NH!

H
M
I

IHHHII

I
‘

100
829
THS_

'l
I

 

A STUDY OF SOME METHODS FOR
“ME PREPARATSON OF
3, 4~DIMWHYL4~ WNTANOL

Thesis far fha Degree cf M. S.

MlCHEGAN STATE COLLEGE

Pkiiip Geralé‘ #:1st
1950

THESIS

    

1'?
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1
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(‘0’ ‘ .73 n 1 I f . g- 91 r .fi: _.
A Qt- I I- - J. u-‘b- \ Iva Q L J -u .- “'O~. \er
Q r *' . . ‘r .‘.' f
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0. '1.- 3 .m '- V . ”~I"
“:..-finals L1 ti .5; J J~Jn\- 5’ a.
l. t r ‘a.
A \C‘c

(-
‘.

fubmlttefl to £59 ¢chccl cf firalnata
‘jricultura and £39119: Science

State fivllfiffi of s.
in partiul fulfiilauat u: 143 roaulvcmfi;tn
iur the ge;rua cf

tuL1el of iichlgau

‘5' 9 >1 ri’I- t-lp..:-
nib-m0

i » - . a;
- " 7 . ‘ ‘5‘; k' ‘..

'epcrtmsnt of-Chamistry

."r' q: ' , S ' ‘A r‘ .1".
} ‘x’;p~‘V"Uo-‘ "ll £“"L

fine autiur wishes to exfirean his singer.
appreciation t0 Tenn ?&Lph T. tustcn,

r. Sur;un L. Searner, and r. aalxh L.
ficIle far 1 cl? xvi; ul un.erstug;ing and
3'41-551'0 riuria“ t;;9 conrae of £3-13 work.

(a

831600

“‘01"; -‘s c.av~\' $3.03
..f...‘ -- U. sr'ooo» “-0-

Intro.ucticn ooooooooooooouooooooo
' Xfiflrlm"1'lt81 00.000000000006000...

Cmmicala 00000000000000.0000...

‘rfipnrstlwn c? Ethyl Z-EyJP017-
,4- izethjlpentanoata .......

-uhwipd 10a of :thyl E-Syiroxy-
31.4- 3.3.231. 3'1331'Lt51..0610 0......

Ly,ru;eaatioa of Ithyl 3,‘--1-
37$;IlffiniGUOEt9 0000000090000

“jfiroganolysia of Lthjl 3.4..1~
ifltkfl-l-Qéfltfiflfil 000000000000

kttfirvtci ogradatiun cf Lthyl
2,4— lmetajlpontanoata 13.32rs

iacusaicn ooooooooooooooooooooooo

Tummary o.ooooooooooooooooooocoooo

Literature iital 0.000000000000000

Page

(5

10

15

El

IIJTI‘LOJUCT ION

In the year 1941, Luaton and Agett (1) reported
the preparation of 3,4-gimethyl-l-pentanol through the
reaction of ethylene oxide ani the Grignard reagent
of 2-bromo-3-methylhutane. This alcohol hai the
following physical orooerties: b.p. ISO-lezoat 740 mm.,
n0?3 1.4261. d%? 0.819. No derivative was reported.
In 1944, Schmerling obtained a sample of this alcohol
from Huston and reported (2) that its 5,5-dinitrobenzoate
(racxyetallized from pentane) melted at 51-520 and gave
no melting point depression when mixed with a-eample of
the same derivative of an alcohol which he had Obtained
by another method. Agett (1,3) had oxiiized his alcohol
to the acid ani prepared the amide (n.p. 95.50) and the
aniliie (m.p. 67°) as derivatives. Hie proof of
structure cousistei of reacting 2-bromo-5-methylbutane
with sodio-malonic ester, hydrolysis of the resulting
malonic ester followed‘by its decarboxylation to 3,4-

dimethylpentanoic acid.

Ha H OHS (.333
main-pgugr e CH(C0002H5)2 Na‘ .... ens-éH—ca-cmcoocwyz

A;

'n :b _._q- __-— ‘_-“_’n C,
5 do

..9 ....‘r
gap.) q. 3 $7!” _ r. \ rt, ‘T‘lr'l 813.. .4” 1'2" “
a 3.“- I. o. “x’.- A ‘- 2 L: I ... \__ ..

nucnrqcx;l8tlon “

 

:cTLufi in 19;; (4) an; to iccro in 1349 (b) have
Corres;.n a: «1th Vfihlwn censurnln; the 1.:utlty of the
reporta; acil. cth acre unatle to outsln ea anill e
or an 03140 with the retestei melting :oint (1,3).
Eertcn liciei that the 3.4-;imct-3lyantanciv eel; pre-
parei in Lie la oratory gave an emi.e melting at
lZE.3-l:7.10 an; an axill.e meltin~ at 139.7-110.c°,
wuereae Lo: cero reperte. values of 137° an: 111-
111.50, resgzctlnelj. ”he latter ha: also yre_srel an
8100;01 sit” a ?,t-.1;1trttfiazoate melting at £2-t2.503.

Lave e 8;} hurler (6) :uri a e etuiy of some
optically active cempounle, have renortei the prep-
aration cf 1.3 .cxtro lac“:? a? ?,a- that titaniancic
sci; (n.c. lLQO at lixm.), ethyl 3,4- :metgylp;ntcncate

. - "‘ o-e t I ' -
(bop. 1r!) at 7c.) “72.), an; :..w- .1r:-;.+t}.,_,‘l-l-acrzta:cl

(“09. lm4v BL ?UJ rm.). these were 5:6;5rej by 1L6
followini as; JHCG of reactions startizg eitn cynically

quinine salt).

u {Q- J ’1 1.-
“'o-c , .4 Cgfggfi 1T3 rue

C:_:3-KI;A“|_~H-A.L« -U .~'.r.l _ A: C:33.\-’Li-iv :-CI; " l ‘I

.. .I" i
3‘31‘... ‘g'
'- ‘

 

” 033 C33
— -: ' “fie-Ch-ifi-cuz-cxpgg

4

These cczwc n s were intermcifihtes for inrtgrr
synthesfe agi n" cell. gerivetivae acre re orted.

The irlfiar; TH“?u3fl 0? tie present in.eetl;etlun
was t; e;n:3cs:2e 3.4-.imethjl?entaacl an: 3,4-41methyl-
pentancic acic 1: an niaciivocel maria; an! to hetermine
the pxgnical §7~*?”t: e cf their .criuailwae. ”he pro-
nocc; act vi ct aynthzaie was tfrc.;h tFe infernatsly
reaction as ceilin;, ielca. a scent; ctjcctive cf 1a
in'entlgatlcn cal to attug t tc Laplaie ant prove the
str.ctare cf the unsaturatel esters anion are groieced

upon lei; ration of the/G-byzroxy ester.

-3.

anl leavers

"n ’,rw
9r"! Li“?
7 ”Q. - “’3 v1 [1
CLSOCJ“'_,;§--.;12-C 'kC');5 W
l. f! ‘ /.
th’C’2U3

girl 631-:
‘1‘: 61‘.” é¥.“1‘11 (‘1‘? . ‘7 _ :2 .‘I
( a- I; J. - ' O-"’.'I2 i0- ‘ C(l ."\ H01
b Q U

A critical ilsctesion c? the iaformataky reaction
has been coepilei by Shrinar (7) and will not be lia-
cussed furtucr.

Earlier workers in this laboratory have utilized
the iaforrateky reaction, folloaei Ly .ehygration, for
fine preparation 0. isomxric unaaturatat aliphatic
esters (9,9). ihelr DPUCGJure was followel in the
work reverts: in this anger in order to ootain compar-

aala iats.

-4-

 

 

 

Kctfiyl Isc'r.9:l het.te “as obtaine. from
that a. {:-5R icapeny, an; dries cvcr rotaasium
car?“ '°c before use.

itgyl uroaoacetzfe was need as Detainea from
t.e “cs “ha“izal 3043333.

. s ...-1'. - r-~ :--- '~ ~v 6' : t * ' '
:..n £5.16 ' a:; A. ".I. .118, tfihlVJIJLI'fll‘) 2 r1353 . :1 b3 GC‘ta-Li'led

h

t" .e 31. ..‘,., n; . v . . ., .3... ...?» ._

lz‘U"; l~o'.‘ fita’m.» tile"... {Juim .I'lc a UVwi‘ 8"»! :..; 143‘} “1.1.8 Sav'Pfll
I) ‘ Q, o ‘ _’; ‘q,
ju aca- I .

:.I4A'Q; "d; -« II: 13 "a ;..4*\. s. ‘L :..}, :. ..I. {*I’G 1-9, “as Ilse 1 E3
3 (‘ .I. 1. " '5' 0- ". Vv_ ’ ' ._.'. . ~ r '« ~a ... H
b— 1'? ...! . h . (‘1... .. ”5.3 0) . . C'- i.. I}. 3:. M C¢‘ ‘ ‘L.al . (J'_.;?‘£‘y.

ttly from a ccmnerclc

'5
(t
J
u)
a!
L:
a
(it
3,.
'5
O

I P :\ .-. a- Q a a q‘ .. ’ .fi _ .
a.» '3 flattnuw t-l.e ea.nlyst,

...... ‘ fl 3 . -,.9.
PL 33.? L” a ,otaaaium nitrate raglan
'. no J l" " .: ' " t. ‘ V:-

93’ r. \r. a. 3311'. I". 31:? ‘c‘ la.‘u.

. acce;v:d Iron tn rican Flatincm works.

C
...!
"1
C '2
"‘5
(

' 3
I. a
~4-

9 catalyst Containing barium can
fire arci, asccrning to t.c vet 0; given ., agains (13),
:y .r. 3. L. Scorncr in laid.

1' z. 9 .-.. 7v. ,'_,_"' ”a 1 ~ "‘ II... ’5 .f f

‘...3 1%.!) Tet/‘21 L981 ‘9. U L435“. w.- 0 L‘Pa-lo rm
J. T. Lakar ‘ncmical iomwan_ an. «as parified lunadiataly
Lerore the reaction by the uethoi oV ”laser a“; Johnson.

”Te also «as :314P865 in Lot (1300‘) concentrate: sulfuric

‘0.
-J-

Icifl coutalnlufi & few “reps 0? a mean rate; nitric
Iclg. :ftzr lb signiel tLo a rface pf the zinc became
brigzt. 1.9 821; 5&5 )8Cfiut81 a4; :Latilled water
a.ded an; {QB reaction allowe4 to grease; far 3 few
minutes. titer was :45 Le remaining tel; frum the
zinc wit: more distillei.iater, the water FEB reucved
ts'zinsing several times with acetone. The zinc we.
dried.by heating it with steamin.an evacuate; flask

(aspirator).

‘
l"
- -I-

7‘ _ 4" ” '. ” . . ‘ ‘ ..
31:”: .mf. ~ 9’ ' r..-. 0‘ . .Qtvl 3-:.v9 ....'.X'.’-? 5‘ 9-un-A. t L. .91-

. .L, L i t
o --.. I: “M‘s-.I..-. m ED- -;‘—.w.- - Lx-q» . -‘ - -¢« #99140“; -

 

In a Jr: :33 +1. fL;r—nec e; flaeg fitted aLth
a E; ital Ll Etlrr~r, a L“ 9w.m~thr, a 330 El. sepera
tury funn.l an. a Icfigx ;L;;c.ser, L.e 4'36? 931 cf
5:1:h my: ;roLectei by a calcium ~Alerlge eriag tune
we: place: 41 g. (u 25 mol ) of peelils; to mesh zinc
(see item: ale, p.§). a aglutiun of £3.J (.LJ 3.910)
rethyl £¢-p:ufiyl ketcne, 93.0 5. (.SG male) etiyl
trenda;~tate, en; 1%3 n1. Lry Lenaene was pie GJ in
tfie aeseraterg gunngl ax. ahttt EJ m1. at this aulutlon
was 3.30“ ta 1.0 21.3 13 thi flask. The reactlcn as.
initiate. L; £13 a ,Lticn c! 5 m1. of ethyl ue;neeium
'xe::re: :3 it; ranctl n 0‘ etLgl :rem1-o an:
etuer nclu‘i n on e cans r: gaze um. IT 133 reaction
LIL not grozcee ea .':Irel, L;£t was a 311$; :21? I
‘iurc-.urnsr Lu nga.te a cgntinuii reaction. 7:3 Po-
mainin“ BMIQLLQK from tie a: rater; fangl u;e a-Led
wit; stirrlgfi st eu.g a re.e t..Lt y,utla re‘L 113; we.
we .tu; 2.. Cgll a;thIon re Li 9; event EJ minutes.
The ruler pf Lg; reaction mLx are cgaLie; {rem a LLLLt
QeLLLI LL 5 “Lgty 3 llgfl green aft ? the f;rst Be 319-

neuter; e Litzcn cf Bultticn, an, bets. .9 a gull green

mixtJro es z.J PQthLVa gr04Peaaea.
1‘ ‘.

feflux a&l kuLIHUUJ mL g hfiatlug iv? an aguition-

81 1; hens: 3;; l;e r.sct10n c110ael to soul. tho

-7.

contents of L49 :lee; was poureJ into 300 ml. lee

COlJ (13M (vel.) sulfuric acl. tit; vigorous stirring.

fine sci; ltjtr L89 se3areteJ an. the benzene eelutlon

e tracts; igrice altx :3 ml. portiuns at benzene.

fine UOQLlDBJ extracts tare WESuel successively with

53 al..col. by sulfuric atlL, 90 ml. 10 so lam carava-

ate, ED fll. col. 3; sulfuric £01., an. finally with

coli water, an; irle. over eu;;.rous soilum sulfate.
fieo-mol~ Leformatsgy reactions were also run using

a Z-llter tlree-Le -beJ flask (no tge;momwter regulre.)

.2 moles) ethyl iremoaeetete,.172.5 3.

(”J

an; ?H7.$ g. (

(

tDJ ml. eenzzue. . use reaetlens regulre; about one

melee) fiatiyl leuwrugyl ketcne, lt4.5 g. zinc and

D)

tour XOP‘Cur e~41t10n of the reactants. flftcr refluxing
for about l~ hours, the reactlun mixture mes alluwe; to
stani over-nl;ht. The reaction mixture was by rolyzed
by Dourlax late lBJU ml. lee-cold 10; sulfur c sci. and
werxe up as iescrleed above.

Three of the nae-half mole runs deecrlbefi above
were fractlcnelly_ lstlllei through a be x 1.4 cm.
column pecxe. with 1/16 lnrh glass helices. Tue head
on the column was of the c011 ILZLer tyne an; was Je-
81 me; for istilletlen un er reLuceL pressure with a
texc off Q;rnlttlg' total reflux when lealrei. Swell

ate of a few .rees mere taken at egort intervals

of tin., ellu in: tge calumn to come to equilibrium

-8.

'.- -..... . - . I _ ‘_, _ Q . . I,, ' ,r‘
tetaeeu zeta. ..e 5:49 ef t”e {re t-.ns tarLe. Irua
Lag Lg SCViQ jvefis earl an. t;; refr"tlvt L: e: of
Pfiltlu. the Lunfifi to L eerve tze “v- Pens e1 thfi

i

- :9-*- 1 =‘ ~-'.. 'z-rsa,” -' I ‘2 .
seleratlen. ...utt t3 L... --.ul»<-t 51.5.“.‘savea Lego

‘
I

tle :rezeJTe I98 rel 3e; ca. tie ce:;r iractlunetu..
1J.Pv3j eflter, tftclue. in 516143 of 74 , h£-, and
a“ rea~5rllv:ly ($5562 on one-half mole ef PcezlfiutS).

Llatlllel at g.-Qs T. et 1: m. QFQESUYG en; he: I re-

. O
{FE-CL 1;} .. s. «C {I b'. l."‘: U 'Clt- 2.3 ..- . fi- cer‘ic :4: trig ta‘t

0
~ . ' 1‘ I . (- ) ..v .. f c ‘ ' O
.or ..o H; rtz.1 ‘FJ- was »V3.tLte.
f . ‘ . .. .. ' w it " v. ( _. I ~ ‘ .v.‘..'..-'r *9}: " l ‘
{HLLJa‘a kc. ‘ :.. )1 0.-..‘w {‘.J- 3-.-,‘a- .-'.r€4t..J‘l-yw .'tiw.\}“'u°
. . .-. .. :_ ? -"-"-"I-" r- "\ a ‘ t!
..-b‘-.‘;: .. ;- 1-2.9: £51.th ‘ ...: 1Uo4l‘t .: .r.
a u! U
' 4* . . "’1, " ' ‘ ‘1 A “'V"? ‘ .2 a.
‘ U. u 19 U.’-i'.-" I“). ‘J t'. U.‘U\r'\dh“8't L.
« ' f\‘ ' ~ ."..-~ .7. r. -. )1 ' 1,- .
.t. .._‘ . Uowa.‘ ~46." c). U. u’l'31...~3 _'r‘,.

at. 2,9 9.;341ta 3- 00593516 £-

a;
r. "y ‘ g I. fill-l? 1- I It; . ‘ ‘0
'-. . ~.---.«I.... \Jlgau-i k.- . L. ‘.3Jxm I‘d
', ‘- - ... J P if - , - .. .'J
.. 1. hi); ‘ 1J.LJ r I" 1'3.E-"J‘t 6‘

II.- Dehydration gg’fithzl S-Hydroxy-3,4-dimethzl-
pentanoetg.

 

The dehydration of the hydroxy eater was carried
out on the cruie, undiatilled proiuct from the
Reformatsky reaction (A) and upon the pure, distilled
hydroxy ester (3).

Procedure‘g; In a tyeical dehydration, the crude

 

product from a two-mole deformataky reaction was filter-
ed into a 5 l. three-necked round bottom flask fitted
with a me-hanical stirrer and the contents d-stllled
until the distillate came over clear to remove any
water present. A reflux congenser was connected and
250 g. phosphorus pentoxide was aided slowly with
stirring an: the mixture refluxed four hours with the
aid of a heating mantle. As the reaction proceeded,
the mixture became a black resinous mass, stirring be-
came difficult and was discontinued. After standing
over-night, the dehydration product was decanted fro-
the sticky black resiiue in the fleck. To the reeidue
was added 150 m1. dry benzene and this was refluxed e
few minutee and decanted. This procedure was repeated
with 150 ml. more benzene, and the benzene eolutionl
were combined.

Procedure §&_ One-hundred-forty-eight grams of pure
ethyl S-hyiroxy-S,4-dimethyl-pentanoate from the three

half mole Reformateky reactions were placed in a

2 l. three-necks} round ;o:tom {lack containing
QED :1. Lry ;enzene on; treated aith 173 a ngoenucrus
pe to Kite as above.

In an atte...s;:at to sci-errata tie Leo-mum unset-c rate3
eaters wgich {)Ull he to Fafll L7 th e;enydration of the
hyLroxy eater, LLQ Lenzene eclutlcn was LLatilled through
the same column use} in the faulatlon of the hjzroxy
cater. A va CUE :um) 898 use: to obtain the caired
a caeura. T.e follosir.~ ta lee anew {L8 results of these

‘Latlllttlcne.

 

t?"l Sol.

20

 

 

T-‘T‘ Oil-.11 3' 09.. 0m. (*:1 3'91":"it V n _
1'3 Ext--'J'Jizl) 70'»); e 1.4?)71-Lo't€:‘i\)
4.73 b 44‘.» n?) 7.3 104 :4 a‘i-le‘q '3‘);
?-13 49"Eis) LL..3 lefigfii ‘30
14 L43) 3.5.: induct.

It‘ll: 14(3) ’0‘: le‘tn Title ‘1’...)
17-1; Lo-53(3) :.J 1.4? ;.-l.é3-:¢
1a-:J ' "forcei coin n” 14.; 1.4:l:.-i.e323
Ll-hfi "forcsi coLcan” 19.5 .éf u-l.é:;f

a. krcm 1&3 :. of cclgl 3-‘y;i cVI-L,é-‘7*~tlylfi‘utnaonto

(:roeu.ucu , 3513). litillatlun tgzo rh a rd x 1.4
m. ”,;5 e t;pn eel nu pihhci alth /ld inch TILES
e-lic : ’

b. the czrica i1t?ll* its: for in: nrrzfince of “ .IUX”1

EPO ;:a w v .e on ewv rs.l fractions. 'rcction lJ
¢a*wr= a h€:"fl;t1V8 (Cblvfl4u3) TQGCLIU“ a”; .0. la Ln've

-11-

b. (cont.) 8 positive test. Fraction 10 gecolorizei
bromine in caroon tetracnloride out no. 19 uii not.

c. "Force; column“ means that the tractionating column
was heatei above the boiling point of the uistillate
in orLer to force over as much of the proiuct an
p0881bleo

 

 

TABLE II8
Fraction Tap” OC.('.".11 1736191715 n020
1-4 47-60(9) 5.6g. 1.4329-1.4432
9-10 74-70(13) 11.5 1.4401
11-12 74-75(12) 9.7 l.4418-l.4é31
13-15 75(12)t075(10) 11.0 1.445585
16 81-93(10) 1.3 1.4425
17-24b 92(10)L003(7)' 49.6 1.4354 *
25 "forceJ column" 8.5 1.4376

(mostly 1.4504)

a. from a two-mole Heformatsky reaction by proceeduro A.)
p. 10. Distillation through column oescribei in Table I.
b. Fraction 20 gave a ne&ative test for hyiroxyl group
(Corie aitrate test). it 113 gecolorize bromine-carbon
tetrachloride solution.

 

 

TABLE III81
,., .. o , . n 20
I'I‘aCtion Cop” Co‘YflIIE) weight D
1-2 60-62(13) 10.03. to 1.4595
3-8 f6(10) 40.3 1.4395
9 55(5) 7.5 1.4430
10 66(8) 6.5 1.4430
11 69-Q1(8) 4.: 1.4396
12 81(8) 6.0 1.4323
13-21b 04(a)-es(1) 61.0 1.4315°
22 65(1) 7.0 1.4328
25 70(1) 6.9 1.4376
24-25 72(1) 15.0 1.4382
26 ”forcei column" 1.2 1.4400

a. From a two-mole heformatsky reaction by procedure A,

-12-

a. (55.5.) p. ... :5511155'5 t 5.. u 5.15 5 :5
3111-13 1.
' ~ 5” --w. 5, 1‘5- -55 r n :— . -- -a~~
.I. Pat-tlud 1-3 '34“- & :Jua iv. t --t ..w. ..J 11.4,",1 ”£021,
( uric ulzr-f5 i 51), but .1. LL -153515r Lrum me-
e r595 15.r95'15r1 5 soiutl n.
c. 3155. {P55Liona are asuerwntiy 5L 5: 5 :3 r5?'
631 r.
.5 ...a
a .I 45'
O f a ‘ -52")
.__£Ji:;. L£"1 -I.. “l ‘E‘ t

 

1.5.55 1.3.11.1 I(Ll) - I "'09
m3-‘:"d 'S'iC'.” (Lu) -. 0-.
“ -41 tu(9) LL.3
4--b; {3(g) $1.3
LV-LQ f’-'IJ(;) 17.3
o-J' gJ-.'}";.) 1.0:;

CI:

I-k.

V;(;)-;Q(ll) l

V‘s/‘19;

'.5 4.51133 .4"U5'-(ll) 2.).“
:T-J L3-3Lill) ngb

 

1.4;73-1.GSJJ
lQQ‘LvJ-lo‘ELiJL}
lo‘:3Ju‘(~.-l.'5. 1.51.-

-5vlation)
104‘15‘JL-Lo‘3'.

:.U.
I r - .1
1. 550144-]. 0‘; 1:, J»
104:1. '~.‘
1.421L{411‘Lt

~‘ f, 4..
evaztn...)
l.‘ r'o‘,

0‘19; 1U

1.5353

‘0

&. Lrom twu L-55L5 ‘eformr -tak* reactluns by PPvC¢*5uP$
1", D. l ""0 lat, L L 15.51.5530 ‘4 IL‘i' :..: a VLF-J X 1.1 C "Q 11.51.13? 1.43:“
tyge column p.225:j w’th "/h 1 cu 321r0m' 55L155s.

.fl

9.31.10 £-
PE "

_l

-7. n 2Q . 1.4.3:.ce’.‘
ary $9.1.E31" .

ractiens

5. .o \.
r 9,41! u, ..l. L}

be
cc

5.. ...rau . 3’ vr
‘1 In! .5 no A JgJ A

in £tt9' 1 to :5rtg5r 55555 to tfle 1Ht5rra 'Lta
fractions 0 tai' by he .istilla:.io -5 chLan in Taglea
I, TI, 5 ; TII ,3 -5-9 15;;3 an. r5;15tllliu; the
.iffermnt fructicua 555 555,5555351.

-1 3.

t ‘ . ‘ ' 3" " I .. u "' ' 5.5 ‘ .55-- ," “ , - ._ ~ I
"v .Cljb .3 'e‘ ‘. t, J'l I: ' t- gums. L. J’l-:J-‘.;.5to871q§.1.0

t. - ‘o- . -.-.. . P . J‘.-- 0. '.,-.,..~9,. -I’ - ,0
(1:... :~ “6 1 3.0%....113 $r'dm . 0“JCt¢U a "u‘i.'§1‘£ 116‘. 95CtLve

{‘13
1" ’3‘“ '3 Q - 1 a” :‘fv
.1 .~ g I - a. ‘ I".
. ... .)
_ , '- 0‘ ‘5 ..4- - )— - 'q-. ‘
'0 ... , . '8 9 l x
5. :-I‘). L; 1”“: by. .L. : J.\D~‘o 5
' l ." ,1 ... l a" n- .- .5 "f,’ 9' 4". "5-" _‘ "7 'VV ...
.55. .454”? 3 V.U§-'U"J7 L_. ‘.J.u'./'_ 5.;1 L-.
a 5' 5 "~ rflfi 4 a “19*“ .5
.1 L. ' ',.. " g‘. 5/" du‘fl“ & . v. '.o‘ "J’Od ’ :f' .
.I.
'l ”t t: r‘ 0". ‘ .-. 4-. (fl I ‘-.l F " n q . .
- . - ““H‘ u.'~"-JJU‘M ‘2’. .U‘v'r HIV '50,.
A ~‘ - ' .o r. .' r- r v «‘3’» w
»' . h «1‘ trd.'§§": . ‘g-é.'.i Q}. 5

i 5511 10.3537 E 10.1: 3 Ii

-14-

«n C

III. '? re aticn (i. ’t :1 ;, - lfietbyl-we ta Oats.

4:

A 10a 9 assure by rcfisnation a paratua of tLa
Cwnventiaghl t,ie was used.

In the ‘1233 hygruyong iul 1;L ttla we aplacéd
u.?&35 5. CT £.am'a :latinum b71;e catalyat'fiz 5.: g.

(3.1 :01?) of ‘nsnturuta: eat r of :.p :3-La° at 5 an.

L8

an n:3 1.12:3, rag 1L 0 :1. 02- eclute etr71 aICLLcl.

The aifiicm fiha Ytfifihtflle 0&5618193 £51 {111$} With
hydro e3 In 0: er to raxuva $11 of 1.9 air. Tinally
hygruhauation was startai at 84 Litial hy.rcgen pren-
sur 0 of 43 fioun;a. fitter fun? huurn Gaflki g the
pressure ha; -ruppei to 4J.9 youn.a. it LL53 fioiat no
furtLer L7;ru an absorption was observafi.

An alfiitiunal 0.1346 g. catfi.7st‘1¢aul 1%.8 g.
masturatei estar were a £64 an; Lge grensura inrrefised
ta 533. £ft7r is: n;ura snaking th éreaaur- had :rcpdcd
only two yuan a fit. O.Q$¢7 (.05t813'8t "A“ was a £03 and

‘.‘u‘.-- -- .~ ’.. -. « ”7. s“ .-.-.. ‘ -.. '. '3. "v"
‘§4&!‘IJ‘ ":..: ‘. La-I‘ it.b'-t ‘ i 'cr'1~ 3‘. Y..." ‘ .0. e fill-Id 8. "30‘s- ‘1 ‘ 83-15131.

*5

from tgo 201118 was tsetc, «Stu promina a carion tetra-

cilurlia ti¢ ch: Irxfi valor wan ramuvef, in 1*atlrg un-
aaturutlca. "» LLe Lottie was a Sad 0.1134 g. of platinum
0x110 cat£.7szur"sn; snakin; ugntlnunfl 5»? 830122? {cur
Laura. “La “PU.uCt, Lgucuar, still meculurlzafi a bromine
solution an; thus etvaav a to quLaln acme unsaturated

otter.

I"
. ._, c

Lt t.fn ,uiut the c Lnlgst was filters? Pram the
aglutlen an. aaa'e; aith a;&oL:18 at 31 glacial. the
cugwins; blag L110 sexutlvn 8&3 .iatilLefi, ins alchbl
gain; F8m0¥fi$ at eLmus-geric press.ra an: Iufi Qatar
distills, un.er tgc re.¢:e; wrcssure uf an asairztor.
To Lucae PuLVCtI ugs a :9; 0.343 f. of glatinum 0 lab
catalyst ”.' an: L3 rgganatlon qucara; afirulgte after
a Drassgro ,rao fry: :; roun.s to 4b.2 roan s in six
ficura. is acclcrlaatiu. cf tru$¢na in eur~.a lfiLPfl-
ghl;rt a tan notaf. ¢Laczatalgat mag filtfiPGJ from
tza acluLicr :3. 1L: .iatlllation was carrisl out at
utwvsr tPZ‘ firesaxfia tirfi.;h a no ifie; Tla‘3&: flaak

2-.” u . "1'. .. . ' '. ‘ _ fl 6“ 9-: ‘ ...
Vita. O U'ZI.‘ ..a..L-;- VASTJ}. («Abe «(n/115 l).

Ltgyl $.4-“1metaylpantanueto

.... , .‘ __ . ‘ C F? _ £3
rrgct;on 3.9.. C. flairxt n.

 

 

 

92-173 ------ -----
173-17fi 4.3 5. l.filrb
174917v 4.1 1.41:4
17;.1-1711 3.9 1.41:4

1753’1731 4.5 1.4170

1723-on 5.6 1.4172

1»

A
\I

(Kain-fish}?

%?raasgra, Vvfi mm.

Y1 l~ (fractigna 3-i) 3 33.3 3. 3? {3.1. Lasefl on
0.2 30195 pf unssz rate; estar. «13 31:1 weal; "robazly
,9.3 b an ;ucrecs¢? if 1.; unxntqvaLei aster 33“ been

|_ :- ..- -. -. .,_.O.*-,..' ,-_.,c-,.' .-. ‘ P..-..,. - '-. .0
raf‘.‘ 3 A L firm"? an,» )7 ¢:;?:i~'~'.nl \L 30631} ‘1 ur‘é k. a 1'5 .uCtsong

'.‘

-“o pre5arfltian L: Z,é-iir1fit;31-p¢htu uic nuifi
((14.8 rhs 7Jttb§=;'t-2;¢ :4] 41.! -131. “if: Uri.le 51‘ (1‘: )0 13
BL i-inLn test t;Lg was :1336fi 1 m1. CaneztraLeé

. J "t '. 0 ‘ . " ‘ "‘l ‘ “' -- .' '.‘ I ‘ ' '- ”
‘0- -JVU3 hm£uu ‘6' LUEJ :1“. ‘35" -u:&-‘ ..AJ n .15!“

9’

Th.'ato,
:..; 2.. :1. shyly)" 7.3.15 an; “:14; y. at. 43‘3" for
tiltint? miguws fl.‘ 1.1.137. (700143... ts :90. 1:12. }-u:1‘.n@.j £91.
at 0L:yl :.ioLlaet;3I-;entaaoats was flwfiei an; fillcaed
t4>ILLLL Lg? 1 hVLr alth 0C0581wufil agakiav. Lita?
hoatznw at to” fur tsenty minut a 044 than at 53° for
five mlnu ea, 2 al. of €31 r was a.med anj tne mlvturo
coolafi. fine JBEI?EJ amiie £3110: to precipitate.

y;rolya:s cf t a ast:r to L a eel; an; raga? atlun
of tLa £2140 thrwugh the 0:11 cLlor1.e proved more
successful. Eva? ”s'fit .s soLLum. hygrgxijs, 3 ml. water
ax; 2 3. 91,31 3,4-L1:&L1V1-pigtmnoato more placaj in

L tuze 03L I: “I :91 until {Lu layers Lo-

cama ml“ ills (3 hvurs). {ft r coglinf, {E6 mirture
w&s axtroctg. a th at er to :e: vs any unsaLL u: . 3
ester. tgea :Ha aulu ivn was 31.1fle; "it: 1% ml.
3 hy;ro:L1u-c eel. an; the 311i rcmuv04 by extraction
with fuJ? 13 ml. pU.L1998 of Lt z~ne. $.13 ;uuzeno
ablation ”as zlatllle; t0 zeaa.e any regaining water,
until Lga Lbnlahb Lara 090? cluur. 1g% -6 aiming bea-
zsno-a ii eulutlon was placa; in an a 13th test tub.

331 6 ml. tbi a? Chlurl.9 as: aLdei n1 tna mixtuyo

-17-

Logic: on a 81832 .at; :04 winULGa. 4fter COLlinfi. 1L
uaa EQUPG4 iutv 1 e-col4 sun entr5m.~- mm alum hy-
4roxigo. £ n.1ta wreripitato [9* a} 33$ L8 rear; sLall-
143$ frum 5‘;ouul akcgnul. 2410 3,%- 4149L441-" ta L10
£L14 8m1.0 nails; at 1260-13903 824 gave tho fulicfllnc
a. 5.1 ya“.

Itewrsx L731; u; t5.u75 4: 11.71.83 10.84u R

i; to :arafil. (i .41) OoU‘JLL-‘74SQ U. “4341.223.
Lt. 'UQ Uovla‘ ”('05. 0001;43450
I-4n1 £5.32; C €5.21:

. E Puma: 11.58% B 11.73? H
it. Saupla (a) 3.39:3243. 3.3313 63.

"orpectoi leuma

5», 27”“, 743 mm 6.0;41 m1. 0.4434 ml.

‘ K V 4nd 10.;34 11.37- 3

The ms“; mcLLo. cf analysis was followai in the
nitrugzz". .61..\..1*:Ji:;:.tiu a ram: '16:. in this payer. Tim
instr44L L144; 41263 Ly L134er1 an» L124erl (11) were
£0110%94 utilizing the 4r: loo carbun .1ox1.o genera-
Lor fiPufOLGi ty prauwb‘b an; Hollauoi (12) an. illus-
trated on pa 9 $7 of h:a;arl's LOOK (11).

'130 met 0 followa4 for carbon 334 h;4rugsn

analysis was also that given by SL¢4erl (11) am. the
n

COIL .ustlcn tn :5 was oraparei wLLu he ";om;1natlon

r.

3..

111:: an 1114etr ate! in E15;3rl'o Luck on ma 9 110.

-13-

The 9:111 a of 3.4-41mstiyl Jesters-c acil ah.

t

graduroi by a similar £61104 to tLuL usefi a4Lv0 fur
tgo 5:140. Th6 n-1, cglurl e was irap4r94 as suave
5;. 5 :1. 8511136 in Ed m1. 4r? 4enzu a was 8.46; and
Leena; on the steam 13th. 719 5:111 a gracipltated
out an scaling an we: filtaroi as; rocryatnliized
from napaoua fl.cohcl. ‘19 3.4-41m3thylopegtanoic
8013 63111 a meltoi at lfifiio-llfiof. 811 gave Lre
£011L41ng a al"$1l.

Tug ryz 81311 “C: 75.43? i; S.&Cfl 33 6.3a? E

 

 

'flt. Campla 3.CSG?CB .. 0.836177 3.
Torract;; Vblflflfl

5 _. :fi‘ .0 ,.

“a. “ ‘ 3. 7‘3:- v.3 0.3:‘14 :01. 0.2377 Ll.

. J 1
3 A k a“ L‘.Ol a {3.7:}. :1
IV. T3”r‘ %wu1;sfa a? 0:33; 3‘&- ifl+t‘glgjfirtchzate
L5} 15"- L._._il- "UA :..-2.20;.

 

volJ uni fitte: aith a pressure gauge IBI usai. Th!
vessel was mounts; in an olootrical control system.
Tbs ccurse of L33 ve4uctiun 398 follunoé by muting Lb.
prc304re ire; at the a grating e¢7eraturo.

recauaa no Lobster pump was availault, tau maximum
pressure wau that of tha cylin er. It maul: Le jeairablo
LJ usa hi hi? arses4rel for thin tjga 0f ra;uction 1f

jassl-l@. (11. 15).

-13-

To test the apparatus, a sample of ethyl n-caproste
was reduced to l-hexenol (15). Twenty-nine grams
(0.2 mole) of ethyl n-caproste was placed in a suitable
~lass liner (16) with a pin-hole halfway between bottom
eni top. 7"ive grams copper chromite catalyst was added
and the liner placed in the reaction bomb. Lfter the
bomb was sealed, hyirogen was passed in to a pressure
of 1500 poun e at 25°C. then heated to 250°C, the
pressure had increased to 2510 pounds. After shaking
five hours, the pressure had dropped to 2000 pounds.
On cooling to 25° the pressure was 1150 pounds. This
would indicate complete reduction to the carbinol.
Consi ering the void of the bomb at 500 ml., the volume
of the liner was determined to he 70 ml., the ester
volume was 55 ml. and the volume of catalyst was about
5 ml. This leaves a resultant void of about 594 ml.
The pressure drop calculated should be 357/ .394 or
906 pounis per mole hydrogen absorbed, or 562 pounds
(25°C) per .4 mole hydrOgen required to reduce the
ester to the alcohol.

For the reduction of ethyl 5,4-dimstnyl-pentenoste,
21.8 g (.14 mole) of ester, b.p. 64-650 at 9 mm and
Hg? 1.4595 was placed in the glass liner with 5 3.
catalyst and the above procedure followed. The pressure

at 2500, use 1550 pounds and at 250°C 2510 pounds. After

-20-

10 hours shaking at 250°C, the pressure had dropped
to 2230 pounds, and on cooling to 25°; 220 flounds.
The volume of ester'being 24.5 ml. left a void of

:;b ml. or a theoretical pressure drop required for
J.é2 moles hydrogen of 57 x .42/ .585 pounds or

sea pounis at 25°C. The product was filterei.and all

product rinsed from equipm at with ethanol. The die-

tillation is recorded in Table VI.

TABLE VI}

3,4-31methyl-1-pentanol

 

 

Fraction 2.9.,9033, nfizo Weight
1 to 157 ' 1s3746 0s9 8
2 157*167 ‘ 1e4258 0.8
3 167-168 1.4267 1.4
4 168-169 1.4267 1.7
5 169 1.4267 2.1
6 167-169 1.4267 2.2

£5

Distillation through a 20 x 0.9 cm. column packed with
l/16 inch glass helices.

**Pressure, 746 mm.

The 3,5—dinitro benzoate of 5,4-dimethyl-pentanol
was prepared by a method similar to that used by Smith
(17). One-half gram of the alcohol was placed in an
8 inch test tube with a large excess of 5,5-dinitro-
bensoyl chloride (prepared by fusion of 5,5-dinitro-
benzoic acid and phosphorus pentachloride) and pyridine
and was heated on a steam bath 5 hours and then cooled

in an ice bath. Five per cent sulfuric acid was added

-21-

until the ‘tr of pyrZLine was $18.Lnr§s’ an” a faint

.4 as

oicr of Lus airshol coal, to o.ser.es. fitter cooling

4 a r rrtgcrstor, tTe precipitate was

"1tere; so: treats: with 127 so ium cachcnets to "e-

x e. . . - s- .-. . s g‘. ‘ ., v, - ‘ r
lease 1 a ,zrrfins free its salt a 11" r r“

g :....I .u..:¢a.. u
‘l‘

H
p.
f:
’3
C
a...
:3
9
L,
...-O
r9
O
(*3
r?
as
U
o
L)
I
E)
O
(1"
O

V. retan‘teg Va reinitin of ?th?l 5,4— 1~ut 313
3.13.3»,

 

tollouig; the r0 edire used by lu.-ton, Scrrncr,
and fytrgy (3,5) for Lie 1 satiricatien of irons ric
onsets; Lte‘ esters, an attonpt was mate to character-
ize sore fractions iron the .Lstillsiion of the un-
saturate; esters oLtaine; 23 the Lezyj. ratio: -f the
reformstshy reaction pro3uot.

rCVOJ on; five-tenths graze (.343 sole) of

o .
unsaturate.2.este r (L .p. 51 , 2 mm. ., “h 23 1.4555) was
mixed 31th 51. m1. (.045 role) of 1.7 3. L3 re an

peroxide in t-outyl alcohol ani 2.5 ml. of 0.51
oanium tetroxiss (t-tutyl alcohol solution) (2 -) Kid
placed in a refrifierttcr. e sol tlon secs; .e trosn
colors 3133' hit-31‘]. lift-Cr 81.8.1333; over-r3133; t in H).

P

(D

frigesator, tze iroiuct ass 3istilled un.er rs‘ucsd
pressure (as irat r) to PETQVO the t-uutyl alsohol.
.srls o rcnlorate” solution was frersred by
3Lsolviug 11.5 g. of hexa;itrsto anionium ccrats in
a mixture of 133 :1. of Listillcipsattr'ani 70 ml. of
721 err: 3:1; oo13;. This one then $113: 3 to a total
volume of 2.; n1. sit; 'stilled rate r.

§.s r‘o: us from the above dist: lation was treated
«its fine sesLVe small portions of the "eerie; eerchlo'3 ate"
solution until a re; coltr was no loo er formed. Air

was Ersan three“; the norms: solution ani into a test

-23-

tube containing 2,4-dinitrophonylhyirazine disolved
in 203 perchloric acid. No precipitate of carbonyl
derivative was observed.

The solution, after this treatment with "ceric
perchlorate", was wade alkaline to litmus with
potassium hydroxide and the mixture refluxed three
hours. Air was again drawn through the warmed solution
into a test tube containing a 2,4-dinitrephenylhydrasine
solution and a precipitate was formed. After three
crystalizations from ethaiol this derivative melted at
118° - 122°.

A second degradation of this same unsaturated
ester failed to give a 2,4—dinitropheny1hydrazone.
Fraction number 22, b.p. 95° (11 mm.), nD?°
1.4570 (see iable II, page12)'sas treated according to

the procedure described above. No solid derivative

was isolated.

-24-

urine ins causes of tnis invest: atlon, the

:rimary garages of tiis “9?; has been Believed,
gsiely to zynt seize 3,é-gimxthyl-l—u¢ntsnol and
3,a--inctzyieentenoic acid. fieprooriate derivatives
have been made iron 0833 of LLGEQ.

T‘s tuiiinw of the uctno; use; in the syntzesie
to? fuse - "until is 849W] L7 L93 eggstiofj 0:") 732.;6
4. This syntutsfe inv,ivei the -afirustsky roastion

L tween not yl 13.;ro1y1 k tins and at 31 .Pymo-

f4

acetate a: it: {Cumutiofl of wt yl Z-L; so 3-:,4-

i1$ULL31¢35£LLHfifiieo Txis/fi-Ey-roxy coins was isolated

in a pure at fa tram only three of the seven runs.

fro yiol.s in t use tflrso runs were 74, :6 an: {a per-

cent. I

“but, t;us pentoriie was used in the dehyiration

of the/g-a,nroxy ester.. :evurai times Dore, .iatillcd

p%33;Poxy ester ass ni a; 32th Duos norms ongtotifo

an} Lsnxono uni rteUrei in prior to Lrina about the
:ehy:ration. iguaiiy satisfuct r; results were obtains
ed HLEH sz cru;e, un.:s ilisd/fl-Lyiroiy ester in

Lsxseue aolu Ion was free; of water an; than refluxed

.-, ' '. .r.‘ _ . - -' ~ >3. ._ 3'
Ultf. (’ -..._ ‘7..\.Y'.a. pa'ntuxi._.6.

:ehyirttion of ethyl 3-n3.roxy-3.4-iimet1yl-
pentaioate snonii give three positional isomers,

one of wui h A mag exist in both cie an; trans forms.

Cuff" "l a
1. ' .. " -
VII; , ' ” Mr I.
L-Q‘- ..‘v- 'uqu" ..3.‘ A
U S
I F‘?‘
‘1‘ LL"?
- A ' V5 , , .
7’- =3 . "mac.“ x v ‘
U 6 L. L
{Wit _. e‘
‘ s e'a
f‘f‘q 1"" 1' u - r-~ r. ' rs
_-. ~ . -|,-_ 3- .l v "Y v ‘V('
0w- up ‘)

in Ltitxgt was ends to so arate tncee Leonora.

‘

listion of the esters from the .e334ration

an-

.- .

Tue 'st
Paaxtiou can u rri x Ont By moans of a :e.sxe Lyn.
uoluzn -ached «it: 31583 or nicnromo tslicse. tr
ova rose of ins sc;aration was foiltaei by coilucting
small.fructions ant ottaLning the refractive iniex of
sec; of these. Taoies I t roach IV (,a;es 11-15)
record tie r suits outaiisd.

The fractions listei in Table IV were flFEEiiei
were as statiy than tLUSS lists; in tables I turou h
:11. :siscts: treatises tgrcugh sum 9r e9 .ecolcrizsd‘
a lro lie in at: on tetrsr iori a solution, on: hence
E estrrs. fLe total

_ .- 3" I"..' '. H- .. ..-- t". ‘_ ' , - r ’3...
1‘3 . y... 1-.-»): in; 112 L. U1. d479rw. (£433.: 14,-0.3 sub?

.3
0
H
3: f-
a
C
r
“J
(L

I

»cisnis used in tno Teforxatsky rfiattion.

Fractions 70 and above failed to decolorize a
bromine solution. irom a consideration of both
boiling point and refractive index, there qopeared
to be a cousiieratle quantity ofrflahyiroxy ester
recovered during the iistillation. From this dis-
tillation there was recovered 133 g. or 22.4% of the
li-hyiroxy ester. The distillations recorded in
Tables I through III were similar to the one Just
described, although the separations were not quite
as clear cut.

An attempt‘las made to characterise the un-
saturated ester which was reduced during the course
of this work. ‘he method, used by earlier workers
in this laboratory (8,9), consisted of hydroxylating
the unsatuxaied ester to the glycol and then cleaving
this to aldehydes or ketones. All the work carried
out in this direction failed to give sharp melting
derivatives.

Reduction of the unsaturated ester produced in
larger amounts, b.p. 58-590 at 5 mm. nDZO 1.4595, to
ethyl 3,4-dimettylpentanoste, b.p. 175-1760 at 750 mm.,
nUZO 1.4164, was accomplished by low pressure hydro-
genation over platinum oxide catalyst. The amide,
m.p.-1se-1se°, and the anilide, m.p. 108.5-1100, were
prepared via the acid and acid chloride by the con-

ventiond. method. The melting points of the amide and

axiliie cohfsre fav;r&-ly hit; all r cargo; 1 luel
0206;t trots c? ifott (1,3).

Itlyl 3,4-iimathjlgentsufate was re;uc d to
3,é-.im:thyl-1-pcgtancl by ”if& “ressure tyircfen-
olysis o;nr con? P s remite catalyst. The 3,5-
iinltrohegzoate of txis alcohol (m.p. 43.3-20.50)
was pro are . lgls aoltiaj 30137 agrees sit: the
values re uric. by CLLu.rlinr (2) an: Lofihsro (5).

tails VII compares the :hyeical constants of
(l) 3.4-;invthyl-l-3sutanol and its Jerlvstivas and
(2) the dsPLV8L1Vu8 of 3,4-iiasthylpentahcic acid
u-i;h have been re orte: by previous nursera with

those outside; in the areoent strk.

owduahofhor Mn mmhwarh:

atom assumed qaaan.;sa nu~-»ma n.nnu;.me Anagrams.a Ansel. Muses

.evaaspeq nameless

.0

novoasoauon m.aaauana and h.wq-mi
.eoaosaam o.nna-s.naa n.smann.ena
”mum:uapofixoo macaw .s

Ravsueos so m.nn menus“ Ammvagms.a Ansrvmma-owa

   

 

 

 

 

 

 

 

Lfluflehomw P‘o Celt...» ”mo 0.0.01.0 ‘OHOWM “IOU I.“ «flirtqfo q.m0.m
el 33¢ ceded rumocasn
Inhanunnuua.wi
was“ umoCsunrraurusaw:lwdu Hursnu. ensfluwueén aqua

U:.fiRY

IA).

1. Stay :-.; roxy-3,4-:iaet;ylszntanCste
has been :“Cparefi tyrough .Ls Icfcrzatsay reaction
Letssen Letkgl Isew~opyl ; toga an; ethyl rumo-

acetate an. its ingsical :riuertics is or:.:nel.

3. :tzyl thy.roty-3,i-..Em t‘ylpm tsgoate
tas been ieL;.raiei to a mixture of 13o: :r1 0 un-
sat: rat a. cat are by me; as of pacsnhorus rtu-srids.

3. fizuyl 3.Q-£lmuthjl93htanhte has then gre-
. iby the catalytic hydrogenation at low pressure
of the unsaturatei esters. Tia atiie and 8511130
were preyarei as self; derivatives.’

4. 3.4-.imethylpentanol has been areéarei by
the hviro,s.,iion an. hy.rom noisesis of the unsatur-
ated ester DVzP supper ch mium oxide catalyst. the
3,2- i.itrote: .soate of this cat r has t;en hrsoarcd.

5. the a itinr points resortca by :gett (a)
for the anti e ans .. 111. '.e of u":¢-.u1"..t.‘ "1 Mutt: (310

as}; have t on To 3; to {8 in error.

l.

2.

3.

4.

5.

6.

7.

8.

9.

10.

ll.

12.

15.

LITnRATUhE CITdD

Huston and Agett, J. Org. Chem.,.§, 123 (1941).
Schmerling, J. Am. Chem. Soc.,‘gz, 1458 (1945).
Agett, Ph.D. Thesis, Mich. State 0011., (1940).
Private communication from Dr. Avery A. Morton to
Dean R. C. Huston.
Private communication from Dr. J. C. LoCicero to
Dean R. C. Huston.
Levene and Marker, J. Biol. Chem., ill, 505 (1955).
Schriner in Adams, ”Organic Heactions', Vol. I.
John tiley and Sons, Inc., New York, N.Y., 1942,
99. 1-37.
huston and Goerner, J. Am. Chem. Soc., §§, 2504 (1946).
Huston, Coerner and GyBrgy, J. Am. Chem. Soc., 19,
see (1948). 9
Fieser and Johnson, J. Am. Chem. Soc.,‘gg, 576 (1940).
Cheronis and Entrikin, 'Semimicro Qualitative Organic
Analysis", Thomas Y. Crowell Co., New York, N.Y},1947,
p. 187 (8.59).
Niederl and Niederl, "Organic Quantitative Micro-
analysis” 2nd Edition, John'Wiley a Sons, Inc.,
New York, N.Y., 1941, 99.79-150.
Hershherg and iellwood, Ind. hng. Chem., Anal. id...

‘3, 505 (1937).

-51e

14. 1 kins, "leactions of hydro;en", >hs Lnivcrtity of

Risconsoi Trass, (1317), on. 13-14.

15. fiixins an; ‘CLFLPB, J. in. the . ioc., gfi, 19nd (1:31).

15. zolksrs an; I kins, J. rm. C a". moc., his 1143 (153;).

17. Lialns an; Framer, J. an. t.e . .00., 3;, 4.43 (1“9).

1;. ”with, 9h. . thesis, hick. {tats v011., (1; 4;).

l}. fmith an; use, Ina. :fl:. Cho2., Anal. 11., ii, :33
(1911): 1:, 123 (1343).

20. tiles an: iussman, J. in. 4351. Soc., 3 4, 120‘ (1331).

‘3 .‘I
.‘__Q.

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