

2«totaytohg& tb&ta*o d ito lto in 25 isl* csf etooa

9$

tfltoofefaff&ti*
(§4.

to M M

aoa&tim m» added, Saa coo h m , B g*

of Brenda*

in 2$ al« of aasfccn tetoo&Lor&do-

a® m o tlm sdtelm taa to m ta fe d to & gejmmtoy ften el and lasusbod
Is?lot t&tfe 100 A * p o rto w of $$ io ilw i m&amtm »eSU*ttm and «ss®
«m » m tn r*

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to m fe ta to was sttwed M U M ^

^

o a a to

eanosntoted resiciae mm

inB jeetetl to n o n d io i£ U a to n t to m p e a t o ssotoriol ra p id ly Be->

<5tiBpOW0di# A

fofr# ywwMMrtfcly frmwyft fOpflOtod by StOWfcrt

a m i m t t i i (9 2 ), t o d js m ii tin t tin p ro te i m o ltin g f m

jjy^t^iCTli Qf lOSBMlttW OH

UpGB AttMtopbOd

t y WOSETO

jrtS$6&Cvi£$3
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m

go g* (0*1? main) of 2*otb«3aysnfc3^i

OanPB2^#(s 3EH§Kt $mmOf ®HMn88tW!3 UWB pJOISSSeI 2M m 4»50$**►• wffiPO®*"fi®(!«©8w
■flfcA

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S^w^S"

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g!

w

■“ MF

f@ t o *U pem tigr MimmS aofetim was added, a t o°c., in cn»

t o a M f to rs * *B & g* <®*1? t o * ) ef baton* d lt o it o la !& ?&«
'Of o ia m fM *
m m m&

Bn m o tio n iitoaire m
an t a s M

stirred fo r an additicm l two

pm$mi&& fo r Ida® m c tia n of &*neftay»

wms&& tbUNW» g ib beoriai* M nm s**! prifSaim on of t o c *to
m o tio n p n te st, by w o w d ie tilla m m resulted in doetssposliim of
wwSO @aw0r*HUhh*

H m i& o tt cC

to
i« M

to tia & ft id ti* XAtfatos A lto im m
o f l^ th c eq f^ «m ro a|^ |T o jaa ©

pmmtaxm ssailagrad fu r t o sto ic tio a o f 2toScos®sseitol t o -

%r M to ta n to fN tt

to w m

t o p t t o t o a f t o t o t o f B to to X ,

t o f t t i CM}# A % rp ta l p m p m tim fo lla ta .

la a 1 -1 . te@ s-

t o t o C M s fttto idtk & «toanl<aa t o m r , top^iig tetoL and
p m llo l f l l # i i i to & g fw i n lM i a x v to e c to a a a a r and t o w t o ? i am®
t o t o $ * t u* (0.15 m de) o f l i t o w aito isis* i^M *Sa t o

mm*

f© t o

H M

2GC i& . o f

m spm sim m a ©Mad, in

n il fe w * * solution of 31*2 g# (0*30 md®) of 2 -to ta ^ w to ^ t to to a ®
m #v £a&* o f

uKw&t

©SUr^.

tiuiflt

M«**.t

<*.

©twisp*

dfcj&l

*®8i st*$9S9S reaction

-WfW\i /A

jti^'n>‘irMi¥i^ iS

aMJU#

— .Jfc Jh

^aJ[^uJka.wM^ii.

am raid

^.4^ , ^ibf

1>la4

a t it a x i f t e tw p n in tixn fo r an to tfe to iX t o to sw , cooled to ro m
I g n M t e i m d Jdo t& * o f m t© r e m o fla lly added. 1 1SD ssl* oaantife?’
o f W $ saMWS®
f%nfr ©tts&a*

'f i l tdsaa

to dSjiioXr® tb s sdnnlxsin hgfdrcscido#

|jH j| gepfeiSB’
bsd is ^ tiso

toh 7
5
>

i& y ay

eg66®aet®5 ta is®

porHow of #tor* to atop teet&M w
n*®©tolto^

^asv,^^ u ttfe

p g t& ftM l o f m ts r

«aa4i8itOT

iw itc s lj dHed

atyft tbe etlsss? ism rasaofed .la ®^sm«

opw

m^rd^cam

fh o a M i^ y a l

t o stot&XX#$ to s r to n to $mmmm to o n # a &c3Q »# a to m
nto 3/M tob

(27 m u), ^

liilito*

1#W 1#

to

to ton motion <to
tm
@
d*t 32-33°

t o 0S^» to ed m t o tte ito m into#

A tm m d p m p m M m ® $$m m m W

fiM d *

C^^CB 0 m t o fo llto n g amOds** M a O a to t
0 f 3®M*

ato ^si® t o
c# l^#20| L, 9 ^ 1

Fatos 0 , 15 *1^1 ilf f .431 S, 30 . 38. & mmU &%xmt o£ sdid

P d ^ ttto o m tw to f t o

M # w M U s ig liip id w w a ls o practiced la tfc ts

97

m o tto u

A

w a g * a fa w tim M m m t o h i& t o lla g

t t o m t o * m t e of M i*
W rnm m m
fM to m a « tth LitM am A lu is ta i
fc ^ d rl^ s ^ to p T O tto i <e£ l-Etto^2*«®®poaptopK>paa©

to

p w te ®

to $ $ l m sm m § m » m

to to ' t o t o t o «r 2 * * t t o r

m m m t o t ato to jr d a a to to t o t o

m$&<sUm a£ g ^ tte ^ a e to i to to a a . A 3 5 ii g. (0.30 n to ) <pa»tity
of

m xm m t o $*7 g. (C4£ to # ) of l i t i t e it a t e a

IgP&PljgOO
S
H
f©
'

to svAKottai product digyilad at

a|p 1*1*379. A ?7$ p lt o o f l-tt^ ^ ^ ^ m p e aito p aro p tf^

h is

^yimsipyt wmsgmM

A

tifttefeifciiMfclMlbjIh^4

'*%''tyrtnifrt

•rfft'i'vittfr

Tk

S*yfii

o» ®>«ee* e* ic ^ e i s , 26.s e .

gasr© t$s& leuAcwtog ira iu w «
iriihvirwri

^ft‘7tv«°ii.

im *

<311-.*8 'KJ .y^.

.__

m

(2£ » .)*

cb tato d
oaxcioat©Gi
■»

•

o , tfl.? 5 j e , 5>-?Z{ s , 26.113.

A StoisS&t gjpnatssr* #wswt c f Id ^ w b ellin g mtasrl&X m® produood £h
to n m w M m *

Bmm m XM pMgmmi® m tto a l mm to o to u r e d .

off M^pc^^nWQa,|^|s»opiuc®
& a .300 aft*

jO to » ssp ip to a®

dasoribod,

w ro $ ta to A00 s&. « f to a te ta a t o r to . 2.3 g* (0.0 6 a to ) o f lltb im

tCUtoaua fepMdt* A AT g* (0 0 2 to ® ) ^ a to it^ of 2<*pwpa^mU-$l tfctto m d is to to la 3© A * o f m&y&mm atos? w

to#s£# la to ty stoat©®*

to t o toeO, tytieSto mmpmmlm* t o 3 t o « ito te s m s im to toss?
aaaCtas to «a additioml to h m m , e©tod to was top®mtur® to 2CC

ml. of im tsr ‘o areftiay t o t o

A 200

q p to ltr of 1C£ suite&o to d

9B

m& t o

rnm M m

Tjqsbs? m a m p m M *

t o mqpmom & x m

m iI ftftn eM mtfe M am t% e&. prnMkmm af otos*. ft* tto r
«**S orplto I^/ar to * w t e l , « # d Q * solp&to ootoa gullat^,

M l t o « tt*r t o «WMto j& 3 t o »

X«Tiro*«*MfrtoMj^^

m m xm »t i##os m *)$

i*h m * af%m o
r?
8
#to M
S
iM
d
u

m rn rn m i wrn$v&® $m

m m t o fo U e to g to a lta *

Q rtm lm m *

«• SMTI ft> 20.531 S, B3-»- ito fti 0, S>«T5l B, 30*S9u », 23.&U
t a t t o o o f M tttw q p w to l IM &m ns t o b BftfeSss to to a s s

MnoM.« of 25 g# (0.1? jato) of
K.

tM im

idtb

m

g> \v#G9 BOjy&J t f juJwaaiii aSJOraiiBi® isgrarao©* ojr o&poriMKWL tow**
f 'S l f t

Ttliti Jrtj*fr jiML s-

JU |W ^

'*4 iff Jfc M■iriMia n HtttH» T l h .jnw w g ffrttff MIIH

a

.v f M

ln « M i

> A k«M rat^lfcU ^P

^

JL

Ifri ^ ■ - ■-

nis^ei^ ds8®tib6cl, rs^sltoe? & tB© fowsfetloij of X-fai^cKyS?*1
*
mmm&rn&tvsmm la M

to rotestto praftiot aiatllXod at 6&°

(13»*)# «
§
** 1*3W
$* toMtol m »3$to for

g
a
s
r©to fcO
toiog

Stolta. CtotolWtt G* 5?*00f H, XG-.Hi 3, a.? 0 . Stoinii o# 56.951
a , 10.925 S i & « ii

M to O . p M ft o f a M # b o ilin g Xfcp&8 m m t o o

Hto&lGa of l^atecs^««mpU»3prcfa^
to & 8 ^ * ttr tto e to P to M N *
t o am a t o l t o oortioet
to w r t o

te to

m%

oooatiiiig to t o p h o t o s of Boot,

c m ).

< M « tilt o i m g?m £« 3 ftn p to i p * p a « tt* i fe iS iflM .

a
30 ca. o f

absolute #tta@ X la a I'S s i. fla s k m o adtlod a 0.01 s«&e < p s a tlt^ c f

99

tft#

mmwpton mid 04* g, (0.01 .mL©} of sodium iydJXGdda di©~

t o t o m 3 riU ctf m ttr#

J» * m a to loo «&. M

t o e lt t o e t o t o , mm r le to 2 M
f e iii® *

, © te s to a g ID $a.

g. (o#0X a to ) o f a ^ in i^ c c b iw -

t o t o a le to lf© toaitU aie were a t o it o mad t o ra o iltia g

m m m wm t o t o to u r m item tm m irn m t o a t o * filte re d t o t o

t o IS X to te m e catoed 3& r e ta e . A fte r ©ooling, t o raaiesr c x y to l*
« i i to P to to m a f t l t o t o

Hem e b to a te e tia to u

t o so lid d a v te to * o f I t o M t o w i v t o o p M
llt e m t o ® to r» ie t o
toMdl*

s w lto mb

0 m t o fd H to a g re m its .

o* g t.U i Ji, knUkt 8 , 31.80! »# 10.30. r o to i

U4*$f &s X X #2i I , 10.26.

c e lm *

c , U3.91J K,

S is tite to a to e t c f 1 -e to s r, x-pepcogr t o

lH ^ td ^ ^ ,as3©!sm.pt*o|^ptisi@s reg ftted &a tbs f<smt3»cii o f <me^s colored
M ilt

eoald ssot be

to e$^sta3Hs®®

A'ttSKatibe to BseOt
wj-Mi 3«»||liso^btiiwl<3 AxfiBitiffids
v * *fp^f(p

1^*tr

|. * W H W ! IW

*#WK^.•***».* 0 r

Ha *

.IP*-

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w.Wi 1 i

Jf’"*' w l>p i«<p^wiw*i '»'

'l

m

Mt

^ l1 n y j g R W '
■ “ i-i

t o t to w w » t o t o 1 ^ 3 g* (0.01 to e ) of 3-«Atr©«*

iftto O io « rtp M 4 e t o

t o xm etto

.p*

•■*>*.

0*03S »&© o f t o l^ te c ^ ^ ^ m rm p to p m p a ® .

me

toto mm? mHem timm tm

to u t 30 smwde

t o sOteto to coca* tom tr t o p of a 1G# to u rtte of t o t e tto to d e
we^e to e d to « O A pw ttone*

t o to e m e stokm rig e ro s s lr b eto ea

to & to a s o f t o t o t t o

t o roaoitca M totee q to & ar

asmmc! s& ©Hr em eitoncy. t o drop ef & 35C tytoaH orl© to d s o te
t o e w m to e d t o t o t o t t o e m e t o t o r ig o r t o r *
t o t o a l me- «£*to m * p rm e fM » *

t o s to -to ld

A t t o it o crystallisatias© to n

XDC

adorns fcsatoa <* dilute ocstdte maid* according to to direotiaaa of

W&MMm (lot), flkitoL Hm tt&UmSxm l^ k o K s r^ m ^

mm

4hq£Uvad> X“tttagr* Inaropeay a»i l^tc^2^!?woaptopro|®jKi*
Attojts t© toot
*ltk 3 « jH to tttto to y £ Ofclorld©
M a 791M
Kto t to * ««»■ iteto 2.3 g. (O.Cd jsk&s) of 3,gntotto**
fe M to o lt e t o a»d Q .Q 5 m M o f t o Xml!kQ8^**siaTO

wm

Hw top® -oT ffrldto

t o t m # gsatly t o M

adto to ©tolpsa to

vmcUcn*

i®
9&
®addsd to- tSa# &M
Kt tost*
A

ULJltL-jri!Hl jm.iti?

fcfifttfM.

...ffrri' nl 1

lll'M'i

d t f t w (Jlf

. . '*!■..■»

piJtr%i*

u fiittr*

4UAM4U4fe jeULiWMIMJLk

.—..

- - ■- ^ —-■ .jJL - ■ . . A

« te t

^ iw

J ^

J iw i

rilikJIV mil lyalw Mtfll'dtfc nil *ff *^1 4

i a itTli

rfHi

dt

&mk

not s o lid ify. lbs

tdtfe nttar a»yi

40(1 $BNB®(|i0% 3m3kMmt %&

dapopedU
to

^®»8}®8*va wpG&t t I^CSSPCW®- wMSEwttE^^.

tfcws foa^tiion ntelaw® tsoiwi' vls^o^o lo t
m |$*y*aya

F to drops of ratop

tSaan ^tsddino tm
#

M # IJ0Sf®r iw^il »Q^^iwM3r ®Si 4^£3flHXt $$$.
iWifffi rtlMgMI

to to t

t t a to %ts*®» u n til t o £mm of hydrogon

o tt a to M t o to apps&r (atofc fifto n to n to )*

4 l& v n ^ a

.

tasnsfwyod to a porots
ftw6S®pSS %& mPlllg
jfcA. —-

m m 6U to * m w m >l or dOato acatkt &eS4a accord­

ing to t o proowtor of M M t (3£&)» also Jfeltad. t o fo&otrfog
iw

ttoegto l**ttw«y* l*ppop^ and

A tto p ts to to p u ? t t o
B in ito |to @ rl«
ta^mmmm o f t o Mlk^r*2-^®r«mpfeorropan^s
to folloitog p?©«to Is p tto to tfto to t of Si^isr, Stoarfc
m$.

(3Ui)« In a X0&A-« csirm^od tosk oqnlispeti idtt a roO^xr.

®m®mmm*$ m m

pSmo®&

to aa* of tooOssto atozsol aad 0.023 g. (0.01 nclo)

101

o f eod&sm.

to tb U o olatica m a added OXX mol® a£ the l-eOkajQr-2-

sw ^pbopropns feXXomd by 1 .5 g. (e.C& male) Of d l0 tly l IlK&lOcblcrO**
a e e ta l.
hour®.

fhe reaction sslactw© m s heated under re flu x fo r fo u r to fiv e
tom m& ©f the reaction m i indicated by the c la rific a tio n of

the icd atio n , which remained dowdy during the p recip itatio n of ©odisisi
fhe praetpiiabad s a lt m e collected on a liirscfc funnel and

eW orld®.

m i washed several tis&m w ith « a U portions of absolnt® ethanol.

tim

f ilt r a t e and maMngs war® treated with 10- s£L. of water and
a c id ifie d to ccngo-red paper w ith coaasnlmied iydrooiXoric a d d *

fbe

a c id ifie d s o la tim m a evaporated on the stsem-bath, to obtain an omngered o il.

This o il m a taken up in ether and washed w ith m te r and

sodium bicarbonate eo latio n . A fte r renewal of the ether, the crude
msimptmeetaldefcyd® m a obtained as an camiga-red o il.

An attempt to

prepare the 2 ,lin d^itro ^b eayll^m aon e, by mans o f the procedure of
Shrtxtsr and Jhsoss (12 6), fa ile d to y ie ld a c ry s ta llin e product,
follow ing l^lk€K7-2«»rcapto|3«>paaaB were used*

|Sfi6^SH98y J»

lie

lmthaKy^S-raercapto*

pvO|W&|PW^® IHStl l^ttvflBiy^^BBI^JWOprOJSQQ*

Eeacilon of l,2HSpcayw3m*tlm(y?&op&^ w ith Xdthlnm Alusdmm
% drid#**-l»epftm tim o f l^%thc»y*-2-p»opttiol
2a a 5 0 ) ml* tteee-neefced fla s k provided w ith a sealed s tirre r,
r a f t a condenser and dropping fbanel war® placed h g. (c.X mole) of
lith iu m

i^drid© and 100 :i&. of anhydrois eth er. A solution of

26.lt g . (0*3 mole) o f l,2^pzs^3*wthoasypropan® dissolved in 60 s£L.
o f absolute ether m » added in three-^sartars of an hear.

Vigorous

102

ra fta d a g m s obaersrad threw ghmt t o addition period,

fbe reaction

s fe tere m s s tirre d and twOawtd fo r an ad d itio nal three h airs, and
then 2& ml# o f m%m m s caraffcl3y added.

The restatin g licjaid m s

decanted end the adlid m aterial m s washed three tim e w ith 30 m l.
portions of ether#

The o x ifls a l Ihqpid and ether extracts ware conMned,

'dried « w ai% dra*s sodium su lfate end the ether was removed jjg mono.
5*2® concentrated residue m s d is tille d through a 2x1*0 cm. Fanske-type
column incised w ith 3/16 inch glass helices# A 72$ y ie ld of m aterial
b o ilin g a t 118-118*5° (?U7 m * ) f Jjjj> I M X ) m s obtained.
values fo r l-m © to *y-2»fro|»»0X are#
14#&? (S^)#

The reported

b . p# U 8 .5 ~ u y ° (?6£

seu)

t o c-mphthgrl u re to n m s prepared and recrystallised

frois 60—80° petrdm m ether* ®# p. ?1#5-?3°C.

The mixed melting point

w ith the e^mphthyl w rsttaa of the km m 2^ to «y-2«p ro p & »cl obtained
from t he

eatalysed condensation of «eth fin i eyyt propylene oodde

showed no depression#
U m ctim of l,2»B p^^3-^teK yp ro |»ae w ith Lithium Atainura
li^ d x ^ o ^ irep am ttm o f l-Ith c s ^ -p ro p e a o l

This redaction m s carried cut la t o same manner as described
fo r the reaction o f l^-eposy*1^

metesyiropin® mud lith ia m a ta im m

hydride, except t o t 5»? g . (c.15 mole) of t o hydride and 30.6 g. (0.30
m U ) o f l» 2 ^ p s ^ 3 « ^ « O T ^ P ^ e ware empicyed.

A 78.3^ y ie ld of

X«wbtaiy-S-p^penol m s obtained, b . p. 128-123?0 (735 ®h*)»

l.h o h l,

The physical constants reported fo r th is compound ares
b . p . UO -130.8 °, a^° l.l$ 5 8 (ICO )*

t o infrared spectrum of t o

103

NdftollM k product and th at o f the oondeamiion product frost tbs a lk a lin e
catalysed reaction o f ethanol w ith propylene odd® w e id e n tic a l.
Baactica o f l,2«Sp<aQr3*Ta«pciOTt^|ane w ith lith iu m ixluminua
Bydride—Fipepamtiai o f l-Proposy-S-propmoX
M i reaction m e carried cut as pew icualy described except th at
35*1 g* (0 .3 mo®) o f X g 2 r^ m ^ y ^ g o p m jp p o p ^ w e en joyed . A ?0.5$
yie ld o f tbe redaction product, b a llin g a t Htf-lfcS0 (7h7 m .)f n |° 1.1028,
m e efotained.
ares

tbs reported physical constants fo r l-ivopaQ r^^proinadl

b * p . U*8*5~21i50 a t 730 ms. (10b), nj?° 1.1030 (1 0 5 ).

the infrared

o f th is M aterial and th at fo r the product Isolated from the
a ila a in # cataXysed ocndensaticn of l-propm ol w ith proiyXen© aside were
id e n tic a l.
Reaction o f X92»Bjx^3HUfopT!pa5S3r|^pRiie w ith llth iu a Atodnam
J^drlde^reim saticK i o f l-Isojwopagjrfc-propMicii
Fran the reduction of 35*6 g» (0.30 mole) o f l,2^p co or3^o |afo p a^r*
propane w ith 5*7 g» (0.25 mole) of llt h t e alumixinm hydride, by expert*
mental procedures already described, there was obtained a 9i% y ie ld o f
IHUKJpropcsy^

feeding a t 135-13?0 (7 b l ***), ^

reported mu*®® t o these constant® are*
■ f * • * *

< » » •

* *

8 I* ,,te ,,,, *

1.¥>67*

The

b . p. 137-138° (760 ss».),
tid 8 - * * 1* 1 ^

tta* for

tbs product isolated f r a the a lk a lin e catalysed condensation of
£~$»ef»a®i w ith projylane ss&de w eciL id tetlq el. A coasidembX© amount
o f viscous h i# b o ilin g m aterial m s also formed in th is reaction.

IflU

S asn to* of
w ith Lithium Ataiaum
l^ r to --to p im ite m of l-^ tey-S -p ro p am cl
t o redaction e f is3*7 g. (C.30 mole) of l,2-epceqr3^tcQ qrjroj»8e
W ith 5*7 g* (0*15 mole) of lith iu m atadimra hydr&d®, by axrarlrafflatal
telii3U$*a« prtotauO y i M

M

2~p?©iamGl 3m m & $ j t m .
14i3£2*

dfj*

2 **m w m l « *•*

, resulted in t o fow m ton of l-b a tcs y-

t o compound d is tille d a t 73-75° (20 raw ),

t o pfcytiUal constants reported fo r l*^atcogr-

b* p . 7 lr7 b o ° (20 aa.)» a^0 1*2070 (ID G ).

red spectrin of M s

X and t o t fo r t o

t o in t o -

product obtained to m

t o a to H a © catalysed ocodsnm tto of X-taui&nol w ith ppejylen® acid®
were Id e n tic a l.
Josa&tlcn m jdrnJiscssymetoyx rmissnes
w ith M U g l Iodide
jb.Jt.JE ,*m M4

JdkSS

1 Erf j U M M k n u k m t • v l t a ' i S

MMHMiakaai.pl

Hi® most satlsfactOKy result® were obtained, whan th® follow ing
pwsdur® m s u tilis e d .

In a 300 m l. em®*»®eSto flas k ©quipped w ith

a r s f t e condenser and! c a lc ta M a rid © diyiag tab©, wore placed 0*05
mole o f t o to llto s m tto l tfcitoa© m d 1*5 moles of fresh ly d is tille d
n © to l iodide*

H IM a g ita tio n m s prcsr&dod from tin® to to © by a neg-

n etic s tirre r*

t o reaction to te © m s ailcwed to stand fo r two m et® ,

filte re d t o

t o residue m to d serem l to s s w ith acetone* A fte r cm

i m y t t o lt e t o a to m tooXat® etoaeOL* t o m te ria l molted a t 215°Q.
t o a c tin g point reported fo r te to to to X fc s tta s Iodide ins

2X5°G.

( 15) * M& m om m met attempts to is o la te t o l,2-diiodo-3*-alA<a53rpropme,
presumably is t o © to r jrodact fcanto in to e reaction.

In each

105

m*®# a fte r m m m X of the m m s methyl icdide, d ls tlD & tlm of the
rm id a a l lim pid under reduced pem am ® resulted la m pid and apcteasive
d®c0®ipo@itlcai,
a*

4 7X5 |4 fli4 o f
m s H o t o f 5.2 g . ( 0,05

iodide m s isolated from tits
o f 2-m tii«y»stfcijrl tfcUmii® aaS 213 g*

(1 ,5 m ftm ) o f aetfayl iodide* I t a i the m c U c a t£a» m s lim ited to
on® week, * 5?5 y ie ld m s obtsdnsd, I&gicyXng a acle xn tio of 3*5 of
raetfcyl iodide to 2mattoofaetiggL th iim a t, and a two week reaction
period g m * only * 23% y ie ld of tbs tx'is^i^lau lfaaiam iodide.

In & s im ila r fashion, a 72$ y ie ld of trim tbQ^sslfoniam iodide m s
e&ialasd £vm tits reaction of 5,9 g. (0*05 a d e ) of 2*ettesywfcbyl tbi«*
is m * sad 213 g» (1 .5 at&aa) o f m tfy l iodide, A second g re p m tia n ,
« fa © 2$ 8g the earn «$*&atitissa of rmgaa&s, resulted in a 565 y ie ld c f
the iodide, when the rm a iim stoteafe m® woxfeed-up a t the sad o f cue
week* Ey mg&cyiag a two m #c ym eti.cn period and a sad® m tt© of 3*0
o f aiefehyl iodide to

tM im a® lewered the y ie ld to 185

o f theory* A 225 y ie ld o f ts ta ttg lm lJ ta liia Iodide m s obtained ftxm
a reaction using a mole m il© o f 3*5 and a m o tlm period of m * we#:.

From 6*6 g* (0 .0 5 »k&®) of 2-grop<agwt3^1 th iim n e sad 213 g.
(1*5 m tim ) of lasthyl iodide to r e m s obtained a 66$ y ie ld o f

XG6

iodide* \% m %tm m l® ra tio of n a to l iodide to
%M±mm. wm tim m m tl to 3*5, m d t o rm c tim t im

to mm mm»

t o y ie ld

of

t o iodide

tax to & $

of to o s y .

p*
Ita e 6*6 f * (0*05 in to ) o f 2^«d^p^|x30^Bi®tl^ thiinaae and 223 g*
<1*5 «*&«») o f cioifcyl iodide to r e m s obtained a 6?5 y ie ld of t r i mato&kmxtmtem Iodide*

L o w in g t o racXe m tio of m rtbtf. iodide to

2“^pE*opo3iy!aetol ih tiraa© to 3S » lo w e d t o y ie ld o f t r t o t o t eolfaoinsi iodide to 20$ o f to o x y .

$rc®i 7.3 g* (0*05 mole) o f 2Hmtaxyraetbyl thlixasae and 233 g*
(1*5 m & m ) o f setfcyl iodide to r® m a foraed & 65$ y ie ld of trln e tfc y l*
salfm & m Iodide* 4 note ra tio o f 3*5 o f nathy! iodide to 2^tcgy»sfcfcgrl
reunited In an 10$ y ie ld o f tbs erti!f |0Wfo>at iodide.
Beaotlca of S ^ to ys as th y l tliiim n e
w ith M y U lt& to
In a 500 A * tbre«i«^Esd fSaak shipped w ith a sealed s tirre r,
m D m . otoersM r «md dropping tan aX * m s placed m « to r aeration of

prepared by t o method o f C&lsaa, j& £L " (12L), frosa
65 *G g* (0 J4L » 3 s ) o f ir«*mtyl bromide and 8.6 g. (1.23 g u t.) of
lit t e t a .

Uo t o s tirre d sto3»M«. m s added, in fo rty jd n a to , 26,28

g* (©.10 stole) of S H t a t t h i i r a n a dissolved in 3C stl. of
m & 0 rm a s to p *

t o reaction utofetre m s stirred an ad d itio nal three

m

to n s , ««t m $M mwm&
$
s
bto to n p eato intoan eqaal volasae of le e m to and to a t o r lay er ssp ratad .
v im go A * wnmmm o f M

t o t a ty to s id e to n tim and t o ra to a s e

ware cabined w ith t o M$*m m phase*
w ith anOX porbtoa of water* m
e to r t o
P « w

m c to «

ttm e to r lay er m s washed tw ice

t o e to r p to * was to n washed

n eu tral, drlad a a r M t r t o t o t o

t o residual lig ild t o fractionated t o e r reduced

tbrmgh« fcsOk owu faato-lgrpa colum jacto w ith 3/16

helloes* Hie to n fM tic n d is tille d a t Hii~XL6° (?ia a s .),
l«ls053* t o ptpaloal cmatasfca reported fo r butyl a lly ! e to r are*
b.p. n?«flK3afl° c?63 m u), a jf l*i££T <12U)* A yield of 11% ms
im3Jy$ed#
t o a t o t o phase m e a c id ifie d w ith concentrated hydrochloric
a t o to p recip itate 1-fcetanebfcidX as m o il, which m s separated,
ttgsmiian yjmtw* m g
to

to

three t&aes w ith 25 !$1« Bcrtlcne of rontaae.

p m & m ssetrato eoashhto m th t o o n t o

dried o w Q riarib®.

Sufeset*to dlst& tobieii to m # an 18 i nek mgreejE otoaa afforded an
W y ie ld o f 1 -b a to e th io i, boiling a t 9tr$6® CTli? «bu). t o la tte r
m s characterised as r tu iy M ,4 n liz & to ito y l s u lfid e , sup. 66-6? *5°*
to - reported b o ilin g point of X ^ it o t h ib l is , 95“9?° a t ?6q am. (1 6 ),
t o M&y&g p to t o f t o

d a rim to e is reported to be, 66-68° (1 6 ).

Haacticn of M&bos^ethy* to ira a e
td tb Hi#nyHitbium

to s &m*Mm t o t o sulsm peftt 'm&Mkf were put-©rased in a immser
M antie& l to t o t described above fo r t o reaction of n -butyllithium

VjB

w ith

th at to.O g. <0.25

sm& o)

« f fe ra e -

bsa&aae fetid 3*5 g* <©*$& g .-m t.) o f It t h t a m m usad to p»$a*e ths
required p fe i^ m th to .

a l^ X ®fcfc®r* b . p. X lM lS 0 (? l*l sw .),

was o b t»to d is 7i*j£ y to ld .

The oibsr product of th is re~

a e tta * tM oftaw O g mm m st$m d is 83$ jrisad* b . p. 70* 73° (33 am *),
fend m s oim m afauim d m th * £ ,l*« d is itm p to y l gfcatyrl sul£id®9 m.p.
TO«&21°.

t o rtporfcad maltteg point fo r th is derivative is Hg-X21c (IS ).

of 2-Iso|®c3p«®^i9ftil^l Ihiirfen®
w ith But^lXibhMrs
IM s raeteloo and th® .wbfflepsmt prodnot iseO atim wore carried
oat feoaoapdteg to H » ©sspsrissiatsa p ra< *to » ppw iaaSy described fo r
2 ^ ta p *fe th $ L tfeitwasp fetid fest^UltM asu

f r a 23.?6 g. (0 .X8 xaeOUs) of

tbttxaa® and m o ilme sa h iiica of but^Uitkfewa,
jr& faw d f r a SO g« (0 »bk jsc£U) of iHaatg?! broniide and 8.6 g* (1.23 g .-a t.)
o f X itk ta , t i m

us® obbatod a 53$ grioM of iso proi^i a l l r i other*

feeiH&g a t 80*82° ( 71*1 sbu).
<730 aa») (13©)*

Ib is efcfcar is reported to d is t ill a t 82-33°

Xb* othsr raacfeioa trodsei* lHwtsaaothldl* m s ©bt&iaed

in a ?ii£ 3&«Xd«
le&eticg* of 2 *X » e |ro p a ^ » % l thiiraa®

& » M a t& m of 23.76 g. (0*18 iad®) « f a -iia o j^ x ^ a s tl^ l th i-

imne with a

solsstteii, prepared fsTGiS ItC* 0# (0 <*2.5* H2cQ»0^

©# toraiete«^n# * xkJ 3*0 g* (C*5o

af litk la% r@mXteu in a 53^

ID?

fM A o f ls©ppo0 l

ased a 75J5

o f thdtepbenel.

aH^X O ta r d ia tllla d a t i2 * ^ e (T ill m .) .

T&e iaoppon?’!

Tb© sported b o ilin g point

m 82*83° a t ?3Q an* (330) .

of S ^fttopam vttyl Tktirna®
td th B u ityliltiilari
«P ' »

A

,a^ K l W 4 i n V < W ^ W H < M n r > c

o f sa*po|§& a!3gd © t e ©ad a ?0$ yio ld o f IHsatans-

tflWWSt

ts m the ita e tlo a o f 23.76 g. (0.10 sscle) of fMPfopaqr*

M A y 1 1Mi«assa s ite sHmtgdHthts©, ppapo^ £sm 60 g. (O.Ua *»&©) o f
sHsstgft hvan&cia axssf 8 .6 g* (1.23 g*«at«) of l i t ! t a * ©rai&qjrlng aq^ad-*
aanM . trtM q p N i

# m M «

a t 9&*$l® <?h3 « u )f

mm

1*39X7*

Tte a«pro?gd a lly l © to r d le iilla d

®a@ Xitaratair© m2»os fo r tfci® ©Unaa?

t>. p. 90*98° (780 anu), *(jp 1*3939 (129).
aaaottsn o f 2-f*npflnyn«fclgl IM iraa©
*Mi

,,| „.w

J © «| if Atii J i m m

Baaotlm of 23*76 g# (0.1 8 ®©X®) o f S^ppsjpoKgraatfcgd thiiiesn© «dth
an ©ibsr m l& tlm o f ttaw odlltaiiiav sxwgaxad i*eei iiO X g . ( 0.25 lad©)
o f b£csnad>«» mod 3*5 g* (0*5 g .-a t*) of lith ls m , ©saileyteg OKpwiw g ta l

© toaslr d©a©j&b©8# w aaltea In th® fo zm tim of
a33^1 © tte*

(737 « •)#
(760 isa}»

70* 3?M bi.

7h® ether d ie tm « d a t 89-91°

10920* W * « ® s p rt is repoatod to fcodl a t 70-92°
1.3739 (12$)•

fiie ©thas* product £rm tM s ra a e iim ,

th lo fte c a , wa# dbtatsaod la an 885 y itild *

m & m m o f aHStostynfttipl m im n ©
Idtftb
f* m 21.21* g# (0ol6 isAs) o f 2 ^ t o ^ w t o i thilm a® sad m © to r
m M & m flC ta *^ itlig s *% j*apM «ti A m & g . (0

bwislds

ejc&®} of

8 .6 g» (1.23 g .< ftt.) o f UtMssm t o w m * ie o la to a h1%

VUtol of atfcgrl & xm © to r m A m & & ytete of X^taswrtM ol. t o « % 1

«33|& « to r 4tom i*A * t 66*6?° (7I»7 w .)»

1.302. t o reported

fttto ® fo r f i t y i *aag& flto r a w h* p. 6 6 -0 ° a t t o w . (128), n j*

1 .3 0 2 (131).
Bwtotdim of B H M taq m ttg l S iiiiiu a
m te
JtbtMnwA *1 jt A, lr-.f

to 'M o tte n Of Z M b

g. (0.18

igtti* $fi etfcsr adaatlcgi o f

bm*

«&©} Of 2«*ethaxyttethyl th liran e
, cfctaliiad £3ft$3 I4.0 g. (0 . 2$ Eic&e)

o f b w n to 8i«i*e and 3»S $ . (0.$C g .m t« ) of H tfa ta , resulted in a i*2$

yield -of «tfegrl aUgri «Waw a i i « 8 ^ yield «f tbloifeantiU 71® aU^l
aU sl ®ti«r distillod a t 66-6?fc (7^-3 zo .).
am otion o f 2<#tt&«yajsiiayi tM ± m m
n itk a ii% llltM m
k 70% y ie ld o f IH ju to e tk lo l m s iss^atsd is m 7km reaction of

20.8 g* (& .» adto) o f iH m N m & m tityL tfeUUnm v ith an e to r solsitlcn
of

obtained t e

60 g. (0.1& sadla) o f a -b ety l bresa&de and

8*$ g* (1*23 g .-tk t.) « f U ^ litB *
a v tlg l aX 3# s to r , sad t o

t o ie tbs Iw b o ilin g point c f t o
psmtstemt m ilcysja, ca3y a

Ill

1mm of

©tor im isolated, b. p. i*a° (71*6-5 *» .), ^

&*37$6* t o liA m te v t m 3m & t o to # m m as# reported «si

yuSHtt* a t 7S? * »

^

b* p.

l'3773"i<3&3 (132).

M m U m of 2^imxsgym%btfL M im d

X m t o reactim of 2O.0 g. (c.ac j*&#) of 2 *ii*fc to to to £ to to a ®
ilt b aa a lto ©S&itto of p t o ^ t ib t e , psefarsd frosi Uc g, (0.25 aiel®)
« t to®«^asi»ew md 3.5 g. (0.5 g*-%t«) of U titim , to r® me dbtairsod
a lk% ytflsMI &f

dm. t© t o telgb r o liiflity of m te&l a lly !

ftto r* wxA t o sggtor&attttsl proeatiisre ®TiLey«itf, no m fa tfl aH^d ether
n®#- s^tnaU^ isolated.

*&t&

t bospbto

HI mApO Hi* <$&®*Si®©s£#d J u ili mglLpgfXt WIwh & W M M w * W#Li,
iA

W

HliWiTi<rrti ■■■* ift Jrt m1.^ frrft^ifff

i S i^ i A t A s fc # J J f c J lM . iw

% i* il A-*'Vs

M

*i

A . ’f it <> m i ■ i»v m iH iA » n

lilac s a mSxtar# oosapossd of 33.2 g. (G.ao ad©) of p rifis d t r ls to l

p ta |M i® t o

21.6 g. (0.2G noXe) of S M to o n o to l to in u a a .

me fitte d n itb © 1«30 *» .

t o flask

cobim packed m th 3/16 iooh

glaaa hsMssss, t o a w & a& U i totanc d is tillin g bead,

t o reaction rto *

to © m s tte O ^ distH X ed a t a t o s fto ic pressor#, rsMcsdng d is tilla te
a t mcli a m t* t o t t o d iatm & t© toipomtar© r e t o t o ta t o
h5«*tj6%*A t t o t o

©£ a f ir # t o r period.,

range

t o to p aw tto © o f t o

rM d U to . n ftto te l rto a S a g 4n t o d ls tn ia tic s s fla s k bad rsachsd I8 0 °d .
A t t o # p o to H i.3 g. (0.3$5 aoi® ) o f a lly l c h lo rid e bad been obtained

312

ft# ti& atlttA tft*

o f t o cfclorid© gave 11**6 g. (0.19 raole),

ft 9SV fU M * «f P # ftiaga 4 iA ft^ b. p. Iili.8-b50 <7bJU m .),
a ® U tm tu r s m te ft fo r m &

%MM*

(T & « ••)*

X«1&16, (333)*

m t

b . p.

M fttH X & ton o f t o colorless l&$xld

laa t o d tsti3X & tim fla s k * t o e r raduead pressure, mffordad
J M g* (0.2D ta to ) o f M ftH y l tM c s io ito to tft d is tillin g ftt 82«63°
(5 # » •)*

X*i&60,

tb is

X«iML« t o reported jiiy s io a l constants o f
mm

b* p* h f (0*5 ssa*)» ioS-ioS0 <20 a a .)f

X^bb&n «§P X*bM0» (1C6) « to ® a qpsktltetA ** y ie ld of toetigrX tbicoo*
to s to tft mm obtained. to n t o m t$ m & d ie t illa t i m

mm

bifttsd tifom® 180°# or kept s i abort th a t topsm tsir® fo r long p erio d
of' t o t * tbs Its p M te&mm t e k colored end gRibscssjaQnt dis& iX l& tia*
M ls d to fl& s

yield s of t r is t o l tocnGpbosj&ai©.

best i m l l t w @

i t t M

Bo

wfem trlfttbsrl tospbit© m s cajftcpad in ©Kaess*

X poasCbls sKjflwmtoft of to* rosalt is found in tbs v««fc of tastt md
3m m

(X& ) 9

«bo d b a m e d t o t t o o n c t o s t o t o r m d U y undergo t o m l

iM m m Am Um to ptacfcorotMoOntss *
toot4 «

c£

tfettmn*

v ltft B to to X Ptopbifeti
A s&etam oagpoMd of Xt*#S g* (0«2C ml©) of Z ^m id xjl t o i m a s mm

33.a g* (C*tC w a s ) o f fs M S iy l gbospbltft m s d is tille d , p lo y in g t o
f t p p M W t o and esspariimmt&X froosdur* i m i M

for t o reaction of

t M ir t o K itb ir is to X fbeftffeit** oeospt t o t fara to a custom

istm obXcrM e tm po ( t o ) w ®

to ta lle d to c o lle c t any propgftme

m

:pi 14&Mt«dn At to to of ttsnie tows «f ^istmation, the toipamt e # «$ t o r t o it o b&4 smetowl 130% «9 s t idiioh rsoint boating nets
aiaeggtftwto* HM
M
BmdtsttU&ttm of to UcpdbS p®tot*& gm 39.2 g,

©f par® tris ib y l ibtcnoptowplrafca# to a to a t

C©4$9 lK0ui)f ft 99$

« f t o Mfet»Sa& &t t o bre<^s**ctoHm tataablcrjU te tim tm , M lcsd ag
m rn m m

sm ® m & a fi% y m a «r xf2-^2^cs^ojwps0, b* p.,

331° (T&«6 »*)* a|°

M«

to Xitofttare vaOnas for tbla dSbrttos

b* p. A3HWS* (760 » . ) , ^
Imssito «f

%&9k 0L3U).
(ifijflto M ltift)

taSUhU %vUito$1 Fb«spMta
3SS

fdLXonad la tM « ra&otten

has

tbft

smub

ta em gy pstfm st ft# t o t fo lX e to in t o deso3furiaatt<m o f 2«i!M ttyL
A tU is* (OniiO a to ) qpanfeify ©f fttfcptone
ffiilfida

66J* g* (0*b0 nto) of toietfcyl jtosapblbci war©

<■

th to o s to to *® t o ise&ato la 9k% ytftW* Sem toat of t o
to s a rtftl la t o b ra to *a s n to t^tool^orto trap®, followlag is tto to
pvcMfttonHlf ftttM w A ft 93$ atoW ftf i t o l t o dtocaddft* b* p. 30*32°
(HEHCL » * ) » a|P 1*$39D* t o rt^ to a d to o M i t o to ® d lb reto © ar©8

b . p. 3U° (3U» a n .), 4 °

< *#> •

BM fcltin e f 24M2a8Siwwtoi H).iXm m
td th tiifltiQ d . Ftoft&t®
o f ft atoetwti &©&tfttoag 20.3 g» <0.20 m&a) o f
t o l t o t t o 33*a g* (0-20 aoiU) e f triat& srl jto y to itft*

by ggptototeO. to to o to ftXaaft^ a a t o t o , gw« a 9t$ yi®3jd of raftfcbyl

Tlij

b . p* }# 0 «&

m #L

***., a jf 1.3786,

« w W s t o mte&L &H3& a to r

t o rs p o rtrt r # s ix l

b. p. 1*2 .5*4 3 ° at ?57 r*a.# a| 0

I»J??$*&.3803 (332) . t o a&m p ^ te t jj» tills pmct&oa, trtetigrl
W M ttib M fa im , m s M&Smd i& $kf, $&& d#
SneHfia of 2*€tos*yi3®t#X toixassi

uttili

t&abillAtim of & mtetfsmz om pm ti of 23.6 g. (0.2 aol@) a£ g-stosymlfeQfl tM Sanat a r t 33.2 g» (0 .2 mab») a t
m a ta l

jtiospiaitQ, by mc$m4*

atom s# to o « to d » ssisaalirt in t o fm m tiU xi of vtfepi

a lly l viator# b . p . #y° a t 12$ anu*
t o t o i © to r am *

A 9 # 3T3SM m s

1.3392.

t o lit o & t a a m3it@s

b . p. 66.$?° a t ?o3 m . (128),

1.3392 (13 1).

to ator mrtact i» tbis smcUaa, tolathgd

■ f e f r > 4 <mtm

is* OM TliSOUl*

to d & m of 2H topo^m >tl9l to to w i*
u ltb & le t3 $ l Fbogpfeite
S&sfcUlstiGn off a s fe ta a ccnpxart of 26*1; §• (0 .2 w to ) o f 2"*pF0|xagr“
aatfegs. M

n

« r t 33*2 g. (o*2 iss&a) cf trtsdixvl to » s & to , #

mtxtal toteS^a« p r t r t r toatod, $ev« a 93$ r l ^
« t o r , b* p* 90° a t 139*8 a s .* n jf 1 * » , a *f 1*3968.
o w te ts & »*

b* p. 90*92°,

m s is o la to la 9f$

1*3919 (12 9).

<&

*xj4tfi~

rrosyl allyl

t o rapsrfcad
to c ra jto B ja ia t*

3U5

vitfe M w & , Hwajidte
A mSasto® emjs&isd. o f M *k g* (0 ,2 »©1®) o f S K o o to to to fe p X
m & m rn mm 33.2 g. <0.2 anft«) of m & e tm « d M *® & 1 frM fb tim t o

^ s tille d «N»«aPtlag to t o Sto*to&% aX pooeoctafe described t o 2**rmp£zp~

m M 0l l&d&smm* A 92$ $±®M. of ioqawfgrl &X2$% s to r m « obtaiasd*
b* p* £M J3° a t ?i& mu ■t o boSUag point of tid e ether is rspestad as
M 3 0 a t 730 m * , (330)*

M fftig A tb i^ io jtic s to t® w s obtstod la 9S$ '

jte M .
fsoRoisxcaa os.

ieuaxxvsw

v&tfc

StofM t®

B M lH fttto o f m msftmm ®mpam& t& 29*2 g. <0.2 mc&e) of
'^t'.iwfti'OTMiiti'iiitrtttiw^aft»A~ArSwm^j

W B W :w
4Lntm L + m n ifa-

SmwuS

$j#h
^ ’SS

fSl*

§0

tv-#3 imSMf ok ysaajrexi rian m w a p
*w<n?6 (iA

t Sflw4

A m m s A JwAklfattitft

phosphite, by p w ito O y described fto to u o e , resulted ta t o fcraatloo

* f n-U rtyl tfO jd •ti.f®’ 6 . p. m e a t ?!* m ., n§° 1.1)053. A 97% jriaM
of t o m m t o

s t o it o .

t o llto s & te e ra to s t o th is oiimp «o»i

fe* p . W J H B fP a t 763 a**# a§° i*l# 5 7 <12ii).

t o © to r product o f

to n s t o i t o , tv M tg l t o t o i t a i t o e t o dbtetod is ic c * yi®0d.
as& otta e£ 2"to acaq ff*to l, M Issb®
m m fttm tiy i s to ffe to
to

!$»®sctar@ f©Honed la th is m o tio n t o s im ilar to t o t

diinckJM t o 2 to th to a s to & to ito ® t o trtsthsd phosphite, aKcepi
t o t t o to fe ttte to t t o t o a t 20-& 2 m . ptm m xre. A 16.6 g. (C .l
to * }

o f 2 *^ to c o p w to i th llv tt* t o

26.6 g. (C A to *)© £

316

mm

Bsaayi a lly l a to r s b . p. 8^° a t

In 73# $%8M* fbe recorded b o ilin g point is 05°
i t 3$ sira* (Uj&)«

Tim e to r ppoteb o f th is reaction, taelstfcgrl tides©**

ptopb&te m s c&tftlnad la ?T3f yiH st. A cmsld&mblQ assamt o f p©3ymslc
m to ta l KM also foamd in tb s sm ctto i*
newbie© of

Sulfide

i solution, o f S i g* (0.5'

' <iyclto®«n» sulfM ® and 316*2
jt a f b t o out charged In to a 2$C

<0*7 mis) of ^iatillmi

pm & m fA p described.

lb s sdKtea m s

collecting d is tilla te a t snob a ra te
nemlaad a t 7?*"82°d. in about £ im boors

th a t tbs

t o r e k i ©eXIeoto an
i o f qF&okmmm, b . p. 81*62° a t 7h7 m ,,
2D
o f l«li530. to s s m ines am reported fo r th is cyclc&ikane, b . p* 63-o i

1J4533 (337)• After wwwsl o f t o mcc&8G t r is t o l ptocspSdt© a t
m s obtained in

y ie ld ,

art using s p to ia r proportions of
in t o d is tillin g pot beoajas s lig h tly
m s caagOste, and trls tfy l

fa®£tm t o svoQstiim of
I

Baaotltti « f M S * * * ! SM&sese
w ith
A 27*2 g« {0*2

(0«2 m is )

2-pt-jsnyl thiinsns assl 33*2 g.
to g e to r and d is tille d under

117

fW toad prw am n ,

pwam km d sso eito t o

A $J% y ie ld of

wm Asetosd, b , p. 53-££° a t 30 mu»

Sid

% X«SWfc* »w *«os*tacl H k 9 8 t o this aMswm w®* b* p. <&-£3° a t
28 w w , s f X*$i£2 (2 3 6 ).

m e th y l ih U n o M t e l i m e tr n m in m

$ i« M * 4 m tta r t o p anaw t of solid psJysweio m to ta l wm s$*xlae©d

in mm em otion.
to o tlo * of 2»2-m ^tk3^a®tfcyl IM&mm

with ftMfcgpi fto s M ts

Its®®. a i M m

o f 16*a g. (O .l sad#) o f 2,2n!l#fttops»tfcyl iMisws©

and X M «* (0*1 & & •) o f *«a$i$$3Xto tv i*ttg rl tto jM t© m® d is tille d

tsssttftng to iip d M t iii tM to p s s sO im t^ d a a crfto , an 8?$ yie ld of
iMgpfostyi ^'i*rfxi>yia?.na^t <n£m dbtttosdy' b . p. 121123° « t 7to » - , ng5
1*398^# lUm Htsp&inwi ss&itsit *# **
10983 CHS)* I M

b* p» 3L2o*i2li0 a t tU t an#* a§^

f i

nan lo o to sd in ^3$ y ie ld *

Ba&etXaa of
•w ^WPW pI*^* TlWBW^^Knw

wl'fl**

®-wyy leWWiiWr^yp

*■*

wOTn^

with M s tlp l Ito jh ite
A IM i sflU a m i s i t fto k # apippsd w ith a tto a a a a to w e ll, and

p w M s i «&th a 1$ iaab f& p ittx o cto a m d imnabls ta k e -o ff distilA atXen

band, ma d w p d w ith 1 2 g« (0, 12 «& *) of
psoissna and ay*U g» (0*12 m 3 *) o f p a & fto trlo th y l fto p b lts *

‘t o

m o t t o a&s to s m® s lto b ! to stand t o I s w i r t o r to e s , and then
wm dosGy t o M *

B is tilla te was o d to to d in the- m a p 38-bo°&* An

8*1* g . p a a titr <* d to H la ta was oollaotod*

l^sd istm atico o f th is

w ts riiO , t h r o # a short fftokai «3toas g»vs only ass to o tle s *, b o ilin g

na
a t 38~3?° (7kl*7 an*),
iiV tfy l p * w l afctor*

1.3563# eorropcqdtog to a $1$ yio ld of
IM S o tto r is sapearfced to b o il a t 38.3-3?° 0 k & ).

Fm ottom ttoa of t o X&gito vm&M® to th» d is M H atic n S tem , wa&o&
p m m m , m rn s m W g* o f a

s^f

boding a t 8cc (1*.S » . ) ,

ii|^ %d)k&)* M a tty ! ifc&ca&jta$&it® to rapoapfesd to boil

a t h$Q (OS m *)*

m mu), a jf 1.I&30,

IJ J M ( M ) .

m 8?$ $teiM q£ tbto &wgami ma obtetoai* 1 oonstoarably laager
d to tillM g w ? lm (tom rifrfibm te e a ) m a m ^ito o d to tfeto rm o tio ti;
a® mmt&mS. to t a t s«$atow3 to to o re & fjiio a o f Im B ttM g n ftty l to iim ia s
w ith tr&e&b^X jfeetofeto**

w ibb frts b & ^ l F ta jM ta
n utotoPS O
O
fttpO
S
O
d Of 2bX g. (0.2 ®cto) of
l^ttagr4*«am

w$ 33.2 g. (0.2 saoto) of rarlftod ta?leifc@
?X

ffraggfetoe* W mportow&d

psrni&tety ttoatood, 0 m a 91$

yttiU of #to|& ppo^rl otar* b. p. 62-63 (74? » *).

tog potot to r tfato a tta r ton

Tba repertoi bod-

b# p* $3*63 *4° (78c « • )» (ib o ).

Tto

o tte r pm M ot t£ tMss ■sm otlm , t r t o t a l ta m o ta a ite te * m s obtatoasi

to 8M ytoOd* A

i«

tabtog period ma ^iplq^d to tbto

latosttoit»

Im srttei of l^I¥o|w-2*s3®p<3artop^psi^
s&!& tr to ik r l fta p & it®
o f s to te ® ooHpoaed o f 26.8 g* (0 .2 m te ) o f I-propcs?y~

a^flNHOftytoivotont and 33.2 g« (0 .2 mcto) of t n e t a i jto ffe ii© , ®rloying

11?

t o r n m tm m t jr a t f c r t
m m , b* P* 8?*?C° {?ia a u ) , i f

* ^ p « to t o to ® s to r t o *
& » o to r

y t t o o f dtrsreryl

shorn,

1 *» U

t o p tg w to l cmsfciat®

b . p. 9 0 4 0 . P (?68 m .)* s f I . 3B08 ( 13? ).

;*« *» « *,

t o o u t o s t o t * m s Obtained in

12$ y to s f* A tM m m hm » d is tllla tic s i jwried m s enpiogttd in tid e

Msttau

a ® wm<Mm mm m m M m t a sseto toe, t o afto to*tr

hm m o f t o t o g , a® t t f M p m U o f t o s to r m s isolated t o m m
$%mM o f t o

to a to x tocrog&a# to te *
A ^ te s tto i
tt>a Cf IStH otbtmmi
v i a 3 * is * r A lecM ®

S f f i i l a t t o jt s ® to » d a to M u g t o o t t o c to m s a tim of «toA©
o & ifln #ulXM©s t o

2 °m to ^ m to A to is a a e s , w ith loo to a c o la r to g h t

stliooiidlSg, o^So^Ssg sodfoa alfcoscidas os c a ta ly s ts *

no $wpi®
aw* iph

inffiT .^ aii-J* ^ ,--

■>if lS~«r'-« « ft tm^wlft MiTKif m

lo e w s r,

swaitasn immmm worn iSttifiw* iii saoh Mjstaaoa*
m

l l ' -ff ■‘rinrji-

li

i A f> itiliti MM

n M M U k

J | gm B>i¥ p 'i A p ifrh iS

"P mm .

.«•*■*. Jfcl* k

f l ‘fcffc r t l A r am n l m, .«,

p^rnm dm U m of t o cp&lo mlfto mm to' oily vsacUca observed,

t o M t e f e g p w ® i w 0 m m iKbklltoi
In * 5^0 »&• te® a«*w sjto $$m k fitte d w ith a msQM s tir z w ,
mQagc s t o t o s r t o

p to U J l I t o m

p r o r tto w ith a to s m a a e to t o

avossfdxke t o t o * w t i& a to <k g* (2-fc w t o ) of Mtoaa©1 t o 1*6 g.
<0JD7 g « "*t*) « f t o t o *

t& th is v lg to u s ljr s tto e d s o lo tim m s to a d ,

la to s % vtobat# 1B»5 g* (0*3? « *to ) o f pm&Smm- a a lfld e *
tu rn

m s t o a r t o d to a g t o

hm m m 9 a?to g t o
to

3fo t@^p0®a*

f ir s t h a lf o f t o a d d itio n va rie d )

la tte ? *l»g eff aetttoem & U i hast m s s r o lto t o

-to o to a bom m ga it® fe ttfcid .

& a s m o tto M xtaira m s roH m ad

220

fm m mMtkloml tea© t o , mod swtm Xtod idtU 6~H skOj&mIc aoid,
& $ g» ^ rs fc i% «€ p&m m m . M m m im mm added to t o solatlcm aad
i t w # set aside mmai£0& * A fta r m m m X of t o «k<mnmi * t o a o l*
a T to M

« d -s e X M » te i& X 3 fW to d , ukLefe eoiltS not bo t a t o r

'pnpif&ad* 4 tseoaad papuft&Usi* «|ie^i2sg t o to r e
«MBnAi# but vMte t o tm tM m

of so-

MSd a t 0°b«, «m carried oat.

Sato^wt workup of to areaefcia&nSactare £W* oh2$' to above aaRtioaed
aat@i*iaX« S irila ir reseXtsf
ig|y| iypyt |f tj|^ |lJ|(

2-i^tlCT^EeotbyII

oiHpswed u ltfo iadbutyisB®
flyy? jsetlBSsci, and

tb tim n a and ato n al respectively*

idtto
4

nas tria d * In ufoich a jinolo xetlo of XsliD of

p^optese su lfid e to e to X &Xe<M. w e used smri t o alkodda oatal^raits
c n itto *

t o su lfid e m s added to a mfXaselag s o la tlm of t o alcohol*

to asd a t o
to fa id *
iM

aud of t o m OSiM addition, t o im o tic n ittetare beoane

a a M ftl o f t o somm* e to n o i le f t a thick pcljRaerie s a to S al

ocnld net b® d is tille d tm to vadoaad pressure. S isd lar results

w i dbtataad n itb

tU lin n e w*& e to a o l.

121

If *

BXSC^SSXCt? A® aBSOLfS

A p M to mump of t o litm tw m rerto® nuraercus references
<*tol»g « ltb t o ttoiXcss to a to m mMm of «aa& mcleoiMXic reagents
m t o toons of mOobLq iito r , (2,3*i*,S) soetmcetlc ester (1,2) t o
epiteteeto ester (2,82,83) •
t o I n itia l elss o f t o p m in it nocb wm to discover suitable pp©~
a t o t t to c i; © tod bo ussA to bring t o u t t o ccadaosatiGn of tb lireass
« ltb im to i s m to lto M p t o f t aaoli as ssalmie ester t o acetoeoetie
e s te r, torsfegr to to i& g a w ry useful a y a to tie approach to organic
onUbxy ©OTpSOOdS*
eiy&ar §&u iMaaBat»S9f \©j? «susi wporcoG th a t iw ^pl* © lefto oalfM®®
4^4iUMbrftaO

*ti n«tf nit

A *111 *KfUUMtBfc1Mfc'0i3.4tktfMk.

r^ d ily

W af \

rtr.lyf.n-

-MktfKSaM

A j u jn

e iiii efcl^X. cymmbeetat®, in the presence of

etii®du$s, bet not w ith
Wsmmm$ i t t o

Aft

m&ciiabe or e tiy l acetfiacetabs •

M t t o t p it o p by proper selection of

©m«*

d itto s , <W q to tia M ^ m M be acMsvsd w ith t o la tte r t o la b ile
t o t , t o ^b&gM&onP of diethyl m la m ts t o
to to o e tic ©star hp p o t t o s t o

A

mri#y «f ©otoni® were

ioetnbgtoo sulfides m s investigated.

including aaiydrats ethyl stop,

p^A am m $ aH&rtyl © to r, d te e fo m , t o

tto a ly d re to a n , bait regardless

o f t o t o r in to ic ester or o o o to o o to eater wm used, t o to y reaction
SVKftwt iso lated m s p O y ^ c p o ifto e or ia to ty to e su lfid e*
issstoces, t o ester coapcaeat m & recovered unchanged, t o
q u a lita tiv e to tm i*

la aost

in nearly

Be w aiter t o t o r t o reacticas were carried cat

122

a t vem topem tnr® e r b® lm , or a t t o r a f t a topesatures of t o
so lvm t is to * to y to a w ftc su lfid e m s cbtained. V a ria tio i of t o
r t o t e s to® $mm am or t o few# to several my®

to okngQ

t o course o f t o re&o&tm, t o m jo r products s t i l l being su lfid e
is&lpaers*

t o u tilln u tA m of

d ila tio n techniques as m il as etim gr

toe ©
£tolt&
G
ft sis© fa ile d to- to p to pslyim rtsation rc a c tim

to

to n being fto to m tft*

m m m ryiag t o

o to to n g agent from t o t e ,

O'upy^ib or- BSB, to m catalyst, to t o acid ic condensing agent, A K a ^
did t o

prcraefce e to m a e ilc ije , to y pdfem* f o M t o i being observed.

t o a ttm p M sU ^d tatto csatelyto by toydroaa alto nu ia trio lO crld e

m fiires additional

Bate (& ) t o reported tot aalonio ester

could be re a d ily e ll^ la to by e to le n e md.de using toydrcus t o t e
t r t t o n r t o * to glee * —butyrolacto® in nearly qaaatlt&tive s n u s t.
re p e titio n o f to e
to

by t o t and Curfcis (S5) in d ica te d t o t

r m o tta p re d ic ts to e r to d by t o * (8 Ii) to e a c tu a lly t o

ester**

te ta to iS ig ® product § « d a o rw tly l e th y l m lcssate, b is -f^ c h lo ro e tiy l
m ta a b e t o

recovered m im ic to w * w ith no * *baiyr©la©t©a® being

Mested* our cm to e s m tS to t o In aoeto w ith to n e o f Bart t o
Gurtis <S#)«
As a re s u lt o f t o M M m o f «^sy3atlcn" to occur in the above
stadias, apparently bemuse o f t o ease v lth v t o t o
undergo eslf'^eaym eirtotim # «

c la fin sulfides

attentio n m s directed tow toa t o

o f toiasm es possessing a higfesr degree of s ta b ility ,
to to n t o , t o follow ing to e ® types* aUccs^sstlyi, t o t o J y t o tiy l
to dMkyltontoOyl tbttJMi *m investi^ted.

123

/ \

iK K % *G tM E 8|

CD

/ \

/ \

C!is

<m )

in )

m & the omnpoiiiid* o f type ( I ) oefcibitsd l i t t l e im & m ey towards

$K3gnMffittttUftf aad eo&M b® kept a t m m toperatur© t o sos» tftm
wltlMNKt mrnHrng A ip w id A l® d«fc®rU®atto. Bs®a® acmpcands *®r® obtained
la ®®od yield s by e ith e r o f the follow ing general metfecdsj 1) by tre a t*
a « t o f th® eonwsxjndiag glycidyl ether® t&th *$t® ais petasstot th io eyaasnte a t m m i*R *p»ntoe ge* below,

A

/ \

/

s\

* mm *— *» IH>-CHa«C
B
—
0!ia *

Em Ois^ ^a£%#

©^3*3% #

B
O
C
S

SijHct

o r 2 } by to a tm stst o f the corresponding glyo i^yL e th e r with &sp®ais
tM a ire a * la tbs prase#*®® o f sa e q iis iliH b amount o£ an ad d *

&©

pHbydrcasy t M w s t e salt® wMeh tom sd Kara hydrolysed to the iM inanea
sipem treatssssnt w ith m&mm mgxmm m&tvm carbonate*

Bse yie ld © o f

2<^MzwegmU&l tfe l& m n tti sm m sm rizm S la Sable I , and th© a n a ly tic a l
C2S&1S®- 3m flWwWI X I*
Jb*.

M «*

Q k k l

ml

t T

B® l #2^p£ssy»3^Brca^|TOpajaes vsqptod la the abeam reactions,
vm

fcwpursd to m tb» bdebyW as by tsm tm n t w ith soUom Sqydrcedd®G®
i
«^bs,«GB-GBa-a i. *

m m — e»

0
/ \

lb® yields of glyeldyl ethers ar® recorded la Sabi® 1X1.

12k

to

ware prepared by Urn follow ­

ing Mftfrumm..

y \

OH

to y ltito «st farixtyfeta* ««• ffarw* in tol@ 17,
W
'P'P « IPW . W •Pf.l

to < w ^ s a s csr ty *» n , t o follow ing
11®*© ttiilis a d e
T» T W * iw

W

^0
E«®Sa ♦

M

0
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®«p«ds m Motto to c®iM l&r^ay, if not sci©3y, of to

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ft» i l t e i t o t would M to b e t o tw m AAm of an tscesark a te te o
m® dbtitood*
Stas y ie ld o f substituted asstaomsraaptaa m s found to b® <jxtta
sensitive to mob factors as t o nriLs m tlo of arains to tb ito a e , pemmoo
o r abaamss o f m solvent, type o f solvent, and nature o f t o product
t o t , i t m i c to rre d t o t to tin g on eqpimaLar- nistura of
f&fm ridlas and 2-«iim ytiseft% i thiiw rae a t re flu x fo r twenty hoars, in
t o absence o f any solvent, gave only 21 .E# of t o attoo-^mrcaptaa.
to n t o to tin g period m s H a tted to t o to r s , t o yie ld increased
to 3X«3$« to m a twofold aaeoms of piperidine m s mplcyed, and t o
reaction srfxfctire r e fta to fo r t o to r s , a 60*6$ y ie ld m e raaHaad.
to m t o reaction m s carried oat in a non-dcnisiag raadium mob as aalydrous
s to r o r t o m e , an e^tesO ar s tix te e o f t o aboro reagents ^ v a &
7 1 .3 * y ie ld o f t o a ito o « m im p te *

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to

length o f t o r e f t a period t o l i t t l e or no o ffs et upon t o y ie ld ,

135

In to s s preparations u tilis in g a non~icnizing solvent.
« M l t i m m Obtained w ith

S im ilar

tfciirane (Table V ) .

in the rencticns of w a r& d lim w ith 2-^ th o xyo etlyl end
S‘*® tosyaethyl tM im n s m m likew ise effected by the above fo oters,
f© illu s tr a te , yield s were in the neighborhood of $0$ in those prapsra**
tic a s u tilis in g a 2*1 ra tio of to n s to tkiixaae and e ith e r anhydrous
ether o r ben tos as solvent, whereas the y ie ld dropped to about Uog
when t o

solvent was cn&tM L

Although some polymer fo is a tlc a aceast-

ptosd a l l o f the preparations, the proportion wee fo r less in those
gsw pfoitoa# p lo y in g a solvent and a mole ra tio of tom s to tH ira n e
srsfttsr t hen one.
The shove chserm tlcns are slsd lar to those reported by Bras (7 3 ),
fo r the reaction of ethylene su lfid e w ith a v a rie ty o f amines.
The reaction o f d tetb yltoa© w ith 2-mlkcay»©tbyl tbiiranes requires
special © < to d to tia a , in view o f the e rra tic results observed. A re­
cent a r tie le by fonanumr (8y) described the reaction of methyl and
eth yl gpLyddyl ethers w ith d ie tfcy ta tes .

I t was reported th at no

noticeable reaction occurred a t ordinary or elevated to p e rata re s, even
when t o to n e was used to a t o to threefold encess. Howmrsr, when
agisous sototlm s o f t o awtoe were ®a|lcyad, substantial amounts of
t o to sate d ethers o f dletlylam to o to ian ed lol were iso lated .

P rio r to

im ag in g t o u t t o above work by Pmemarev (8 ? ), we had attempted t o

raao tlm a of a-ethcsyraerthyl th iira n e and 2-tv^possyiaetfcyi th iira n e w ith
d ie th y l m im using pretoara© id e n tica l to those employed w ith
piperidine and morpholtos. t o n t o assess dtethylasnlae had been reaom l,

136
to

concentrated reaction product m s subjected to d is tilla tio n a t

reduced p m s u s *

however, instead of iso latin g an anincnraerc&ptan,

a t t o r 2»props8$ra8etoX bhllmis® or 2~stoKys»thyl thiixans m s re­
covered la alao st cjaantltaiiv© amount* A fte r

of the above

mxk by t a m r , i t m s f e lt t o t to two xmgsats bad asrely fa ile d
to react and t o t t o presence of water m old be required to bring about
re e a tim *

la a pmpum ttm using aqueous diaiiylw aine and 2-propeasy"

sajthyl ih iire n e , according to tbs procedure of Fonemrev, a nearly
em j&ate poXym riaation of t o tM im a e ©ceurrad, and t o icnina couponm b m s vsewered unchanged*

t o QxpXftnation fa r tbs la tte r resu lt

m old appear to be tbs observafcicn by Bms (? 3), th a t io iia ia g solvents
re a d ily jroaote tbs p o lym risatim of ethylene sulfid© in tbs presence
o f xustnes.

Bds cat pled w ith tbs fa c t th at ethylene sulfides are much

m re susceptible to

to ** tbs corresponding oxides,

m y m fM a s ty Fcnemrer ( W

m s able to e ffe c t a reaction whereas we

obtained only polysier fcamsUm.
An in d t o it a t o t reaction bad occurred, in t o absence o f m te r,
is found in t o recent work by Wright (9 0 ), t o reported a s ta to r
s itu atio n In t o reaction of too#yeidaldefcytf® d ieth yl acetal w ith
nmmtgieous d ie th y l aasiiis* t o reaction was thought to give t o aadno-

Sfc

w m m m * (c

to w e r , when excess arato lad

b w t M oved t o t o regaining m te rla l subjected to vacuum d is tilla tio n ,
s
to y t o s ta rtin g th lixeas olTg-A:B^B(oal9ks) a m s obtained, indicating
t o t diethylamine is probably s p lit cut re ad ily frm t o above tone**
mmmptea*

Such «& m jS tto tla i could apply equally as w e ll In a ir case.

337

X» tetor support of tid e ccntentiaa, t o
associate® O k ) » y bs sited*

study by S ^dsr wad

to y cbaarto t o t t o highsaHw&ling

M tnraM M rm itoui d e rtto i r » altos? ethylene or iscbutylena su lfid e
t o to n e s sssiM t o be obtained pure by d lto U fttls a under reduced
gm tW NU

In, s t o Instances, m m w m xe re d is tito tic a s gm * d is tilla te s

«C

lewsr is s m p to t o t e e o tito *.

t o r suggested t o t

to

fo r to e® d b sssm tlM is t o t t o toae-naarcapfeans are

,

subjaet to to n to dtcs©positl©n, aaeoFding to a it o r <a? both of t o
fcO Iw in g m e t t m *
fyil^^BgiSE

Egl$2B«Chj| *

♦
t o study by l&tgjbi (^0) t o

E^S

✓ \
0ES—0Ba

ear own observations strongly suggest

t o t t o sssoto x m o tto $# lb to ' m U %» responsible fo r t o results
observed#
3mm m to r in te re s tin g result© m m obtained te a an in v e s tig a tio n
o f t o re a c tio n occurring batsmen t r l« t o i p to p h ite t o t o products o f
rin g B a sis® is o la te d £xm t o
w ith mwm8&x%r to n e s *

re a ctio n s o f 2 -b lko sysethyl ifetiawaas

t o ste ^y mm I n it ia lly ca rrie d oat w ith t o aim

of ra to a g t o MMpto*gmp« «ad towfcgr irodaelng compounds mtih
'HEjg

a©
to s s structures, t o

or

By unequivocal synthesis of

© cn p to M o f t o i r properties, t o ^ le s tim of

t o d irectio n of rin g opening caused by attack of secondary to n e s upm
S^iSlecnysMtol toirem es could fee detctoned.

I t was f e lt t o t t o

138

l*S p i» h la » o f s to c te s a o f t o to r© taro h m » weald be easier sad
iMMHl sshjsoi to <psati<m than those containing & mmxAvbo^gFaip in
addition to the s to r and &*si»o Iteagges* hcwwrar, to - reactions fa ile d
to p m m d m m pw t#& a f t r sam ple, fn m the sm ctlon of t r ie t o l
fM c fc tt* m i l^ b b « y ^ * s ^ ^
mm iM & iM I a M

f im

m ^apropm m t o r *

o f wfebjft a lly l s to r and a rtm < m

*M«fe to m ssebjaotel to d is tm a to n flailed to 0 m any appreciable
s m m t o f Im b o ilin g
M f t t t y l phosphite are temm to remove a m to from a great v a rie ty
o f fom lng ccsa*
pm $® w ith jd te jta m u i to nitrogen bonds (91) by raaotion w ith aminos,

m trtle s # e tc *

In

a rather esctansive lis t o f compounds t«y^«w
( jy i) M (m )9$ (KHI»)?S(0R)a bare bean prepared

m
m h

■ In view o f to s s fa c ie , tbs n a te s o f tbs reaction which ©scars
to m

asainoproianes are treated w ith

IH o tly X p ta to te becomes s w to d m *

t o t is to aay, i t becomes

mem m *aiM »t as to a ir «n * W 1 ®tfe®r to O d re s o lt, and why the m aoral
# f both tho aaste- and teo&ftc^gsm p is not axKKpsctod.

Jcsssidering

oio© &mlm tbs case o f
m
a «►(StO )af ■"—**» vh3< K & a*<)i#«vlia ♦ (bsh3,(>h)rS{Oiirt)a
♦ ® fflt I t i® not possible a t the p re s to to © to say which oessars f ir s t ,
the m ® m 1 o f t o riArc&r&o- or a id a o -to o tim or t o t o r t o processes
■fcawmrtiiel.y-

t o s td d e to o ito ito to t** ( C;shi0H)FS(cdt)af is a

139

te M

eompamd (sol), and m s efets&ned 2a m i l am m ts la the

m fc *

The law yield® ar® preassably due to th® high temperature® and

1m g hm U ag periods which m m mr£v&®& In th® above reaction.

In

iURsoft a t th is ©ontenticxi, i t tom ham atoam th a t aisddotbicnopfempbate®
undergo ssveral secondary reactions. Far eoc&raple, they undergo a more
or less ready cs& M U m to the S # IO (o a *)* analogs daring fjavifloaUcns
operations aaoh a# d is tilla tio n s and c ry s ta llia a tic n (1 ).
Snforsm ti^i i® availab le about reaction of th is type.

M tU e precise

In addition,

amidotiiionopfco©|hat©s are subject to thermal decompositions and various
dleproposttem ticus a irin g attempted d is tilla tio n s (91) •
fhe reaction of tris th y l phosphite with the product isolated trm
the reaction o f 2-nethcByaiethyl tM ira n e w ith norpholine likew ise pro­
duced

a21yl ether and an unidentified ajRidobhXcmophosphut© or

d e rim tiv a th ereo f.

S iraiteX y, the Redacts isolated firm the reaction

o f 2-efetaymatfeyX tM iran® w ith both piperidine and raorpheXlno, produced
e t ly i m&& attorn and praaisaably asjidothioicpfcosihat^.
s u lfid e In anhydrous ad ven ts cleaves a t the p rira ry cazfecn s u ite * bond In raaciicsi® w ith ofl&orina o r brom ine, forsdng b is (haXoprond) d is u lfid e ® in q u a n tita tiv e amount® (8 1 ).
la the present Investigation, the action of bromine m 2-*aath®«ymUitfX m d 2-©tlic®3W tly l th ilraao in anbydsms solvents m s investigated.
nm reaction p tm m m y occurs by a step-wise process sim ilar to tin t

proposed by Stewart and Uordts (3 1 ), fo r the reaction of propylene sul­
fid e w ith halogens •

12*0

Bra —

4

s

*

tK}-GBa«CB-^GHa

Bp*

_

94
I
BP

i
R’<j~J&ifCii-ChsrB r

PtaAW**«/*

W&v*

E * 0Hs#a ^
however, to n t o

crude sto u cts were d is tille d under reduced

p essare, » |d d decomposition m t in and ncm of t o expected products
were Is o la te d . An analogous situ atio n t o recently been reported by
S to a H t o

ta n s id * (^2) in t o reaetlm o f trtotejylsn© su lfid e t o

b rto a a , in which non© of t o

clo&vage product ©cnld be iaolat&ci t o to

tttssp&vs doooapositlfln a
Am Uabl® evidence (1 6 ) Q em m tlag t o coarse of t o reaction of
sfcai&e aXksne soltU m w ith Xithima atahann hgRMd® indicates t o t t o
observed reduction in d u cts are t o net resu lt o f ttnors«a» rin g fis s io n .
B o rM Il t o

his associates (16) were t o f ir s t to damcnstrate t o t t o

to u o to a o f onsswastrioaBy substituted elksne suindes, such as
aetbyXtMaeyoXopropro t o n^^ltM aoyolopropun® , gives ris e to th io ls
la which t o ssO te a t o retains its lito g e w ith t o mar® highly
substitutad carbon ate»«

Eo fo rm tio n o f pcinapy raercaptaa, resulting

liil

tx m t o

of t o secondary c a rto -s u lfa r bond, was noted,

fbe

muMmlm production o f secondary xaero&ptans in these reactions m s
inberfrebed us Iw tlw in g in it ia l attack by altoinoH^dxrijdc Icn C&IB*")
on e it o r t o
fis s io n o f t o

primary carbon a t o or on su lfu r, w ith t o resultant
p&aary m ito m tlfU r bond.

In t o only o to r

s tu d y so

Asr reported, Moors ami Porter (68) observed t o t reduction of nHbesyl*
thiacyelopfopaas resulted in t o ftam ftlcn of 2-octunetbicl, w ith asm
o f t o iflaracrie l-c ^ U iio th ic l M u g reported.
In th e present m |k , t o lith iu m aimainum iydride reduction of
several

tM itrufw * was investigated.
8
/

SB
x

fl*K3ig»CH««Cila * liAXB*

1

E ^ t <-eiK% and/or ^0Ba«0Hs«0B3-Sh

t o resu lts o f th is study are shova in tab le 71.
In ecssflst® accord w ith t o results of previous Investigators (1 6 ,6 8 ),
a© evidence to indicate t o feam tlo a of any p rim ry th io ls In tos®
rmotlcms was obtained.

fu rth e r, no indication was noted t o t any of

t o reactions proceed iscsaerio mixture® of e to rH h ic ls .
B ald s m m in t o m m of 7W5JK# except in t o case o f 2-pSaanasy~
methyl tld isw M *

$«®*e solid peaymri® su lfid e m s produced in a l l of

t o reactions, bat m s especially p a M

in t o reaction of 2-toncasy-

istwtox MiMnaxm w ith l i i h t a atataans hydride#

t o observation of

peOgmr fo rm tlo n , a lto u # not mentioned by BordwaH sad his associates

(1 6 ), %m in agreorasnt w ith t o reseat work by llocre and Porter (6 8 ),
who reported t o t n-hejsylthlacyclcpropaa® produced only wmXL amounts

11*2

^
a

3
*

&

a

a

8

58

«?
f»
tvf

S

St fit St

*

8

<n
Ci

CN 0\

a a

**3
42$
o\
«

SK
9

I
m
|

»

3

«

S

§

3

fit »

5

OS
&

|

I - 8

H

S

ts*

CJ »

SS*

8

^
fc-

6 a
q 1
H H

a

a

4
*

ST

9

i*

8

3

3

3

<3 8

S

8.

'I ^

I

f

1l

It

',.3 O

3

O

^

-5

lid

of the expected wwmpims$ the sajor pwedtoot being a pdyraaric sulfide.
® * to s a tto of rx& p m wee aeaaated to tocOs® an anicnte polysnari-

saticn process* bresaght abort by attack of the ahnaino~hydride Ion m
the allsflpif sulfide*
35a t o pem m t m m , a m m anoint of high boning liq u id m s
*1*® pwdaoed, ta li ncHld not be obtained pure. A cleterrainaticn o f the
a p p w te te BKOecalar w e l# t o f the higher b a ilin g n o ta ria l fanned in
the reaction o f 2-rmethca^tethyl tb iiran e w ith lith iu m aluminum hydride
0 m a m In # o f 32b* A possible explanation fo r the abore observation
m y be the fo llo e iag *
A
/ \
CBa-O^Ba-CI^OHa *

L2A1B* — *

A

SII
I
0K3-O-Cli8-CIi-Cii3

f

8Bs -0*Sb,-C H —CH,

S-Clia-0fa-Cii,-0CH3

.^ e s%-O-CKe-CH-GUa

(e ta .)

(A)
AaaonHag to th in schwa* t o Xitbtam meroapfclde formed by t o
in it ia l ita g opening of t o m S m m , attack® a seeead molecule of t o
tb iira n ® , fom lng t o cm jm ad (A) of sjolocalar weight 2XD. Tide type
o f side *m © to n is fw «M «B ar abssnred in reactions of cyclic sulfides
w ith irncleopfemc reagents ( M u ) .

In support o f t o a to ® fo K iiiX atiai,

i t m® found t o t use o f excess L1AU% increased t o y ie ld of monomeric
m m tptan by aereral percent* w hile t o asom t of higher b o ilin g m aterial
was decreased*

Alttm kgt prtomvy sad secondary alcohol® m y be d iffe ren tiate d by
4 *&»!&.©

te s t ($%)* no such simple means is availab le fo r

d ftm ta fe ig whether a campcwBd contains a primary or & secondary aaar*
«sapio-grottp» A color te s t {$$) has been dsrised fo r disttagiisfaiag
fcstsean te rn a ry and primary or secondary th io ls , bat ofewiotMOy la of
no value In. tb» present study.
fiats, In the present prdbla® any proof o f structures bad to be
based s tr ic tly upon une^tivcdsl synthesis of the two possible alkcayjufopyliaeroaptans, ft*y* a ‘W*a^ r fi* **i "fflfdy between tk d r properties end
tifooi# o f the reduction narodact tiataiasd •
1&e induction o f 2*etJwn^iwstfeyl tM iiu u could give ris e to
Oj^a-OKiHjj-GB-CBa or C

a*3b» depending upon the di-»

section o f rin g ^ p m in g , therefore these two isomers were prepared by
Independent xm ctlons end compered w ith tbs isolated reduction products
Use follow ing jrepamUwe reaction schemes were eaplogred.
®-QE#< % < E s*OI£ ♦

CjjE^jI ■ -& «» 0^x8-O-GBs-GHa-GBa-<)E
(t)

& aug» a # s^-=0B8«GE8*<Ba*® r

C ^@
*0-aBa<JEa«*aE8«8H

(m )

<n)
/ \

•

Ga^ e«*0 -GE8-'wB-*-UEs * 11411X4” -? * 0 ^ « 0 -O iia«aE"CE8 1

(I? )
SH
G
aEs-CKJEg^CB-CBa ^Jft|gBiai

(VI)

Fdrs

^
**
G^i5«C«G
B3*Cb»Cii3

11£

Seacttm of tfc® mmo-acdisn to tim & n of 1, 3-profsaadiol w ith
eth y l todMe p re X in $6% y ie ld ( 9 6) ,

Im t o n t of I w ith ^ospfcorcas

tribrosslde proceed I I la $&% yield (97).
was s a to p m tly obtained in $t% y ie ld ts m I I v ia the th ic u m ® *to d
(f8 )«

Comparison o f t o

physical proparties of th is th io l w ith those

o f t o fwdaetion product t o *

thiissne showed no

s tw ila rliy *
t o exact course of the m o t t o of propylene aside w ith alcohols
(99«&00) t o hem established tm so aetto * A ll availab le evidence
in d to to th a t t o a c M m ta ly ta d m o tt o to d s to a a t o m

o f t o two

possible rin g f t o t o proclact©# 2 'm lto n *0 fto l" » l and l«uikosyim Ta»el-2*
On t o o tto hand* t o to lls ® catalysed: reaction leads to fo x m tto of
Ogfljf ‘W1*!1 1*68869?# mmcfly t h®

^

As illu s tra te d above, l*wtheaypK>pKaol-*2 was prepared by t o base
catalysed m o t t o of pwofytos cxid® w ith ethanol.

This m m compound

was to o obtained £$m t o redaction ef ethyl glyctdyi e t t o by litfcias*
almatora JysMde#

t o tm p m ftim of I f by th is la tte r procedure has

met previously to n described#

Oumwsieia of I f in to t o oarm penriing

t o s t o f t was scao ajaito d in A?$ y ie ld * using j t o i t o i tribroadd®.
A p ia * t o M a im

tohod was «*&cyad t o t o eyato sia of I I fr m V.

A It7$ y ie ld o f ¥1 m s realised# A comparison o f t o properties of th is
y ^ te riftl w ith to s s o f t o

redaction product obtained f r a a-ethcKgrawbhyl

thttosas showed t o two to be id e n tic a l.
t o «—

» ra&gm ts essAoyed fo r t o conversion of th io ls to ©olid

d erivatives, such m 2#h «titotm fctato nB en ® (101), 3 ,S -d to trc to a c y l

e b ta to ( W 2 ) m d 3 « *itto |fc to l± c aniydild® (U«2), js-oducad a fly
t i m u i Xi<7zlds o r o ils to n applied to the alkeay^wsroaptsns prepared
la t o

p fm n t stody.

M € ^ c5 ^ 2n a® j^ ^ |x p o |ttae did yie ld a solid

2 « U *d to to fta n y l tb to e to r to n treated w ith 2tl*n^trooKlorcb«n8sei»
tu t t o b tg M r sw&ers o f t o aeries gave only thick orange colored o ils
ut&oh ooaM not be indeed to orysstemse*
This $m m w ®m Im also been to e m d by 3wallan wad Soord (103),
t o to e d t o t

vo ild t o ta n crys tallin e

saeraory or lead to ts * t o by Snyder t o his aesototss (7 5 ), t o ware
unable to Obtain t o usual solid dwdv&tlves of alkcesyihiGls prepared
by t o reaction of alksne to fld e s w ith m iiou® alcohols.
m s ahim to obtain, several

Snyder (75)

derivatives bv trw asfosndne the iaarw

r ^ r amya in t o

T

ABB ♦ GX-GMa-CliCOCalia)* » M S *fe to » j& i ♦ R«&<h9^ i( 0 ^ &) a

Ap$&mM,m of this pveosta* to to aakoxymsroaitos prepared In
to

pnMNKt 1iMfe* to e v e r, fa ile d to produce any solid d erivatives.
t a t o r evMsaos In regards to t o directio n of ring-opening r*ro-

m m by t o

m to o p M llc a tta c k o f .01%* cn S 'vlkcK yiaetb^ ih iira a e s

see detained fey a study In v o lv in g g ^a sto sya sth yl th iira a e .
m m , t o folXcwtag procetoes m m involved.

la th is

H tf

A

*

Sfc
I
im k * »«»»«■» ® 3-<XH a<IMJE3

(I)
/

0

OH

\

I
Cffia*^K%<asH3lia

(n)

T
A

&r

G%OHg

Ufe^Gii

an
I
***> uH3-c«ci»,-cii-<ai3

a% ^^E ^G |i*€B 3

<isx)

(i? )

a ® pfoyale&l progartoe o f I and I? war® round to b® in Q m $M ®
*a*ant»

m m m m » t o solid

to o a to rs of I and X?

w w pMgaarad and a to a d M atin g point d ^ to m to tlcn towad nc a®~
$&MiMdUiRI»

In H # t of t o ato® m iM sum * to r® would &ppm* to bo lit t le
doubt m to t o a o ta l dirsetieaa o f r in g - fto io n to bo otxpaotod in t o
m M ® U m o f 2-fiOl£C0sp!0t i ^ l tld&m m ® by lito u ia a ta to n ® fcydride,
Ag vrnitim w i fg w to ® ly , t o sgfntosis of glycol aenoetorg by
t o w d teirtto of &fo$j6&L a to m nitfc lito n m alunlauza lydrid® had net
p w io a s ly feaan **port#3*

& view o f to e situ atio n , a b ria f study cf

to g pspfeioisto a m o tta mg oarriad cot*

m

2KH2Sa^J|l-«Ci|,a ♦ LIAlis* — •*

i *

ch3#

a ^ ,

and/or

ir o ^ .

2te «Mb to te m s , only a a a eto w y it o t o l- s t o r w s iso lated .
9m s to o te a proof o f lisa pradaots saro based cm a ccmpasieai o f t o
jftyM tsftl p!© prii«M t o iafsarod spscto 0?»lflO,l£>5) of t o eospctos
obtained In ton® raduetiesaa, t o tos» c M a ito from to alkalto a
to O y to o t o s t o tt o o f

odd® witfc a lto o la .

t o l& to r

x t o i t a la to m to in ro to a s m to o jM lic attack or slkcs^t ic o ,
p ^ io m tla U ^ at t o p to s y m ehm a t o of p ro v e n * cadda, giving
r&s® to-

data is anrwwBj^gori in t o la TTCI.

& aorapariston of to p foto t® of riaipopaning fc e to by to «usUcn

o f jsatteil lodida u M t ettelsa# smlfldaa ®yd amidde® reveals t i tfela or
no s fc iila ritiy .

t o a s a ^ ta , 2-iodoaycloliasyl a s tiy ! a to r m s obtained

frost i^ lQ tm m m m $M Q $)» to ro a s tr lm ti^ ls u lfa ito iodide m s iso­
lated fro® <s^©l«tosto «n lfld » t o !a®to& iodide (1 5 ).
t o reftotic® M m
t o w t o by W a p to
s a lts to n tto lm ® t o

s to s ft to ld © t o alken© mxlfidss m s f ir s t
to

R ia lt o a ccapias: mister© of

jr o fy lto « O to s s t o s to y l to ld ® ,

% ©mplcy-

lag a largo mossa of sastol io d to * Cutorcjr t o co^rorkers (15) m ro
a%1* to is o la te trimetbyX soXfoato iodide, using t o la tte r t o solfldos.
fb to M i t o R ars t o u # t to iarolv© t o follcw ing sfesps (1 5 ).

a om w on o f mm mmtm& fm m m ss o f

ms i^ h K o x x ^ m w m s

M M ) bx m hiA U u w m onou o r £& icid tl e w
rm xsmxm a m ia ccmje^tios of
m n m M oxm mm a lw s

ahb m

GB
I

J$MW3$&QB

E

*%#*

4

CEa

118-118.5

B

Oia*

118.5-119
128-129

4

sSK$»
?u?
765

JO
%

14*010*
1.1*01?*

735
?6o

14|060

Ih l

1.1028

rWOwlb
n » id

ii©feraaca

7U
63*1

99

78.3
81.1*

100

B

C-H*b

4

flpCg&jp 11*7-01*8

8

artS ^o 31*8.5-11*9 73C

1J030

70.5
58.?

4

1-0*8* 135-137
i-0aB ,d 137-138

IhX
7m

1.1*06?

57

14*0?0

53*2

100

73-75
n -C ^ e ?i**?it.5

m

1.1069
1*1070

00.1
80*3

100

B
4
B

1 3 0 -1 * .8

20

1.1*058

101*,105

4 » LJ4X1* *®aa0« .m o f # J i # l ©tbaa*.
B«
csatal^z®a coidoas&tias o f tro ^d e n e cscida w itfc an a lco h o l D
B$wla*l ppoparfei^ (far o®apud«oa) of S-^lkis^a-piropaaoXa*
^3:Mi5©ffeJaeEBra^X^5^©|'4&iM33»^ b . p . 1K'**13C,2^/75$ *®a#j g !^ I J 1O70 (99)3
a ^ th a r^ l-fa p o m n o l* b« p . 33?*5*138 /?60 raa*, n|w 1*1*100 (100)1
. p. i& o .s -i& P ftx m . , r & h h
^ -Is o p *V |W l-p ro |« a o l #b .p . lia -S itU ® /? ^ w s ,j£ ^ .ij0 9 U , (XDO)j
p^toaor-l-pspopm ol* b . p. 78-?8.£°/2G uvu, *gwl.i»392, (1C0)|

>

A

.Glia

F3? v ?^ch f

«
gm
w
i
g
p> G
«
w
«
w
Q «
£<
W
m
4
»5
* Q
m
M
o
aQ

ff

e
w
g
t > G~~C

< ♦

(CiigJgSI

Xn the present investigation, a study m s made of the e ffe c t of
saetbyl iodide upon the 2-^llE<a^wtfeyi tfciinanes.

In general, a tenfold

mcese o f m etiyl iodide m e essipLcyed and the reactants were allowed to
stand a t room %m pam U m fo r a one to two week period.

In each instance,

(liable 1X11), trimeUyXsulfondiam iodide m e the only so lid m aterial
produced. A H e ffo rts to iso la te the l-alkca^-2,3-di-iodoproi»nes war®
w ithout success. l i t t l e or no pclysaar formation m s detected, and yields
o f triiaeth ylailfm iw m iodide m m in the neighborhood of 65-70JS. When
an esccms of methyl iodide m s not employed, yields averaged only 23*17$
o f theory.
lik ew ise , a comparison of the products formed by the action of
-4

upon th iiranes and «ri«an»a repeals l i t t l e or

no s im ila rity .

Urns, the reaction of a lk y l- or axyHlthiam compounds

w ith ethylene ©aides results in the formation of alcohols, whereas these
same reagents bring about the desulfUrlaation of ethylene sulfides (1 6 ).

For emmpil®, the action of f^m ^llithtam upon eyclobsKsne su lfid e results
in the Jfarastlcn of cy&Xchassatie and tfciopfcanol (as the lith iu m s a lt).
SiaH arSy, oyolchoMn® and m n ta n e th io l are obtained from cyclbbessne
und batyHithSam (1 6 )•

Comparable results were obtained w ith

ethylene and propylene m lfid e .
fh« a ^ o p ria tto n of s u lfu r fro® o le fin sulfides by organolithiura
hag been interpreted (16) m involving an in it ia l attack by

151

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t m m o t t t m m j m m m iodide m m w x M m n m
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toe

reagent d ire c tly m su ito r, followed by ds&mge of

& w u ta M H lita r bend ftotog ris e to as &ectron p a ir wfalch tton sto ttl*

tROMcm&y or mbsoquea&ly in itia te s a l,2 «® ito to aiiaa reaction to fossa
to# o lefin end Xltotosa Htereapttoe.
It*

s

A

> o«-««c < + *a t

K

S
I
> S — -C < • * > OQ < ♦

14*

*

iW L i*

2b* rasceal o f suitor ism orpnosa lto r empanel# by $jsenyllliM im
baa p rm tato iy te rn toasrrsd by M

a g , J & ii* (93)# to© fam d to at

dipbeqyi dtoulfld® and ptoaijyyjtotoja produced diphenyl sulfto® end ti&cr*
i f jjpffl (a# to#

s a lt).

In t lit pneesnt In res tig etleo , to® reaction of 2«#&kcayia®to(yi tot**

#&to

^th^fna .^ryi totyltototoia m# I yirogfr*

Cb@®8BVed to ftt frffto

» I t me

ffif^ainril g 1f

reaction to occur, giving ris e to a lk y l a lly ! etoera end l l t l t e t awrcaptide##
pv# W

ISais# tos reaction o f SH^bosynatogrX to iiM » o w tto ytMttiyfriith4«rs
U fttfl a lly l etosr end $5% of totoptonaii# B u tyllito inia gave

Tt% of b utyl ®32yl ottoor end 81$ o f l-butenettelol.

Frcsa %be reaction

of S-proiraysaotliyX to ito aa* sdto s & s n y llito ta tosre m e isolated a 7C-%
id U d o f a-p^jyX«wlXyX #

t and B&% of to ic jta s o l.

c f n -p ro jy l a lly ! o tte r end W

B uiyllitkLua p ro

of l^ ta n s to io l.

Itoa raaeticn of

2HS^rop€Ky®etbS?l toitoaas « itb p l« «a iito to ia proceed tooprojyl a lly l
e t$ w In S»3$ y ie ld and totojfaenol In VS y ie ld . bOban b u ty llitkU m m s
«M|ftflyed# im p e e ^ l a & y l #to«r m s obtained to
th ffti to ?ii$ y ie ld •

y ie ld and 1-tutans-

S to ila rly * a b2$ yie ld of etoyl a lly ! stoer and

3$3
•a 31$ y ie ld o f tfeiflgtwnril w i bbtateed firan the xm c tlm of a-sthcsy*
«»W®1 ih lte ita mad &m&X3M&&am* BotyXilthiasa 9 m a !*?$ yie M of
•W flft • 1W - sttoar mod m %k$ y ie ld o f IH s ita n s ib la l*

Fma ccaajarabl©

©speidjssats using 2«EiBtfefflQ w l^ ttdUUWMi* 4 70% y ie ld of 1-fcutanoand a 71# y ie ld o f tM & p zm til m m ctetatoed*
Aft

as to «$r atbaok ooears m staffer In sU sA m sul­

fides* and m carbon In

eaddes im bzm presented % Berdsell

ami iiis associates (1 6 ), ah® suggest that the difference in the nods
of attack In due 1} to suite being aoro electropositive ami pOariMibl©
tfofff! osyrgsa* 2) Him awgi.'i.i f^t4M3n<wa»tifiyy dipole*

3)

AH* fact that

dttaAsi&t a t t r Hm dlmliMw, m&imtfl laHdes, etc. is kaewn to bo
to

by

I^

in

type

xesctloifis *
M em Kty Seofct (106) las reported th a t the neaotim of simple
<w4<g<aai- t>ifr.h trle th v l bbGSt&dLba resu lts in tbs redaction of tbs
epoxide to tbs corrosptand^g d e fia aad ajddaticn of tbo phosphite to
trie ifty l ghoj^h&te* Itar © M il# # «ba» m plsiasnt s m u ts o f t r is ti^ l
jhosjfcii® m d e itb s r Stlgdsao o r |* e i9&«M ©adds w t heated In a s ta in loss s te a l besi> a t iS & w tf1 im s w m til tm m , Id # yields o f the

e«an?esps8iljandnfin sadtsdMlyl phosphatew
sreobtained.
Xa the present Im a tifftfL m * I t vm observed th a t a a e ly heating
an e n te n te ssisfew® o f irl© ti$ X p to p h ite and sto len © or pragsdane
s u lfid e a t it s r s f t e t w i t e s

fo r a short period eff tla s resulted

in Ato te m tS m o f M stfagA tbtoo^osphate m tb the eisnliaaeoas

301

Qmer&mSm

13s# th ito n o to t o ecm &ptoing aaaaturatad cosapctos*

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(3 # ^ )* ? — s* JKa*CKa ♦

(Cabg0 )3l$

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1a #a®h Smtaaeo, t o re a a tlm p e to to , w ithin
q p s a tlt& tto t t m H o f

to c a o fto fta t# t o

lis iita ,
to

C to & a to m t o d lto s ito ) t o a r mch is lto r cm diticus to n to s #
# to « to w ith t o eorswwsptoiag oaqrgaa analog® „ 2a genes®!, t o t o t
M M &ta im m d stato d w ta a a lig h t asoes# of t r ie t o l pho#|Mt# wee
e m r!*to t o

t o re w to s i halted a# asm a# t o to fw m tar© of t o re ­

action mit o r # m « M

t o b o ilin g point of t r it o y i tMsmof^osptoto.

s© » M lo & to a o f t o scops of this, desulfurisation proo### was
ga&to ir m stadia# w ith o to r thUmctas*
SBWBfSssd in

21*

In

t o mmm&X results or#

ssreral o f the oora?«#poEKSing

nav# sab|#obed to. the astlo# of frrig th yl Ffoe&i t il.t# aadso* ocsa*
oosadStSoa®# Pcof ®aa8|B4>» * 4 ^ m ktemm mm m&m®& w ith trl« to & p to iM ie , a s to lm t y is M s o f « H y l

c it a t o t o t iiw t o l to o s o fta fh a t® m m iso lated , h em m r, when
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tto w is # , S’to h asg to h g d thilaw a# t o

f t o t o t o t o & tk lto n # gee# Mf$h y is to «C t o <w rm #pxm m & 2W
* 3 !# l ff!tM«« to sm ® t o cssie#s$totssg tto b jrl t o b otyl gi^eidyl © to re
to w r to o tle s ! o to itlm © 2&l!sd to react w ith ir i@ to l pboeifeite*

1SS

t o X M V i yiaSUIa i» t o desalfbadsatiai, im c iio a s war# obtained
t o n t o to te s *® MpcBMd* esmtatod a pfcenyX ©r pfesseg^r gpcup
(fu M I* IX ) •

th is im m m in yi& M ja t o lt o t o Im e r s ta b ility ©£

t o f **toayX to te s a * t o

£ r? i» © « y a ® t^ to te m ® a® ersaporod w ttb

SHOlq0, cap 2-n0kcaggi»to^ to te w s *.
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to ® i w i %

to a d t t o M *

AuMfcMn, to w y t o

J « n to (107) reported

t o t «jm i to ta l& g a adsEtar® o f <H«to3. diw O fide and tria tty a . fbc*|tof*e
ftor s w s il b o ro , good yield s o f te& ettyl, aeaotooptojlsai® w ri diotbyl

salfido iaBom Obtained*
*
m ar « m )3

(at0)«F

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m s®

^

asst +

tse®©e®at*lir#d to izsrdbre a i»*cl®©phlii,c

ffofo

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mm$M v iM i t o s to m p « f t o otoaqr l&teg® by t o displaced m dm lc
®p©oi®e#

TfPr ifl Wr

W

& aa&atom* to to to to tonas^toiftotie© of toetfcyX to®-

jfelft*

a U t o t o a lt o d * to jMMratom# H a fto a (108) t o

aussociato t o n

bis

to t to jasss&itos «•» ewevted to to cams®-

p to ia g atoases t o t o to e tlg l it e t o t o to- t o a t o t to a a e jto rta a t#
yt o M l t o g t o t o * * *
as S X to to to fe

ME ♦ F<©Sfc)a ~ ~ * n

* SP<®)3

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it s m Q m to le r a te ® t o

s e re ra l fesera, o r a t roc© tem perature id e a

to® s fto tea m s

%&to ultra?!© !® ! lig h t♦ m

to toe irto to a *

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to ® ra d ic a l

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f « s d $ t, in itia te to® to r n m o t t o o f trto to y i g te jb ito v ito « p *
raptoue*

I t m e fb rto a r ctoermd to u t as analogous ra d ic al zm otice

®©®ww®d teen d iedfM e® ra ® troatod w ito trtol^dL ito e ^ ito e In to®
prss^w^s®

fre e a fedios l ecuroas #

t o toXLm inz cimln pm m m m m m to p raed , e lto
as* ♦

(ito )3r —

(IMD)«~*e»
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Ulto stppd to to® toultelmtim of toitoae® by trtoH^l t&©8~
to ito * a t o t o t f t ia Is t t e f f t o it o a to ile r to tto t m area by Scott

<3C6) M®r b t api&iQBbl** t o e , a m o to fM llc attack by phosphate aa
e lto s r to g © toon atom could p to e e S & te to ia te rash a® to® follow ­
in g *

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tM ttto ® bate fU H d M its t o fo ® » $ ta of sw sm l
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4

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J* Am. CtMMR. Soo#f 2S» S0C2 CXPS3).
3 . ¥ • S. OrigEiby, J. Bind, J*
end F* &• te tiio iia s r,
J . Am* a t e * Soc.,
2606 (l£ li2 ).
&• S . J . B ris to l &i«d B* F# Bsteeiofe, J* Am* a te * Soo., 7k, I1O83
(m 2 ).
5 * a . A* la t e * !« B« ateleaeorfch, F . a . Archibald end D. s*
Alesender, 0am* J. tes&rcfc, 23,1, 186 (1 ^ 3 ).
6* h . M. Sm&mr and w . A te a te r , J* Am* a t e . Soc., ^

2X7 (1 $ *8 ).

? . S* ttim tedn. mad ft. B* tedsrson in ft. a . X ld e rfio ld 's ^Heterocyclic
Oorajranids, f c l. X,M Joltn VSligr and Sons, Xne*, Bern lode, IpgO,
aisp* x*
8* E . L . m o l Itt if* S . it e m * * " S te le Effects in Organic C te d » t*y ,H
Jote W iley ond Sons, In c ., Horn Xoifc, XS#6, pp. 1 0 6 -llk .
p« 7 . S* Steens in 1* H. Beddf s "Cteiafcisy o f Uw&cn Compound®, Vol.
X?,» E lsevier C o., It e m , E agtad, 1P57, Fsrt A, Ctap. I I *
10* A* Sc&onberg, tebsnri&QO* " i s t t e der C rgM jiscte C te te ,
fo x . IX ,» foplm r, S tn g p rt, JPS5# H>* 1WHL&.
11* M* B sX epte, BaU* soc* «Mm. France, ££» 71*1 (1920).
12* H* BeXepino, Corap. rand*, 171. 36 (1P21).
U . V . O eiio f and S* 1 * t e t e ijt e , B. S. la te n t 2,1$S,66G <19kD)j
a t e . A b str*, Jh , 2 8 6 $ u w )«
H i* M» 1 . Snyder, J . M. S tm P t end J . 8 . X iegter, J# Am* a te . Soc.,
& 2672 <lpk7).

35.

a* a.

J* Q & m atg w. Danes snd ft* s . hm th, a* c te . Soc.,

282 (1 $ $ ).

,

16. F* d . M M L k . M. Anderson and 8* a . P itt, J . Am. C te . Soc.,
24 1082 (lp $ 4 ).

170

1 7 . If . a*& aft and w. S«

<*• Gte»« Soo*, 317 (1950).

18* tf* £avl«8 and ¥ . E* Saariga, «?. 0I m» . Soc., ?7i* (1951).
W * * • la c b lw a r and h * *te*ik«l, ffcaaab la te n t 797,621 (393$) J Cbea.
A b fttr*, i£U 7322 (1936).

2Cs* s * W t a t t r uni 1 * <fcek*l, g . S . la te n t 2,0914,837 (1937)l obsro.
Abate*, J ft, 8$*8 (3937).
21* 0 , 0 . jf* Calvanor, V# X&vieft and K» B. ffeaftackar, J. Qbm* Soc*,
1030 (3$i6).
22 . F . G. B o rtM l and B. If* Andersen, 3 . Ass. Ohesa. Soc., 2£, 1$59
23* 3f, Bag$a and F . BiccOal, Gerasan Bataan $31,016 (1936) 1 cfem* Abate1. ,
jf e ^ 0 8 <3936) .
2U. W. Bepgn and A . Fraytag, Gartwn Batm t $96*7?li (W kC)i 01m . A b str.,
JE, 5?09 <391*1) .
25. f . Barr and J . 1 . Speatasaa, 3. Soc. I^ara C o l., & , 238 (19 iiit).
26. S . Blackburn and B. J M lllp s , J. Soc,

%ara C o l., & , 203(1915).

27. W« A . L azier and F . I * Stgatago, 0 , 3 . la te n t
Oban. Ababr., J$, 3935 (3914$).
28. h* G ootan, A . Benita® and 3* 1 . Baker, J,
1680 (39 58 ).
29. 0 . A .

Ifevta, A m ., 3Mh 2J5 (1859).

30* 0 . A*

tfe rte , A m . oM a. a t 1% ® ., (3 )

Abu

2,396,95? ( 19146)3
Qhm. Soc., J&,

ES 1*33

(1859).

31* J . Trogar and 7 . ttoran g , 3* w * can*#, £&, U5 (1897).
32 . A# m a M L , B a r., 3SU 1633 (1895).
33 . f . v . B lcbtar, »0rganis«Ba Gfcaala, V d . 'in ,® F rled rick Cohen,
1923# P* 9 *
3St. M» Baleptm and F . M e tM i, C©sapt« ra n i., 12&, 358 (1921)I
Chan* A M * ', IS , 1283 (19a ) .

35. H. maiina and S. ^cbiitosas»ir, M S I. soc. cbim. Fmnea, 31.
703 (1 9 *3 ).

171
3 6 . H. M

m&

m and P. fo£Sms&, M l . soe. e t a . Famoa,

136 (1921).

37* X* A . t a t * ana F . P. Tm m m , 4 . Am. C ta * Soc., & , 3508 (1929).
3ft- a . m iM m m a

mi.

a m . e t a . ta g * , 3i , 109 (1922).

39* I * I'm m m m and I ,,
A M r ** 33U 3068 (1937)*

( t a r n M o s t 636,708 (193k)i O ta .

k0* 0 . 0 . T ta * and P. F . K irk , J . Am. C ta . Soc., j S

2396 (1953)*

I4I . V , ColtoF, IT. S . Sfctmt 2, 183, 86c (3939)* Cham. A b str., J *, 2395
0 $ # )*
faft, S . 0 . Jena® and I . S . M d , J . Am. O ta . Soc., & » 2k52 (1938).
10* 0 . 0 . anas and s . L . Q itaaa& aia, J * ., <1. An. e ta * Soc., 7k, 33k2
(19 52 ).
104. 3 . Bodforas, B a r., a , 192 (1918).
k5* 0 . 8* tadS ng, I*. M* o« mx«a and L . H. caran, Ctaistasy and
ta M ftq r# 887 (1951 ).
k6. L , W# C. m iss ta t k . I . Own, 0 . O ta . Soc., 81? (1952).
k?* B* 0 . BayndMa, 0 . A®. O ta . Soc., |g * k95l (1957).
k8 . S . S ta le s , Or. and 1 . F . L ats, 4 . Mm. O ta . Soc., §&, 3168 (1956).
\0 . F . 0 . B o r ta ll t a

W, A . k t a t t , J . Cffg. O ta ., ^

636 (1958).

$D* A# Sebmbarg, A . S . I * fts ta k and A . B. M. A . Saaracttr, 4 . Am. O ta#
Soc*, 22# m m (1957)*
5 1 , l i . S ta n d in g and J . S la g ta t, t a r , O ta . A c ta ., &

833 (1920).

58* A * S e ta ta g and 1*» v» Fargba, Assn., k p * 176 (3930).
0 * A . S c ta ta g , A m ., l£^k. 37 (1927).
5k* A * Sektoatat «nS 0 . S ta ts , B u r., jg , 2351 (1927).
55* A . S c ta ta g and M. 2 . t a t e t * B* O ta . Soc., 307k (1939).
56 . II* a . Ittlliig s r , J* Am. O ta . So©., 22# k?92 (1950).
57. S , E« t a t fta te n , J . Am. O ta . See., 22, Ikkk (1951).

172

S®* J* 0. Q tira a r, W* Xfcriaa and v . 1 , Savig®, J. Cim . Soc., lASo

\S?S*) *

28. ?• SidgtiUfc, ^Organic Gbntfjrtay « f Stifcrogan,® Oxford Univ&reitjjr
**» » *, * » Soafc, 1937, pp* 289,291*

60* J# 3# larding and i . I# Gsam* 3 . O m . Soc., 3£28 (lg & ).
& ♦ B* Staadingwr iad F* ffesmlisger, Bar*, j£» 291*6 (1939).
m * h * m r#aa and 1 . %mmmt B ar*, ag, 7$* (l$b2>.

63. * • S . M U t , 4m Crg* Gban»* 23, a 6 (2958).
& • 8* II* & m tiard m& I . ta & a s i, B ti* . cht». A cta*, j&» 2985 (195c ).
6 5 .E . w*

ig p m

ansi » . «?* fin s**, Tm m * fbraday See.,3$, 805 (l? U O .

66* 8 . B*Gatliri©, B. ¥ . Scott and 8. ISaddingfcon, J. Am. Ohm. Soc.,
A , 2795 (1952).

67* K. W. E ta fM and W. *♦ cava, frane, Sfcaaday Soc., i& 952. (1951).
S . C* 8. H ow sad H« Fartar, J* (Bmku Soc*, 2062 (1958).
# ,. S. Ite m 1, B iaao rtstta, Bnirariatty of toad, (391$).
78* 0* 1 * C m & igiua
A* W.
! . J. i r n , ¥ . B. Oidm and
w . 1 * irn m , 4 . Qtom*
M * to * (1951).
I I . K. A* M e m and E. S. M a p *
111, 206 (3 5 ^ )'*

<1* m m atah H at. SSiSI1* 8"ti8KEKtejElti8y

72* I * it* UmSbmm and B* a* Ifc n tle r, J . erg . a im ., jg , 863 (195b).
73* 8* 1* i m * d* Qm* a im *, B3SB, Z U 757 & 95X)l 8 im . A botr.
W 3 U8S0.

7b. X* B*SelmolJm rad P, B« S po«*i, 3* As®. OJm* Soc., 32, UTO (1957).
75. !u R*Sapier. F. W* Stawurt and 3. B. 2i*gUF> 3. An* Obeau Soc.,
*675 (is fo ).

76. I * M* Hiwl® and F. S. WcosbairsI, 3# C ta * Soc#, 189li (391*8).
77* 3 . H# Stew art, Abstracts o f Uapam Praseaiod a t tfce 125th i&seMag

of the teestan CimicaX $osia%i San m nciaco, California, A |H 1,
19b?, P* 691.

173

76* 7. 7. Aldamm, M. M* Brab&kw end V* &. Basted, u* 8. S&terat
2#212»l]Oi 19101 CJm»* A b s tr., JS U6S (1910)*
If * S. 2* jitg * m a?. ©fcalaciicl QOsu, |g , W

(3958)* ©fees* Abstr, S L

6©* H* CHIjswsi md 1 . A . >MS»# 7. Am# Gbn* See., 1&, I8ia (lfb 5 )*
81* J* »* StMUri md ft* I -* C raft*, 7* Jus# Cite®. Soc., jfo* 588© (3952).
8a# S# A* fflMewssa m& A* S. Oopc, J* Aau Ciwn* Soc., J|£, 1KL2 (3915)*
63 * 8* S. MtteKfe* S'* L . cafe and a. 1&& ^ l ,
a ft < W )#

Am. 8bm« Soc., 2SU

% * ©• It o t , 4* Mm Qbm* Soc*, 2 i» b©f8 (1953)*

05* U* Hurl §M 0* Cejpfcis, «1. Am. C ta . See., XL 3136 (1955)*
$6* S. I . IngoXd, "Stractaa*© md Mhsmiam in Oygmic Obamiatay,®
OrasalX IM w ts i^ r fM P# XttaM* Horn Xovk, 3953* ©Bap. 7X1.
8?* ft# @*l&cMwsrafe, «?. Am* Otau See*, ,0 , IO (191*6 )•

§8* J* I* twaaatad, H* K ilpatrick saad M, XHs»ta&ds, 4, Am. Cbas. Sec.,
S L Ii88 (3929)*
3ft* F
*a
* Vm wm m , 2
£
u
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feiM
m l -M
s.*

1
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9
5
3
5
13i»».

Ahttsr., Ifi, &7b (395b) •
ft©* 4* B»HH^bfef 3* Am* Ctmu See*, &

!6ftb (395?)*

91* 0* M.Ke«wOA|»?lf#

Scrapouffid»,« 4dm. Wileyand

Sea®, la© .# lira? Xw kt 395©# ©Bap* 30•

fa# J* ft# Stcmrfc and a. li* a m titf* , 7# Am. Cfem* See., XL 21*3 (Xft53)*
93* A* SctonNafg, Bar., &

23? (3933)*

ftb# E# 4m Lucas, 4m M * C te # So©*# *gL
95* li. m rnm m % 9 % **., M * m

( Iftjc ).

Oftft?)*

$&» b* t # Smith And J# A» Spring# *?* Am. Qlwn« See.#

12?6 (1943).

97 # ft* F. Brown and S. H* wm Qalick, J# As. OJaae* Soc., XL 3D7f (1955)*

90# a# a# U rq itet# «?. V. a&tos, Jr.# and R. & M *r, ^Organic Sysfchasaa,

Coll* 7c!. IJJ#® M n WHey And 3cm, In c., flaw ta fe , 2935, P* 363.

I lk

S0 *

t e a * and A . Sadia, J# Am. Gftem. Soc., 2&» 1251 (1950).

IfiQ * £ •

a. GtewoaS, and

B. X . 5te*@ , J . Am. 3 t e . Soc.,

680 (191*6).

m . ft, W. Boat. I*. 0 . m tm and ft. 3D. ffortan, J . Am. Oban. Soc., £ 4
1985 (1932)#

102- ft, Tsiwm tm , J. A
m
. ate. Soc., 3 * 3661 (1929).
303. I*, a , M ila n and C. S . B o te , J , A®. C te , Soc., <•&, 651 (1930).
1 *4 . 1a. L . Gcas, ft* 1 . ftdacn and l>. h . a r t e t e , J . Am. G te . Boo.,

u u **> (392t).
1&5* A* A . M f t #

a . (tea, O te *, RISE, Uk» W © (3914).

3M * 0 . 3 . S co tt, <T. trg * C te * , 3&, m s (1957)*
107* I * X . Jkccbaon, R. d* Raw^r and l . f * Jcmsn, J . Am. C te . Soc.,
2 2 , 606b (1955).
108. ?* ft. R o fta m , ft* J . Ra«, f . C« S te e n * and ft. S . liansel, <f. Am.
O te * Soc., 2 |, 6104 (1956).
109 • a. B allin g and

ft. f&binowitE, J. Am, ate.

Soc., 22 , 5326 (1957).

110, w . a . t e t e and B. o . O te a , *?♦ a t e . Soc.» 22, 713 (1911).
m . a , s , nan t e & t e , O i*p te % m tteaa, 22, 39 (1952).
312. M* FloteKtellteo and 0 . 1 . fo lte d , J. Crg. a t e ., 12, 831 ( W k l ) *
m * 8* S ite s * and1 * V tit ite t, J* Am. O te * Soc., 2&* !U t8 (19B9).

lilt. f. I.Todsan, a, 8* M 3 t e and S. Q* Rite, «?. Am. ate. Soc.,

&

tim (3950).

115, a. 0 , Bteteaon and ft. Soateteas,

jL £8? (1935).

116. B. X* f t t e t e t * 8* <1. mgneaala, »♦ ft* 8 te * , A . 8 . te s o ,
S . 1 . l i s t e n t e S. X, Bi&fwctt, *y. Arn. O te . Soc,, 22* 5893 (1953)*
117* J* A* Van Alte, Osrpite

22,

5 (1952).

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