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9h. Manual of 2.3.3451”th 2-Putm1 and
2.2.3.!r1utly1-3-Patm1 with Phenol 11 th.
Pros-nu of Ala-1m chloride

37
Bum-1 Brutu-

L flu-h

:1th n th- emu School of in. “china “at.
0011.;- of tantam- an Applied. 301m.
in: mm fulfills.“ of tho "gun-
mtn for the hem of
m or 861110!

Donn-on of chad-try
191:6

. ‘ ADKROWLEDOEMEHE '

9b Dr. R. O. lhuton. grutofnl acknowledgu-on‘

1. Ind. in upprociatlcn of‘his guidance and
sinner. insorout during the court. of thin
work.

331613

QABLR 0? 00312399

Introduction..............................
littoflul................................
l:por1nnntal..............................
Papa-“1n of hookah.................
OMmum...........................
ncflvsttvu.............................
13:11:10................................
Namibian...“.........................
Sn-ary...................................
Dibllo;rnphy..............................

0" 0‘ N H;

12

19
21
26

27

INTRODUCTIOH

Altheugh.previcue vufltere lu thle laboretcry have coudeueed
2,3,3—trluetlvl-2-pentenolu) ma 2._2.3.tr1u¢hg1-3.pumo1(2,3)
with yheucl in the preeeuce uf‘uluuluuu chloride, the etudy cf
the-e condeueetlcue rue etlll lueuuplete. '

Preofe of etrueture were lechlug (er hath ccudeueetleu pred-
ucte lecleted. In the ceee c! 2.3,3-trluethyl-2-peuteuel, only
e elell elouut ef'the cerbluol rue evullchle cue to greet 41rr1-.
cult: of preperetleu end eoue doubt exleted concerning the purity
of the coupon-d ohtelued. Iu.the ecudeueetluu e! 2.2,3-tr1uethyl-
3-peuteucl. the previous uurtere obtained producte whoee phyelcel
‘ ceueteute differed greatly;
rut theee reeeoue. it see ccueldered deeirutle to continue

the etudy of the cundeueetlcu e! the two cerhlucle with.§heucl.

HISTORICAL

.h ceupdete review ef the litereture dealing with elkyleticu
ef ere-etic nuclei would uhvicuely be beyond the eccpe e! ens.
yeper end weuld he ueedleeely repititieue.

lay previeue pepere(h,5.6) have funiehed hrief end feirly
couplete eurveye. Iu edditieu te theee reviewe. exteueive eurvcye
on the euhject c! eluuiuuu.chloride in erleuic cheuietry have been
nude hy Ireueleiu (7) end lhcuee (5).

Since thie werk ie e etudy e! the ceedeueetiee.et tertiery
eliphetic elcuhele with ghoul in the prceeuce cf elu-iuuu chlor-
ide. only theee reeeeruhee deeliu: with thie euhject will he ewe-
Ierieed. .

.Alkyletiuu e! ,heuol hy ueeue cf tertiery eliphetic elcchole
tell; ell-inul chloride. wee firet reported.hy'luetcu end leieh
iu Septeeher l93h et e leetiug'ef the Alericeu.0heuicel Society.
tertiary huty1,tertiery elyl, end the tertiery'hexyl elcchole
were coedeueed with phenol. end the reeulte. publiehed ie 1936,(lQ)

were ee fellow-3

9.2.22.1. 11.29. m
1. 2-Hethyl-2-prcyeuel ho
2. Z-llethyl-Z-heteucl 5h
3. 2-Hethylc2-peutencl 56
n. Hethyl-B—penteuol 50

5. 2,3-Diuethyl-2-hutml In

In 1935, nfter the report node hy lute. end Heieh to the
Lnerienn Ghenienl Seoiety. hut prior to the {cruel putlioeticn
of their reeulte. leukemuih end lennreve (9) reperted the con-
denention of tertiery hutyl end tertiery enyl elcehol with phenol.
to obtain 60-701 the mm phenele.

The inventigntion wne continued hy Ineton end ledrick (11)
who mceeefully condensed the tertinry heptyl nlechele with

phenol.

£9933; Yield )
1. Methyl-641311301 )1
2. 2-Methyl-2-hexnnol 65
3. 2, 3-Dinethyl-3-pentnnel M
h. 2. 3-Dinethyl-2-pentnnol 27
5. 2,3-Dinethyl-2-pentenel Rh
6. 3-lthyl-3-pent enel 30
7. 2.3.3-Trinethyl-2-hutnnel 26

in the Ienntine. the etudy of the cctyl eleehele hnd been
undertnken by Andereen (2) who conduct m or u. nethwl «m
hntyl cerhinele with yheuel to ehtein rether lew yielde e: eon-
deueetien product.

Alcohol field E!
1. Methyl-j-heptnnel 25
2. 2,2,3-1'rinethyl-3-pentnnel 21

Snyder (3) repented Andereen'e werk end then coupleted the
inventigntiu e! the nethyl ethyl hutyl enrhincle. In the enee
of the 2.2.3—trilethyl-3~peutnnel. the eendenentien product oh-
teined ty theee workers hed different neltin; yeinte.

Unfortnnetely. the cone derivntivee hed not been prepered end it
wee inpoeeihle to eecertein whether the producte were different.

or the eene. with veryinc degreee of purity.

M Yield $22
1. Methyl-3-heptnncl SO
2. 3,h-Dinethyl-3—henenol no
3. 3.5-Dinettql-3-hexnnol 61
h. 2.2.3.!rinethyl-3-pentenol 21

fine etndy of the ectyl eloohcle wee continued hy Leotden (12)
who condeneed the dim-owl nethyl cerhinole.

. Alcohol Yield 51)
l. 3-lthylo3-hexenol 36
z. 3-!thyl-h nethyl 3-pentenol 5h '

Iueton end Guile (1) ”no...“ the dinethyl eql cerhinele
with phenol in en enteneion of the etudy of the cotyl elcohole.

51.2%}. W
l. 2 nethyl 2-heptenol 1o
2. 2, 3-Dinetlyl-2-hexnncl 36
3. 2,3t-Dinethy1-2-hexelol 59
h. 2,5-Dinethyl-2-henenol 65
5. 2~tlethyl-3~ethyl-2-peutenol 28
6. 2,h,h-?rinethyl-2~pentenel 65
1. 2,3,h-1'rinethyl-2-pentnnol 23
e. 2,3,3-‘l'rinethyl-2-pentencl 2

e leter pnhlieetien hy lueten end co-workere (13) corrected the
yield of ectyl thenel ohteined in elhyletion of phenol with

2,3,3—trinethyl-2-pentencl to W.

5.

luetcn end neloy (1h) oonpleted the etndy of the ectyl
elcohole with the condeneetion of the nethyl dipropyl cerhinole

with phenol.
W Yield Sfl
l. 2. Methyl Lhcptnnol 65
2. 2. 3 Ill-ethyl 3-hennnol 1:1
3. 2,33: frinetlvl 3-pentenol 60

IIllue. n etdy e! the elkylntien of phenol with tertinry
eliphetic nlcohele initieted end develeped fully hy lueton end
hie ce-worhere in thie lehoretory. wee conpleted through the ectyl
elcohole with the ynhlicetion by Benton end Holoy in l9h2. . in the
eight yeer period. twenty-nine tertiery eliphetio elcohole here
been condeneed with phenol, derivntiwee of the nlkyl phenole were
prepered. end the etructnree of ell hut three were proven by eye-
theeie. She three elkyl phenole for which proof of etructure ie
mu inching ere: 2.2.3 trinethyl mm Ivar-u) phenylnethene.
2.3.3 trinethy 2m:- hvdron) phenol-«hm. end 2,3,1; trinethyl
2(pere hydroxy) Minothene.

mIKIfl'iL
I. Preaeticn of Alcohole
i. 232. kffluthlL-l-Pentenol

me elcohol wee firet propered hy clerk and Jonee (15) by
the reection of pinecoleee end hethyl negneeinn brenide. Snyder
(3) end YenDyke (6) eleo prepered the elcohol in the em nenner.
the procedure need in thie work wee quite einiler with liner
mietiene.

Sin nolee (11th grene) of dry negneeiun turninge were pleced
in e fire liter, three-necked fleck equipped with e nercury-
eeeled neohenicel etirrer, en illihn oondeneer protected by e
celciun chloride-eode-line tube. end e lerehherg dropping funnel
(l6). etout five nillilitere of ethyl hrcnide were edded. end
ei'ter weiting e ninute or two for the reeotion to etert. one hun-
dred nillilitere of other were edded. i'he reneiudor oi oi: nolee
of ethyl hrcnide (65h green) wee diluted with five hundred nilli—
litere ef other end edded through the dropping kneel et the rete of
two drope per eecond. When the motion wee proceeding eetieteo-
terily ee evidenced by hrieh toiling c! the ether, two litere of
other were edded through the condeneer. he renninder e! the
ethyl hronide eelutien wee then edded dropdee ee repidly no it
wee poeeihle to do no without externel cooling of the reection
fleet. The tine required to propere the Orig-erd reegeut wee eix
houre.

no reection nixture wae enelyned hy diluen'e (l1) nethod,
in which on eliquot wee lydrolyred with etenderd ecid end heck-

titreted with etenderd heee. i'he yield of Orignerd reegent eh-
teined val 5.7 eoloe. 95% of theoretical.

L eolntion of five nolee (500 green) of pinecolone end five
hundred nillilitere of other were then edded to the etirred eoln-
tion of ethylnegneeiun bronide et the rete of one drop per eec- .
ond. i‘he tine for couplete oddition wee ten houre. rho reaction
nixture wee ellowed to etend overnight before hydrolyeie.

Hydrolyeie wee eoconpliehed hy pouring the nixture en ice.
dufficient 25% eulfuric eoid.wee edded (ehcet 600 cc.) to dio-
eolve the heeio Ingneeiun eelte. The orgnnio lnyer wee eepereted
end the equeone portion entreoted three tinee with 10% of ite
velune of ether. the ether extrecte end the ergenic layer were
oolhined end washed with wetcr. 5% eodinn ocrhcnete eolution.
end wntcr. end dried over nnhydrone eodinn enltete.

i'he ether wee dietilled of! through an eighteen inch Vigreun
freoticneting colunn end the reeidue frectioneted by none of e
heeted 1'pr colnnn (250 r 16 ne.), peeked with one-eixteenth
inch glaee helicee. ueing e totel condeneetion. pertiel teke-off
heed.

three hundred end twentybfivo greue e! the cerhinol were
obtained, o yield of 50¢. honed on the pineoelone need. the index
of refreotion of the carbinol wee checked periodicelly ee it die-
tilled, to insure purity.

3.9. - 61.620 c./20 In.

ago - 1.1658

lerly rune in which the hetone wen edded nore repidly,
geve only 35% yielde en wee chteined hy VenDyh-e.
h. 2.1.} frinetgl-Z—Pentenol

i’hie elcohol wen propered hy lcrtcn end Been (18) through
the reecticn of 2,3-dinetllyl—2,3 eponyhutene (proper-6 in 15%
yielde tree pieaeoloee) with athyleapeeiu hronide to chtein
e yield of 38% heeed on the oxide. rhey eleo ohteined the
eloohol in 6% yielde fron ecetone end tertiary enylnegneniun
chloride. lueton end Guile (l) prepered the nlcehol hy eynthe-
eining 3.3-dilethyl-2-patnncne end reect it with nethyl iodide.
eeplcying e nodificetice of the Vhitncre-Dredertecher procedure
(19). Yieldn of 2-51 of the carbinol were ohteined.

In 190% Grignerd (20) dincovered the reection of orgnnic
eoidn with elhylugneeiun helidee which given tertiery elcohole
in netiefectery yielde. neiley (21) extended thie work end pre-
pered e lerge nunher of tertiery elcoholn, uning ninple Grignerds.
fhene nethodn were epplied in developing en inproved neth of
eyntheeining 2,3.3-trinethyl-2-pentenol in yielde of 25$.

Briefly. the cctenol wee prepered in the following nenner:
fertiery ewlnegneniun chloride wen prepered end whmted hy
penning in cerhcn dioxide to yield the cold coupler. Addition of
excene nethylnegneeinn trcnide yielded the cerhinol conplen which
won hydrolyned to ottein the oerhinol. d deteiled procedure for
e two nole run of tertiery enyl chloride. yielding one-helf e
ncle of cerhinol, follown:

 

_ , a _ n.

l. Prearetion of fertiewl Chloride

The chloride wen prepered by e procedure edepted free the
preperetion of tertiary hutyl chloride '(22). i'ertiery enyl
elcohol wee nheken with enoene concentreted lvdrochloric ecid
for ehout ten nineten. depentien of the chloride. wenhing with
eodiun oerhonete nolutioe end weter. drying ever celciun chloride.
end frectionetion, geve e 60$ yield of pore tertiary aeyl chlo-
ride. 3.19. 82-83° o./7uo we.
2. Preperetion ef TertiWeiun chloride

The Orig-erd reegent wen prepered in the unuel nenner. low-
ever. ineteed of neing iodine ct e cetelyet, neverel nillilitern
of ethyl hronide were added to the Ingneninn. end when the re-
ection eterted, one hundred nillilitere of other were edded
through the condeneer. fhen oddition of the enyl chloride wee
nede. end when the reection wee proceeding netiefectorily. eddi-
tionel ether wee edded to the fleck. tor the two nole run, e
totel of nine hundred nillilitern of ether wee need. The rete of
eddition of the helide wen criticel end neinteined et e rete of
eheut two drope per three neoende. he tine of reection wen four
hourn. rho yield en deternined hy titreticn wee 50-60}.
3. derhonetion of the Grim

the procedure wee teken fron Or‘e_n_i-c gathenie (23).
Oerhon dioxide, fron e cylinder fitted with e needle-velve. wee

 

penned through e trein conninting of e eefety—fleek. twe concen-
treted nulfuric ecid weeh hottlen, end e nefety-flenk. into the
etirred Griperd reegent which hed previeunly teen cooled to 0‘0.

h eolid cerhon—dioxideoelcohol cooling heth wee found nore

10.

efficient end convenient to hendle then the ice-eelt hnthz
reconnended ee e einple neeiie of centroling the telperetnre
of reection. fhe tine required to cerhonete the Grignerd re-
egent ehteined in n two nole m wee two to three honre.

1:. Preperntion of kiwi“ Bronide (2h)

hethyl hrenide wee genereted in e three liter. one-necked
fleck. fitted with e oondeneer which wee connected h: gleee
tubing to e porificetion trein. i‘he trein ccneieted of e eefety-
fleek. three 251 eodinn wdroride wneh tettlee. e Mott-fleet.
three oonoentreted enlforic ecid weeh hettlee. end e finel eefety—
fleet. he outlet wee connected to n f-tnhe which eer'ved no
the gee delivery tube. the ether on of the Q-tnhe wen fitted
with e gleee rod. to eerve on e plunger to prevent plugging e!
the gee ontlet tnhe. he plunger wee held in pleee I, e lnhri-
eeted rohher eleere. in neeh the one nenner ee e glycerin-
eeeled etirrer.

dove: hundred end fifty grene of eedion hrenide were edded
to the generetion {leek which conteined e eoletien of 235 grene
er nethenel, 5110 grene e! concentreted enli'oric ecid end 50 sini-
litere of weter. i'he fleet end ite contente were then hented
gently on e eend heth.

The reection fleet wee e three liter, three-necked fleet.
fitted with en Allihn condeneer protected by e oelcinn chloride-
eede line tote. end n nerenry-eeeled etirrer. Eighty-fever grene
(3.5 nolee) e! negneeinn tnrninge. enfficient to prepare elightly
nore than three nolee of Griperd reegent. were pieced in the ‘
(leek. end three hundred nillilitere of ether edded. ihe gee

11.

delivery tube wee pleced in the third neck of the fleck with
the end extending below the enrfece of the ether.

in an edded safety neeeure. e two-wey etopcock wee in-
eerted between the gen generator end the pnrificetion trein, no
that exceee methyl hronide could he penned out of the eynten.
if neceeeery. to control the reaction.

When the reaction eterted. en edditienel eight hundred
nillilitere of ether wee edded to the reection fleet. {he re-
ection wee completed when ell the negneeion had heee canon-ed.
fine for conpletien wee nix honre.

5. Addition of Mummies Brenide to the Acid Gonplex

Retiweting the yield of mid. to he eheet one nole. three
nolee of nethyl Grignerd provided en edequete exceee. niece
only two nolee were required th'eoretioelly.

the fleet oonteining the ecid coupler wee fitted with e
'gooee-nech‘ gleee tend end e condeneer net for dietilletion.
the Grignerd reagent wee edded through e dropping funnel quite
repidly, in e etreen. fhere wee only e elight reection end
the ether hegen te dietil. lther wee renoved hy dietilletioe
until the reection nixtnre wee eyrupy end the tenpereture hed
rim: to 6096. met one end one-half litere of ether were
collected. l‘ive hundred nillilitere' ef enhydroee heneene were
edded to the reeidne end the eelntion refluxed at 65-70%. for
four heure. he addition of Brignerd reagent. dietilletion of
ether. end reflux wee conpleted in e dey. (Hote- it wee cog-
geeted by Dr. G. 1.. Goerner of thie laboratory thet it night he

eefer end were convenient to exit! the benzene to the ecid eon-
plex prior to the edditiee of the Grignerd reegent. then,

after addition of the Orignerd reegent. eel-rent nny he dietilled
off until the proper tenperetnre ie reeched.)

6. lecleticn of the Carbinol

'flie complex mixture wee hydrolyeod with ice end cuffieient
25% euli‘eric ecid to dieeelve the halo eelte. About eeven hen-
dred nillilitere ef ecid were required.

After the unuel eeparetien end extrectioe of the equeoue
leyer with heneene. the oonhined extrecte were weehed with weter.
5% sodium lvdrexide. water. end dried over enhydroue eodiun eul~
fete. leutrelieetion of the elkeli extr'ect yielded e enell enoent
of dinethyl ethyl eeetic ecid. i'he beneene wee renoved by dietil-
lotion end the reeidue wee frectieneted hy neene of e Ioneke
eelunn. I[he yield of eerhinol wee 25% of theoreticel. bneed on
the tertiery enyl chloride.

1.2. - 63-61%. /20en.
nag .- 1.19413
11. condeneeticne

fleet of the eerlier werhere in thie leheretcry who condeneed
tertiary alcohols with phenol need either of two nethode. In
the firet procedure devieed by lueton end heieh (10). the eloehol
end phenol were dieeolved in petrolewn ether, end the eluninun
chloride wee edded in portion. Ihe eeecnd procedure developed
by Kenton end nedriek (n), ccneieted ef euepending the nl-innn
ehloride in petroleun other end edding e eolution of phenol end

13.

cerhinel in potroleun other dropwieo fro-Le dropping funnel.
etteupte to oondeneo phenol with the certinole under eon-
eideretion, by the nothed of lneton end Reich (10). geve negep
tive roeulto. the phenol being recovered quentitetively end the
elcohol loot through docenpeeition by eluniuun chloride.

The nethod developed hy letordnhl (25) to effect condolen-
tion of one oocondery eloohole with phenol. end leter need by
later end neiey (1h) in the oendoneetion ef tertinry eieoheie.
proved eucoeeoful. In thie uethed the ole-dune chloride wee
edded to e oolutien of phenol in the certdnel, no eelvont being
need.

A. 2.}.i-Iriletyl 2-Penteno1 end Phenol

A one liter. three-necked fleck wee fitted with e glycerine—
cooled uncheuicel otirrcr end e two-necked nddition tube beering
e celciun chloride tube end e thereoneter reeehing to the hotten
of the fleet. the third neck wee cloeed with e well-rolled cork.

Ewe uolee (188 green) of phenol were dieeolved in one nole
(130 green) of the eerhinel. rhe oolution wee pieced in the fleck
end .S‘Iolo (67 green) of eluninun chloride wee edded in portiono.
Initiel edditiono were of the order of two green. The tapereture
rooe te 35%. elnoet ieeediateiyaed wee neinteinod by control-
ling the rete of odditien.

.efter cone ole-inunrchloride wee edded, the eelution bocene
light brown. end with continued eddition of the cetelyet. it
turned deep purple. Only teen eneunte of hydreehierie ecid
were evolved no roveeled by tooting with ellonie pdeeed et the

outlet.

111.

After twoothirdo of the eluninun chloride hed been edded.
the reection nizture hooeno quite vioooue. neceeoitnting olowor
oddition of cntelyot. do etirring contined. nfter n portion
of nluninun chloride wae edded. the nixture beeeee eeheiderauy
leoe vioeouo no the oetnlyot wee incorpereted into the reection
nixture end given the opportunity to reeet. i'ho tine required
for cenplete oddition weo eoven houro.

lent wee then epplied by none of e weter both end n ton-
pornturo of ho‘c. weo uinteinod {or two houro. During thie tine.
greeter qunntitioo of hydrochloric ‘eoid were evolved then were
cheerved in the oerlior etegoe of the reection. After heeting,
the reection littero wee n dork erQngo color.

After etending overnight, the nixture wee ”drowned hy
pouring it elowly on erected ice. with etirring. the orgenio
leyer wee eepernted end the equeoue leyer eutrncted twice with
105 of ite volune of ether. The ether entrncto were-added to the
phenolic leyer end the oolution wnehod with n 5‘ eolution of
oodiun hicnrhcnete end then with weter. the otherenl eclution
wee dried over enhydroue eediun oulfete.

the other one renovod by dietilletice end the rooidno free-
tionntod through e 10 inch Vigreur oolunn hoering n 12 no. cide-
ern. be wide eidoern helped prevent plugging due to cryetelli-
notion. do n further eid in freed‘imetien, the colon wee
heeted hy neeno of e coil of Ghronel wire.

The following frectiene were ehteined free 1.25 neleo of

eerbinol t

15 .

i. so-120°o./12 no. - 13o grene - yheaei
n. 120-15o°c./12 nu. — 15 green - nixture
m. 150-115’0J12 nu. - 1235 green - elhyl phenol
iv. reeidue - lo grene
rrnction III wee refrectioneted neverel tinee end the
following freotione token:
I. 165.161°c./iz en. - to green
11. 167-i7o°d./12 an. - 1n gran
m. 110-172°c./12 nu. - 2h gra-
i'he totel weight of neteriel in theee freetione wee 138
grene end .y he coneidored no the crude elkyl phenol, e yield of
535 of the theoretioel.
i'ho crude neteriel wee purified by recryetellientien free
home. It wee ertrenely eoluhle in the eolvent et rcen teupere—
turo end eryotnllioetion wee eccenpliohed hy dieoclving the phenol
in ebout three nillilietero of eolvent per gren of oolid end ellew-
ing it to eryotelliee in the icebox. i'here wno only npprorinetely
30% recovery. eo thet it wee neoeeeery to coneentrete the nether
liquor to ehcut helf ite volune to teke e eeoond crop of cryetele.
A third crop wee recovered in the eene uenner. Producte heving ep-
prorinetely the eeno nelting point were continod end rooryotel-
lined in the eeno feohionu oraduaiiy. two eeie frectione which
were indicetod in the firet cryotelliention. were ieoletod: one
nelting at ebcut 75°c. end the ether nt ateet ioo-uo'c. he the
producte booeno purer. nore eolvent wee required. end in the leet
etegee of purifieetion. ehout lo nillilitere of hounne per gren

16.

of eolid wee need with the lower nelting product. end ebont 20
nillilitere per gran for the high nolting product. In n11. n
totel of eeveety oryetellieetione wire required to eepnrete the
two produete which omtellieed he tiny white needlee.
I. n. p. 80-81%. Yield «- 28 create

11. e.p. Ila-119%. Yield - 6 crane
beetle: 1 ie 2.2, 3—trteethy1-3(pera mun) Mlpehtehe
end fraction II, the nornelly expected produt, ie 2,},3-tri-
nethylo2(pare lgdrony) phenylpentene.

Bone neteriel neltihg below pure 1 remained end m u-
dou‘btedly inpnre I which would he terther purified by edditionel
cryetellizetione. Swenty—five grene of neteriel nelting in the
renge of 65-75%. remained.

Materiel which boiled below 165°o./15 ee. oh redietilletion
of the elkyl phenol (motion. wee edded to fraction II. boiling
et 120:15o°o./12 II. and the eeetthed treettoh rediiatilled eeverel
tinee to give:

I. 123.13o°a./12 en. - 11.5 gene
11. 155-165°c./12 m. - 5 ere-e
Ireotion I wee extrneted five tinee with 500 nillilitere of boil-
. in; weter. The nintnre wee filtered hot. the ineolnhle oil re-
mining en the peper. being returned to the fleet: fer the next
extreotion. On cooling, the wnter eolntion. tine needlee ed’
tertiery bntyl phenol eonereted. he tertiery bntyl phenol wee

ieoleted in very enell qnentitiee. only ten grene being recovered.

17.

D. 24213-i'rinetq1-2Pentenol end Phenol
The procedure need wee identioel to thet need in Pert i.
he freotione ieoleted were:
1. eo-120°c.l13 ee. Yield - 130 (re-e - Phenol
xx. 120-15006J13 en. Yield - 20 grnne - nintnre
Ill. 150-175°o./13 ee. uem - mo crane - elkyl phehe1
IV. reeidee 12 crene
heotion Ill wee redietilled eeverel tinee end the following tree-
tione teken:
x. 16u.16e°c./13 nn. - 13 green
11. 166-169°c. [13 en. - 95 gene
:11. 169-111°o.I13 ee. .- 21 grene
hoet of thie neteriel one over in e feirly nerrow boiling renge
end the whole could he meidered the crude elkyl phenol. i'he
weight of product ohteined. ee indioeted ehewe, wee 132 mu. e
yield e! 51% of the crude elhyl phenol, heeed‘on 1.25 nolee of
the eerhinel. . ‘
'fhe crude neteriel wee reoryetellieed ee deeorihed in Pert
A. end two predate were ohteined ee tiny white eryetele free
honene.
1. mp. 79-80%. Yield - 3i crene
n. n.p. 113-11%. Yield - 8.5 gee-e
”notion I in the nor-n1 product. 2,2,3-Trinethyl-Mpere hydro”)
phwlpeeteee. end freotioe n. the reerrenged product. 2.3.3,-
trinethyl-2(pere hydro”) phenylpentene.

18.

An in Port A. there wee 25 green left which nelted none-
whet lower then pure 1. which could he fnrther purified by eddi-
tionel reoryetellieeticne.

ledietilletiee ef the ellql phenol freotien ceve e enell
quentity of lower boiling neteriel which wee edded to the
120450" freetien. which wee then redietilled eeverel tinee to
give two very inpure frectione.

x. manure/13 ee. - 12 gene
11. “3.165%. [13 ee. - 12 gene
heeticn i wee entreeted five tieee with 500 nillilitere of
boiling weter to chtein three we of tertiery betyl fiencl.
111 much of derivetivee_

A. o( hatnlurethenee

he nethed of trench end Uirtel (26) wee need. fo one (I'll
ef the elkyl phenol wee edded one nilliliter of A nephthyl
ieccyenete. A few drepe of en ether eclntice cf trinethyl enine
were edded to cetelyee the reection. i'he reection nintnre. pre—
tected free neietnre hy e oelciun chleride tube. wee wereed en
the eteee-beth for cne-helf hour. 0e cooling. it eelidified.
The eelid wee entreoted eeverel tinee with boiling licroin
(h.p. 90—120‘0.). in twenty nilliliter portione. end the ineol-
nhle neteriel filtered off. he ck nephyhlnrethene cryetellieed
no white pletee end wee reoryetellieed three tinee free ehcut
twenty-five nillilitere ef ligroin to e conetent nelting point.

I. L: Dinitrobenecetee

he pyridine nethed ef preperetien wee token free Shriner
end heen (27). the product oryetellieed in fine. white needlee

19.

free elcohol end wee recryetellined twice to e conetent nelt-
in: point.

c. leneoetee

fhe eene nethod wee need ee in the preperetien of the
dinitrcheneoetee. fhe product cryetellieed either on white
needlee or clnetern fren dilnte elcohel.

Oiling occurred when the hot elccholic eolution wee diluted
with weter to the proper extent end then ellowed to cool. 'l‘he
difficulty wee evereene by diluting n cold elcohelic eelntien of
the product with weter te incipient cloudineee. he clendineee
wee diecherced with e drop of elcohcl end the teeeeete eryetel-
lined in the ice-hon. If oiling reeulted. edditienel elcchcl
wee edded to olerify the eelntion.

The heneoete of tertiery hutyl phenol cryetellieed eeeily
ee white pletee. free eloohol or dilute elcohol.

nixed nelting pointe‘ ef the ccrreepondin‘ coupounde lee-
leted fron eech cendeneetion. end of their derivetivee. ehowed
no depreeeion. Ilei-t hutyl phenol end ite hennoete checked with
thet which won reported by llueten end leieh (1o).

Anelnin

‘i'he 0R nephthyl urethenee were euelyeed for nitrogen by
the eenionicrc [Jeldehl nethod (2e). eeeplee of fifty te einty
nilligrene were need. end the e-onie evolved wee eheorhed in
us horic ecid end titreted with 1/100 hydrochloric ecid.

20.

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21.

1918008310!

Severe]. theorieo heve heon propoeed in en ettenpt to explein
the necheni- ef elkyletion of mnetic nuclei with elcohole in
the proeence of dehydreting cetelyeto. hut no one theory oeone
conplotely eetiofeetory. fheeo theoriee hove been thoroughly
dieoueeed hy previoue workere in thie lehoretcry end need only be
nontioned here.

luetcn end oe-workere hed cheerved in their eerly inveetige-
tione thet the elphe cerhon eton of en elochol not be under
otrein in order to creete en ective hydrcxyl group. fhie genereli-
netion, ee proven experinontelly, helde tree for eronetic elcohcle
and uneeturntod eliphetic elcoholo.

Setureted eliphetio elcohole exhibit verying degreeo cf
eotivity, depending on their etruoture. fertiery elcohole hove
the noet ective hydroxyl group end condenee neet reedily; eecondery
elcoholo condenee loeo reedily: while priest: elcohole which ere
loot ecidic. do not condenee et ell under erdinery conditione.

foukemnik end lenerove (29) propoeed thet en odditien con-
pound of the type nelzon end 361 were firet forned. lho other
deccepoeed to the olefin which then reected with Whlcric ecid
te fore en elkyl halide. Thee. in the preeenee ef eneeee eluninun
chloride end on eronetic ring col-pound, ell the couponente necee-
eery for e typicel friedel-Orefte type reection ere preeent.

A dehydretion nechenion wee propoeed by Helene end down (30)
to enplein the elkyletien cf benoene by elcohole. i'he elcchol
wee oeid to he dehydreted firet, followed hy oddition of the ring

ncleuo to give the elkyl beneene.

22.

In oiniler type elhyletione. lchreel end liederl (31) end
weleh end Dreke (32) eloe propoeed the delqdretion nechenion.

hoerrengonent of elkyl phenyl ethere heo teen propeeed ee
e poeoihle lechenien. oince it in known thet ouch reerreneglonto
occur to give good yielde of enhn phonole (33).

In thie lehcretery. work carried out by Evert (BM in 1938
led to the propoeel thet eddition conpounde of eluninen chloride.
the elcchol. end phenol ere firet for-ed. hie conplon neleculo
being unetehle. reerrengee to e nore etehle. configuretion hy
eplitting out eluinun chloride end weter to yield the elhyl
phenol.

i'heee necheniene ell ettenpt to onplein the fcneticn of the
ellql phenole. hut do not onplein the reerrengonont which epper-
ontly occurred during condonoetion of the elcehole need in thie
inventignticn.

In eech condeneeticn. two preducte were ieeleted. fhe con-
poundo ehteieee in eeeh once. which nolted et 11s-119°c. were
identieel ee ehown by their nixed nelting point end thet of their
derivetivee. ‘l'he eene wee true.of the ccnpoundo nelting et 79-60%.
end 80.31%. in further evidence. the enelyoio of the euhe
nephthyl urethenee’ of ell four conpeunde ehewee thee to he ieeneric.

e reeeoneble enpleneticn of thie phenoIene ney be developed.
beeed on the work of beta end Ampere (35). Yhoy etudied the
fregnentetien of elcohole hy condoning highly brenohed eloohole
with benzene. elhyl henoenee of lower neleculer weight were he-

leted end it wee ehown thet only by reerrengonont end fieeicn ef

the originel eleohol could theee prodnoto he for-ed. e.nechenion
wee propoeed in which.en initiel reection'hetweon elnninnn chlorb
ide end the elcohol yielded e couple: nolecule which.deconpoeed
to produce en.elkyl notice or cerhcniun inn. Sole of the entice
which failed to condenee nornelly could forn.the elkyl helide or
it could loee e proton to fore the elkone. The elkone could then
odd e proton to give two cerhonien ione in equilibriun. one of
which hed n tendency to reerrunge to e tortiery butyl configure,
ticn. They furflher prcpcoed thet e tertiery hutyi group edjep
cent to e poeitive cerhon er en nneetureted cerhon eete up n con-
dition fevorehle to chein rupture. In thie nenner. the iooletion
of low noleculer weight elkyl heneonee were very eetiefectorily
expleined.

Bnheequent inveetigntione hy Berrett (2h) end VenDyko (6)
oupperted thie theory.

Applied to the elooholo under ccneideretion. the nechnniol
propoeed ehove would lend to the following eeriee of reectionet

tor 2.1.}:trinetgyl-2-pentenol

 

H .—
98 ~03 c- §~;o - e101}
CE —0 + £1013 —& C ‘6 -c
6
H ‘, .,
O “‘0 0" "'O -+ 3011 01

01

23.

In nornnl elkyletione. the cerhoniun ion will reect with

phenol with the lone of e proton no shown by Price (36)

H
.§: 0 .
030+. ago‘;§:g __> Hom‘j‘fr}
. a .

c
d

J

rho portion which feile to condense nornellyun thie ceoe prec-
ticelly ell of it) would have n tendency to reerrenge. ee followe:
o— * _——-> o— «c
o - —-c 6 o - +
d

It night he ceneidered thet the netlvl group nigretee between
the two force. with e greeter tendency to fern the tertiery hetyh
configureticn with ite lower energy level end greeter etehility.

then eech cerhoniun ion reecte with phenol to fore the
elkyl phenol.

leoletion of tertiery butyl phenol wee not unexpected in view
of the findinge of heeton end coworkere in the benzene condenee-
tione with bunched elcohole. Undoubtedly. reerrengenont to the
tertiery butyl configuretion followed hy eoieeicn of the noloculo
led to fornetion of the tertiery butyl entice which condoneed with
phenol.

i'he eene eeriee of reectiene nay he epplied to the condenoe-
ticn of 2.2.3-trinothyl-3—pcntencl. fhe fect thet the two producto
iocleted were identicel to theee ohteieed in the condeneetion of
2.3.3—trinethyl-2-pentenel cerrehcretee the belief thet en equili-

briun enieto between the two eerboniun iono. the feet thet

25.

reerrengeuent new occur with 2.2.3 trinethyl 3-pentenol wee
ehown hr Lenghlin in en onpnhliehed reeeeroh (37).On.dehydretion
of the eloohol. the nor-e1 product and e leeeer enoont of the
reerrengod prodnot wee ohteined.

The structure eoeignod to eech of the compounde ieoleted
wee heeed on the neohenien of reection. Since the tertiery
hetyl configuration: at tho Ioet etahlo. the produt coma...“ in
lerger quentitiee would he 2,2,3-trinethyl—3 (pore may)
phenyleethano end the other product. no eupported by thie theory.
would he 2,},3-trinethylo2 (pm hydro”) phenylnethone.

The pere poeitien wee eeeigned to the elkyl groqpe hr eeelocy.
In ell of the twentybei: tertiery nlkyl phenole whoee etrnotnree
heve heen prove-.hy eyntheeie in thie lebometory. the elhyi group

wee enhetituted pere to the hydroxyi group.

26.

SUNHARX

1. 2,3,3-trinethyl-2-pentnnol and 2,2,3—trinethwl-3-
pentenol were condensed'with phenol in the proeenoe of eta-inn-
chloride.

2. Zeoletion of 2,3,3—trinethyl-2 (Pere hydroxy) phenyl-
nethene and 2,2,3-trinethyl-3 (pare hydrory) phenylnothene
from eech oondenention furniehee etrong evidence of reerrence-
aunt of both elooholo.

I 3. Iregnentetien of the eloohole to e eli‘ht degree wee
prone by ieoletien of enell ment- of tertiery hutyl phenol

in eech oeee.

9.

10.

11.

12.

13e

1h.

15.

27.

BIBLIOGRAPHY

heton, l. 6. end B. L. Onile ....... J. in. Chem. Soc"
51.59 (1939)

Lndereon, J. I ...................... ILS. l'heeie. liohi-
gen Stete college

(1935)

Snyder. L ........................... 3.3. heeie, liohi-
cell stete college

(1938)

m‘. Io ‘ eeeeeeeeeeeeeeeeeeeeeeeeee none M1.. “1&1-

Stete college
832)

Ieloy. O. I... ...................... PhD. i'heeie. lliohi-
pn Stete college
(1932)

'enDyke. O. I ....................... PhD. fleeie. liohi-
Btete college

19“)

trenelein. G. ileninuohlorid in der Mullen cheeie.
Verleg ehenie Gull, Berlin, 1930

them. 0. A. Alanine- Chloride in may cheeietg.
einhold. low York. 1 l.

Intern-1k. I. end 2. leeerove....J. Gen Ghee. U. 8. 3.

n. 6. $61 (rags) o. d.
30. “3 (1936
Ineton. B. 0., end I. Y. leieh.....J. AI. Chen. soon 58.
‘‘39 (1936)
mm. H. 0.. m 0. '0 lodriok...3. “e nae 3°C. 59o
_ 2002 (1937)

Knoton. R. 0., R. L. Guile. J. J. Bouleti. V. I. 'eeoon
J. Org. on... 6. 252

(1911’
London, I. I ................... .JLB. i'heeie. Iiohigen
Btete college (1938)
heton. R. 6.. end 0. R. Heloy....l. AI. 611-. 8a.. 6‘1
2555 (19“)

chat. I... end a. I. Jenee.......J. 1-. am. am” 3k
170 (1912)

16.
17.
1e.
19.
20.
21.

22.

23.

2h.

25.

26.

28.

29.

28.

Pieter. L. P ...... .... rinente in
eet e

 

Mo
3d.. Pert II. P. 312.

Gil-en. 3...... ...... ..J. in. on... Soo.. us, 150 (1923)

Norton. 1'. 1.. end B. B. leee...J. in. Chen. 8oo.. 58.
21”? (1936)

whit-ore. LG .. end D. E. Bederteohor...J. An. Ghee.
306:. '55. 1559 (1933)

Grinerd. L. .................. .Bnll. Soo. chin. l‘renee.
31. 751 (190h)
Deiloy. D. L ..... . .............. NJ. heeie. Iiohicen

Btete college (19“)

Eileen. L. Organ: getheeie. John liley I done. l.!..
' 1932. Collective Vol.1

1’. 138.

Gillen. L. 0525;: mtheeie. John Wiley 6 Bone. LL.
1932. Collective Vol. 1

1’- 353.

Barrett. 1. 1' .......... ... ...... H.8. fheeio. liohigen
Itete 0.11.;- (19:12)

Deterdehl. II. I...” ............ ILS. neeie. liohigen
Stete college (19140)

lrenoh. I. 3.. end i. I. Virtel..J. An. Ghee. Soon ha.
1736 (1926)

Bhriner. 1.1... end 1.0.heon.1dentifioetion of Dr-
eio Oogmgde. John
Wiley 6 Sone. H. Y..
led 3d. 1940. P. 138.

a. t. o. A. 0. 2h. 97 (19M)

i'nhervenih. 1.. end I. firemen}. Gen. Chen. 0833. 7.
333%937) c4. 31. 5778

hotenne. J. 1.. end I. J. “trend. in. chen. 8013.. 59.
. 370 (1936)

floored. I. 3., end liederl. J. 3.3. 1-. Chen. 3oo.. 57
2525 (1935)

'CICh. Le no. N I. no Dm.....3. be ch... 300.. 56.
3713 (193‘)

33.

3h.

35.

36o

29.

hith. B. A ...................... J. in. on... Coo" 56.
3718 (193")

Evert. n. n ...................... x.3. outwit. liohisin
Stete 0.11.5. (1938)

heton. R. 0.. end J. Lonepere...J. Or . 6h-.. 9. 1101
(19th?

Price. 0. 0...... ................ Ghee. new. 29. 2th (19M)

ihitnore. I. 6 ................... J. in. Chen. 800.. 5”.

3272. (1932)

  

Qt... 2.332

  
 

size-(PA. . m... Futit... 1-. .
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