 

THE $YNTHESE$ AN'D SYUDY OF $QME
SUBSTETUTED PHEN‘X’L Viv-(H, N‘DHJKYLAMENG)
AMWL SEU’LFEDES

Thais Far m {3W 0'} M. S.
MECHiﬁAN' STATE UNNERSETY
Roger Allan {Bafdwin
1956

{THESIS

 

 

 

m smrzmsxs mm mm or 50:23: 31:33-21? 71732::
N’“"ﬂ m -( rummmmw mo)

I; {I t“ r (u u w t . 'f'ug,‘
Marin at)»: A 31“:

37
Roger Allan Baldwin

A THESIS
Submitted in partial fulfillltnt of the
ruquirmantu for tho dust” of
MASTER 01' 33013333"
Departmont of Chemistry

Michigan Sat. Uninrnitar
Ea“ Lansing, Michigan

1956

ASK Emmamzztzm

211. author would 113:. M «prom hi: nine.“ appraiuion to
Doctor Robert a. saint“: for his gamma. and suntan“ ﬂux-om!

the course a! thin war}: and during mo prams-anon or this mariph

m In , y 0‘, \1 AngI" Pl
'- "AIEI‘MYO C: 0510.; 4%..”3

”NJ “71%
ILﬂ'rIIQq . o I a o a I O O I o I o o o o o o o c a o o

nemm~ 01w
;.:!.m~.f?3.:.~1.w;-3....-...............o...

\ﬂ". 97*.3'8.
Enigml'rt-AkmlulQOOOCOD0'...IOCOCOOCOUO

w(ﬂ,ﬁ.malkylmino) am .2 or g—mbatimtm phm
shilfidQ S-‘ydrachloﬂdos and ﬁﬁugl £0d£dCC o a a o o a

a. or EﬁnbititutOG :mmeMI’ O 9 O o 0 o o a a a a
((3,3-Dialky1mim) :31be micridi Kyr‘arochloridu .

¢€"-'?*t'ﬂ'
-r“~-"'~A-‘thIODOCOo-QOOOOOCOIIIO.9...

EIBIJIQ'2‘RAEIWOIQOO.Id0.£00....CO....

VI?‘ 0 O O O C U C O I U 0 I I O O O O O O O O I C I I I O

p
'53

aggsz

TILBLE

I .

II.

III.

IV.

L19? 0? 9“9L33

(u (l:,:I-I)ialqulm¢im) alias-'1 ~53. or wwtﬂwimgzmyi
sulfide quntcrmry 12:49th 11:31:13; at hydrochloricin .

Uﬁtﬁfuﬁlallqzlmim) {812’}. wg or g4astlzoxyjﬁmmfl Gulf 1:30
hydelloudCQt-ooootouooooocone...

Wfff,1a’-§3ialk;rlemino) an; «5; or keliloroyhewl unlﬂdc
hydmcidar1§OGOron¢auovav00......

W(W.r~fa§ialkylmaim) any). cg or kmt‘nylphanﬁ mlfido
hytim03210?1iiﬂa...........o.ao.o.n.

10

222:2 snrz'zrtzszs mt) 32m? 0:5" 2 33133-1"?I'i“U’E’.~-I.ii
22:22:22}. to 412.221.2122.! 72.222120)

AL?" TL ”KW; 17"?"51'5

137
Rog-r am Wu

MI ”mac:

Sabin“ in mun). fulfillment of the
maimed. for iho any“ of
mam 0? 3012303
newts-21¢ or Quaint:

Year 1955

 

A!:‘-‘?‘3‘F.£ "1'

7-m- pruw‘ study again with an innatigntinn of mhstitaud
phony! 1112.71 lulfidnu having a "ﬂint-y min. gran;- on tho “mm
carbon of we aim chain. The study um undertaken tines curtain
U(2,u-d1mbncuum mino) nmzwwi mud“ (1) and simian;
ranted command: (2.3) have bum nportod as useful local mun».

11313;: a amoral proooduro which involna the interaction. in an
alkaline solution. of an 9;- or gab-tum“ thiophonol with an amino-
alkyl chin-id. hydrochloride at in. "flux chant-am. of £130 mo-
tion Mamm- for a two hour pariod "mud in 1.13. fox-much of a
total. of Win: prwiounly WtiodkMBﬁ-Bimbatitntod amino) alkyl
-2_ or g- mbaumhd pix-11:1 Infidel.

1“1
2m 2m! )
U + 01(322)‘ ’Rl MRO 2 “g?

'rho mm“ "to chameﬁoriud oi that as their hydrochloric}. ml“
or as man- quntornnry anhyl iodidou.

”mo radii} amilablo “imam chlorido hydrochloric!” and
for thc prowl-Mia: of thaw (ﬁﬁcdinlh'lmino) um moist: of thn
sulfide: nu p -diothylnminoothy1 chloriric. 3 MWINniwu-pmpyl
chlorido.ﬁ -azmchyimim-«memyzumx ohlorid‘t. Z~P1Fr1dim¢lh
prom chloride, and b’ .mrrholino-nppronl chloride. Th0 ubotimmu
on ihn benzene ring uccupiad position: 01th" oriho or 2am in tho
mlﬂdc um. and included mob atom or group a: chloroo. nuhyl.

amino. acatyimino. and. asthma.

1.

It‘s 23122222222212

Ho 1:153 and R. D. Smuti. Jo Am. 91‘.“ 300-. 2-1:. 5102 (1952).
1?". Ludunna and J. 0. supp-a, J. Plan-mace}. Exp. ﬂax-up" wk,
no (195:2).

ltpatain and 2.4!. 22.3”. J. Am. {ﬁx-m. Soc... LL “0‘39 (1955).

1””‘w'2'w‘ﬁ “I;
‘3' c "4‘14: .N’k’ J: I'q-I-

:2 :0 pmasnt «may dado with an investigation a: a urine 0! new
tub-mutated 1:129:23}. Eli-‘31 ﬂuids-m havimg 8 tertiary mine may on ma
terminal czarbrm a! the altar!» 0mm. ﬁzia immtimtian wuss 2:022;th
first. by ‘13. rawrt at Kim and ﬁtﬁzuail (I) that carbninﬂ) 43:3,;‘3-(11-
mzbatitumd minohali -'1-;1:any1 sulfides pone“ nativity at 106211
mmatimzica: ”madly, was derivative: of 8-salkaxy~kuminobanzomel
containing tartiary hummus mum (2) have hm twang-tad an moan-at
monastic: and finally ﬁzz-stain and ﬁnger (3} reigns-t that mm- and
diailq'lmainoot};m 03mm of mamainonlimwbimaoia acids proved in be
highly when" and wrung-10.231213 am local anaatimsics vi t‘n nimimly
low toxicitim. As a connaquonaa of thaw-.0 Hyena, it was 21112101”:th
that by varyim; the mbatituenta on the ham-mo ring Mus, also, the
tsrtiary mint: ﬁrm in 2320 side chain of mahgtitutnd ﬁat-say: mumm-
miimnlkyl mlfiﬁau in mania be manihlc to 3:105:21". magma—Leia ox-
}:ibitimj; hip-j! unoathetiu activity with low toxicity. and {our irrimtim.

{mix the 22.212320010221321 swings. which will be conduct“ by
annzhar gram; of invmtiggaiora, and are than no! a 1.422% of this than“
can Malamute moss 695259131413 at 193211 wwﬂmticn.

Etinca main-a. and alkaxyl- gran“ were pmuimnt in ma mags-32mm
damn by ”iguana and Myer %0 have local anaaﬂmtia pmyertiea. it was
of incur“: to 1220322329 3 series a! oﬂho— and para- amino and «ZR-3x321
whaeimbw micgaxomln for the pun-.399 of converting six-«5:3 to substi-
tuted {hwy}. aizqzl mlfidna. 2n midition, emu art-.120 and prim aub-

uitutad thiagl‘annolu containing mathyl. chloro. and acetylnmiuo gamma

a

«are mind. The: martini? nitrngg‘m cantaining alkyd 230122.! and incluésd,
@411 ethylmzino, 5 utlimethylmai m-n—g'.r0;.,;?‘1, ﬁ-naﬁe’l- 6 mumzzgmmzm-
“2.31. 3' -;:i;,.eririim~m1m3.:rl, and Unrnr;hoiimon-yrowl. In general,
use (inquired mimd mum” were obtuinad as £3.21: }:.;.r:.'.mc}2lorielo mun,

but a fem awn waves-tad to ELM: mrvmgazsdim; quhtartwry 3:2th with

methyl iodi do.

”1:35:23 1:22

'E‘iwra an two gnarl gamma-ml 229%};on by which tho doaimdU-(Hﬁ-
“unmanned amino) 1:12:21 q, 3,1 car gmhaiituwd 5232221521 sulfides could
he premrad. ‘rmaa an indicated in i': e {9119:1336 mansions.

Einrting with a subaeimtad 6221053392201.

7:731 Stung} 305

q(”?2)nry‘! 2:; ’ﬁ‘l, “4&13351
w...)

an}: 3) 3:}. 22:2: An 22:22 + 33222-22231
§ 25:31; “-9

or starting; with a sartinty 323313333.

 

332222 + mrcsseznna .......) agﬂcaﬁnmz

at 52222235232

“the inner method we utilized ﬁn. to ﬁrm randy amiia'asility of
tho masonry mimnlkyl chloride: and since 233“ 31.162: 0! the sulfide
were nutiaiwied frm the last “my in this mitotic Coquette».

Racer-ind in tho literature are a '1in variety of metimda for gro-
garimx €110 substituted thiozhamlu Maui“ in than Iynthasia of the lub-
etitutod ﬁnality} minmlivl sulfiﬁea. Ikmloavy and Cumin (‘6) “32:22.er
Miim;h0ﬂ31813(31m131609 by than catalytic rvyduction. which they clawed

ta be quantitative. of the oorrosmndim; niiro commie using “Minn

oxide and an initial. knit-cam :masura of tmnty-i'iw panda.

 

{PC-3' (PG-232'

In a recent patent, ramimthioﬂiml was prepared by the high
321‘qu warogmtian of marmtobammthiawlo using. a cobalt mifido
catalyst (‘2').

Maoﬁziophamiu were also yrommd in a convwnimt mtiwti by
Slim and Gainer ((33. in their named. an aqueous solution of tho
i-ohioro-Q or knitmbanzom and oodiuu nifidn hydmto mu unused
fur cigﬁit hours. followed by neiiifiaretion ﬁnish ewe tbs maimt'nio-
phenol- in good yields and this 2:»th ma 0:21;..ioyw in prawn» work.

1‘0 K3?
2+‘Sneﬁ ---—-) O 2

in carrying out the interaction of the maimthioghamin M210) (3.!-
diailqrimino) nil-""1 chloride: to obtain thaGJGﬁﬂ-dinlkyimim) £12231
-g or gran-wine 23252231 321191693, 1; nitrotgnn atmosgzlwro mm rosgui rad
cinm 15230 maimthioﬁqamll were I'm-ring oxisiiud to their dimlficiu.
In all. but om was with sulfide: 02’: t2. tips 1223-321. it we fauna that
in order in obtain n crystalline hydrochloride darivatin of tho
tertiarymimnliwl «2212132293me uulfiduu. it ma nacumry to noetyinta
tha amino group. 2233-” within of this nation vars dwrmtariuai as
their quaturmry methyl iodide «it rather than as the hycimohioridn
talt. Is‘i‘n graviouniy unregurtmiéd(33.3-612113531321130) 23le1 .1 or 2-

ucatylmimwowi with!" "to sugared in this terin. and their

5

zz'oyertiec are tmzririmd in Table I. In addition two OJ (3:.ir-liiﬂlkj’lc
swim) rdbﬂag-maino;:hmwi sulfide; mam {remand and their grannies
an summarized in Table I.

'52:. mtlmxythiogimnoil mare grayizrmi momsﬂﬂiy magsiruying the
gmoadura of {inter and ii—ruiaaz‘s (7') alumna}; in 3.02! 35381313. in this
maths: tit-tho or yarn misidina was {liamtims‘i uni then treated with
yotauzimu ethyl mantimta. 21232213323 12321213133“ of thus mmtlmto £01.
lowed by acidifiwtion. and than «tam-a (intimation of tha reaction
nixturu yieidm tho urn-:29 methoxythiomami which 1m purified by dia-

tillation unzinr "rinsed Lraesuro.

 

 

'i‘ho Iodiua units of the wetlmxythiogimnoio on reaction with the
um, a{mii:23.1~:;I).a-:zsino) ui‘t‘vi chlorides remitted in tho 3271545229213 of ten
new utmrkdiaikzrinmim) aim/1 -9. or 53.921323123392211 9211216193. .2 m
of tho 13:}!350521 anti cat-mum]. praperties of them. cozazmmdo are 1.21221013th

in ﬁlbl. 1:.

$3.535 59.5 «$3139.... 9mm .H 4333.. 9:35.? ELM $333390; .9 $930?
«.333: so: vamuzsuumuuew A. .«ozuaﬁﬂeumRR .o oom.tnﬁmnéh?£ .A 51.6 03?; #3.»? muumﬁmfﬁm. on.

 

 

9m 34 :mém ~.m mm; .33.. a? mac mung cm mécm. a: $53.- m: «.1 Vnhmﬁwu
o n 0 o 0. .. r O N 3.... ZHNU .26 .x 5. WT..- . RM”.NL$..-

mm m mm; 3 S mm S...“ cm: « .som an afﬁx ._ f c6,” 3,. .. a;
2 _ ., . .....m.._n~..£. .. .. n m . 7K m“

w? m ~u¢ 052$. ~ a o; 3.3m ”more a c «.5. 01:: wins; a w... u.» A r» tag!

3;.» 8d 3.3 1m 06 0.3 "ﬂawkao 9mm 79% a: ma”... ¢.m,mm£.n ”NE...

a
a; Rim 3.? mg ma 53 “awn mm a S Ragga nmxmﬁa m: ﬁmammunwﬁmgﬁ

mm; 3d 33 mm; m2... ~23 Hmmmcﬁzﬂu wsam. m.m..:m~ ms ma.....__§a ﬂimﬁmﬁﬁm 9:.

 

 

 

 

mm; 1.6 5...} mm; 3. m.§ Ewmomwmmdo a mum? Macy: mu ompnémﬁ r. 93......
m m a mi r... c v + r 4
as. no? M330 saga.“ a? 3.. do...“ .m mu Nd an
m conning
II > Hi.
nu 93.334303? so agave“ .2932“

m husband—ac 0.3.353 uhﬂnnd3a3§anuou¢hm .3 d... 6.036 Aﬁgﬁyigiomva
m

an a wig

.2153.»- I... 1.33358. .. a

$0.10.? «bug I C 533.3% boa non-sham

 

l‘

141

{

 

35 :4 «min Mung TM own 8.881..» 1 1.: u... HUM. Ly Hugging-
3.: a; a...“ «.2 E can 6308:»? a $1: ”89. a. .mbnaanmw-
3.2 3.» Sam 3: o.» «4% amzoﬁmﬂu 9: T8" n89. an nOnAwET
8.2 cm.» Rim *3 0.» 9mm Saginaw 99 18a 7 ago. «OM33.
~53 #4 3.3 93 n; {mm ankmmouuwio 2 1.9: n80- m... a ﬁmnmﬁvu
9.2 R.» 3% “.2 3 in. gmommgw 9: is a. as? .. Gamma?
3.3 2.; Ram. Nd" .2 9mm sancomwﬁo mm @794 use. a. cumﬁznawﬁvn
«Q2 «5 1.1 32 E 0.8 gomnﬁw a .1: .1 mac. u-€ﬁ»€.-
8.: 2.» 3.3 E: ma... 7% Hommomwmmm mm “6&2 $8.. .7 a-m8~§=£~57
3.: :2 3.3 w: 8.» 5m améwumm 2.. $5 a. n8? .mmauauﬂmﬁ...
u Inna nun-i=9.” 2.3”38 o «all: 3w; 6...“... an «x «a

 

 

 

14311

if

i§;|-¥£! I! D‘u‘.’ 1“.» aIl' i;-;l

an O acanﬁﬁﬂunn .338 aghoﬂoauu no «u 3.7 “alggniﬁts

an.»

an “and.“

8
This chlorgthﬁthsmnla clinic! b» 1:2“ 51129;: from the maimdalombm-
15mm! thwagh the kiwi may}. math—Mean em graviazzsiy «Semribasi for
the mrrnzmudim mgr-martinis;ham}.a. However. only than rﬁ‘ilomthio-
item]. used In. this mrk mo grunt-M in S‘s-.1: manner. ﬁlm-o tho mutimd
cf ﬁenmm, PM} 3:0”, and roam: (8} gave batten ﬂuids. M W‘s-u inlay“!
for at» {reparation of yetiomtniagmwcl. In this pmce-iura. if
ﬁlorqbnumnasulfanyl chloride um Max:925 with uulfuria amid and zinc

30mm? to 31?» yields as high an 73 puma of incldoroshiogﬁwmlo

.201 T?!
w 7

Intemctiozt of ﬂu. Indium chlorotldngimzmlatu with w{?3.35-d1a12<31maim)

 

allay]. dzloﬂdew manna-d in $1.. pmmrrzuon at nine (dimﬁcdial‘wlmim)
alkyl -9_or gcleomﬁmmzl nuifidsl which are no! rmrdqd in the ohm-
iwal literature and «mm on name of their 3325;51:311 pug-art!“ urn smo-
ﬁmrlﬁcd in Tum. III.

hunmr, reactions of never"). (ofﬁﬁkatnl‘xyxmina) 9.12531 chloride.
am. 1 and E-ramthylﬂzlnghmh 11*. an album rem-cum ”malted In :11.
xramrntion of an additional four zrevioualy mmisscribad QM Ef.2!-d1!allg:1-
m-alno} ditty}. 9;- er rmcethzphm'l min-ﬂan and the-so, as their hys'iw-
chick-Mu mite, with a far: of their ﬂannel mpsrun an mama“
In mm“ 17.

Using the excellent method of Mum and immature (9), memora-
iirowl tmrrhoiim and piwrlﬁina mm gremrmﬁ tron the interaction
0! trinethylwo chlorobmznido and :wr...}'~nnm or zi-igarmlm wgioying

para dry human, as a ”nation $9311..

.onouonoaoho 33 ~23on @3923: I n .3qu «banana: a I «nonulungohhoou hon 3.350»

 

 

33.; R3 no.3 0:2 93 99 «.833an an em 6.. an n mamavnm 8-
S: no; 8.3 92 3 0.9.. «635$ v.8 .19 a- a. 0:35-
8.3 an; 0.3 v.2 3. 9mm mammﬁmﬁo mm «19: m. .8- «OM35...
3.2 .36 .33 3.2 m6 axon «anaemia». c $.33 6.. ma a Gang...
8.2 93 3.8 1.2 Na mam «Sugar—So mm 914% mu 8.. umnnwgva
3.2 «mi 8.? 0.3 93 $6: ~83:me .2 979mm” 8.. ma amnnﬁvuncaﬁvn
3.: am.» ~33 0.2 93 ﬁr. mania”? in 12 m. 5.. .mmsirwsv-
3.: mm... 3.3 3.3 93 was memamﬂwmso a. .312 8: a. «mﬂnENBV-ﬂmﬁ...
kg: 33 3% .1: 93 was Newman} 3 3.: a. a- swansmazﬁma...
a m ,o a m o . v.
«as» 25233 nausea 33.» 604%: nu mu «m
w .0053...

 

mm .ouﬁoﬁoouoz .332.
«honmﬂozoé .3 on 3.3. “833384153

a: an

428:. 5388: Sun 2.323.589. .. a

 

3.2 8;. 2.3 1: E 3.3 gunman». m. I: a. n3- Damn..-
3.2 n n

3.: a; 3.» d: E in 83633“. R .32 8.. a. m 33-

8....“ 3.. 9.8 «.2 a.» 98 8mm~m2o as m4..." .1 n8: canﬂnﬁﬁuaaa...

3.2 a.» 8.8 ~22 m.» 98 ewwaumnnao an Toma n8- .7 nuanﬁmazmmno...
a {u o a - m. a r. - i t > z
152 3.37.0 in.“ 2%: a}... nu m- «a

1.0.5.39.

 

aim
N“
«WW

ioii.

 

I.

 

.f-§‘i§l‘i!i"$ ‘lla .

.octogpaz .323 335% .8 .1. 33 ”833.184.... 3

ha 39

cw

2 mem o 61{’3§!233‘:3r ‘32:”‘5 3 6 “1:4 932531 + 6 km
:1"

Thom cmoﬂdm can“ have also beam “emu-M by the not. drawn om
method of firm growl-1mg the 011li {mm tho chlorowa‘irln (in). by
trmﬂng tho mum: with an aging-yin.» mammary amino, and than
converting the slknnolmine to 1m wrrnag'nndlmg chloride by Hanna of

zttlnnyl chloride in nm-.;rrh-ous chlorofom (11). an a tor-action mam.

< Eel—.51 + 61(GEE;33301! ----9 “(63:33:14)?!
Guam-72311021 + mug i :-(cz~:25ncz-u-::1 * 302

T'ho 391mm} wetland on;.1eynd in mm synthnu ot the mbstltuwd
5.1203291 tertiarym-una sulﬁdes from the Malignancy-aim]. ﬂuorides
and mbatihxtad ;.1mn¢r1thiol mm carried out 111 they fanning: manner.
Tim substituted and maroezﬁem um unwind In qufiélawt sodium
hydrant-‘19 to nmnmlim but}: 1‘ and thowmﬂkﬂmlqlmaim) aim-'1 chic.-
ldo hydmchlorldo. 551:0 alkaline mlutlon of th- uarouycizlo was but”
to its reflux tetrammturo and a water solunon of tho dialzq'lamim
altar]. chloride mnlrochloriio salt was added drown m3. 9.31m” memory-
and ammo- substituted ﬁxlogaemlu oxidize res-mil)! in MM. reunions
involving such commando wan carried out in a [:1 vegan humanize“.
Fanning the Minion of the mums amino hydmuhlortia solution.
tho ”action mixture was up n3 1:. reﬂux tesa;m.sturo for um noun.
after which H mm ullomd w cool to roam ta;.;r_.-emmro. '33:» any layer
which had formed was cxtmctrad with farce rerun-ma 93.9%” mm tho

cascabinm! other ammo" mgr. mahari with; tan pars-mm iodim hydroxide.

12
than oi th mtor, followd by drying over anhydrous ”@331“ mlfato.
The other solution of the sulfide mo filtered. ooolod in an ice ban
and than saturated with dry hydroggon chloride ms. The resulting
hydrochloride salt of tho oulfid. no collected by filtmiion and in.
other 1‘11”an 1m tasted {or complete rot-son]. of the amino sulfide by
passing; mlzﬁitimml hydrogen chlorido gas into the otlmr filtrate. Ito-
prowl alcohol no used to rooryltollizo the hydrodxlorido 39.1% gener-
ally.

In preparing; tho motor-nary methyl indido who of the amino lul-
fidon. the othor um rammed by evaporation and tho ramming dry oil:
amino sulfide was treated rill: methyl ioiido. Hothyl or ethyl alcohol
to: the aolvont mod to purify um" commands by recrystallization.

13o difficuliioa worn commit-«rod in tho ”actions of p «nonm-
ominnutlwl chloride, 5 -61mﬁzylmaino-n-prowl chloride, 3 omrgholioo-
n-prozo'l clzlorida, or K-piporidim-n-rropyl chlorido Ii 1.?) to. sub-
stituted nryl normptano. Houovor. tho reactions of aL-mthyl- @qﬂ.
mothylmninootfqu ozzlorido in alkaline media mold vary likely have re-
mlted in tho taxation of two isomorio sulfides. It in known, for
ommglo. that l-dlothylamino—Z—ohlotor-moans hydmcﬂxlorialo yiold: the
roarmmggnd product, P-distwlwnino-l-pmpanol. umn basic wuozyauusz).

Ii

0
Maw-wow "‘3 3 mm “‘“ﬁ 5 """1"""3”7""35
a J .2“ I. “Y Lu 2 .-

i'his rmrmngmont 10 an omaplo of mrtioiyooion by a neighboring;
group, the nucloophilio amino mug, in a oimoleacmmt roaction. The

initial "up in the mohanim of this tut-o of reaction in a preliminary

13
intrnmloml-ar di Bzi'lacmznrst ”action or ionimuon offoctod by that

naming-Ml” nitmgoa to for; s (333113 921123.: salt (13).

(:1; ILA-22' _ :sz F in
- . R' ..,. - ' " + C). +“'?" -'-- ?' and or -4- -E".‘
c I

In the con-m or dinmttylzmimi902222932121 chlorijo. this would yield the

{:43

int 9:22-3:11: on,
1 2
\ * I,
\‘g’
1233/ ‘55:}
Cl“ 1

“was: by a mmloogéjlio ion molt} Vary gnmmly oomr at 0.32. loo.“
subgtiw‘aod carbon“) duo in tin mouctin affect of the mthyl grow
to give the rmrrnmmd {Much ﬂavour, if the initiéal stop in the

foremtion of cyclic nihilism. lair-malt»: ion is a res-vomit“ process,

.'“ \E-m v g V“ "“
'1'?" 'ﬂ 2 113+ ‘2 V Ho/ﬂ'f'h'

mi?“ {2:1 35,, .‘j’ «(5' 0H3
U 13 L1. 7‘ k \

,2 M W

3 Kg ”.m- a".

«3" 5 ‘ H

0

duo to ixxtamszl axial-01mins; attack 1v moG-Mi‘no grotto ml the ”who!
no}; in also a reversible attack by a. molmphilio tlziolnio ion than
the above equilibrium when. would Ea obtained due to the wincizll of
niorosoopio mutability and the irociuot “cloud muld Do on. most
thomﬁwmmimlly “able.

Evidence for a mixturo of pas-winch ms imiiwtmi h: in: tool that

it am diffimn or immsaihln in mm More; to obtain a cry-shun”

1‘4
proﬁnot with A sharp melting; wigzl. i lira—ad mulling range was foam-3
in several yropuro ions uttar rogaﬁtwd rocryotnllizntiona from various

solvent combinations. A: m. prawn new, it 1. not. knom which

190mm.- s-ro-ios'rinotao- or it than in manual] 3 mixture imbued.

3‘ WIN-Diniglamino} nl‘gl ~29; rouboiitutod 31“ any].
Sulfide ﬁzdrcchloridog and Mothicdidol

 

(3 ~31othylaminoethyl-o-chlorOphonyl sulfide hydrochlorido
pH CH

. _ 2 3 a
-&0 O‘Hr 0 ”V1
@431 a? ﬂaw m

2 vi; 3

Into a throo-nsckod 500.nl flask.oqu1;;od with o roflux condsnsor.
stirrsr, and drapping funnol sos poured 22 g. (0.15 nolo) of archloro-
thiophonol dissolved in A solution containing 20 c. o! sodium.h:droxido
in 80 ml. of rotor. To this was added dropriso from tho dropping fun-
nol 18 g. (0.1 nolo) of disthylnminoothyl chloride hydrochlorido din.
solved in 100 ml. of sotor. tho stirrod reaction solution woo hold
at its roflux tamporaturo during this oddition and then for an addi-
tional two hours, at tho ond of chich tins s light ysllco oil had sop.
oratod. Tho oil was removed and the aqueous layer was oxtroctsd throo
times with 100 Id. portions of’othor. Tho combined othor oxtrocts and
oil were washed with 100 ml. of o 5 percent sodium hydroxido solution
and than with 100 ad. of distillod rotor. The other was dried ovor

onydrous sodium sulfnto.

After drying, tho othor oolution of aminosulfido was filtered into
s dry throo-nockod 500 ad. flask fittsd with o stirrer. condonsor, and
o dolivony tubo for admission of dry’hydrogon chlorido gas. After
cooling in on ico bath, hydrogen chlorido on: bubbled slosly through
tho stirrod other solution. Tho shits hydrochlorido was romavod by
suction filtration sud tho filtroto tostsd sith additional gaseous

16
hydrogen chlorido for manplotonooo of rmcticn. ﬁrtor rocryamllizso
tion from isopropyi o1co‘nol.23.3 g. t 1.053 colon. 63*.» viola) of n
dzito crystallim material which mugs at 113.9%. nro recovered.
Analysis of tho mmgmmd for carbon. hydrogon, and sulfur gave tho
following rouults:

Calculator! for '31; it?!” "W123 E, 6.35; G. 51.5: S. 11.“.

{5093311. H. 6.86; C. 51.“?49 (1... 1102?.

5-1iotlzylominootlo'lug-c‘zlorol. 1 .11 sol...“ wdrochlorido

Following the procmiuro doscribod above, .23 a. {0.3.5 cola) of
g-clucmthioghmol diosol'md in 80 ml. of rotor containing 1'20 3. of
sodium hydroxids worn trontod with a solution of 3.5 1:. (0.1 Imlo} of
diotlylmzinoothyl chlorido lard-00211011119! in 10:) ml. of di otillod water.
Tho roddi aha-yellow oil mo trmtod as in tho yrwloualy doocriboti
[‘ropnrntlon of tho lochlnro isomer. Tim chi to lurdrmmlorido which
moltod at 1223-1231.?3" um “crystallized from dry ioczsrozyl alcohol
and mug-ma 21.6 o. (0.073 mm. 7:217? yield). 1mm“ of :21. mn-
oound for urban. hydrogen, and sulfur an" in following; ”cults!

mammal for c1212. :12: z-z. 6.33; c. 51.53; :3. 11.2.

1:39
yam: H. 6093‘ "4'. 51.28: S. “.250

p.121otlarlminoothyl-E-mthomyhonyl sulfisrro mucwlcrico
ICE,” .1

‘93:?

3-0575}: 3'3“ 9 5:11

3
2 ‘3
‘3’:

17

Using 20 3. (0.1113 mic) of Emethoxythiwhonol dissolved in 130
m1. of 20 garcons by weight aqueous sodium lddmxldo. and 100 ml. of
a “I.“ solu‘don contaginimg 23 3. (0.1334 male) of dictmlaminoet‘wl-
chloride hydrociﬁorlda and 15911291111115 the upgrimantal procedure d30-
cribed abuts, than was obtained 25.6 g. (0.09} male. 6?}? yield.) of u
whit. hydmdmlorida. The lnttar minim}. um recryutnlllzed from two-
proggl Meal-.01 and had an obwrvad ma. ting paint of 132-133.5°C. An.-
alyaiu for cal-ban. wax-agar“ an: sulfa mvo the following data!

(ﬁnding-ted for engages-.1131: o. 55.7; H. 5.05; s. 11.7.

Vanni: a. 56.53; E, 3.16; 3. 11.56.

5-731 ethylamina othyl-g—methomhawl 82:11th lydrochlori .10

0372333
Ss‘ijCHzﬁ/ 30331

“ \ a.

'12) the aqueous alkaline ”uremia“ of an inmlublo white “1‘
faulting {mm 92') 41;. (0.1%} min) of Q—reﬂimwmlopheml being plume!
in 100 m1. of 20 pnrmnty by night 51‘4an sodium hydroxide, in:
mum 25.5 g. ((1.136 min) of diathylmninoatlzylduorida hydrochloride
ﬁiamlvad in 191') m1. of “Mr. 1‘1!th carrying out than reaction as
(Inscribed abuva, a yellow 01]. ”gamma. The ends hydrochloride»,
16.3 g. (0.059 3610. 113.515 yield) on remyttallimsinn tron 130;:0153'1
alcohol. «1'..me tram solution as 3 mm which was crystallized by
Itirrimg in an 130 bath. It: EH91. ting: paint v.23 127~9°C. Analysin

far aarbsn, hydrogen, and sulfur my. the following results:

u
GW-IMEX‘Qd ‘0: 619833013153! 6. 56.7: 5. 80053 3. 3.1070
Faundu C, 55.61; 11, 1.87; 3, 11.32.

€.1§‘1at§:ylmrzimot}yyluznaceWimxinogzhanyl 5211 £111.10 methyl 106.11%

ﬂiaiﬁzﬁ<+ 2 3 .
I 123-127;?!) I
CF33
1?"? 3?.
u
0

9a a Ioluuon made by Muscular; 12.5 g. (0.1 mole) of g-ammﬂzzo-
phaml in 190 :1. or 20 venom by ”mm mum: sodium hydroxide! and
cantninad in a ‘31)!) :31. an}: fused with nun-at. "flux oomlanaer.
1111911111113; tannin, and a nuwgm gan- danvary tuba was adds-d 15.5 3.
(0.0.95 mole) of dietwlmimoﬂvl ﬂuoride hydwahloriﬁn dismlwd 1a
101’! ml. of mm:- Sam otirmd rmmtion Mixture mm 92511121) 112$:th for
a four hour period #2111! a animus stream of nitraﬁgan @213 was bub-51936
wrung!) M. Khan mo motion mixturo hm: cooled ‘0 mos-r. tmzyom‘am
It was Gama-tad with ﬁbrin 100 El. mrtiono of “heat. T11. 001113112911
other extract: we" 1-33de with 100 m1. of m Fatwa: 3011113: harm-31min
and than with 109 a]... of 2:219: aft” «itch tho ether Inﬂation 1m: drhd
OVa-r mmyr‘imul Indium Italian, and filterrui.

an» “mom: of tho “but by omgamum 20 m1. (0.2911019) of
mania anhydrtdo um added tea the rmﬁéml an. 131. rwatinn mixture
mm Mama ha in bailing point and than 33113111 into mtar. m ro-
tating solution can wads Iligiztli Man: with radium rgrﬁmxma musing
an on to "mm“ which ran axtmated with “I." and 43-193 cm: an-

hyeiroua tmmnaim sulfate.

19

The ether Inﬂation 11m:- daomumtian from the: drying 215.3112: and
treaty.“ with dry hydrogen chloride gm remand only in 01. mum:
of a manor-yawning “any ﬁner-act. 2m. umtarial In. nmtmlizod
with m pare-ant stadium hya-Iroxida, (Sigmund in 01.22", “33% with an»
and than dried over 2.12112321er urqmeaium mifnto.

Tm nth” was rammed by w'qmmtinn and. the in» min. was
”mi-ad with most-:31 10:31:19 to mm: a brain solid midi on turntab-
ligation from absoiuzo atlmml yielded 8.2 1.3. (0.0;? m}... 21% yield)
of the qmtozwsr‘y methyl ioéidu unit which smite»: at 155-66 3. Ami-ail
for «urban tvdmgw. and sulfur am. the {abutting maul":

Calculated far 13152252290“ 12. 6.2; 2. 112.2; s. 7.85.

Found: 1%. 6.31: C. $5.33; 3. 7.55.
E «12191123112111mothyi-g:.ncat;r1mimxboay1 mind. mum iodide

:2!
9.212221“? 3
e? ‘3\ .
at
5° 3

3

Following the method of the Lrevisuﬁ }.r2;aration. a 1-1)!) m. M

1.

winner: mntaining 16.5 a. (0.6635 min) of diazlzylmnimothyl ci'zloriéc
hyzlmmgloriac ms uddod to A refluxing solution of 12.5 g. (0.1 min)

of arminomioymml di smivsd in 130 m1. of 20 pat-mi W night
Immune sodium hydroxide. sm- nst-zitim: oil: amino. after isolation,
no acatylated by mac 2: 23 m1. of acetic mi‘warida and 1m» 0021"er
to its what-nary ml: with ﬂair-31 iodida in yiald. after «natal n-

crystanimtiom {rats absolute «1:32:01. 10 3. (0.021623 mic. $.62 yield)

33
of white product which melted at 121525.500. Analysis for carbon,
hydrogen, and mm: gave the following remit"

Calculated i’or 015112532201: H, 6.2; o, n.2, s, 7.55.

Found: a. 6.11; c, no.1; s. 7.88.

E -Diethyleminoetlwl-g-mtlwlpheayl sulfide hydrochloride

CH
(£23222 2 3 .331
$22an

“’3

Following the experimental method previously deeoribed. l? c.
(0.1 mole) of @ odiethyleminoethyl chloride hydrochloride dissolved
in 100 IQ. of water tee added to 12.” g. (0.1 mole) of p-toluenethiol
dieeolved in 100 ml. of 20 percent by uiat equeone eodime hydroxide.
Heating this reeotion mixture at its reflux teapot-attire in e nitrogen
atmosphere gave an ineoluble. yellow oily amine. Following the ulnar
eeperation and conversion to e hydrochloride eelt reeulted in 23.2 g.
(0.089 hole, 89% yield) of the hydrochloride which one obtained ee
white needle: after recrystallization from ieopropyl alcohol. The
product melted et 120-1.0. The following data vae obteined by enelnie
for carbon, hydrogen, end eultnrt

Calculated for 0133223!!!)13 O. 60; H, 8.5; S. 12.2.

Found: 0. 60.08; H. 8.51: 8, 12.23.

@ .Diethyleminoethyliuothylphewl sumo. hydrochloride

o

. " o
..
.-
.
V
a
.
0'
IV
1

.
. e e
-- -.-

 

531

22: 12.1; a. (0.1 m1.) at ytolqu-mol (unsolved in 100 mi. a:
voter conteinim: 20 5;. of eodiun hymxide was added 1? a. (0.1. mole)
of Q weﬂwlmhwetwlcﬂﬁodde lemons-m. di eeolvod in it!) 123.. of
water. ”too: the reaction mixture had boon refluxed under nitrogen
for two More. at yellow colored inwluhle oil topaz-sated from the re-
action mixture. From this oil: material. or following the notional:
described method of iwleticm and value emit formation there me oh-
teined 18.7 5. (0.872 mole. 7:325 yield) of A white hydmomoride of
the amino sulfide ehioh on reoryetollimtion from improwl alcohol
ml ted at lfiibl'iﬁﬁt’c. Amlyeie for euro-m, hyxlrom and malfur awe
the following results:

Calmlatod for grommet: a. Go; 1:, 8.5 3 2. 13.2.

'5’:an :2. 60.15; 1!. 8.366: :3, 12.67.
bullion thylminoaonprowl-godslomghewl eulfide hydrochloride

0 Hill
From 13 3. (£3.09 mole) of g-ohlomtE-xiomeml dioeolvod in 190 ll.

of 20 pox-mt by weight. someone eodiuh laydmxide and wading; to it

in x. (0.052! was) of X-dirmtlwlmimipmwl ddorido hydrochloride
dieeolved in m0 ml. 0! water. there we obtained an insoluble oil
after e two hour reaction period at the reflux turn-More of toie
hixture. the oily wine on motel-ted to its hydroohloride and the
letter on recrystallisation from loop-row). almhol. am." e mm

oryetelline yroduot ehiola: oeigﬁwd 6.5 g. (0.03.? mole. 36.155 yield)

22
and melted at 127-8°0. m. following data. was obtained by analyeie
for carbon, hydrogen, and sulfur:

emanated for unannsnaa c. h9.6; H, 6.115; 5. 12.0.

Found: 0, 149.72; a. 6.511; 3. 11.95.

K—Dimethylemino-n-propyl-g-chloroihenyl eulfide hydrochloride

CH
: < 3
'1‘, ﬂ! CH J .HQ

0).

Interaction of 1h.5 5. (0.1 Hole) of g—ohlorothiophenol dieeolved
in 100 ll. of mter containing 20 g. of eodiun hydroxide rlth 15.8 g.
( 0.1 Iole) of K -dimethylemino-n-propyl chloride hydrochloride ie 100
ml. of Inter resulted in the fometion er en oily mine erter e reee-
tion period of two houre at the reflux temperature of the reaction
mixture. . Reection e! the mine in ether with geeeouo hydrogen chloride
gen 18.9 g. (0.071 I010. 71% yield) of e pure white hydrochloride
product melting at 126.54.276.63. after reoryetellizetion from iee—
propyl alcohol. (Analyeie of the «Impound for carbon. hydrogen, end
enlfur gave the following date!

Calculeted foernBuHSClza c. has; a, 6A5; s. 12.0.

Found: c. 149.32; a. 6.56. 3. 12.13.

X onime thyl winwn-propyl-g-o ethoxyphenyl so). fi do
CH

sweoracgzeims .1101
'3

m

?3

”:30 20 g. (0.1!: mole) of kmthoryt'niogheml dies-mead in 100 m.
of water containing 20 (g. of sodium hydroxide me edded 23 a. (0.1“
mole) of! K—dlmthylaminow-17.1.0331chloride hydrochloride contained in
100 al. of mater. The wine eomm ted an on oil «after two hour-e o!
heetiogg at the reflux trainee-tare of the reaction mixture. Conversion
of the mine to its Wdrocmoriaie ae gzreviomly described more. 25.2 a.
(51.096 mole. 52". yield). of the hydrochloride one. 11311.4 at 130-
131.5%. often- recryotollicntion from icon-owl alcohol. .czolreie for
carbon, hydrogen, and cmfur give the following one... I

ode-dun rm- ragwuzaom o. 55.0: H. 7-71 8. 13-8-

Found: C, ELSE; H. 7.73.) 3. lgelse

2r e-iill'rw tl'iy'l ma limiter-reg; ylugaosetlnxygh any! F111 1" {Se hzfs’lroolaloritie

(2::
V /‘I‘.3
, 32, e’321\a? V l
t a: ‘ ‘3
1' 3

“me addition of 21 a. (0.133.i mole) of X-dimethylemino-o-propyl
chloride hydrochloride «ileeolveci in 100 ml. or enter to 2?) g. (0.114}
mole) of ﬁrmemoxythiopheml which had previously been diesolt'ed in
100 ml. of not»: containing; :20 g. of sodium war-oxide roe-.11 ted in the
formation of e yin}: oily layer after a too hour reaction period at the
reflux temmture of the reaction mixture. Folutioo of the mine
nod ocmmreion of it to Me hydrochloride .i'ollomd by recrystallisa—
tion of the letter from ieogroyyl alcohol yielded 1%»! at. (0.07 mole,

537?? yield) of e yore product which melted at 113-???" Amiga: for

2*:
carbon, hyﬁrngan, and mﬁfur gave the follmidng mounts:
Calculated for 612390?*GGRI o. 55.0; F. 7.7; s, 12.2.

Found: 3, 534383” R, 7.73; 3, 12.253.

3’. Dimothylmino-n-propyl-g—winoﬂuql sulfide methyl 10:11:10

I’mu 12.5 a. (0.1 m1.) of bmainotlﬁfphoml dissolved in 100 11)..
of an per-coat by night aqueous sodium hyr‘imxido and adding to this
wlution 1‘3 45. (0.095 ml.) of X-dhmti‘gylmoino-u-propyldllﬁﬂdo
hydrochloride 1a 100 m. of moor. tumor an “magma of aux-03m:
yhldod an oily amino after heating tho ”action aixmro at it: ro-
ﬂux temperature for two hours. am. on to: extracted with other
and dried over nmzydrwl mmeoi'w mum...

After tsunami. of the “not by «maturation, tho residual on on
reaction with methyl iodide rosnltod in a. yellow oolld, which on to-
erynnllizntlon rm absolute swam). gays 11.2 5'. (£1.03? mole. 33.53"“3
yum) of 3 units motallino mama have a melting point of 133.1%.
analysis for oar-hon, "wax-own, and m} in: @710 the following mount:

Caz-ammo m c 2321323“ 3. 131.0; 2:, 6.0; 3, 9.1.

1
Found: 8. 1mm; :5. 6.03; 3'. 9.01.

5-21:“trqlmim-n-mm-E-aoevnwﬂmaﬁa-«fl sulfido notify-1 1061‘.“

£333

:- . .30 n2:

Egao.teu.,.2£:-@3 I‘
v.23 '0’

25

Ingloying tho proviouslz donorim trauma. 112.5 a. (0.1 m1.)
of g-mzmshaommol attached In a 1m 31. of 80 pormt by «last
aqueous sodium hymn“ “I" snowed oo mm: with 15 a. (0.095 ml.)
of K-dtmthylminoun-trowlohlormo hydrochmrmo. wood to tho halo
Iryluoronytao solution. in 910 form of a mo n1. aqueous oohnlon.
Tho liquid aiming obtain“ from $110 ethn- oxtrno‘ no “31mm by
heating u with 20 ml. (0.2 no“) of mono anhydrldo and thou the
reaction mixture I... poured into 530 m1. of utter. Houtmllmtion of
this column with 192-: sodium harm-01140 "mud in m. ”Lon-Minn of
an on: material, which an” isolation and drying reacted ummtly
with methyl mam Go 31" a mu. oolld quotas-nary cult that recrystal-
lhoo easily from mammal. m. qmuomry salt. 18.) a. (0.0%5 no]...
119% yum). melt: at 1M°3. am: Noam! £0 turn yellow on tunneling.
Analyuo for carbon. woman. and sulfur an. tho following; tomato!

Czﬂoulntod for omneﬁa'm c. L$3.1: B. 5.9; 3. 8.12.

Found: C. I4.2.73; H. 5.98; 3. 7.97.

Xdéorphouno-a—prowl-Worummn mud. hyuoomormo.

s-o'g‘zggmzrgo . HGI

9h. oddiuon to o ablation consuming n c. (0.076 no.1.) or :-
ohlonmtomml. 100 In. of no». and 15 a. ”dim ”moo. of “.5 c.
(0.07} no“) of b’ mrphollao-n-prowlduortdo hydrochlorido 410-

mlvod in 100 m1. of mtor ”malted In tho sop-oration of on any min»

after a no hour period of naming; n tho reflux humans-um" of ﬁn

26

”action aiixiuro. freeman of Rio oily amino, dissolved in dry other,
viih gaseous Marceau chloride produced s gum which solidified on
balm; not as”. for oometimo. m1. mtorial yielded. after "crystals-
nmmn tr... awn-om alcohol. 19.14 g. (0.053 mic. 3.323 yiold) of
a hydrochlorido rizh a melting point of 1:47.5-1‘£.5°0. Analysio for
carbon. hydrogen. and mint gwo tho following data:

Calculated for 01311191333512: c. 50.6; 2!. 6.2; s. 1033.

Found: 0. 50.63; H. 6.146: 3. 10.31.

lﬁﬁorﬁmlimon-gmwiog-cmoroghenyi mind. hydrochlorid-

mmca ”0.321
2 2 A ,

‘rho addition of 15 a. (0.075 moi.) of Udmrwouno-o-pmpyi
ohlorido hydroohlorido disnolna in 100 :11. of water to 11 g. (0.075
moi.) of Mnemmiophoml in a oolution o! 13 a. of oodiuu hydroxido
and 100 a)... of water followed by heating tho rmtion mixture at ap-
proximately 100°C. for two hours. resulted in ﬁn fomtioa of an in»-
soluble on. “tor ”paranoia a: previously indicated and conversion
to tho hydrochlorido an. than no obtained 15.6 3. (0.0605 no]...
5“ yin“) of product iaio‘n I" rather insoluble in 130391-0in alcohol.
Tho cry-M11130 hydrochloric}. mliod at 13h.5.z552c. Tho {allowing
an: no omitted to main“ for carbon. hydrogan, and mm:

column“ For 013319303012: 0. 50.6: R. 6.2; S. 10.3.

Pound! c. 59.“; H. 5.521%; 3. 10.368.

X-zéomolim-n.pmpyi-g-mthommenyi sulfide hydrochloride

m
mafia-’32! O . 8’31
‘3 ‘4

{Ema quantity, 81 g. (0.105 mole) of X—mrﬁniinmb-yropyl 03:10:10-
hydrochloride contained in 100 :11. of motor mo arid-ad to 15 a. (0.107
M10) of rmothowthiog‘ioml diuolvod in a «notion prepared from
20 g. Iodim hydroxido and 2.00 m. If water. Following; tho previouuly
doooribod gonami procedure. 23.} a. (0.77 no}... 13.535 yiold) of a
white crystalline hydroohiorido mo obtained which 3.!th “crystalliza-
tion from impromi alcohol uoitod at 155.6%. am. following data no
obtained by analysis for carton, hﬁxogm. and sulfur:

Calculated for owazzozvscis c. 55.1.. H, 7.3: s. 10.5.

Found: :3. 55.67: H, 7.37: ‘3. 10.05.

Kovorpholimn-pmpylog-uothoanyl sulfido hydrochlorido
meonaonzg \o . 1-2131
following tho mention upland above, 18 a. (0.09 ml.) of
Kmmuno-a-propyiohlorido hydrochlorido contained in 100 n. 0!
motor we added to a reﬂuxing oolution of 13 a. (0.093 ml.) of g-
aothowthiophoml unsolved in 1.00 ml. of rotor mot-aiming 12 g. of
sodium hydroxido. Tho hydrochloride. pupal-ad u dosoriboei provioudy.

wig-.34 21.3 g. (0.01 halo, 78ft yield) one} no Sound to unit in the

range of 1h6.5-1’+8°0. laptop-:11 alcohol 1m used to roorystolliu

26
tho compound. Amlyoio for carbon, rgniroigon, and mlfur an" tho fol--
lowing ”mitts

Calculator! for cmazgogsa: 0. 55.”; H, 7.3; 5, 10.5..
round: o. 55$“ a. 1.3% a. 19.7.

5 diorplzolino-mpmwi-g-mthylzhowl sulfido hydrochloride
on @22ch . rm
3

From: 12.16 g. (0.1 ml.) of gotoluonothiol diuolvod in 100 ml.
of 20 poromt by night mucous oodium hydroxido and adding to it 20 c.
( 0.1.010) of U—norzizolino-n-propyldilorido hyiroohlorido in 100 :1.
of motor. a colon." oil was obtain“ “to: two hour: heating at tho
roﬂux tampon-own of tho rmotion nixturo. Tho oily min. was puri-
fied and converted to it: hydrochloride which had a pink colot. This
crystallino hydrochloride altar hing dis-01nd in improsz alcohol;
trootod with ﬁorito A and “loud to oryotallizo an" 16.9 g. (0.059
solo, 59% yiold) of shit. product in tho form of until“ which melted
at “1-9.0. 1. 1:11:04 halting point of this not-rial with tho "ox-tine
hand... Zmrymlino-n-propyldnorido, with which n u. oiznilar in
appear-anon. mo found to to in tho romeo 125-13500. which sham they
ur- not identical. Analyoio of tho pro-smut for carbon, hydrogan, Fmd
mm gun tho tailoring; data:

momma for ownaatmzl: o. 53.1.; 1.1. 7.7; s. 11.1.

Found: 0. 58.10: 8. 7.50: 3. 10.93.

5otfowho}.ino-n-xxo;yi-g-mot‘wlﬁsenyl ouli’ido hyciroohlurlalo

is 3323533; 2) . F931
:35
3

'90 o refluxing; solution preﬁx-ad from 12.15 .5. (0.1 molo) o! g;
toluonathiol. 10!.) ul. of motor, and 20 a. of sodium hydroxido no mido-d
an a. (0.1 m1.) of U-mrpl‘zolino-n-jrowl ohlorido hydrochlorido dio-
oolvod in 100 m. or motor. ”Foo oil vizich oopttrntod attor o two hour
ronction poriod mo gurii'iod and oonvortod. in tho general manor on-
ployod Mon, to o oliahtly Link oolorai hydrochlorioo which after
boina: oiooolvnd in hot ioopropyl alcohol, troutod with iforito A, and
allowod to cryotollizo gave 22.“ g. (0.78 molo, 78-f- yiold) of o puro
product with a. melting point of 1:35.5-16‘}.5°C. A mixed moltim; point
of thio mtoriol with ito ortho immur doprooood tho melting mint
ton dﬂfjrﬂﬁﬂ. Analysis for carbon, hydrogln. and sulfur gave tho fol-
lowing data:

C‘nlculntod for o HBBN'ROCII c. '58.“; H, 7.7; 3. 11.1.

111
Found: C, 58.6: H, 7.61; 2, 11.01.

5-};foryholino-mprowl-a—aootylmimﬁaonyl ouli’ido hadrouhlorido.

”:1“:
ES 3
O

A 10") ml. oquoouo onlotion motoinimg 19 g. (0.095 moi.) of
Y-mrpholinmn-propyl chlorido hydrochloride no added to a refluxing
oolution proparod from 12.5 g. (0.1 :nolo) of ymimti‘ziogzhonol. 1m m1.

of water and 20 g. of oodiun hydroxido. Tho resulting insoluble» oily

30
amino obtainod during a two hour reaction period was oxtraotod with
other and driod over anhydrous sodium sulfate. Aftor tho othor ooo
rumored by ovnporation. acetic onhydrido was added to tho amino ond
tho nixturo on: warmed almost to ito boiling point and thou pourod into
water. Tho rosulting aolution was nontralizei with 103 sodiuﬁ hydrox-
ido and tho oolii which preciﬁitatoi woo racov9rad by auction filtra-
tion. Tho nootylatod amino aftor recrystnllizotion from leoyropyl a1-
cohol melted at 98.5u99.500. Analyois for carbon, hydrogin. and sulfur
gavo the following data:

Calculated for 0153;233:2902. o, 61.6; :«7, 7.55; 3. 3.0.9.

Found: 5. 61A; 1.", 7.57; 3, 10.81;.

ﬁho froo amino on: diosolvoo in othor and.hydrogon chlorido gas
on: passed through the solution ronulting in the formation of 11 g.
(0.03% molo, 35.2% yield) white, other inooluhlo hydrochlorido. Tho
hydrochloride, after boina rooryotallizod from ioOpro;yl alcohol.
molted at lSh-5°O. Analyoio for carbon, hydrogen. and oulfur gave
tho following data:

calculatod for 015R2332
Found: 0. 5km; H, 6.37; s. 9.5M.

30261’ C, ﬁuouz H. 7o03 3. 9070

X—Morpholino-n-proLyl-g-nminop.onyl ouli’ide dihydrochlorido

3-6? CF CF ﬂ 2”"1
7:2 -2 ‘2J '

MI?
. -
s’.

   

A 19 5. quantity (0.095 mole} of K-morpholino-mpropyl chloride

hydrochlorido dissolved in 100 ml. of outer was added to a solution

31
proporod by diooolving 12.5 3. (0.1 mole) oi‘ common-.mphonol in 1.00
ml. of 20 poroont by night qquoouo oodim hydroxido. M'tor o two
hour reaction poriod, undo!- a nitrogen atmophoro, tho reaction nixturo
yioldod on inoolublo oily amino. Tho oil mo oopurotoo. ciriod. ond
oonvortod to ito hydroohlorido in tho manor doocribod abovo to giro
9.6 is. {0.029 uolo. 31% yioid) of o ohito hyriroohlorido. Tho pnro
product. obtainod by recrystallization oﬁ tho hztiroohlorido from othonol.
moltod at 198-200°C. Analysis for carbon. hydrogen. and oulfur so"
tho {0110.133 (iota:

Calculatod for 01353203213312: c. no.0; a, 6.83; s. 9.9.

Found: C, 107.92; H, 6.88; S, 9.53.

5-?iporidiu-n-irowl-thlorophonyl mitioo hydrochlorido

3532632” 2"..-2.‘ 0 En

Tho quantity. 116.1 g. (0.071 mil). orb/opiporidioo-n-propyl
chlorido hydrochlorido diosolvod in 100 ml. or oator no added to o
ooll-otirrod oolution, ot ito roi’luz tmporotnro. of 10.5 g. (0.073
nolo) or g—ohlorothiophonol diooolvod in o oolution of 100 ml. of
rotor and 15 a. of oodim hydroxido. Tho reaction was oomp‘loto at
tho ond of two hours. “tor tho nml oxporiroontal eporotiono ozo-
ployod obovo. tho cmdo hydmchlorido no rocryotnlliud from iso-
prom oioohol. 'l'ho product Ioié'lld 19.7 g. {0.635 toolo, 90.51% yiold)
and bod o. noltin; point of 157-158°O. Tho onlyoio of tho mMpound

for carbon. bring“. and oultnr can tho following data:

r‘ ‘1 E5313 . ‘. !=; “.n- . . .
mlmlntod for 6116'21' 128 P, 55 O; . b ,. ‘5, 10 5

round: a. 55.02; H, 7.05; s. 10.7.

Kul‘ipori d1m~n~propyhg~ohlorozﬂ1owl oulﬁdo hydrochlorido
3.53Em12mt2n > . 3'31

Tho Mouton. ovor to too hour poriod. from o dmpylng tunnel of
15.3 g. (0.078 halo) of U-p1porid1no-o-propyl chum. diooolvod In
100 on. of no" to o oumd tanning ooluuon of 11.0 g. (0.079
molo of g-ohlorothloyhonoi dissolved in 100 ml. of «to: containing
15 (g. o! oodlm hydroxido roounod to ﬂu «nation or on mooluuo
on: onloo. Tho hydrochlorldo no propane! from thin amino no mo
mm uooo obovo fallout! '03 n. roorlotdlimﬂou tron “sprawl
aloohol. Tho pun cryotzauno hydrodalorido “whoa 12 g. (0.039
mlo. 56:: now on nun-m u nos-9%. Analyoio at u:- comma for
carbon, hydmgon, and mm can oho [0110111313 do“:

Calculated for °1loﬁaz"mz' 0. 55.0; a. 6.9: a. 10.5.

Found: 0. 55.0: H, 7.38: 3. 10.26.

X-Hpmditto-n-pmyyl-Enootyhmimphonyl oulfido wdmohlori-io.

I: :IR‘JJ.
on. addition of a 100 an. aquoouo ooluuon containing 19 a- (0.035

nolo) of 3-p1poﬂd1oo-o-mpy1ohlor1do hydrochlorioo to a ourroo

33
rofluxing oolution of 12.5 g. (0.1 mlo) of wimthlomonol Moonlvod
in 100 al. of rotor and 20 a. of oodim hydroxido rooultod in tho
tomtion of on inoolublo oily mino. ‘20 provont oxidation of tho
mino oulfido tho ronotlon mo worried out undor a uitmgon otmoﬁnoro.
Tho othorioxtmoto of tho motion mixturo voro dried and tho othor
mo "wood by omwmtion. Tho rooidnol rm mlno om troatod |with
20 :1. {0.2 oolo) of oootlo mhqrdrido. md to toiling. and your“
into mtor. ﬁlo rooulting oolution woo mtmliood with 10%! oodinn
hydroxido and tho solid hydmohlorldo which fomd no noooorod by
filtration, diooolvod in othor. and on trntnont with hydrom colon-v
ido goo (on o gun ohioh oolidiﬁod on being out ooitio for ootoo tiuo.
rho hydrochlorido no rooryotolliood from looprowl alcohol. had an
mmm: mint : 17h.5.175.5"c. and void.“ 16.2 g. (0.33 no)... 50%
yiold). Annlyolo for carbon. hydrogon. and ooltur mo tho tollooiu
data:

Colmlatod for GIBRZSRROSCM G. 58.5; H. 7.65; 8. 9.7.
Found: a. 55.51:; E. 7.67; I. 9.66.

3’. Pi pori d1 own-proyyl-g-nothoxnhowl on). :14. Wdroohlorl do

OCH3
Tho intonation of 3).? g. (0.105 mlo) of U-plportdlooan-ymwlo
chlorido hydrochlorido contained in 100 ml. of ootor oith 15 g. (0.107
mlo) of 2-mthoxythiophonol dlooolvod in 100 ml. of tutor and 20 g.
of oodima hydroxido rooultod in tho {emotion or an amino which 0033b

otoo so on inoolnblo on. ‘r‘oo amino, :3! ooolood in dry othor, mo

3L;

oonvortod to ito hydrochlorido with mooouo hydrogen oblorldo. It
moltod at 128-29°0. on» bolas attached in hot impropyl alcohol.
trootod with Korito A. ond allovod to cryotollioo. Tho amount of mo
hydrochlorido procawt obtainod mo 33.} a. (0.077 molo. 73.5% :iold).
Amlyoio for carbon. hydrogon. and onli‘ur moo tho folio-ins data!

Cnlmlutod for snowman: o. 59.5; E. 3.0; s. 10.6.

E'ounrl: C, 50.87; 3-“. 507; 33. 10.61.

0’»?lporiolno-n-propyl-g—mthonmhonyl oul fido hyxiroohlorido.

s-cyzacfezcﬁzoj >. 531
0-0033

‘mo oxgorimoatul proooouro utillood in tho vot‘oooio or thio m.-
torial mo tho om no that uood in tho provlono yropomtiooo. Tho
quantity. 15 c. (0.107 molo). of g-notbonrthiophlml dlooolvod in 100
Ill. of onto: and 20 mo of oodim hydroxido too olloood to mot
vith 20.5 g. (cunt ml.) of b“ ~mparsa1mn-pmmmona- hydrochlor-
ldo. oddod to tho motion {look no a 100 vol. oqooooo oolntion. to
yiold on oily. inoolnhlo mino. Thio on oonvoroion to lto hydoroohlorb
ido in tho tonal manor oomtod tron tho othor oolutlon oo o m
which lotor oolidiﬂod on Ming oot ooido tor oooo timo. rm. condo
product on rooryotalliootion from iooprozayl alcohol can 26.? g. (0.0%”
aolo, 83.5% ylold) of o puro hydmohlorido bolting at 150-100. Anal-
yolo for aux-hon, hydrogen. and oulfur gm- tho following onto:

calculatod {or clattegmcn o, 59.6; a. 6.0; o. 10.6.

round: 0. 59.33: a. 8.216; 3. 10.68.

35
ddﬂothyl-Q .dioaothylaminoothyl. u-nothomzhonyl oulti do hydm ohlo rido
9H c* '
mmog ’3 .xm
J‘cHB

”3

ﬁxio oooyound, on tho froo amino, oao ohtoiood by tho gradual
addition of o. oolutiom of 2?. g. (0.1“ mlo) of dimothylmimioompﬂ-
ohlorido hydrochloride: in 10": ml. of motor to o ttirrod roaming onlo-
tion rropnrod from 20 g. (0.11%) mole) of Emthoxythiowoml. 100 «1.
of oator. and 20 g. of oooiun Imitation Tho initial ottompt to pro-
paro tho wdrodzlorido rooultod in tho iomtior. of on unmotollio-
ablo gum. Tho mu mo oiooolvod in 15 pox-cont oodimo hydroxido om!
tho aqueous oolution mo oxtnctod with othor and driod over anhydrous
ooolun ouli'oto. on. othor mlntion mo filtorod and hydrogon ohlorido
goo woo bubbled through to tom :1 some: hydrochlorido ohioh oolidiﬂod
on balm: oot oaido for oozi- .otizao. Tho proonot ortor {17o tom-rota).-
lizotiono froz": ioonogyl oloohol wigs-bod 3.2 a. (0.051 oolo. 36,?» yiold)
and had no bolting point of 17}-l715.6°€3. Analyoio for carbon. hyomgoo,
and sulfur moo tho following data

Cnionlntod for 0122610 ml: 0. 55.0; 15'. 7.7; S. 12.2.

Found: c. 5h.9 9; n, 7.91; a. 11.96.

OK-E-Fothyl-GudimthyloninooWl-g-Mthoxnhonyl mlﬁdo hydrochlorido

on
623321;“). 33

Following tho pnviouoly doooribod procoduro. 15 g. (0.107 toolo)

36

of goothoxythioihonol diooolvod in o oolotioo of 20 c. o: oodimo hys-
droxido ond 100 m1. of onto? no allow! to roaot with 16.5 £. (0.10“
mlo) of dimothylominoitaproyylohlorido hydrochlorido. acidod to tho
taoio arylmorooptan oolotion, oo o 100 ml. aquoouo oolution. to 310.!
on insolublo oil: amino. 'mo froo amino mo connrtod to ito hydro-
chlorido in tho 111ml manor. and Goo to ito oolobnity in ioozzropyl
alcohol mo uooodingly difficult to purify. It had an outing point
of no-na“c. on. amount a: m. hydrochlorido obtained nighod 11.1
5. (mouse; mlo. but yiold). Anolyoio as tho compound for carbon. to.
dragon, and mm gnvo tho following data:

Calculatoti for clgyamosn: 0. 55.0; E. 7.7; '3. 12.2.

Found: 6, 55.22; R. 7.87: 8. 12.10.

0( -3€oth:lo@ -dioothylooinoothyl-thlorozhonyl mlrioo hyorodllorioo.

égéj‘IEQO R ’11
\4

01

mo oynthooio of thio mtoriol mo coniod out in o ultra“ ot-
Iooophoro. g-mlorothiophoool. 111.5 g. (0.1mlo). no diooolvod in
100 ml. of ootor oontoioina 20 a. o! oodimo hydroxido and 15 g. (0.095
nolo) of dimthylminooiopropﬂ chlorido hydrochlorido in 100 m1. of
rotor mo oddod to tho rofluxing olkolioo oolution of tho 135103171.
aux-mm. tho "muting oil: «duo. oftor ioolotioo and drying no
contortod to Ho hydrochlorido by bubbling gamut bydrogoo omen-too
tho-cog}: on othor oolotioo of tho onioo. tho yawn“. ooo vow

37
difficult to purity and no omlotoly ooluhlo 1n 1003:1'0131 alcohol.
It woo rooryotallisod by tho addition or othor or oyoloh-oztono to tho
command dissolvod in loom-owl alcohol. Tho maaunt of mtoriol ob- -
tamed "1fa30d 31.2 g. (0.08 mlo, 5M yield) and had a. waiting mint
of about 90°C. Mmlyolo for carbon. Hydrogen. and sulfur gun tho
following data!

Coloulotod {or 01181733012: 0, £9.63 H, 6.155; S, 12.0.
round. a, assets; :1. 6.59: 3. 12.36.

autumMﬂmmmn

g-Chlorothiog-homl
SH Tuio holoarylmroaptan woo promrod

()9 h: folloolng tho mothod or Sohnrioonbaob
and 2:51: nu). In ”8' throo-oookod. 509 an. {look ﬁtted. mm o «um.
thomuotor. and dropping found. 51 3. (OJ molo) of g-omoroaniuno
dlooolmd 12: aka «1. of ooncontmtod hydrochloric acid mo dioootiood
ﬁning 28 5. (0J0 mlo) of oodhm nitrito oontninod in 80 ml. of tutor.
'ﬁao proooolod oodium nitrito oolution no oiéod oloou to tho otimd
acid oolutlon of rohloroaniuno hold at o tmpomturo of O-5°G. by
ammo of on Ice-«1t both.

Tho diuonhﬂoalt oolutlon mo pound into a hot ooluttoo or
potooohm othylmnthnto. propnrod {ton 160 g. (1.0 molo) of tho tan-
thato ond 600 on. of ntor which had boon hootod to 8000. Thu ro-
mltod in tho {omtion of a booty dork rod 011. which mo "pal-Mod.

om! oddod to o aixturo of 111! g. (2.0 moloo) of mtoosim hydroxmo,

38
200 ml. of othonol and 100 m1. 0! rater.

Thio ronotion mixturo uttor 13371115; boon hoatoo at ito reflux tota-
;:.-orotnro for throo boon no diluted with too iitoro or onto: and
noutroiiood with oonoontrotod hydrochloric acid. “rho rod oil which
"mi-mud oao diotiilod at about M In. pronoun to yioid 23.5 g.
(0.162 mlo. “14$ yiold) of; light yoiloo ooioroo rolﬂorothiogmoml
boiling at 75-80°C.

g-Chlorotlaiwhmol
61 Using tho proooduro doooribod by Bow.
Rapport and £001.11“ 8). 120 g. (1.85 mio) of
83 11:10 duot no oddod. in 1 bolt hour mind.
to o otirrod mixturo prowod from 12 g. (0.3% on.) o! g-ohlorooon-
oonoonifonyi ohlorido. 720 g. or ioo on! 130 mi. of oonoootmtod
mifurio acid. 'i'ho "notion nixturo no hold out 0°C. during tho
addition of tho doc and for too odditioml noon following tho oddi-
tion of tho metal dust. Tho roaotion miztnro mo thou carefully mmod
to its roam: toeszpornturo and on odditioml 130 m1. of concentrated
sulfuric) acid ono added to it tollewod by tho addition of. in man
portion-2o. of 1m 1;. of oino duot. Tho ro-aotion nixtnro mo tho: oot
noido ovor night undo:- oo otnooyhoro of nitrogen.

Eaton: diotillation of tho motion mixturo monitor: in tho forlo-
otioo or o. white oryotnnino oolid in tho diotinoto. i'ho ooiid no
filtorad onto a Bach”! funnoi and driod ovor calcium chloﬂdo in a
vacuum dooioootor. Tho product weighed 36 g. (0.25 mio, 73”:- yioid)

and moltod at 53.15%.

g-Mim thiomonol

3}! Following the techniquo dovolopod by
Gum and Minor (6}. 123 g. (0.81 nolo) of
ma {noblomnitmbomzono om added to on oquoouo

oolution containing 183$ 3. (2 moles) of oodium otllfido nomlxydroto in
too litoro of motor and tho rooolting mixturo mo liontod at ito ro-
flux tomomturo for oight hours. on. motion mixtoro otter Ming;
oi loud to cool to room tongslomturo on oxtrnotod oith othor to ro-
mvo o twill moonlit of inoolu‘blo oil. Tho minim; aquooul oolution
no o'oturotod with oodiun ohlorido and thou 210 g. (3 min) of alooiol
oootio said no oddod to it ohioh oouood on oil to «ion-to tron tho
oolutioo. i‘ho oil romvod by othor «traction. driod our onhydmo
oodion mlfoto and tho othor rmovoo t: ompomtion. Diotillation of
tho oil yioldod 62.3 g. (0.5 molo. 627$ xiold) of o oolorlooo oil toil-
111.: at 1133-13700. ot 11 In. which ooliditiod to o ohito oolid on being
oot aoido for oomo timo. “rho product no otorod undor a nitrogen

I too orb oro.

kninothiophonol
a following tho woo upotimontol pmood—
@332 oro and for promo-ins g-ouinothiophoool. tho
intonation of 128 c. (0.81 molo) o! rohloro-
nitrobonzono and tMS!) 5. (2 noloo) of oodimo oultido nominal-auto yioldod
so 3. (0A7 main. seat noun a: wnouoophmi, ouch had a noltim;
point of 26.0 and boilod at 125.7% at 6 m.

int-iothoxythioyhmol

SR i‘ho procoduro of Sutor and Hansen (7) mo

Q utiliood in tho oyntheoio of thio command.

CE} In a ono litor throo nookod nook ﬁtted with
o stirrer, tigomnotor. and ting—“gm; ﬂannel, 123 g. (1.0 mlo) of g-
mioidino diooolvod in 250 ml. of concontrntod wziroohlotio said no
dioootiood by undoing 69 c. (1.0 mlo) of oodizn nitrito oontoinod in
300 ml. of voter. 'i’ho faction tomproturo woo hold ot 0-500. during
tho dioootizotion. Sodium ooototo no mom to nmtrolizo tho oxoooo
acid and tho cold diomnimo oolt oolutioo mo anomaly pound into
o hot oolution. 7000.. propane: from 300 g. (1.8? molo) of zotoooiuto
othyl zonthoto and. 700 ml. of oator. Tho otirrod roootioo mixturo mo
then hooteo at ito reflux tomporatnro for on how. Tho rmotioo nix-
turo mo alloood to cool to room touuoroturo and tho dork rod oil ohioh
ooparutoo mo .romovod.

Tho oil mo oddod to a oolutioo promrod from 115 a. of potaooim
hydroxido ooxi l litor of 95??» oti-mml and tho ”suiting; mixturo mo
heated at its reflux tonporaturo for throo houro at which point 20 g.
of gluoooo woo oddod to tho refluxing rmction mixturo. Tho volumo
of tho roaotion nixtnro mo reduced to about 300 ml. by oiotillotion
of solvoot and than aoidifiod with sulfuric ooiri. A four grmaio of oino
duet ono «Mod and tho "notion uixturo mo otomood diotilloci. i‘bo
diotilloto mo oxtraotod with othor and tho other onroct mo dried
over calcium chlorido and tho othor remand by ovapomtion. ﬂotilla.
tion of tho omdo product moor roﬁuood Lrooouro yioldod 67) 5. (0.163

mlo. “3‘4 :iold) of mtorinl boiling: at 100°C at 10 on. 523‘!!! and

k1

Emmett (7) razor-tad n 1301111»! Paint of 65.9000 at 5 am.

9:2: 0th 01;: th to phml
_. Folloﬂm the oxperimontal meoduro
m
3 Just doocribod for u:- nemmuon of 2-

mothoxythiomoml. 123 g. (1.0 mlo) of
goon! “dine on dimotimtion and reaction with potassium aw). zanthnto
1191604 50.23. (0.36 mlo. 36" ﬁnd) of g-mtmxyt‘niophonol which
had a mixing 1mm of 12L129°c. at 13 m.

b’ (mnmalylm1m) arm agorug mam: 95:12:14.3

 

U-!-Yor1.holino-n—pmpyl chi or! do hydrochlo r1 do.

q p.33 swamzcx . 831

m1. hydrochloride on pmmrod according to tho method donlopod
by Adam and mun-on (9). A oolution oontalnim; 300 5. (3.53 mlo)
of mr-gholino and 360 g. (2.29 mold of trlmthylmo dllorohronldo in
(300 ml. of dry bonaono mo oat Mido at room tawgomturo for om W
with an occasional mas-dam. F'cllooing this. tho “notion muturo In:
hon tad at 1:0 roﬂux tompomturo for throo houro during Ihiah “no a
hoary whito prooipitato formod. Tho proolpitato no "covered by
motion filtration and mohod thrown with othor. Tho othor nub-
lugs and. bonsono filtmto onto combinod and oxtmctod with 800 all. of
'51! hydrochlorto mid. two new utmot no mdo buts mm 103 sodiu-
hydmxido and tho on which oapamtod no utmctod with um:- and

drlod ovor anhydrouo Indium wfnto.

ha

Tho dzy othor oolutiou was filtered into n.0no litor throo-lockod
{look fittod with onndonoor. otirret. and dalivcnr tubo for nwmiooiou
of gnooono hydrogon chlorido. Saturation cf the amino othor solution
with hydrognu dhlorido unvo 201 5. {l malo. k3.§§ :ioli) o: u units
oolid hydrochlorido which was recrystallized from ioogrogvl alcohol.
Tho walling yolnt of tho hydrochlorlda an: l§7~303. It: ragortod malt-

ing point 1- lazinohm.

ar-zipnridino-n-pro;yl chlorido hydrochloride

< ,3- 03132632675231 . 3531

Following; tho proooduro mad for the 3..ra;:.amtion of b’ .mrrholino—
n-propyl chlorido hydrochloride, the interactianio! 275 g. (1.75 mole)
of trimnthylonochlorobromido in 800 ml. of dry bananas with 298 g.

(3.5 mole) of plpwridlno, followod h; cnnv»raian o! the trso amino to
its hydrochlorido gawo 150 5. (0.75 nolo, h3.5¢ yiold) of ~yi$ori-
dino—n—propyl dhlorido hydrodhlorido.

Aftor a oinglo rooryotulliwation from absoluto ethannl, tho molt-
ing point of tho pure hydrodhlorido was BIS-50$. It: rogortod melting
point lo 220.6. {15)-

nghiorohanaenoculfonyl chlorido
$0201 Using the mathad of Ellman and
Eorsolt m5). 139 5. {1.56 molds, 1:22 m1)
01 of chlorosulfonia acid contained in a

half liter Enron-hooked flask fitted with n otirror. dragging funnol.

1*3
and thomoaotar. mo molod to 45°C. by nouns of an loo-salt bath.
To tho cold otirrod chloroo‘ulfonie acid, 6!) .2. (03:11 :aolo, 96.5 ml.)
of chlorobomono no added drown” out a hog hour 15'sriod. 'Pho ro-
aotion tr-tzz-nrnturo mo kept bemoan ~10 and -503 for an od-iitional
two rwuro after ﬁlldb tho oulfomtion mixturo mo sot asido over night
at roan taper-attire.

Tho ”notion nixtnro mo thou pound onto amend ioo and tho
solici product rooovorod by filtration ma driod. Tho crudo product.
weighing 100 g. {0.147 solo. 83% yield) was mod directly for reduction
to thlorothiophonol.

awn-ii?

l. i‘ioniH.H-dialiwlmim) alkyl -9_ o: E-acotyiminwhonyl ouli‘idoo
and two Um,x-diaiky1mino) olizyl gaminopimwl sulfide" ooro pro-
pnrod for tho first ti!» on oithor thoir hwirachlorido who or quit-

ternary mthyl iodidoo and oorao of thoir gradual preportioo no to-

portod.

2. Ton noww(}1,¥i.aialiqumim§ alkali -1 or g-methozqghowl sulfido
hydrochlorido onlto waro ”gym-ed for tho tint timo and that: molt-

ting point: aro royal-tori.

3. $3111. wiﬁiikdial‘vlwim) alkyl -9_ or rental-053191131 sulﬁde
hydrochlorido oalto ooro propane! which on not rooordoi in tho

nix-mi on). litoraturo.

1:. Pour previouol: undaoaribodw (3,!Ldialhrlmino) alkyl -1 or 2-
mothylphonyl onli'ido hydrochloric!” woro oynthooiood. Sum of tholr

physical proportioo oro listed.

l.
2.

3.
h.

5.

6.

7.
8.

9.
10.

ll.
12.
13.

1h.
15.
16.

1?.

y.

P.

J.

:28.

BI 31. 1053313.} ‘3‘!

1!. Kim and 1‘... D. 30min, J. Am. Chm. 2500.. 13;, 5102 (1952).

F. Luduem and J. o. yoga-g... J. max-meal. :xp. Mam... LL33.
no (1952).

1:1. “.121 and 1:. Humor. J. Am. Chem. 500., 11, 1.059 (1955).

J. 00:11an and 1‘. c. Condit. J. in. F321“. 30... 53, 1781 (19in).

A. mu:- and r. x. Sig-$311.50. v.9. sat. 2302,6162 (19%); Chou.
not... {9, 5758 (19166).

cum. and. a. c. Gain”, J. in. Chan. 50... 1;, 17149 (1910).

u. Sutor and H. L. ﬁnnoon. J. Am. Chou. 3300.. 3‘1, 3.102 (1932).

3. Samoa. 1:. it. min-sort. and J. B. b’oopf‘li, J. Biol. atom.
:53, 23:? (19W).

3. Adamo and F. S. Whitman. J. in. “iota. Soc... 2'1, 735 (19145).

0. Clinton, U. J. Finlmdor, and S. C. Laokanki. J. 3.551.621».
500.. n, 3366 (19‘49).

1'. 152mm: and H. 1?. Block. J. Am. Chou). 800.. ﬂ. 1161*} (19:60).

I). Ron, J. in. Chou. 500.. EL 2932 (19W).

Ft. lsloxandor. “Ionic Organic Rmatlono.‘ John ﬁlo: and Scno.

IBQo. KG. York, to, YO!“ 1950. p. 98o

G.

3.

Schmuonbnoh and 3!. E511. Bolt. Chill. iota... LL 1177 (19313).

Jam-1.1 and J. column. 3.... 13, 23.35 (1306).

1*. 1311313131 and .T. Koroolt. 3.2.. 35;. 6242 (1907).

VITA

Nit-3: Rogor Allan Baldwin
Bﬁnﬁz Juno 2, 1931. in vacatur. Illinois.
ACADI’ITIC CAFJrIIZY-Zt

Septeznbor 19149 .. Jun. 1953 16111135111 L’niworsity.
Decatur. Iliinoio

Soptomber 1953 ~ JUN! 195‘ Michigan Stu-to Uniworoi ty,
East Lansing, Michigan

DE‘EEES HELD!

auchalor of Scionco - 1953 iiillikin University.

CHEMISTRY LIBRARY