III

100
699

 

THS_

CONDENSATION OF SOME TERTIARY
OCTANOLS WITH PHENOL IN
THE PRESENCE
OF ALUMINUM CHLORIDE

Thesis for the Degree of M. 3,
James Edward Anderson

I936

 

 

 

 

 

 

 

 

 

 

1"“ .I

CONDEISATION OF SOME
TERTIARY OCTANOLS WITH
PHENOL IN THE PRESENCE

OF ALUMINUM CHLORIDE

A The“ e

Suhaitted to the Faculty of Michigan
State College of Agriculture and Applied
Science in partial fulfillmmt or the re-

quirement. for the meter of Science Dear”

By

James Edward Anderson

August 1936

ACKNOWLEDGEMENT

The author gratemlly acknowledges
hie indebtedness to Dr. R. C. Huston
for his advice and guidance during

the pertomnee or an: work.

331-599

TABLE OF Cflislmflg

Page
maxim l.
I. Condensatiem with Armada 516011018 1.
{5m * 6.
II. Condensation with Phenols 6.
Summary 10.
wgzsmmmz. ‘ 11.
1. Prepare time of Alcohol: 1.1.
A. Preparation of methyl ethyl n-butyl 1-1.
earhiml
Grignurd method 11.
B. Preparation at methyl ethyl tert-
butyl carbine). l3.
Grignard method ‘ 13.
Reaction of WWI eonyl chloride
nth ethyl and methyl madam
halide». 14.
Fineoolene reaction 21th ethyl
magnesium bromide 15.
II. Condensation: 16.
is. Methyl ethyl unbutyl eerbinol and
puma}. 170
Table of Rm“ 1?.
3. methyl ethyl tart-Duty}. mutual and
phenol 18.
Table of Results 18.

c. Hethyl ethyl n-bntyl carbine). and
bang”. 22.

III. Preparation of Derimtitee
1.. .1le and hwy}. eater:
Table of Results
B. adiuphthylurethem
Table at Reunite

IV. Proof of the structure or methyl ethyl
gouty). W W name

THEERETI CAL A?! D WQWLEY

BIBLIO (meek?

19c
19.

80.
a.

81.

fl.

HI SI'ORIGAL

, Condensation of Alcohole and Benzenee

A reviel of condensation reactions brought
about by euch eatelyete ae 3.80., we... P305, 211013.
11501.. Pelg, etc.. hue already been covered by previoue
eorkere in thie laboratory (1).

However. eince thie laboratory pioneered in
the uee of aluminum chloride ee a condensing agent and
eince the problem or this theeie ie a continuation or
the research in the use or aluminum chloride no a
condensing agent, it ie well to review the foundation
work done in this field. The eondeneetione involved
reacticne ct alechole eith either benzene or phenol
or their homologue in the preeence or aluminum chlo-
ride as a catalyet. The aleohole included arueetio,
aliphatic and mixed aromatic aliphatic once.

Aluminum chloride hee been used as e dehy-
drating agent in organic chemistry by More and Neith,
Shell and Seer, Wane. Greebe. Joubert. Frankforter and
Kritcheneky. Frenti'orter and chatnmr, and others.

Hanover, Huston and Friednenn present the
tint recorded condensation of aromatic alcohole end
armatic ouncunda in the prom» or aluminum ”chloride

(8):

When benzyl alcohol wee mixed with a little
more than ite molecular equivalent of benzene, and
the mixture treated with anhydroue 11013, a vigoroue
reaction resulted. with heat and no). being. liberated
ad the mixture becoming dark and peety.

MCI;

O‘HacfiaOH 4 0‘3‘ -----! censwzc‘na 0 ago

The yields of the producte are greatly effected
by the enounte or the reagente used and by the temperature
at which the reaction ie carried out. In one experiment
where the tupmture eae kept beloe 35' and e large
aceee (5.2 nolee) of benzene used, the diphenylnethene
almost equalled in weight the beneyl alcohol used.

This hietorioel preparation is essentially the
method need in the condeneatione today.

Huston and Friedman continued their work. con-
dancing eocondary aromatic alcohole with benzene (3).
Mixed aliphatic-aromatic secondary alcohols and true
aromatic eecondary alcohole condensed euccaesrully. Thue
benzhydrol gave e good yield of triphenyl methane.

mu... . a... fltcbasmca

Hueton and Sager (4) attempted to condenee
the primary alcohol, phenyl ethyl alcohol. with benzene

in the presence of A1013. The resulte were negative

ee for co the production or eymetrieal diphenyl
ethane wee concerned.

merimente thue tar indicated that only
those alcohols having the hydroxyl attached to a
carbon adjacent to a ring carbon condemned

This generalisation was eubetantiatod
when the acne workere found that the primary alcohcle,
methyl, emyl. propyl, n-butyl end iced-owl. and the
secondary alcohol, inc-prepyly failed to condense with
home '

The possibility of condensing the hydroxyl
attached to a carbon adjacent to an unsaturated group
other than the benzene ring was next considered.»

Huston and Sager (4) condensed allyl alcohol
with benzene in the presence or 111le8 at room tmpmture .
Ally! benzene was the principal products

wrencazos e “one .3121, (:nancn-nngcan5

Huston and Gootemoct (5) showed that incon-
deneation reactions with benzene in the presence of
£1613 the cycloelkyl carbinole show a progreeeiwe in-
creaee in activity as the number or carbon stone or the‘
ring is reduced from six to four, or as the strain on

the carbonyl carbon is increased.

/\

 

 

 

 

Huston and Wilsey (a) round that 1.1 di-
phenyl ethyl carbinol reacted with benzene to give
dehydration instead of condensation. l,l diphenyl
-l-prcpene was the product obtained.

Likewise. Huston and Brads]. (7) and Huston
and Haeonber (8) round that neither diaryl-elkyl
carbinols nor dielkyl-aryl carbinols condensed with
aluminum chloride. Instead, dehydration occurred.
Huston and For (1) condensed tort-butyl alcohol. tort-
erl alcohol, dinetbyl n-propyl carbinel and dinethyl
ice-propyl carbinol with banners to obtain tert~buty1
benzene. tert-enyl benzene, dinethyl appropyl phenyl
methane and dimethyl lee-propyl phony! nethane.

Huston and Binder (9) condensed dinethyl :-
bntyl carbincl. dimethyl iso-bnty‘l carbine)... dimethyl
see-bntyl ca rbinel . dinethyl tart-butyl carbinol . methyl
ethyl n-prepyl earbinol . tri ethyl carbinol and nethyl
ethyl ice-propyl carbinol with buzene in the presence
of aluminum chloride. Good yields of the tertiary alkyl
benzenes were obtained.

Huston and Hseih (10) condensed secondary
and tertiary aliphatic alcohols with benzene, obtaining
the aim benzenes. The tertiary alcohols gave the best
results and were condensed also with toluene , n-xylene.
n-cresyl nethyl other end aniscle.

Huston and Sculati (ll) condensed tertiary
hcptanols with benzene in the presence at aluminum
chloride. Good yields of the tertiary alkyl benzenes
were obtained.

Tsakernnik (12) criticized Huston and co-
workers ror concluding that only alcohols with the OH
group closely situated to a double bond are capable of
teeming condensation products with emetic hydrocarbons
in the presence of anhydrous aluminum chloride, and that
the condensation is brought about by a cleavage of water.
i'sukmsnit round that benzene and toluene are easily
slkyleted by tertiary alcohols. Similar results we
obtained by a condensation of the secondary alcohol, iso-
prepyl alcohol. with became. (Note-- This research hes
already been carried at by Huston and co-workers with
similar results, with the exception of the ice-prowl
alcohol research. Isohpropyl alcohol did not condense
with benzene.) _

Using tort-any]. alcohol. ‘i'snkertanih explains

the condensation with benzene es tollcws:

l. MOE e A1015 .___, LlClgOm e HO].
8. 1163101! h; 65H“) e AlClgOH
3. 05310 0 Hal _....__., Anal

4. A301 e 0.3. ____, Amcfifls + £01

The last reaction is a typical Friedel and
Crafts reaction. Equation 1 involves the replacement
or the difficultly replaceable hydrogen of the hydrozyl
of e tertiary alcohol which is questionable. .

Keshtancv (l3) shwed that aluminum chloride
end thelliun chloride could be used interchangeably in
bringing about the condensation of an alkyl chloride

with benzene.

Smmnery

In general we an conclude fro. the work thus
far that elcchols in which the hydroxyl group is ectiv—
eted, condense with the benzene and its hcmclcgues in
the presence of anhydrous slmnun chloride. The hydro-
xyl my be activated because the elphe carbon is double
bonded or is e umber c: the benzene or cycle-mane
ring. It my be activated by being etteched to e tert-
iary. aliphatic carbon or in some cases to a secondary

carbon 83%

Condensation of Alcohols with Phenols
A. review or the various methods or propel-leg
elkyl phenols is given by Reich (10). These need not
be repeated here. However, since this research is e
continuation or the eondenseticn of aromatic and eli-

phatic eloohols with phenol in the presence of alumina:

fluoride, the work in this field is reviewed.

The condensation of benzyl alcohol and phenols
has boon accomplished by the use of zinc. sulphuric acid.
acetic acid and rise chloride (14).' Zinc and zinc chica-
ride have also been used in the condensation of simple
aliphatic alcohols with phenols.

Although Jim and Wcith (16) found that
aluminum chloride reacted with phenol to give e 10% to
113$ yield of diphenyl ether whm the mixture is heated
under e reflux condenser, Huston and others (14) find
that the diphenyl ether is not tamed to an appreciable
extent it the phenol is suspended in petroleum etbr and
the temperature kept below 30'.

In the condensation of phenols and alcohols
in this laboratory the Huston method was used (14); when
e mixture of one molecular equivalent or benzyl alcohol
and 1.). equivalents of phmol was suspended in petroleu-
ether and treated with .5 nolecular equivalent or anhydro-
us elunim chloride, a vigorous reaction occurred. By
decomposition of the dark-red, intermediate product. there
as obtained e good yield (43-45%) of p-bensylphescl.

macaw + case 31“» enumerate
The yield of p-bennylphenol was not increased
by the use of a full molecular equivalent of aluminum
chloride. When petrolm ethc was omitted the reaction

started more slowly. Then the temperature rose rapid-
ly to 65'. The yield of p-bennylphenol was reduced.
Carbon disulphide can be used in place or petroleun
etm r. ‘ _

The condensation of banyl alcohol with
enieele and phuetole took place even more readily,
with the formation or the methyl and ethyl others or
Maul-P113341”-

Using the same technique. Hinton, Lewis and
Grctaut (lo) condensed nethyl phenyl carbinol. ethyl
phenyl onbinol and bushydrol with phmol. The
following results were obtained:

me “Be
Hethyl phenyl carbine). p-Hydrezy 1,1 diphnyl ethane

m to so; yield

0585 $03 + 6535M -——-—9 0635 (:84- CQH‘OH
r ' n

0235 on:

Ethyl phenyl earbinol p-Hydrcxy 1.1 diphenyl propane
87% to 30% yield

(0535}30'3011 + caasoa --—---+ (canauca-cexgoa
Whydrol p—Hydrcry triphenyl methem
«3% yield

 

 

Boston and Strickler (1'!) condensed phuyl
prepyl oerbinol end ea-ohloro-bntyl henzme with phmol
to yield chiefly 4(oq—phenyl-hutyl) phenol.

cons 9:03 + 063503 -—-—--; can5 93.06am
0337 0:37

c635 9110). + (4335011 _........... 0635 (13.0611403

3357 6337

This was further indication that the chloride
and alcohol act einilerly in the oondeneetion reaction.

Huston, Swerthout and Warden. (18) bemlotod
o-ueeol by condensing benzyl alcohol with metal in
the pretence of aluminum chloride. The main product
was 2 methyl 4 benzyl phenol. analler amount- or 8
nthyl 6 W1 phmol and 8 nemyl 4,6 6.1me phenol
were formed.

Boston and Lille (1!) eondenled pooreeol and
bowl alcohol with ale-inn chloride. A 35% yield of
aibenzyl 4 methyl phenol. and e 36% yield of d nethyl
aid dibm phenol were obtained.

Boston and Hon! (:0) benzylated n-ereeol
by the condensation reaetion. 3 methyl 4 busy]. phenol
and 5 methyl 4.6 dibenzyl phenol were obtained.

Huston end Nemnn (81) reported the eon-
deneetion or ally]. alcohol with phenol in 1933.

Huston and Reich (:2) found that the primary
aliphatic alcohols, ethyl, prepyl and butyl, did not
condense with phenol in the presence or aluminum chlo-
ride, Ice—propyl alcohol reacted with phenol to give
an unidentified product. Seo-hutyl alcohol did not
”act. Tertiary aliphatic alcohols were found to con-
dense readily with phdiol to give para alkyl phenols.
The structure or these phenols was proved by condensing
the alcohol with hens”. The alkyl benseno was nitrated,
reduced. dissatised and hydrolysed to give the phenol.
The alkylnitrehcnsenewas oxidised ina Cariusbcub
to p-nitrebensoic acid. In these condensation; a
technique similar to that employed in the condensation
of armatie alcohols and phemls was used.

Summary

When the hydrerl group or an alcohol is
activated by having the alpha carbon attached to a double
bond or be a umber or the benzene ring, condensation with
phenol or its homologucs in the presence of alanine]: chlo-
ride occurs. When the hydronl group is attached to a
tertiary carbon or an aliphatic alcohol condensation occurs;
then attached to a primary aliphatic carbon no condensation
occurs; when attached to a secondary aliphatic carbon pro-

hably no condensation occurs.

 

 

11

W1 Ethyl Ila-Duty} Curblnol

methyl ethyl nnhutyl carbinol was prepared
by Whime‘e modification of the Grignard reaction (23).
In a three-liter, three—necked, round-hound flask.
fithd with an efficient stirrer. reflux condensed" and
dropping tunnel. are placed first a few small crystals
of iodine and than 98 arms“ moles) of fresh, dry
main tunings. The bottm or the flash is warmed
with a small name until the iodine commas to vapor-
ins. and. is then allowed to cool while the nabutyl
hrtmide is being weighed out. 30 on. of a mixture or
4 moles of the halide and coo c.c. or dry diethyl other
is added directly to the dry magnesium. After the reaction
has started and progressed for a few minutes. 200 cm. or
dry ”he is added directly to the reaction mixture. 475
he. of the above otherohalide solution is placed in the
dropping tunnel and added with stirring, not faster than
one drop per second. The minder of the halide-ether
solution is diluted with 300 me. or dry ether and added
at the same rate with stirring. The mixture is allaed
to reflux during the halide-ether addition. no external
cooling oeing applied. It is not necessary to heat the
mixture attm' the ether-halide solution has been added.
Stirring is continued for four hours. Let stand over
night.

12

To the n-butyl magnesia bromide in added a
nolntion or four moles of pure. dry methyl ethyl ketone
in on equal volume of anhydrono other. The procedure
is similar to that stated above for the preparation of
the 'Grignardreagent.

The magnesium smile: is decomposed in a tour-
liter beaker with ice and hydrochloric acid. The hydro-
lysed'product is extracted three times 1lith. other. The
ether extract ie'dried with e nixtnre of anhydrous potassium .
earbmte and calciun chloride. the alcohol is obtained by
treetionel distillation at reduced procure after the other
has been boiled err on the stem both. A mall pert or
the cot“). was redietilled at normal pressure, b.pt. - 160'
with no “dehydration occurring.

Riceesehn (24) gives the following constant”
3. Pt. - 163.9. lace/745 In" 64" - ctr/lo m; of - 0.34%,
D? - 0.3293; n); . 1.42735; yield - and.

The constants for the alcohol prepared in tun
work: B. Pt. - 189° —- lam/745.3 a... 55-115 in; a? - 1.4.273
(Lbbe anaemic); n£8 - maze-7c; yield - 61.5%“: 55$

(two tflfly)e

__ m Table of Rgnlte _w
T SoTvent n-Entyl Eagles-In lie ct H! et nabn

 

 

 

Ether ‘ bromide ketone carbinol
c; CL e: 11101. & m0].- E. “101: @e i __l

 

1. 3.250 the 4 so 4 233.3 4 517.5 61.5%
2,1250 543 c 98 4283.84 234 not

 

 

- 1,.

..IV al‘ lililclllllll.

Bothy]. Ethyl tort-Butyl Carblnol

Tort-butyl chloride was prepared tral.tert-
butyl alcohol and hydrochloric acid. The tertiary alkyl
magnesium chloridaa are more atahle compounds, more nut-
ahlo for roactlon.w1th the carbonyl group than the bromide.
or iodide: (26).

Methyl ethyl t-hutyl carbinol was prepa red in
a manner similar to methyl ethyl n-bn’cyl carbine]. (23).
The reaction was difficult to carry out because of the
colldlrlcatlon.or the Grlgnard compound. Approxrmately
one and one-half times as much other was head as In the
previous experiment. l.feI c.c. or ethyl bromide were
used to start the reaction. Higher tertiary Grignard
reagents are not suitable for syntheses which involve the
addition.or the Grlgnard reagent to the carbonyl group
of a ketcno or ester (26) (27). Hydrogen.hallde split:
or: fran.the tertiary alklehallde resulting 1n.olor1n
formation; The compound was tractionated under reduced
pronoun-e. balling at 55712 n. Dehydration occurred
very easily no that the alcohol could.not be distilled at
normal pressure. It was not found pouxbu to me the
alodhol of considerable unsaturated impurltlcl. The
inparo alcohol wan very unsatisfactory for condonoafilcn
with phenol. .A tarry mass was the principal product or

ouch condensation...

35...;

 

 

14

“Mable of Results

  
 

    
 
 

 

 

“on. w...“

 

 
   

 

301.11 y agne um i u
Ether Chloride , ketcne ‘ carbinol
c.c. 153: mol, m. moIL. gm. mol gnu Q
l. 2000 570 d 98 4 288.3 d 5 10%.
a. 2000 3'70 4. 98 4 288.3 4 o 11.8%
m M": #:r m

 

 

 

 

 

 

 

 

Methyl ethyl tert~bnty1 carbinol was «3180 131:8pr
by treating trimethyl acetyl chloride with equinolar quat-
itiea or methyl magnesimn iodide and ethyl mmei‘nn bro-
aide. The roller ins steps were involved: Pinacol hydrate (38)
was dehydrated and rearranged to form pinacolone when
boiled with concentrated 11.80., (29). The pinacolone was
converted to trimothyl acetio acid by treating Iith NeOB
and Br. (30). P013 was used to convert the acid to the
acyl chloride (31). 50 m. or triuthyl acetyl chloride
were obtained. Equimolar quantities of. ethyl magnesium
bromide and methyl nagneeim iodide tore prepared by
Whitmcre'e modification or the Grignar'd preparation (23).
These were added dropwise to e solution of the acyl chlo-
ride in an equal volume or other. The reaction mixture
Ice. stirred for four houre. let stand over night, hydroo’
lyzed with ice and acid, extracted with other, dried and
fractionated. A yield of 14 go. or 26% of the tertiary
alcohol was obtained. This product showed no maturation '
and gave a {pod condensation Iith phenol. : I

This octanol was also prepared by treating
pinscolele with an equimclcr quantity or ethyl magnesium
bromide (:52). Pinoccl hydrate was prepared as in the
previous manner (28). Pinscolone was prepared from the
pinacul hydrated”). nigh:- was prepared and added
as previously (23). 65 m. or the octanol was obtained
This tee a 63.35 yield. A oondenam' tube is inserted
in the vacuum distillation apparatus since the alcohol
must be distilled at love temperature to avoid dehydration
B. Pt. - 2472 no... 1497745 m.

Equations for the Three Liethoda Used

.1.
1. CM 0 He -——--> 0W
3' 6411ng ‘ “53'°°°°235 ———-+.Cfia“?m‘°cns
0439
a. czza'gmgBr-cans o 1130 MM“ “13"?53-0515
one 0439
Yield ~ 107%
II.

 

i. 2 cascocng, z: (830123 - Stcnam
”hie

2. (Hana: - guns): 9 Hon “(2130123 - 3(31312-5320
‘fig’ B H

3- ‘33‘3’2? * 53°33): ‘ Howe-'9 (nachccwcas
0 c
a

4.

6.

'7.

III.
1.

2.

3.

16

. HIGH 4|» 31'; ‘
$303000 (:33 e O 7 (330)300003

 

(H30)30COOH e P613“ (E30 )SCCO‘Cl

(350)306001 + hang: 0 man:

V

91 9:35
(Hamscgtmnfi ‘H3°)5CX§;M + MgBrCl
(H30)309m&gl + HOE ..—._; (336)30903 «a- H3103

me

Yield «- 26%

Preparation of pineaclone some as in II
. 9H-
mews» CH: '* came—a WWW
‘ ‘5235
<23- 9&-
(330)30003133: + HOE +4 (336)30903 + HQBrOH
6835 ’ ‘ can;

Yield 'P we“

Condensation

The two alcohols prepared were condensed

11th phenol. The Huston method or condmeetion with

A1013 wasnaed (2). Both the method and the quantities

of the reagents were varied.

 

 

1’?

Five cendenaations of phenol with methyl ethyl
n-hntyl carbinol were run. In two of the condensatione
l/d sole or the alcohol and 1/4 mole of: phenol were snap-
endod in 80 he. a: petroleum ether. 1/8 mole of anhydrous
£1613 was added in small quantities. Previous work in this
laboratory gives the method in detail (9), (10). In two or
the condensation: the technique was varied smashet. l/B
mole of nelgwee suspended in 50 etc. or petrclm other.

' 1/4 hole or the alcohol on 1/4 an. or the phenol, c1:-
eolwed in 50 0.0. of petroleum other, were added drapwise.
, The temperature mast be kept below 30‘. Any appreciable .
rise in twpereture results in the formtion of a sticky
use in the botm oi’ the flask, with the resultant pour
conamtions. Yields were not appreciably effected by
the technique. In a final run 5/4 mole of phenol was
used, with the other quantities rmaining the came. The

yield wee reduced.

Janie or Reoultc

 

 

 

 
  

 

Solvent Phenol he at n-bn “m3 he at n-bh p.121}
Pet. Either carbinol ph metham

ole - _ _ , , 33 yield
1. 80 22.8 1/4' 32.5 1/4 17.5 1/3 13 23.4%.
2. co 22.8 1/4 32.5 1/4 17.5 1/8 14 27.23;
a. 80 114.0 5/4 32.5 1/4 17.5 1/8 c 17.35
c. 100 22.8 1/4 32.5 1/4 17.5 1/8 11 21.33;
c. 100 22.8 l/d 32.5 1/4 19.5 1/8 is 29.1%

 

M“ - ..
w i. ‘1 five. “W W.

 

the methyl ethyl “5:1 mm phenyl new
414411104 11% 145’ - 147’]? In. The compound emld m m-
44811:”. It we enabled and Mmtivee eere prqmred.
Andre“

“haunted Carbon .- 31.49% m. .. 10.1,”;

Four cendeuetleue or phuol and methyl ethyl
ten-been 081*me in the propane or 81013 are we.
The pmeenree need prelim}: em emet- reneeed. Thee
me no appreeiable «time 111 not“.

A
a or he ‘
1- ,. 4.. J~~
a” o.— ‘~**m«—-WV.WW~ -

Seven P330 Heat-bi: '13 We
Pet. Ethu' Carbine]. ph nothene
e c 4

1. 80 11.4 1/8 15.55 1/8 8.75 1/15 5 11.9%
a. 80 11.4 1/8 15.25 1/5 8.75 1/15 5 5.4%
5. mo 11.4 1/8 15.25 1/8 8/75 1/15 5.1 15.7%
4. 100 25.8 1/4 55.5..- 1/4 17.50 1/8 11.8 22.75

.- .- *-.—r~w.—r.-¢-.-u—au~w—. . -.-. -V. - 1... WW 4 v- y. WWW-w». ell-na—

 

   

   

    

 

      

The alcohol needin the wetmnepmuu-
antenna. The lethfl m1 “when p-bydrex: 9W1
methane «11415184 on 5001155. 15 lee Med en a m
mete. 11. Pt. «- 51" to 58'

We
calculated Carbon -- 51.455 mirage. - 10.95%
rm Com -- 83mm Hydrogn -- 10.83535

 

 

I Illiil Ill Ill-14.. I], .nllllllllllll I r»

19

Proper ati on of Derivatives

Esters
Bunny). and eeetyl esters were prepared by a.

modification of the pyridine method (33). A typieal
run in as follows: One and a 1181! 0.0. of honey:
chloride 1:: added to a mixture of LB gram of tert-
oetyl phenol dissolved in z moi of pyridine in e 250
no.0». flask carrying a reflux condenser. The flank
is waned with a free flame until the mixture boils
gently. After heating for about coo hour in the hood
the flea): is oooled and then filled with water; The
solid in motion filtered and washed thoroughly with
water until there is no odor of pyridine. The aolid
is purified by recrystallization frun alcohol;

than the enter formed was e liquid about four
time as large quantities eere used. The product was
treated with outer end that attracted eith other. The
ether extract m washed thoroughly with dilute hydro-
chlorio acid to remove any pyridine. The other was
reamed. and the eater Ian distilled under reduced
pressure. If the distilled eater solidified when 0001»
ed. it woe driedbetween filta' paper and rooryotalliald
from fifty per cent alcohol.

Urethane

The alpha nophthyl urethane were prepared. (34).
About 1 0.0. of a-nAphthyl ioocyanato was added to l 0.6.
or the tertooctyl phenol in e 50 0.6. fizz-imam flunk.
A for matale of anhydrous potassium carbonate were
added. A stopped: containing a. calcium chloride dryipg
tube was ineerteh The flee]: the mod gently for t-
mimtae on a steam bath. After cooling, the. solid; impure
urethen m dissolved in ligroin. filtered throua e m
auction filter and crystallized. The crystals tare again
suction filtered and then recrystallized from alcohol. no
tater must enter the flask, during the reaction 31!" dine-
phthyl area might be formed. The mphthylhrethm of
methyl ethyl tort-butyl £9.11?er phenyl hethano was with
more difficult to crystallize than we: tho derivative of
methyl ethyl n-butyl 11-03 13113le mtham.

Analyail .

The acetyl and banzoyl eater: were amlned
for carbon and hydrogen by Fisher's modification od'
tho Liable Motion method (35}. The results are
given in tabular fan.

The maphthylurethane were mlyzed for nitmgen
eontmt. Allan's micro Kieldahl apparatus and modification
of the M0311 method were used (36) (3?). The results are
noted in tabular forl-

2].

_ Aicojyl and Benzoyl Eaters
any), Phenol Esta ”gym.

 

1" he et m p-GH Mom 3.2:. . W Cain. sensed 34.71%}
9h methane 1.4675 mm. Found 0-77.04;% “fig-g
is he et n-bn p.01! Demon amt. «- Color 0-81.24'1 3-8.4531
oh aothone 194'12 m." Found 041.03% 3-8.441
3.; lie et bbu p-CII Smyl 14.91:. - Calc.‘ 0.81.8433 3-8.451';

ph methane 109‘ Found 6-81.4755 5-8.403ié’3

w-

     

._ . Q w—«r.~w-—

   

— M.-._.

00": 1333391 B.‘ 2“". W1.

 

 

 

16 He et n-bn 9-63 91' Cale; H 3.79%
9!: methane Found h 3.38%
2.‘ tie at nah 9-011 91' Colcd R 5:97;?3
pl: mthano found H 'Staifi
(Proof of structure
preduct) .
3. no et m pm m. can a 3.793%
ph methane Found H. em
W —~ 1 W

 

 

Proof of structure

The structure of methyl ethyl a—Mtyl pohydroxy
phony). methane was proved :by preparing the“ octyl benzene.
oitmting. reducing to the amino mound; didactizing and hydro-
lysing to the phenol; The position of tho cotyl gonp no pro-
'06 by Carina oxidation of the nitro ootylbme to p-nitro-
bowie acids The o-naphthylurethon of the phenol Iae prepared.

22

Analysis»; melting point and mixed melting point determinations
proved it to be the some as the c-oephthylurethon or the
original cméenacd phemlc

1.- Preparation of the cctyi beam

The ootyl benzene one prepared by the manta
claim chloride condonution method {2). Three 1/4 mole runs
are made and 55 g. or the product obtained.
8. Preparation of octyi uni-ohm
. The nitrotim or the octyl benzene was carried!
out by an adaptation of Baikal-he‘s procedure (38). on
equal ymight or the hydrocarbon was added slowly to tuning
nitric acid (up. gr. - 1.51) in e 250 cm. flask. Afton.-
the first violent reaction is complete the mixture me
shaken vigorously and dined to main in 1 water hath
It 90' to: one hour, being shaken {rm time to time. Water
on: poured into the neck, the product oepmted. mood
with sodium cambonote solution, dried with anhydrouo eel.
aim chloride and distilled under reduced procaine.
3.. Reduction of mm tort-octyl bmene

Reductioo was carried out by means of u: and
concatrated hydrochloric acid. A typical m is as follows
“(39): 30 an. at tin. are put into a 600 0.0. mono-bottom
fled: titted Iifii on air condense. 100 6.0. of concentrated
861 is adéied and then 20 gm. of p-nitro tort-com W.

E5

The fixture is tuned gently under the hood. After two
new. the W in allotted to cool. The nitro compound
floating on the surface changed into a crystalline mm
Thin we; treated with a large mount of ureter and node
manna with N803. and final}: atom distilled from at
2-139: flask. The amino cmoxmd coming eve: ti 3:31 the
ete- ie 0&1th out. separated. dried with crushed, solid
K03 and distilled under reduced pressure.
‘- Oxidation! of p—niti-o tort-octyz benzene

The oxidation method one adapted tron mm.»-
(as). One and e half We of the octyl uitro compound
end 80 em. of dilute nitric acid (1.80 or 615} wee
untied in e Gerine tube and heated at 130' in the Carin
Motion amen. After ten home zones-shite crystal.
wasted in the tube. The tube Ia- filmed to cool and
Opened. The contents were paired into ‘00 out. of water
and the crystals section filtered. The crystals one
freed true come unchanged n5. tro commend by washing with
e little cooled other. The crystals thus obtained melted
at 238‘~239'. A mixed melting point dotominetion with
p-nitrobmoio acid showed no depression.
5. Phenol from p-emino tert—octyl benzene

A typical diuotizetion is ac follows (40):
4 1/8 an. or Woo tart-octyl hwzcne are treated with
2.5 he. of concentrated Ham... in 15 6.6. of neuter. The

mud salt formed is suspended in 500 a.“ or water. After
cooling 1: an “a bath to 5’. 1.9 an. or ”dim nitrit-
m 8 0.0. or water 1: adflod drag by drop to the stirred
uuapenalm from a dropping tunnel with a 0:11:11th tuba
attached to the stem. Starch iodide page: is asst! to dat-
omino when suffloimt autumn nitrite has been tidied. The
diasoflagtion mm. mt bu acid throughout the ”action .
Tha dinzotuad sciatica is now warned on the
Item bath and subjected to steam distillation. poten-
Dctyl phone]. was obtained as q liquia. The acmphthyluro-
thanlal prepared. It gave the new meaning point as the
urothon or the original condensed phenol. A mixed me]. :1 ng
point determination abound no 43131-335103.

TIZEGIEETICJ-JL AZID SLEEAELY

£5

The reactionbeteeon the Grignerd reagent and
the carbonyl group of e ketone to produce a tertiary
octane}. worked euezeeei’ully in the preparation or methyl
ethyl n-butyl eerbinol. The use of thie same method to
prepare methyl ethyl tert-butyl earbinol roe not mtieteetory
and confirms the work of Whitman in thie field. The 13mph
oration or thin oetenol by the reaction or trimethyl aeotyl
chloride with Ethyl and ethyl negneeinnbnlidee was not
entiereotory, being tine eonemsing and resulting in a poor
yield. The ootenol was successfully prepeied by the react-
ion of 911180010310 and ethyl magnesium bromide, confirming
the work or Clarke and Jones.

kethyl ethyl n-butyl carbinol in much stable:
than is methyl ethyl t-bntyl carbine]... The tome: wee
not dehydrated appreciably when distilled at liar/9‘50 m.
The letter dehydrated than distilled et 1067200 mo

methyl em: n-bntyl eorbinol and methyl ethyl
tobntyl eerbinol condensed effectively nit}: phenol in
the presmoe of aluminum chloride to yield poelkyl phenols.
The method of adding the reagent: did not effect. the re-
sults appreciably.

. Bothy]. ethyl n-butyl carbinol condensed 111 th
benzene to yield ootyl benzene. I
_ ' _ Alpha nephthylmthene are nore eatieteetory
doritetiYBQ for the t-ootyl phenols two are the acetyl

and bennoyl eetoree

The oetyl group take: the position pare to
the hyaroxyl of the phenol as shown by the oxidation
of the oetyl nitrobme to para nitrebenzoio ma.

. MEIOGEUM

 

(l) m unngeetg 3 Though mange: State suing-.1954

(2) Huston and Mom. among-.3”... %2W,l915

(3) mm and Eric“. 11“., ‘9, mine

:4) meta and Sage. “14.. g 1955.192:

(a) mate: and Wet. me... a 2432.19“

(6) hiluy SJ... WNW State calla-.1933
(an Brae-i 2.11.; Wmm' State Coll-60.1934.
is) number mummxwemm State «11.9.1935
(9) Banner 2.1.3.. Wainscot State College.”
(10) mm 151.; Watson State sonogram
(ll) sauna .13.; hangg meg, 5. Michigan mate Collegefim
:12) rmonenik. :.eae.cnu.(u.s.s.a.),g 117.1935

0.3) W 1m” :mcnmw.s.e.n.),§_ 515,193:

{in metm R.c.; mimosa-.30». ‘9, 2975.193;

(15) Jim end aeith. Ber... L3 189.1881

(15) new and crown. Lima-awn... 9, 1565.332?
(1!) mum and Strickler. baseman»; 3 4:17.193!

(18) automates-thou: and Well. me... 353 44.84.1930

(19) Beaten and Luis. they; a 2379:1931

(20) match and m. ibim; a 1506,1952.

(81) 3mm Pd“ Whimm State Genoa-.1053
(28) Huston and In." LAB-Chmmg 93, 43951956
(git/mm. and Regattoher. ibid... 33g l561.1933

(24) Himgohn V" Bull.eoo.Chon.Bolg.. a 369.1930

(85) Adam Roger, Organic syntheein. g 50

(26) 1mm; and Wat-sober. J.£E.Chm.Soe., if; 1559,1933
(27) m: and Blntt. ind... 3;; 1227. 19:39

(38,) Renal 8.8.. Organic Synthesis, 3 8'7

(29) whim '

(a?) “as Roger. ibid" fi 106

(a) mam-son and Baez-mm. meme: 023.com...
Edwards Brothers Inc... Ann Arberfiieh: 1.933.111

(as) Clarke and: Jones. mehmsu... 32; 193.191:
(33) Einhorn and Holland, Ann... :50; 95.1898
(:4) mm: m Erma, :.m.c1m.soa.. go. 947.1925

(35) Fisher 3.1... Labdfien. or Grading... Wiley and Bone
- fies York: 1.934. 245-892.

(36) Alla 1?..- hieetora Thoeig. Elohim abate Collegem
(3?) Pray! 3.. Quantitative Organic Mama-'31.. meme
(:8) Who. Bar" 532. 319.1919

(39) Antietam and Badman. Lehman of CTg.Chae..
Edvard! Broth.- lne... Ann armament 1933. 33

(£0) Mk; 4‘5 .

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