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CO}. EJSATIOITPRODL'CTS OE“ ACETOI'IE

AND 303171 OF THEIR DERIVATIW.:1S

CCIDJZISATI.K‘ZFI’EZODUCTS 03‘ ACkSTOl'E

A30 803?; OF TIE-DIR DERIVATIVES

by

Herbert Ernst Ungnade

Thesis

Submitted to the faculty of Michigan
State College of Agriculture and Ap-
plied Science as partial fulfillment
of the requirements for the degree of

master of Science.

August 1934

A C K H'O W L E D G HIE N T

The writer wishes to express his sincere
appreciation to Dr. R.C. Huston and Dr.
Otto Uhgnade for the counsel and assistance

given him in the completion of this work.

1313 11673

C O N T E N T 8

Historical Data
Definition of problem

EXperimental Data

I. Separation and identification of mesityl-
oxide,diacetone alcohol and isophorone.
II. Diacetcne alcohol
III. Esters of diacetone alcohol
IV. Derivatives of the esters.
V. Physical constants
VI. Summary
VII. Blue print

Historical Data

.1.

Historical Data

The scope of this thesis is limited to a small group
of condensationproducts of acetone which are obtained by
the action of alkali.From the latter we want to consider
mainly the primary compound diacetone alcohol and the two
unsaturated homologs mesitylexide and isophorone.

Isophorone was first isolated by Fittig (Annalen.;;g.
23,1659) from the products of the alkaline condensation of
acetone.Previous to Fittig acetone had been condensed by
means of potassium and potassium hydroxide by weidmann and
Scheeiser (Poggendorffs.Annalen.5§,48.§9,265).and by Loesig
and Weidmnn (Journ. f. pract. Chem.3;_.54).ln these earlier
investigations the authors obtained mainly two producte.a
resin and an oil,named 'xylitoel”.The latter was recognised
by Voelckel (Annalen gg.soe.gg.ee) as a mixture of substan-
ces.Vbelckel and Schweiser both obtained xylitoil by the
treatment of acetone with calcium.oxide,and defined it as
an oil boiling at 200-2200 ,with the composition 0.33.80.

Fittig,working with calcium.oxide as well as with
sodium,proved in his reaction also the formation of mesityl-
oxide and pinacone.For the substance boiling at 210-220“
he found the correct composition 09H1.0 .he suspected it
to be identical with campherphorone.

Liquid phorone was later isolated from the products
of the reaction of sinkalkyls with acetone.by Rieth and
Beilstein (Annalen.;g§,245--1836) and by Pavlov (Annalen,

.2-

]§§,130--1877).Louise observed it in the condensation of
acetone with aluminum chloride (Beriohte.;§.2732--1852).
Freer obtained liquid phorone when he investigated the reac-
tion of sodium upon acetone (Annalen.21§,130--1894).and
Bredt finally proved that identical products are obtained
‘whether sodium alcoholate or calcium oxide is used as a
condensing agent.(Annalentggg,lO--1896)

The name of isophorone was given to the liquid pho-
rone C,H;¢O , which was obtained by condensation of acetone
with sodium ethylate.by Kerp in his article 'Zur Kenntniss
des Kampherphorons,des Isophorons und des Mesityloxyds'
(Annalen.ggg,127--1896).Kerp definitely proved that ieophorone
and campherphorone are two different substances by preparing
reductionprcducts.cxydationproducts and derivatives.

The constitution of isophorone was established by
thevenagel (Annalenhgg1,185-e1897) as trimethyl-l-S-S-

eyolchexenone-5

Khoevenagel synthesized isophorone by condensation of
mesityloxide and ethyl acetate with metallic sodium.Thie
product was identical with Kerp‘s isophorone from acetone.
Hewever,while Earp encountered considerable difficulties

in the purification of his substance,Knoevenagel‘s syn~

thesis yielded almost a pure product.Kerp and hueller.in a
later article (Annalentggg,le,--1898),starting from acetone.
purified their product by treating the mixture with sodium
bisulphite which.combines mmre readily with mesityloxide
than with isophorone.0ther investigators isolated the isoa
phorcne from its crime.

A good yield of isophorone is obtained by treating
acetone with sodium amide (Hceohster Farbwerke.D.R.P.
154.982 . C. 1902 11,1164) .the biproducts in this case
are:mesityloxide,and xylitone,in presence of benzene the
products are mesityloxide,phorone and ieophorone.

Diacetone alcohol,ths primary product in all alka-
line condensations of acetone .sas discovered in 1873 by
Heints as an impurity in commercial acetone of unknown sour-
ce (Annalen.l§g,lld).Shortly later Heints synthesized discs.
tone alcohol from diacctone amine (Annalee l1§.342--1875).
The oxalic acid salt of diaoetone amine was dissolved in
water and the solution treated with potassium.nitrite.Thie
reaction gave a better yield,enabling Heist: to establish
the structure of diacetone alcohol,which was found to be
4-methyl-4-hydroxycpentanone-2

I!
HO" £0Ha‘8‘CH3

his
The compound was identical with the substance found

previously in the acetone.

Emmerling.prior to the work of Heintz.claimed to

~4-

have discovered diacet‘ne alcohol (Berichte,§,24--1873).
His substance was obtained from the treatment of bromacetone
with silvercxide.The author found that he could not separate
the two substances obtained after steamdistillation of
the mixture.He states however that the aqueous solution
tastes sweet.and reduced Fehling solution.which latter prov
parties he attributed to diacetone alcohol.As a matter of
fact.diacetone alcohol does not taste sweet and.acccrding
to later rssearch,hasbpnly very slight reducing properties,
for which.reasons the work of Emmerling is rather doubtful.
The condensation mechanism.and the equilibrium

existing between acetone and diacetone alcohol was studied
by Koelichen (Zeitschrift 1'. Phys. Chem. fi,l29a-1900).The
latter prepared diacetone alcohol by allowing acetone to
react with alkali solutions for certain periods of time ,
then removing the alkali by passing in con gas.and distil-
ling .Distillation in the presence of alkali must be avoided
because it leads to the formation of mesitylexide.

Kbelichen found that the condensation of acetone and
the decomposition of the formed alcohol are reversible reac-

tions which lead to an equilibrium between the two substances.
2 CHSCOCE. {Li— (CH3) 3c: (01-i)cn,,c:ocm8

Both reactions are catalysed by OH ions.The equili-

brium.between acetone and the alcohol can be expressed by

.5.

the following fonnula,provided that the solutions are

not too concentrated.

C (diacetone alcohol 1 ‘ K

Ca( acetone )

The summary of the experimental data of formation and
decomposition of diacetone alcohol by means of alkali gives
direct proof for the law of the independence of a chemical
reaction from the quantity of the oatslyst.The equilibrimm
is greatly dependant upon the tempsrature,diacetone alcohol
being favoured at lower temperatures.The speed of reaction
is in either direction a function of the concentration of
the hydroxyl ions.Deviaticne in the case of weak bases can
be traced to secondary reactions.

Joseph Lemaire (Recueil des trav.chimmg2,69,0hem.2eno
tralblatt,1909,l,1982) obtained diacetone alcohol and mesi-
tyloxide by treating beta-oxybisovaleric acid nitrile with
magnesium methyl bromide . he quotes however that diaceto-
no alcohol is easier to prepare by the method of Heints.When
diacetone alcohol was allowed to react with magnesium methyl
bromide.it was converted to 2-4-dimethyl-pentandiol-2-4

H3 11,, '
CH5.SH:CH2-§§CH3
The preparation of diacetone alcohol from acetone by
the action of alkali was first described by Kbelichen,and
modified by Huester and Heberlein (Zeitschrift f. An. Chem.
A§,67--1905).The method consists in treating acetone with

eolid alkali and not~enough water to dieeolve all the
alkali.ehaking for two daye.allouing to etand for two days
in a freezing mixture,remcvina the alkali by CO,,and finale
1y distilling the mixture of acetone and diacetone alcohol.
‘A more efficient method is described by Hoffman
(Journ..Am.Chem.Soc. §;,723-91909).A round-bottomed flask
is connected with a eoxhlet extractor.and the latter with
a reflux condenser in such a way that the condensed acetone
flows ccntinouely through the extractor back into the flask.
The thimble of the extractor ie filled with calcium.exide.
and the acetone brought to boil.Since the oondeneationpro-
ducts of acetone boil considerably higher than acetone it-
eelf.their vapors are thue prevented from,coming in con-
tact with the condeneinr agent.while the actcne oirculatee
until meet of it is converted.The product in this case ie a1-
moet entirely'meeitylonide.with a trace of_higher ccndenea~
tionproducte and a trace of diaoetone alcohol.

Since the earlier work had ehown that alkali hy-
droxidee form diacetcne alcohol,the next experiments were
carried out with calcium.hydroxide in the thimble.The pro.
duct in this caee was diacetone alcohdl with.eome unchanged
acetone,

To prove that diacetone alcohol was the primary pro-
duct,chemieally pure,dry calcium oxide {Is heated in a eealed
tube with pure,dry acetone.While there wee no reaction in

the first caee,a trace of calcium hydroxide caused a thick

.7-

syrup of condensationproducte to be formed.Thue Hoffman
definitely proved that diacetdne alcohol in the primary
condensationproduot of acetone upon treatment of the lat.
ter with alkali.

Rhintz‘e method of preparatisn of diacetone alcohol
from diacetone amine was slightly improved by Zelineky and
Zelikcw (B. Q5,2857-«1901).

Diacetone alcohol can be obtained by careful oxidation
of 2-3-5-trimethylchexantri01-2-3ub with chronic oxide in
acetic acid solution. (Bouveault and Locouin.Annalee do chi-

mic (a) agate-1910)

H, H 3H, 'H3 H3 ‘
CH8!" 3 “CH3. CONS + 03 “‘9 CH3. 4’ ”CH3. "'* H3
H H. on H, H

Diocetcne alcohol is also formed in small amounts by the
action of sodium acetylene upon acetone,along with.3-methyl-
butinol.meeityloxide.ieophorone and ieophcrone acetylene.
(Hess and Hundcrloh,B. §;,382--1918).by the action of magne-
eium.amalgam on acetone in the presence of waterfree ether
or benzene (Bouveault and Locquin),and by the reduction of
benzoylacetone with sodium and alcohol (Bauer.Comptee ren-
due lAQJlogsu-IQOV).Bauer proved the diacetcne alcohol by
converting it into the crime which reacted with phenylieo-
cyanate to give a carbanilide oxime 013H180333 + H30.
which melts at 104 . 105°C.

w ,, a
ClH’.C/“CH3'C (033 ) a 3 RICH + Cada'NC O
on,

H . .
CH,-§ «OKs-C(Cfla) a mo-g-zm-cen,
He
The oxime of diacetone alcohol was first prepared by
Kchn and Lindauer ( hbnatshefte f. Chemiemg§.755--1902)
The oxime,2amethyl-pentanolo2-oxims-4 was found to melt at

57.5-58.5°.Upon reduction it yielded beta-oxyoisohexyl-amine.

0 OH cma OH '
/ «Chg-owns) .. son + 4H -; )1 .--<:H,..-<;I(C:H,,)«ema
CH, CH, }

Kyriakides improved the preparation of diacetone alco-
hol on hoffman by using barium.hydrcxide instead calcium
hydroxide,a small amount of tartaric acid was added to the
acetone in order to neutralise any barium.hydroxide which
might be carried down (Am.Chem.Soc. £9534u1915) ~Hoff-o
mans process is protected hy D.R.P. 229.678.The patent is
referred to in C. 1911.1,275)

A new separation of diacstone alcohol is covered by

th

(D

British patent 402.788 of Ernest E. Conolly (1933).

The inventor claims the addition of water (about 10%) to
the mixture.subsequent distillation of the mixture under
atmospheric pressure,and final distillation under vacuum.

A.mmdification of the Kbelichen method of preparation

of the alcohol was used hy Oestling (Soo.‘;gl,469--l912).
The reaction mixture was kept cold (in an ice chest) cau-
sing the alkali to solidify.The acetone solution was pou-

red cff.neutralised,the acetone distilled off.and poured

.9-

back on the solid mass. The alcohol thus obtained was redu-
ced with 3 % sodium.amalgam to give 2-methyl-pentandiol-2-4.
This same reduction product was also obtained by Zelinsky
and Zelikcw (B. g5,2858--1901).
11 H H
CH5- »~CH2-CO-Cfls + H31»CH5¢ —-CH3--CH3
on, on, n

The patents of the Trench Sooiéte’dee Destklleries des
deux Sevres . Henri Guinot inventor,claim the preparation
of diacetono alcohol by the action of alkali in alcohol
solution (several patents).0ther patents require a certain

pH for this reaction.

Pr s a sect no co 3 .
Diacetone alcohol is a colorless and almost odorless liquid.
Bp a 163.5-164.5° Bpaa I 77-80“ Bpg; - 63-64“
Bp1, a 75-80° (different investigators)
D° . 0.9555 D35 . 0.9306
It is miscible in all proportions with water,alcohol.

and ether.lt decomposes slightly upon boiling under atmos-
pheric pressure.From.the aqueous solution it is separated
by means of KoniflaOH cr.K;CO,.With alkali it is partially
split into acetone,the realtion being reversible.When heated
with a little alkali hydroxide solution or alkali carbonate,
it decomposes even below 100' into acetone.

Diacetone alcohol is oxidized by HaOBr to give beta-
cxy-valeric acid (Kohn,M.24.767-~1903).The latter acid,being
a beta hydroxy acid,splits off water with the formation of

.10-

beta-dimethyl-acrylic acid according to the following

equation:

H H oak
car-g ~CHa-CO-Clia -» mfg-0113.000}; /c .. CHCOOlI
H, a, CH,,

The electroreducsion of diacetone alcohol was carried
out by R.R.Rsad and F.A. Fletcher (trans..Am. Electrochem.
Soc. ‘1,--1925).Their investigations show that efficient
reduction takes place when the alcohol is reduced with lead
electrodes bur/Ea dilute sulfuric acid at a low current den-
sity.The products of such reduction are 2-msthyl-pentandiol
~2-4 and 2-methyl-pentancl-2

H OH
021,. -CH,,- was car-2 wen-carom,
’ H, on H,

The work of Bacon and Freer (Am.Cl-:ers.Journ. gag/s74“
1907) shows that diacetcne alcohol may be partially reconver-
ted into acetone by the action of sodium,whioh is due to
the primary formation of sodium.hydrcxide by dehydration
of the alcohol.In an atmosphere of nitrogen.a yellow sodium

salt could be isolated .in both oases,however,the bulk of
thfi products consisted of condensationproduots.

Upon dissolving in concentrated sulfuric acid diacetcne-
alcohol decomposes into water and mesityloride (Hsimts).
This same reaction is brought about by small amounts of con-
centrated or even 20 % sulfuric acid,phosphorus pentoxide,

zinc chloride,cr iodine’on heating.(Ref. Kbhn,D.R,P.

.11-

208.635 . o. 1909,1.1282,Hibbert.A.m.Soc. 341755-4915).
Treatment of diaoetone alcohol with one mole each of the
follwbng.ethylene diamine hydrochloride,KCH’and KOH’at 60‘
and following concentration with fuming hydrochloric acid.
gives the anhydride of the compound (CH3)3C(OH)CH30(CH§)-
(coonhmcnacnama. (Icahn and Ostersetzer n. unsanises).
The authors did not decide for either one of the two more

probable structures.

 

CHa\ PH ‘2}? CH3 /OH
/C \ IU‘iacliaCHa i‘il’lg /0\ H
CH3 CHaCOCIQ KCN CH3 CH3“ ONHCH3CHgl‘mg
He
CHs\ /0H
' /C\ (POOH Y ‘
0213 C Ha “SHONIHCII‘ 0 fig JR;
8
CH3\ 0 /HH /CH3
6/ \c-so ona \c\CH . Am:
033/: l x I n 3059.011,
c}{a’C’IH{CHnCH-31ma 0113 ,CBO
ens ‘HH

The reducing power of diacetone alcohol,glycols and a
number of similar compounds was studied quantitatively by
uvnua an Schoorl (R.‘§§,360-~1917.C. 19.16.11.896)

‘A series of common reagents was used,and the amount of reduc-
tion determined by iodcnetrio titrsgion.Diacetone alcohol

had the smalhast reducing power from all substances tested,
and from all reagents tested only Fehling solution was re-

duced.The experiments were carried out in order to find the

.12.

groups responsible for the reducing power of sugars.
Goesta.Kkerloef studied the velocity of the decompo-
sition of diacetone alcohol in a number of different salt
solutions.He concludes that the velocity of a catalysed
reaction in acid-salt solution and in alkaline solution
is always a function of the activity of the ion catalysing
the reaction.Ths velocity curves plotted for the different
salt solutions are nearly all of the same form,indspendantly
of the nature of the anion cf the salt.

The others of diacetone alcohol were discovered by
.Alfred Heffman in 1927 (J.Ar.0hmm.Soc. 9.530).They were e-
xeptionally prepared by the action of the corresponding al-
cohol ipon mesitylcxide.

cur-g - cite-30.0113 + ROH RaO~§H:CH2-CO-Ciia

H3 He

The mixture of th alcohol and mesitylcxide was allowed
to stand with sulfuric acid for ten days,the yield being
20-25 %.In this way the methyl.ethyl.prepyl.butyl.isobutyl,
isoamyl and benzyl others were prepared.The cxime was prepa-
red from.the ethyl ether.and the semicarbasone from all e-
thers.Upon reductionwith sodium in alcohol containing boric
acid the ethyl ether gave 4-ethoxy-d-methyl-pentan-z-ol.
which gave domethyl-B-é-pentadiene with sulfuric acid.

H

a 031%
~CH3-CO-CH, /C-CH . CH-Ch’s

CH, CHRCO-§
H, CH9

~13-

Oxidation of the butylether with sodium hypobromide
, gives beta-butcxy-isovaleric acid
H

onscnacnacsa-ocg’.CH,.coon

J.

According to U.S.Pasent 1,823,704 (1923) the others of
diacetcns alcohol can alga be prepared by the action of
alkali on a mixture of meeityloxide and the corresponding
alcohol.

D.R.P. 246.967 (Doerfflinger c.1912.I.--1928) protects
the use of diacetone alcohol as a solvent for acetyl—cellu-
lose.lt is also used as‘a solvent for—nitro cellulose.

Peter Maitland and Atanley Tucker condensed fluorene
with acetone and alkali,and obtained C;9H300.0n the basis
of this experiment they condensed diacctone alcohol with
9-fluorenyl-magnesiumpbromide.The following compounds were
isolated: fluorene,difluorenyl,019H13.9dieo-propylidcne-
fluorens,alpha-9-fluorenyl-alpha,gamma,gamma.trimethylutri-
methylene glycol.

Defini tion of Problem

-14..

Definition of Problem

The present problem.was the isolation and identifi-
cation of a mixture of high-boiling compounds obtained along
with the unsaponifiable fractian of vegetable oils.Ths oils.
such as cottonnseed oil were saponified with alcoholic KOH
in the presence of an equal amount of acetone by refluxing
for three hours.

Another method to obtain the unsaponifiable matter con-
sistedfln saponifying the oil with alcoholic potassium.hy-
drdxide.remo'al of the alcohol,and extracting the soap with
acetone.

In both cases a high-boiling fraction remained after
evaporation of the solvent,which could be separated from.the
unsaponifiable matter by distillatson under vacuum.

Extracting the soap with.acetone by the saxhlet prinu
cipls resulted in the formation of diacetone alcohol.This
reaction can be explained by the catalytic effect of the
free alkali in the soap. .

Saponification in the presence of hot acetone results
in the formation of a mixture of compoundsurhe extraction
of the uns ponifiable matter in this case being more some
plete,the obtained mixture may contain volatile substances
which are known to occur in the unseponifiable fraction.
Substances of that kind are ketones,and their isolation
would meet difficulties since the acetone condensation-

products which are also formed in this case are also ketones.

~15-

The simplest way for the separation seemed to be the frac-
tional distillation although earlier research on this field
shows that such separation is extremely difficult and un-
satisfactory. .

This separation was successfully acoomplished.H0wever.
there was no indication of ketones originating in the unsa-
ponifiable matter.

Among the products was diacetons alcohol.Upon.expe-
rimenting with it,the aostylester was discovered by chance.
Research in this direction showed that other esters could
be prepared.The second part of this thesis deals with the se

esters and their derivatives.

Experimental Data.

.15.

1. Separation and identification of mesityloxide,diacetone

alcohol and inephorone.

The mixture of compounds obtained along with the
unsaponifiable matter of vegetable oils by saponification
with.alcoholic KOH in the presence of acetone constitutes
an amber colored oil of peppermint-like odor.When distilo
led.even under vacuum.it darkens indicating oxidation.1t
dissolves rubber.thus makin: the distillation still more
difficult.0nly in the presence of inert gases can the mix»
ture be heated without decomposition.

To meet all these requirements the distilling appara-
tus for its separation must contain no rubber stoppers on
places where they may come in contact with the vapors.It
must be free from leaks to prevent air from.oxidizing the
substance.and it must separate with a high efficiency.Fur-
thermore it must have devices to introduce inert gas into
the apparatus.£ree from sir and impurities. &

Experiments in this line showed that all-glass conneoc
tions are advisable to maintain a good vacuum.A distilling-
column according to Podbialniak is the most efficient.its
hight and diameter can be found by experiment and analogy.

Difficulties were encountered only in the introduction
of the inert gas.When the vacuum inside the apparatus is
allowed to draw the gas from the tank by suction.there is
always a danger of air coming in.becauee valves and senses.

tions cannot be made entirely leak-proof.Therefore the gas

~17-

was filled directly from the tank through a membrane re-
ducing valve into a container,which was first swept seven
ral times with the gas.under a suitable pressure.Frcm this
container the gas could be drasn without danger of contami-
nation by air.the only precaution necessary being to keep
the container under preesure.which can easily be observed
on a double gauge (see blue print).

For oontinous distillation a fractionating device was
built in,which allows the withdrawal of fractions during
the distillation.The substances are introduced and the re-
sidues are emptied by vacuum since the distilling flash is
not removable.

The inert gas is introduced through a capillary into
the boiling flask.heated in an oil bath.Another line on-
ters the fractionating device to allow removal of the free.
tions under inert gas.Ths gas is first washed by sulfuric
acid or another appropriate absorbent.

.It was found difficult to trap all the vapors.especial-
1y with low-boiling substances.therefcre a special conden-
ser was inserted in behind the fractionating part.The water-
cooled trap delivers its condensate to a bulb.a stopcock
allows to shut off the bulb.when the low-boiling subdanoee
are all removed.because its content.having a high vapor pres-
sure would otherwise lower the vacuum.

To read the temperature an.anschuetz thermometer is

suspended from a ground stopper on a platinum.wire.

-‘8-

 

 

Distilling Apparatus
(later modifications are given in the blue-print)

o 19.

.A photograph of the apparatus in the experimental stage
is shown on page 13.:he drawinr of the apparatus after com-
pletion is attached in the back.

The distilling column offered another problem because
the inner and outer Jackets have different temperatures ,
and due to the different expansion ,crack at the Joints.To
eliminate this trouble an elastic seal i;- used,vhich.was
first applied by Helmut Gootemoot (H;S.C.).ccnsisting of

asbestos,liquid rubber and De Kotansky cement.

Directions for the use of the distilling apparatus (referred
to the blue-print)

To introduce the sample close 2.4.8.10 and open 14.9
and 12.8tart pump l.Draw the sample through 3.Then slowly
heat the oil bath in which the distilling flask C is immer-
sed.0pen 6.01030 1.6 and ?,and start pump 2.

Close 13,09en 7 and ll.Through 13 flood with nitrogen,
evacuate again,and keep the reservoir Q under a pressure
of about 200 mm of mercury.AdJust 4 so that a slow but stea-
dy stream.of gas enters the distilling flask.through the
capillary.0pen 8 and 10 and close 9.Then tle cooling water
is turned on.and the beaker T may be filled with ice.

According to the material handled the flasks u and N
may be filled with some washing liquid,to remove impurities
from the inert gas.

I is only an expansion flask,A and O are traps to pre-

vent 6121 from sucking back into the apparatus.

P is a manometer and vacuum gauge for the gas system.

When the apparatus is in Operation the temperature
of the oil bath is slowly raised.in such a way that the dif-
ference in temperature between the oil bath and the distil-
ling column is not more than 20°.

To remove a fraction,stopcocks 8 and 10 are closed,
9 is opened and the pressure is equalised by Opening 11
slowly.Inert gas is then added through lS-to maintain the
pressurs.When atmospheric pressure is reached.ll and 13 are
closed.and the receiver is taken off.During this procedure
the distillate collects in G.a new receiver is attached.ani
evacuated by opening 7 while 5 is closed.When equal pres-
sure is reached 7 is closed.8 and 10 are Opened,and 9 is
closed.

When the last fraction is to be nemeved,the flame is
taken off.l4 is closed.and the pressure equalised through
ll.The residue is removed by Opening 1 and then 2.?hrough
7.11 and l the flask B can also be filled with inert gas.

R and 3 are the manometer bulbs.tilled with.mercury,
the pressure is read by means of adjustable scales.The pumps
used are Cenco Hyvao pumps.shioh produce in the described

apparatus a vacuum better than 1 mm.The glass used was pyrex.

.210

Vacuum.fractienation of the mixture.
After two distillations the mixture oouLJbe sepa-

rated into three main fractions:

"so
i. 22-sc°,/ 1mm 1.4418
2. 50-400 / ism ‘ 1.4290
s. 50-60° / 1mm 1.4680

Fraction 1 is a volatile compound of strong,honey-like
odor.It was converted into the oxime which was identical
with mesityloxime (preparations and constants see later).
Therefore fraction 1 consists largely of mesitylcxide.The
fraction wees accordingly distilled under atmospheric pres-
ture.and gave in one distillation pure mesityloxide.boiling
at 128.129°(atm.pressure) sz a 22-22.5°

n33 - 1.4439
Fraction2 was found to be sater-éoluble.and was therefore
suspected to be diacetone alcohol,the odor indicated mesityl-
oxide as an impurity.The liquid .was diluted with one fourth
of its volume of water,and then distilled under vacuum.hesi-
tylenide and water some over first.and finally the pure dia-
cetone alcohol was obtained boiling at 36-37°/lmm
nsg I 1.4240

The last fraction.was examined by treating a small frac-

tion with semiearbazide hydrochloride and sodium acetate.

The product upon recrystallisation was found to be a pure

substance and not a mixture.H;P. 193-194°.Hence the third

fraction must be considered as one substance with small
amounts of impurities preeent.Fraotion 3 was then rediatil-
led under high vacuum until a honotant boiling fraction was
obtained,boiling at 55-56°./ lmm.Thie eubetance,a yellow
oil of agreeable odor.was analysed as follows:
big: a 0.9155
B.P. a 200~20l°
30

n - 1.4e00

Elementary analysis

Carbon I—Iydrogen
round 77.50% 10.34;
found 77.61% 10.51%
calculated for 78.26% 10.14%

003140
Molecular weight by boiling point elevation

found 151.0 ' 146.1

calculated for 0931‘0 138.1

Qualitative tests indicated that the substance was unsatuu
rated.It addelrapidly bromine.The bromide however was very

unstable. . Analysis of the bromide

found 44.47 5 44.01 3
calculated for
c.21uoern 53.65 %
Addition of bromine corresponding to two and more equi-
valent: caused decomposition of the aubetance,hydrogen bro-
mide being given off.Analysie of the resulting compounds

revealed even lower bromine content of the residues.

.23-

It is obvious therefore that bromine added in excess of
one molecular equivalent does not add.but decomposes the
compound.The brcnide obtained is so unstable that it do-
composes when in contact with the air only for a short ti-
me.This accounts for the low values obtained by the parr bomb
determination.The result seems to indicate that the com»
pound had only one double bond.which allows the conclusion
that the compound contains one ring.

Comparison with Beilstein revealed that the com-
pound wae isophorone.corresponding with its properties in

all details.

c.24—

II.D1ngetgge fll33h2;e
1. Preparation.

In a two liter round bottomed flask are placed
1500 cc of commercial acetone with a few boiling chips.
The flask is fitted with a rubber stepper carrying a curb-
let extrector.Tro paper thinbles are placed in the extras-
tor.one above the other.The lower one is filled nearly full,
the top one is filled three quarter full of barium hydro~
xide.end the remainder of the space is filled with‘gless.
wool.

The flash is heated on e steam bath or in an oil bath .

The host is so regulated that the acetone refluxes back in-
to the extractor rether rapidly.£s the redction proceeds the
temperature in the bath has to be reised.After 953100 hours
the reaction is finished.The crude dieoetone alcohol is dia
stilled first under atmospheric pressure until all the ace-
tone is removed.the temperature on tOp of the column being
70‘ when the process is complete.The residual liquid is trans-
ferred to a Cleieen flesh and distilled under reduced pree-
sure.Yield 850 3.
Ref. myriakides.J.Am.Chem.Soc.'§§,534.

The pure dieoetone alcohol is collected at 60 to.
63° / 6 11m. The refractive index of this product is

nag - 1.4240

The diecetone alcohol thus obtained was used for

all of the following experiments.

According to the literature.diecetone alcohol can

.25.

be dehydrated by means of small amounts of sulfuric acid.
iodine,phosphoru3 pentoxidc or zinc chloride at high temp
peratures.

It was interesting to see whether also HCl gas would
give that dehydrating reaction.0ne hundred grams of disce-
tone alcohol were placed in a round-bottomed flask.immersed
in an ice bathihydroohlorio acid gas.dried over sulfuric
acid.was passed into the cooled aloohol.The reaction.mixture
turned yellow,and the color deepened as the reaction procee-
ded.The deep red solution still absorhed HCl gas with libea
ration of heat.After the rate of absorption decreased the
flask'was removed,and allowed to stand for 24 hours.Then the
mixture was poured into ice water and washed thoroughly.The
raw oil was neutralized with carbonate solution and finalky
with some lead carbonate to remove the last traces of said.
Then it was dired over night and distilled.The reaction pro-
duced almost a quantitative yield of mesityloxide.Theyyield
of pure roduct was 80 % and better.

Constants of the mesityloxids obtained:

found literature
3011133 point qu‘a a 126-127 129~130 (corr.)
Density 1):: - 0.8560 egg . 0.8548
Refractive index ni; ' 1.4433 ntfi ‘ 1'4439

In order to prove the identtty of the meeityloxide it

was converted to the oxime as follows:

o 26-

Cne hundred grams of mesityloxide were dissolved in
one liter of ulcehol,and to this solution was added u solu-
tion of 70 g hydroxyldmine hydrochloride.in the smallest
possible amount of woter.The solution was mode alkaline by
adding solid crystalline sodium carbonate in small pora
tione to av id increase in temperature.Aftor 5-3 days the
alcohol was removed by distilling from the water bath.
and the separated oil was washed with twice its volume of
outer,extructod with ether and fractionated.

The oil obtained agreed in all propzrties with the dd.

to given in the literature.(Harries,dnnalen $§0.192).

Heeityloxiue.2~methyl~penteneozvcxime-e.

found literature
Boiling point 133-190°(dce.) 180-190°(dec.)
Bpas 100°C
Density D33 . 9.9443 32‘ - 0.9417

Refractive inde: us; a 1.4910 n95 I 1.4908

A qualitative test showed that diecetone alcohol can
also be dehydrated by the action of acetic anhydride.ln a
quantitative study of this reaction it was found that there
res a high boiling fraction although all unreected diecetone
alcohol had been removed by washing.Thie latter fraction had
a definite boiling point and properties different from those
of either meeityloxide or diaoetone alcohol.The qualitative

analysis showed that the compound must be an ester since it

.27.

hydrolysed in the presence of aqueous alkali.Tho saponi-
ficotioo number proved it to be an ester of diaoetone a1-
cohol.T1o general reaction for this eoterification,vhioh
was found to take place also with other fatty acid anhy-
drideo,ic as follows:
CH, .039
cz‘za-gt-czzawo-czra + ammo-com GEES-gR-CE‘Ez-CQa-Ciia + RCOOH

Tho meaityloxidc obtained as main product in this reac—
tion is a rather pure product and deed not darken in contrast

with the product obtained by other dehjdrotinr agenfiga

Soierc of Dioootone Alcohol.
1. Preparation.
The aoctyleator of diacetone alcohol can be prepared
by the action of acetic anhydridgfifih diacctohe alcohol.
I. Acetic acid.

Two hundred and thirty-two grams of diaoetone alcohol
freshly distilled and oatar-froc.aro mixcd_with 120 g of
glacial acetic ocid.Boiling chips are added.and the mixture
is refluxed for three hours.Then the liquid is allowed to
cool to room tomporaturc.Thc cold substance is poured into
on equal volume of ice water and shaken thoroughxy,in 3 oo-
poratory funnel,whereby unreoctod diocctono alcohol and coco
tic acid are removed.

Both the watoroloyer and ihv oily layer are then neu-
tralized against litmus with sodium carbonate or better bio

carbonate eolution.The oily layers are oombinod.and washed

again with eater.rho neutral oil at this stage is around
170 g.it ie amber colored.tho odor being mainly that of
mceityloxide.fiith a 300-400 mm fractionating column or mo-
dified Claiecn flock the latter compound can be removed
elmoet quantitatively.Pure meeityloxide comes over at 20-400
at 2—5 mm.a small amount of a mixture dietila at 40-50°

at 5 mm.and the pure eater is obtained at 60-63° /'5 mm.

Thd yield of 12 3 can be eliohtly increased by in-

roacing the time of heating.

Whoa 164 g of anhydrous sodium acetate is eddod to
the mixture of 353 g diacotone alcohol and 120 g acetic
aoid.aui then refluxed.and treated in the some manner as
ohove,only 60 ~65 g of the crude oil are obtained which

yield 50-55 g of moeityloxide and 10 g of the acetate.

II. Acetic anhydride.

The boot method for the preparation of the new acctyloeter
is the acetylation by means of acetic anhydride.

Four hundred and sixtyufour grams of diacetone alcohol
are mixed with 204 2' of acetic anhydrido in c. three liter
roundabottomed flack.Boiling stones are added,and the mixtume
refluxed for three hourc.oooled to room tompereturoggeutro-
lized.eeparated and dried as directed as above. “W

‘Around 350 g of crude oil are obtained in this manner
and yield upon distillation about 270 g of mccityloxide
and 80 g of the enter.

.29.-

Proportioo of the actor.

The acctyleotcr of diocetono alcohol is a colorless
liquid with slight but agreeable odor.It is incolublc in
mater,soluble in ntLor,bcnzono and acctcnc.lt boils at
171-17? / 742 1:13. 139,, - 60-62" 131.719 . 72-730
At atmospheric pressure the compound boils with only a
small amount of decomposition.

Density: D33 a 0.9811
Refractive index: n3; = 1.4229

The oaponifioation number gives th following results:

percent acetic ccidx. found 3?.82 - 38.07 %
calculated for c,nt.o, 37.97 fi

The actor rooctc with phcnylhydrozine and cenioarbazidc.
Preparation of the comicarbozone:

Dissolve one part of ocmicarbdzide hydrochloride in
tn: smallest possible amount of distilled matcr.Thon odd
one port of the e3tcr.To bring about tho rooction,add clow-
1y.with stirring a oaturctod alcoholic solution of potassium
[m until a homogeneous solution rooults.Tho semiau-
bozonc crystallizes in a short time in bundles of noodles.
If pctaooium.chloridc should crystallize out,it is necessa-
ry to filter.

The ccmicorbanono crystallizes in colorless noodles
melting at 137.5-138§C.It is insoluble in water but soluble
in olcchol.A.50 % alcoholic solution is used for its recry-
atallization.

.30-

Hitrogen in the eemloarbaxone:

found 031011181} ad for 0911‘ 703118
19.49 % 19.53 %
l9 . 53 %

giving it the structure:
orgcog (CH3 ) 30H, (CH3) - mam-00-33%,

The aoetyleeter of diacetone alcohol undergoes Clai-
eene condeneation by treatment with eodium.Thia reaction
will be diecuesed later in detail. '

Yields of the acetyleeter of diacetone alcohol obtained by
different acetylating agents.

1. Glacial acetic acid
diacetone alcohol need Yield 15k Yield in % of

the theory
252 8 acetate 12 g 3.7 %
meeitylcxide 158 g 73.7 g

2. Glacial acetic acid plus sodium acetate

diacetone alcohol used Yield imp ‘Yield in % of

the theory
232 g acetate 10 g 3.1 %
meeityloxide 52 g 24.3 %
3. Acetic e” dride
diacetcne alcohol need Yield in 3 “Yield in % of
the theory
464 g acetate 90 g 14.2 %

meeityloxide 300 g 70.1 Z

051-

Influence of mesityloxide on the esteritication

When a small amount of mesitylcxide is present in
the diacetcne alcohol used for the preparation of the ester.
the resulting ester shows some difference in its properties.
There is for instance a marked difference in the reactivi-
ty toward sodiwm;While the product obtained from.pure di-
acetcne alcohol reacts vigorously with freshly cleaned,me-
tallic sodium,the ester obtained from.impure alcohol does
not react in the cold.0nly when heated,s small amount of
hydrogen is generated,and the pieces of sodium are soon co-
vered with a reactionproduct which prevents it from fur-
ther reaction.0bviously the ester is tmpure,although it does
not change preperties upon distillation.

In order to investigate the effect of mesityloxide
one tenth of a mmle of mesityloxids was added to the reaction-
mixture as follows:

Two hundred and thirty-two grams of diacetcne al-
cohol are mixed with 204 g of acetic anmrdride and 20 3 men-
sityloxide.The mixture was refluxed fer six hours and tree.-
ted as previously described.

The same experiment was repeated using an initial
quantity of one molecular equivalent of mesitylexide.

Two hundred and thirtyetwo grams of diacetcne alco-
hol are mixed with 102 g acetic anhydride and 196 g of me-
sityloxide.The mixture was again refluxed and treated like
the shire.

Results:

Time of heating 3 hrs 6 hrs 6 hrs
hesityloxide (initial) none 19.6 g 196 3
Yield of the ester 90 g 93 g 27 g
n3° 1.4229 1.4232-1.4246 1.4253
percent acetic acid 37.8 % 54.60 % --~-

( ec’x" di‘ex-AsuxeK\
The results indicate that mssityloxide enters the
reaction.forming a compound which has a boiling point close
to that of the ester.In another experiment mesityloxide was
allowed to react with one molecular equivalent of acetic
anhydride.The product was a mdxture or compounds which.were

obtained in small yield.The following fraction were distil~

led off: n30
l. 50-35° / 10 mm 1.4430
2. 35.450 /'10 mm 1.4465
s. 45-57°‘/ 10 mm 1.4542
4. 55.600 / 10 mm 1.4462

The three last fractions constitute the wanted com-
pound (or mixture).however the yield is so small that the
identiy could not be eetablished.Possibly the mixture con-
tains acetylmesityloxide,which.was prepared by Fittig
(Beriohte.§§,1013) by tls action of sodium on a mixture of
mesityloxide and ethyl acetate.

Diacetone alcohol propionyl ester.
The propionyl ester of diacetcne alcohol id obtained

d53-

analogous to the acetylester from the alcohol and prOpio-
nic anhydride.
Four hundred sixty-four grams of diacetcne alcohol

are mixed with 260.3 of propionic anhydride.and the mix-
ture is refluxed for 10 hours.After cooling to room temp
perature the solution idxpoured into an equal volume of ice-
water.neutralised with sodium bicarbonate.and dried over
calcium.ohloride.

The prepionylester.C,H1°03 boils at 182-184° /'742 mm.

Bpa - 80-81“
Density 338 a 0.9680
Refractive index a”; s 1.4256
Percent propionic acid found 42.99.43.20 %

calc. 42.99 %

Diacetone prepionic ester reacts with semicarbazide
analogous to the acetyl ester.The semicarbascne is however
much more difficult to prepare.The recrystallized compound
melts at “4.51.145 ° It crystallizes in plates from alco-
hol (95%) and in needles from 50 % alcohol.

HitrOgen found 18.52 % calculated for 010H1903N3
18.40 % 18.34 %

The butyryl ester of diacetcne alcohol is obtained in the
same way as the above from diacetcne alcohol and butyric
anhydride.

Four hundred sixtyofour grams of diacetcne alcohol and

«334*

three hundred sixteen grams of butyrio anhydride yield
250 g crude oil ,from which a 90 g yield of the ester can
be obtained.

The propionylester and butyrylester both are more dif-
ficult to prepare than the aoetylsster,beoause the sodium
salts of the acids are more insoluble and occlude some of
the oily layer during neutralization.

Both the propionyl and the butyrylester are colorless
oils of agreeable odor.What is true for the acetylester in
regard to initially present mosityloxide is also true for
the higher esters.It is impossible to separate the impuri-
ties by distillation.

Properties of the butyrylester.

Boiling point 192-195°,/ 742 mm , sp13 - 97-930

Density D3: - 0.9536

Refractive index n’g I 1.I27O

Percent butysic acid found V calculated for
47.31 % CloHisos
47.43 % 47.28

The semioarbasone crystallizes in silky needles from 50 %
aloohol.It malts at 110.4 . 110.8 °

Nitrogen in tin semioarbazone:

found 17.00 % calculated for C;1H3103H5
found 16.82 % 17.24 %

IV.

O35¢

Follcwing the preparation of the above esters that
of the valeryl.caproyl and bensoyl esters was attempted.
In the case of the former two not sufficient chemicals were
on hand to investigate themtthoroughlyolt was observed,how-
ever,that the difficulties during neutralization.become
greater as the molecular weight of the fatty acids increases.
The limit for this method of preparation is rather close
since the higher fatty acids cannot be converted into the
sodium.ealts anymore by sodiumfgarbonate or even carbonate.
stronger alkali however cannot be used since it would pron
bably hydrolyse the esters .The benzoyl ester could not be
obtained by the above method from.bensoio anhydride,the pro-
ducts being mesityloxide and benzoic acid.

Derivatives of tie Esters.

Pure acetylester of diacetcne alcohol reacts with so-
dium.mmta1 vigorously with the liberation of hydrogen.The reac-
tion is analogous to Claisens Ester Condensation.which fol-

lows the general scheme:
curse-on +' H-czraeco-on nae-00411340003 + ROH

As mentioned before this reaction does not take place
when the ester is impure.

Molecular equivalents of the ester and sodium are a1-
lowed to react.either directly or in anhydrous ether.The reac-

ticn mixture has to be cooled in the beginning,and is finished

.369

by warming on the water bath.In order to convert the enol
form of the resulting ester into the keto form,one equi-
valent of concentrated H01 is added;

HCL i

H. e
on,.9 . CH.~COO-§ .cn3.co-cn.-e-OHS-g-cHa-coo-g vCH2~CO~CHs
OH . Ha Ha

Then the mixture is poured into iceeeater.acidified with
hydrochloric acid.The other solution is sashed with water,
dried over calcium chloride and distilled under diminished
pressure.The acetOoaoetio ester obtained boils between
80 and 90 ° at 6 a 8 mm.

Refractive index hi; 3 1.4363

quga - 189.0° (micro deters.)
The ester was saponified qualitatively with dilute al-
kali,and the solution was tested for aceto-acetic aoid.The
color test with ferric chloride was positive as well as

the iodc-acetone test.

Saponification number:

one hour seponified 19.2 % acetoacetio acid
one ' ” 22.9 % '
24 . ~ 36.3 s '
calculated 55.4 % '

The obtained ester was a yellow liquid.and apparently still
impure.There see not enough substance however to purify it

further or to run other determinations.The fact that it has

037s-

a pronounced phorone odor which stsll persists after
saponification and that it is colored indicates that it
contains probably the latter compound as an impurity.
which would be sufficienly explained by the action of some
sodium.on the diacetcne alcohol formed during the condensaa
tion.

Reactions of the esters with aldehydes.

Xetoncs can only react with aldehydes when they contain
methyl or methylene groups directly attached to the oarbo.
nyl group.Such condensations are effected by.means of dilute
alkali.sodium ethylate or hydrochloric aoid.The reaction

is being used as a qualitative test for methyl and methy.
lens groups in positions such as the required.The reaction-
produots are benzylidine compounds or there may be ring ole.
sure with the formation of hydropyrcnes.

In ketones of the formula R-CH3~CO~CH§ the methyl
group is more reactive than the methylene group when alkaline
condensing agents are used.When however hydrochloric acid
gas is used.the methylene group is more reactive.and on this
case only the methylene group can reactIso that only one
benzylidene group can be introduced.

References on these condensations are given in Hans
heyer,Analyse und Khnstitutionsermittlsng Organisoher Ver-
bindungen.

According to the above.it is obvious that diacetcne esters
having the general formula

R-coo.o(cn.),.cna~co.cn3

.33.

can react with only one molecule of aldehyde when HCl is
used as condensing agent.Aqusous alkali cannot be need be-
cause it would hydrolyse the esters.hfter reaction with one
molecule of the aldehyde.which would enter the methylene
group.there is a possibility of introducing another mole-
cule of the aldehyde by means of alkaline condensation.

The work of Ecstanecki and G.Rosebach however shows that
the alkaline condensation does not always consist of the
simple interaction of two molecules.but may lead to high-
molecular compounds,An example for this is the condensation
between bonsaldehyde and acetophenone.ln the cold this reacu
tion results in the formation at benzalacetOphenone.When hig-
her temperatures are used.benzaldiaoetophenone is formed._
Higher temperatures and stronger nlmli cause the formation
of dibenzaltriscetophenono.

In the case of the benzalderivative of diacetcne alcohol
acetylestsr the first product insisted .using weak alkali.
and room temperature was a compound containing one molecule
benzaldehyde and two molecules of the benzalderivative of
diacetcne alcohol acetyl ester.

Condensations.

A.ndxture of 15.3 g of diacetcne alcohol acetylester
and 10.6 g of benzaldehyde is cooled in an ice bath,and hy-
drochloric acid gas.dried over sulfuric acid passed in.

When the rate of absorbtion decreases'the solution has a

brilliant red color.The mixture is then allowed to stand for

0591'-

ten to twelve hours.At the end of this period it is pou-
red into ice water.Then the oil is washed sith.water and
with carbonate solution,and dried over calcium} '1
The oil is then distilled under the vacuum of a water a
pump (to keep corrosive vapors from.the electric pump)
until all the unchanged aldehyde is removed.a hoary oil is
then collected at 145.14” / 6 mm.‘field around 4: 3.

One molecular equivalent of diaceione alcohol acetyl-
ester is condensed with 15.2 g of cinnamic aldehyde.The co-
lor in this case is blue-green.ln this condensation however
the condensationproduct is difficult to isolate.The product
consists of bright yellow crystals which appear on the neck
of the distilling flasksThe product coming over however is
phenyl ethylene indicating decomposition.

Th2 condensation with benzaldehyde was carried out
with the acetyl.propiony1.and butyryl esters of diacetcne
alcohol,with modified Quantities and duration of condensa-
tion.In all cases the yield was around 3.2.4.0 g per one
tenth of a mole.cf the diacetcne ester.(Better yields are
obtained with larger amounts of chemicals.)

The color formation in these reactions is explaiu
ned by the research of Pfeiffer who found that color occurs
among the compound R-CO-A in which R a phenyl.oxypheny1,
methoxyphenyl,cinnamyl and furyl,and A - H.0H3,OH.OC3H5,NH3.
He found that all these compounds add tin tetrachloride

and tin tetrabromide to give compounds of the composition

b40-

Snx‘.2RCOoA .The appearance of Halochromism is attributed
by Pfeiffer to changes in the affinity relationships which
take place when the components add to each other.As the nump
ber of ethylene groups increases as for instance in the
cinnamyl derivative in comparison with the benzal deriva-
tive the carbonyl carbon atom becomes more unsaturated.and
the color deepens.The salts of the particular compound which
we deal with can be expressed as a
as l
/

CaHa‘CH 'C\ ‘01
c (on, )2011

L _

n
)3
Celia-CH . CH-CH so '01

\c(CH,),on

 

 

 

Ref. Pfsiffer.0rganische Molekuelverbindungen.

All compounds obtained by the above oondensations of
benzaldehyde with the three esters were found to be iden-
tical.Furthermore upon sapcnification they were found to be,
not esters,but alcohold.

This however can only be the case if the fatty acid
groups were hydrolysed off during the procedure of the con-
eation.This assumption is confirmed by the fact that the
fatty acids could be proved in the water after the reaction-
mixture had reacted for ten hours.Ths hydrolysis must take
place after the methylene group has reacted with the elde-
hyde because diacetcne alcohol with hydrochloric acid gas

.41.

yields mesityloxide as shown previously.In these reactions

however no mesityloxide was formed.

/0. 8" C Hts /O" 8" CHI,
(cna)ac H (an, ac\\
)CH, + Ono-can5—e» c - cn-csn.
CHu-g .
C Hg .8

/

8H
(CH5); \t
0 =3 CH‘CGHG
CHa-Q
b

2-acety1-2abenzal-l-l-dimethyl-ethanol.
Boiling point l45-147° /'5 mm
D33 - 1.0099

Refractive index has a 1.6128

The yellow oil crystallizes in the refrigerator but
is liquid at room.tempetature.1t insoluble in water,solu-
ble in alcohol.ether and benzene.

T13 alcohol reacts rapidly with bromine in carbon di-
sulphide.The dibromide is obtained as a yellow oil which
darkens and decomposes on the air.It cannot be distilled
without decomposition.In the refrigerator it crystallized
after three days,but it could not be recrystallized so far.
because i. is too soluble in most solvents.or comes down
as an oil.

A solution of 10.2 g of the alcohol in carbondisul-

phide is immersed in an ice bath and 8 g bromine are added

-42-

slowly,with stirring fromta drapping funnel.The carbon -
disulphide is removed under diminished pressure with very
little heat.The riscous yellow oil is analysed for bromine

by the parr bomb method.

bromine found 33.53 % calculated for C13H3.033r3

33.31 % 43.92 %

Molecular weight determination in the alcohol

by the boiling-point elevation method;

found 203.1 calculated for 0:3H1503

found 200.0 204
The benzal derivative having a methyl group directly at.
tached to the carbonyl group,is still capable of reacting
with another molecule of bonsaldehyde.

Sixteen grams of the benzalderivative and a g benzal-
dehyde were dissolved in 100 cc of alcohol.To this solution
was added 20 g of 10 % flaOH with stirring.The reaction mix-
ture was then stirred for two hours.At the end of this time
a red colored solid mass had settled at the bottom of the
beaker.The substance was extracted with ether.the ether ex-
tract washed with water and dried.Then the ether was distilled
off.The residue was purified by dissllving in alcohol and
precipitating with water.The amprphous,orange-yellow compound
melted at 98e100° with.deccmpcsition.

Analysis
found calculated for Csahgeo‘
Carbon 81.23 % 80.23 %

Hydroren 6.87 75 7.03 %

u 43-

Holecular weight determination

by boiling-point elevation

found 497.5 510.2 calc. 490.0

' for cssnseo.
Since in the above reaction some unreacted benzaldehyde
was found among the reactionproduct.there is an indication
that only one molecular equivalent of the benzaldehyde reac-
ted with two molecular equivalents of the bensal derivative.

Accordingly the structure of the compound should be:

2-lO-dimethyl-S-Q-benzal-4-8-diketo-B-phenyl-undecandi01-2c10
The formation of the compound is given by the following

equation:
I!
Cshg'CH . c/COCHa “'t’ngSE§?-CH . c<COCH . CHC‘"°
- ‘0 (cs, ) ,on 0 (ass ).on
/00-cn a cucan. ,coceg
0.H,:0H'= 0 + 05H5-03'- 0\
\c(cns)3on C(CH3)30H

/

0.35.0H . c-co-cn3-0H(can,)-0H3-00-? a CH-05H5
C(Cfia)303 ' C(CH8 )zou

The compound was not quite pure.hcwever the results

are sufficient to establish the above structure.

.44-

Physical Constants.

The densities of diacetcne alcohol and the three
esters were calculated for 20°C referred to water of 4°C.
These calculations were based on the change in molecular
volume,which.amounts to 0.11 so per degree change.21th
the values thus obtained and the refractive index taken at
20°C the molecular refracti ns were calculated according

to the formula

8
1‘5 “ya
u3 + 2 d

and the values obtained were compared with those cal-
culated according to Eisenlchr.
l. Diacetone alcohol.

"'+~‘JO \

D2° - 0.9347 (_%ACELL:M.;{/ \V~vu»3.)

n3; a 1.4242
”2" 31.55

calc. MD” 51.56

2. Acetylester
D2° - 0.9805
n38 - 1.4229
Mb. 40.85
calc. hb- 40.80
3. Propionylester
Di° - 0.9698
n°° - 1.4256
D
up =- 45.42
08.10. MI) " 45-42

.45.

8. Butyrylester.

oalc.

Di°u 0.9501

nfg - 1.8270
ub- 50.04‘
MD:- 50.04

.46-

Summary
1. IBOphorone was separated from mesityloxide and
diacetcne alcohol by distillation and the compounds
were identified.
2. Diacetone alcohol was dehydrated by hydrochloric
aoid.fatty acids and their anhydrides.
5. Three esters of diacetcne alcohol were prepared and
definitely proven.
4. The esters we;e condensed with aldehydes and the pro-
ducts identified.

5. Some physical constants were determined and cal-

culatsd.

 

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10 cot oi mu ioicsi proolem . Accordio; to your letter
a . V

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at; it t-et JOu carried out tie allaline condensation

9-? '~ ~.- ”L‘MH. ‘re -~-7 " - a ,.
Jitlout settle. two desired pioduct , or else

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i loosed up my orixinal noteooor on the

reaction as well as the literature , and found that there i

.E‘ _ 1“ _- V . -— . ‘ . ‘ 1 "‘ ~ ..
Oi in? alkali ”re error lS due to the rec;

‘ . r~. 4 ~ .- . - T, \/- f. 1 -5 0.. I ' _~ ‘
f a Mintahne 1o toe proccQUae as outlined

fore in doubt

'5." ~ 4- . 1 I‘\ ‘3
£135-: L. l CU._LC—L..L

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f4
ci-
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CD

the comoound the first time by mean of 1C 5 alxali,w s how-

ever unable to reproduce the ronction9 and thus had to use

U)

tron or alkali . The corrocx procedure is as
Dissolve 16 g of the hanzalderivative and 3 0
in 100 00 Of ethyl alcohol . To this solution

40 fl haOB ( aqueous ) , slowlylwith stirring

follows :

benzaldehyde

add 20 g of

is carried OUt in a beaker at room temperature , the stirrinS

iis best accomplished by means of a motor . The product sepa-

rates out after 10 or 20 minutes . Stirring is

continued for

a while , and then the orange precipitate separated by de-

(D

vcanting . Th

 

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3281

150

H;E.Ungnade

University of Kinasota
Llnneapolis , fiinnesota

Kiss Jean O‘Brieh‘

527 Hillcrest

03

L

fiast-Lansing , Mickigan

 

 

 

L
‘WLL Sco°{‘1’"/' “mfim WW
.Oefw Km WSwM'M

 

 

 

 

Herbert E.Ungnade

School of Chemistry

University of Iinnasota

Iin=eapolis,flinn. November,15. 1954.

Thank you very much for your letter and for sending the

.. '< H -
I.
u

sample of my compound.I guess you have received the sample cac;
by this time.I have written down the analyses together with other
data which I collected and which I believed to be necessary in
order to make the work complete.As you see the compound you sent
did not quite correspond to the structure tha: I assumed it to be.

This fact,of course lead me to an investigation of the next
higher product using the above as a starting material.

The compound you sent up here new is an isomer of Claisens
benzal-mesityloxide.I prepared a small amount of the latter com-
pound and I am sending it to you in the near future.I wonder if
it might be possible for one of your prep. students to prepare a
larger amount of the substance and determine its constants which
Claisen did not determine.Tne values could then be compared with
the values which I found for my substance.

The preparation is relatively easy,the reference is given at
the end of the enclosed supplement of the thesis.
I am very glad that your research is coming fine,and I hOpe
that you are all through by now with your prelims.
Please excuse typing and other errors which are due to the fact
that I have to hurry because I have still much to do this evening.
Remember me to your Wife please and receive best Wishes and

good luck for your research and otherwise
your

W

 

 

 

 

 

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..~i_-

éflf) SOME OF IT:IUK:DERIVAT YES

Eerbert Ernst Unnnade

 

 

 

-1-

F”

ihe compound assumed to be B-acetyl-Z-benzal-l-l-dimethyl-

ethanol was analysed for Carbon and hydrogen and the following

values were obtained: H 0
found 7.50% 35.95%

calorlated for Clghléo 7,5R5 33.32%

calculated for Clghleog 7.34; 76.47%

Accordingly we deal not as assumed with 013H1602 but with
013H140.In agreement with the latter formula are the molecular
weight determinations,which are within 10$ of the theory.

Assuming that the primary step in the synthesis of the com-
pound 013H140 is the combination of one molecule of benzaldehyde
with one molecule of the acetylester of diacetone alcohol the
structure of the compound would be:

= c
‘g-Chg

If however,we assume that the ester is first decomposed

(I)

with the formation of mesityloxide,the resulting compound should

be benzal-mesityloxide,which is isomeric with the above.

CHg' = CH—CO-CH = CH-06H5 (II)

1?
I..3

(>0

It is obvious that the physical properties of the two possi-
ble structures cannot be very different.Their odor,color,B.P. etc
would most likely not allow a differentiation.It should,however,
be possible to differentiate them by their reactivity towards
benzaldehyde. Structure (I) has a methyl group adjacent to the
carbonyl group which is capable to react with one molecule of benz-

aldehyde,while the structure (II) does not have any such group.

 

 

 

 

 

 

f)

-{.l-

,-..

In the previous work the obtained compound 013H14O was
submitted to alkaline condensation with benzaldehyde,and the iso-
lated product analySod.On the basis of this analysis and the assump-
tion of the Q-acetyl-Z-benzal-l-l-dimethyl-etnanol structure
its formuaa was found to be"033H36O4".

Difficulties were encountered in the analysis though in as
far as little substance was available,and tie latter in an amor-
phous State.

A new preparation of the compound,subsequent purification and

analySIs showed contradicting values

found H C M.W.
6.8 % 6.75% 84.23 % 84.20;

calc. for C33H36O4 7.05 s oo.2s% 496

calc. for c33n3202 6.95 5 35.03 t 460

Gale. for(CgoH180)2 6.57 % 57.59 % 543

The mere fact that a higher condensationproduCL with benzalde-
hyde was formed would indicate that we deal with structure (I)
as mentioned above.

As to the structure of the condensationproduct the analytical
results exclude a simple condensation of two molecules,one each
of the ketone and the aldehyde.lhe molecular weight of that par-
ticular compound would be 274 (conlao) Its dimer does not agree
with the results of the C,H analysis.

The previously assumed 033H3604 is out of question because
the assumption of the ketone—alcohol structure of the starting -
material did not verify.Therefore we must assume the structure

to b8(C33H3202) :

5-9-benzal-2-lO-methylene-4-8-diketo-é-phenyl-undecan.

 

 

 

 

Tie final proof cannot be brought until the compound can be
crystallized from some suitable solvent,or purified by some otler
method than precipitation.

The pro f forwarded for the structure (I) of Clgfiléo would

'1
l
.n.

be unsufficient,however,unless it wens proven that tie structure

(II) does not react with benzaldehyde.
Correspondinely the benzal-mesityloxide was prepared according

to Glaisen by treating a mix ure of benzaldehyde and mesityloxide

in an ice bath with dry ECl gas.The product formed as in the case

of the product from diacetone alcohol acetylester forms a molecular

compound with hydrodiloric acid,giving rise to a deep red color.

The pure yellow liquid was treated in the cold with benzaldehyde
and 10% algali.There was no reaction in the cold.$n prolonged hea-
ting the liquid droplets darkened but remained liquid.

It might be interesting to compare the two isomers as far as
physical properties and derivatives are concerned.Claisen gives
only the boiling point and the 0,3, analysis.

r) .‘ . ’- l' ... . I , ',£ '.,
nef. Llaisen, flxfifi ,fiflfilfllbfihuPVTFJ

 

 

 

 

 

 

Melting - Point of

B-Acetyl-B-benzylidene-l-l-dimethyl-ethanol.

 

 

 

 

 

1.

3.

4.

5.

Synthesis of IBOphorone
(Mesityloxide, Biacetone alcohol and xylitone)

Raw material
Acetone 800cc.
Methanol 200 cc.
Sod.hydroxide 25 gm.

 

Reflux 1 hour per day for 10 days

Neutralize with 002 and filter the sodium bicabbonate off.

Distil the filtrate under atmOSpheric pressure. About 650 cc. of acetone
and 200 cc. of alcohol are obtained before the temp. reaches 66.60 at
which point the distillation is stopped.

The residue is distilled under a reduced pressure of 15 mm. (aspirator)

and the folowing obtained:
Ddacetone alcohol
Mesityloxide
water

H 3 1.427
n 3 1.445

The residue is distilled under high vacuum in the presence of an

inert gas after drying with CaClg. The following are obtained:

 

Mesityl oxide n = 1. 4389 B .p. 60-9Q/4 mm.
Isophorone n = 1.4780 B.p. 90-100/4mm.,198/atmos.
D = .09228 at 20°
xylitone n = 1.5 B.p. lZQ/4mm.
CH3-CO-CH3 Acetone
CH3\ o ,
633,6(OH)~CHZ’CO‘CH3 D1acetone alcohol
gfls‘c = CH-CO-CH3 Mesityloxide
H’s
.033 9H3
c C
of \CHZ HG; 7H2
I CH I ,
0=(> 010113 0: c\ /c\gg3
\\ 3
032
643‘6H3
ISOphorone Xylitone

2 acetone ~ 1 HGH -——» mesityl oxide
acetone - 2 HOH -——-v Isophorone

3
4 acetone - 3 HOH -——v

xylitone

 

 

 

 

 

5

5/

 

5CH[M[ 0F [0/1/0[/V.'.4ALW Cg : 0

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Br

) MP /06—/07° 5/

 

 

 

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Esters of Diacetone Alcohol and Some Derivatives.
by Ralph C.Huston and Herbert E.Ungnade

The lower esters of diacetcne alcohol were discovered as bi-
products in the dehydration of diacetone alcohol by fatty-
acid anhydrides.

A yield of 80 % (of the theory) of mesityloxide was
obtained by treating with anhydrous hydrochloric acid.When
fatty acid anhydrides were used the yield dropped to 70 %,
with a 15 % of ester as biproduct.

The esters obtained by treatment with acetic,propionic
and butyric anhydride were isolated and identified.

The acetylester upon treatment with sodium underwent
Claisens Condensation.

All three esters could be condensed with benzaldehyde
by hydrochloric acid.The seters were hydrolysed during this
reaction,giving rise to only one alcohol:

2-benzal-2-acetyl-l-l-dimethyl-ethanol

The latter alcohol was again condensed with benzalde-
hyde by cold,aqueous alkali.The rea:tion product was found
to be :

2-lO-dimethyl-3-9-benzal-4-8-diketo-6-phenyl-undecandi01-2-lO

Experimental.
Diacetone alcohol esters.
The acetylester of diacetone alcohol was-prepared refluxing

a mixture of 464 g of diacetcne alcohol and 204 g acetic anhy-

 

 

 

umdhuiedzlgo

 

dride for three hours on a sand bath.The reaction mixture
after cooling was poured into an equal volume of ice water
and neutralized with sodium bicarbonate.The oily layer was
separated,dried and fractionated under reduced pressure.
Three hundred and fifty grams of the crude oil gave 270 g

of mesityloxide and 80 g of the ester.The ester was obtained

as an oil boiltng at 171-1750 / 742 mm.

Bp5 = 60-62° Bplo = 72-730

Density D3? = 0.9811

Refra:tive index n38 = 1.4229

Saponification percent HAG found 57.82-38.07 %
calculated for 08H1403 37.97 %

The propionyl and butyryl esters were obtained analogously
from the alcohol and the corresponding anhydrides.
Constants:

1. propionylester:

Bp743 = 182-184° Bp8 = 80-81°
Density D22 = 0.9680
Refractive index n23 = 1.4256
Saponification percent prepionic acid
found 42.99-45.20 %
calculated for 09H1603 42.99 %

2. Butyrylester.

Bp742 = 192-1950 / Bplz = 97-98°
Density ’ D22 = 0.9536
Refractive index n23 = 1.4270
Saponification percent butyric acid
found 47.51-47.§%
8W fa emu/.205 47.23 %

 

 

 

 

 

Semicarbazones.

All three esters reactAwith semicarbazigg hydrochloride
giving crystalline semicarbazones.The semicarbazones were
obtained as follows:

Dissolve one part of semicarbazide hydrochloride in the
smallest possible amount of distilled water.Then add one part
of the ester.Add a saturated alcoholic solution of KAc.until
a homogeneous solution results.

The semicarbazones of the three esters crystallizeibest

from 50 % alcohol.

C9H1703N3 M.P. 137.5-138 °

010H1903N3 M.P. 144.5-1450

011H2103N3 M.P. 110.4-110.8 °

Nitrogen in semicarbazones calc. found

CgH1703N3 19.53 % 19.49 %
19.33 %

C10H1903N3 18.34 % 18.52 %
18.40 %

011H2103N3 17.24 % 17.00 %
16.82 %

The densotoes of the esters were then calculated for 20°C

referred to water at 4°C.The following values were obtained:
0
2

Diacetone alcohol D4 = 0.9347
Acetylester fixflfinflx 0.9855
Proplonylester 0.9698

Butyrylester 0.9551

 

 

 

 

-4-

From these values the molecular refractions were calculated

according to the formula:

M =._a§L;l 42
n2+ 2 d

and the obtained results were compared with those calculated

according to Eisenlohr 8 atomic figurs.

M (found), M (calculated)
Diacetone alcohol 51.68 51.56
Acetylester 40.85 40.80
Propionylester 45.42 45.42
Butyrylester 50.04 50.04
Molecular volumes V (found) V(calcu1ated)
Diacetone alcohol 124.14 152.00
Acetylester 160.45 197.20
Eropionylester 177.46 219.20
Butyrulester 195.80 241.20

Condensations of diacetcne alcohol esters with benzaldehyde.
A mixture of 15.8 g of diacetcne alcohl and 10.6 g of
benzaldehyde was cooled in an ice bath and hydrochloric acid
dried over H2804 was passed in.The deep red colored solution
was allowed to stand for 10 hours.Then it was poured into
ice water,washed with water and carbonate solution,driéd and
distilled under reduced pressure.A heavy yellow oil was col-
lected at 145-14700 / 6 mm.The yield was 4 g.

Identical products were obtained with the homologous esters.

 

.

 

'_ -\_

.‘_._

-5-

593: a

 

When cinnamic aldehyde was used instead of benzaldehyde y
a deep blue-green color resulted upon condensation with H01.
The color formation is due tot he particular structure of the
obtained keto-alcohols,their structure being identical with
those investigated by Pfeiffer.
The condensationproduct in the case of cinnamic aldehyde
could not be isolated because it decomposed upon distillation.
The obtained product was phenylethylene.
The benzaldehyde condensation product boiled at 145-1479/5 mm.
D3? = 1.0099

Refractive index n50: 1.6128
melting point i7oC/
The compound added readily bromine,the dibromide however de- K

composed on the air,giving off HBr.

Molecular weight determined in the benzalcompound
by boiling-point elevation method.

found 205.1 calcultted for 012H1602

found 200.0 204.0

The benzalderivative was condensed again with benzaldehyde
by dissolving 8 g benzaldehyde and 16 g of the benzalderiva-
tive in 100 cc of a1c0hol.T0 this solution was added 20 g
of 10 % NaOH.with stirring.The amorphous,0range yellow pro-
duct was déssolved in alcohol and reprecipitated by adding
water.The dry precipitate melted at 98-100°.

? “‘44? %
Carnbon 81. 3 % 80.23 %

Hydrogen 6.87 % 7.03 % (5; L

3
5/2644’

 

 

 

 

-5-

Molecufr’weight by boilingpoint elevation.
found 497.5 510.2 calc. 490.0
for 033H3604
formula
06H5-CH = C-CO-CH2-0H(06H5)-CH2-CQ-C = CH-CsH5

(CH3)20H 0(083)2 0H

 

yglecular Volume of the diacetcne alcohqlflesters.

vzié

d
V1 V2 Vl‘Vz
Diacetone alcohol 152.00 124.14 27.86
Diacetone acetylester 197.20 160.45 56.75
Diacetone propionylester 219.20 177.46 42.74
Diacetone butyrylester 241.20 195.80 47.40

V1: molecular volume calculated from the atomic values.
V2: molecular volume calculated from density and molecular

weight.

Constants used for the calculation:

D20 M

Diacetone alcohol 0.9547 116.0
Diacetone acetylester 0.9855 158.1
Diacetone propionylester 0.9698 172.1
Diacetone butyrylester 0.9551 186.1
Atomic values:

Carbonyl oxygen 12.2 cc

ether oxygen 7.8 cc

hydrogen 5.5 cc

carbon 11.0 cc

 

 

flglecular Volume of the‘diacetgne alcoholfiesters.

v=2=£

d
V1 V2 Vl'Vz
Diacetone alcohol 152.00 124.14 27.86
Diacetone acetylester 197.20 160.45 56.75
Diacetone propionylester 219.20 177.46 42.74
Diacetone butyrylester 241.20 195.80 47.40

V1: molecular volume calculated from the atomic values.
V2: molecular volume calculated from density and molecular

weight.

Constants used for the calculation:

D20 M

Diacetone alcohol 0.9547 116.0
Diacetone acetylester 0.9855 158.1
Diacetone propionylester 0.9698 172.1
Diacetone butyrylester 0.9551 186.1
Atomic values:

Carbonyl oxygen 12.2 cc

ether oxygen 7.8 cc

hydrogen 5.5 cc

carbon 11.0 cc

«.E‘W‘

 

 

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