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A STUDY OF THE PREPARATION OF SOME
TERTIARY DIMETHYL Am CARBINOLS

Mil-m

A THESIS

Submitted to tho Graduate School 01' 1101113311 Stat.
6011030 of Agriculture and Applied Science in
partial fulfillment of the ”gamut: for the
degree of
mm 01" 801363

DEPARTMENT OF CHRIST”
1939

ACKEOWLEDGWT

mo writer wishes t0 express his thanks
and appreciation 30 'm.‘ R. 0.» Huston for
his assistance in the pursuit of these studies.

TABLE OF CONTENTS

mm DUCIIon
REVIEW or IHE LITERATURE
EXPERIEEHTAL DATA
MATERIALS
PRELIHINARY PREPARATIONS
ALconoLs PREPARED
2.EEEHIL, 3.EIHIL PEEIAEOL.2
2,3,3.IRIEETHEL PENTANOLLQ
2,5,4.IEIEEIHIL PENTAEOL.2
2,4,4.IEIEETHIL PENTAN0L_2
TABLE OF EEEULIS
DISCUSSION
SUMMARY
BIBLIOGRAPHY

INTRODUCTION

In the past, Dr. Boston and some of his oo-
vorkere have worked in this laboratory in the field
of Aluminum Chloride condensatione. So for, the
em}: with aliphatic alcohols has been completed
through the condensation of some of the tertiary
dimethyl m1 carbinole with phenol. and with benzene,
in the presence or almimm chloride ( 1) .

The writer has had as his object the preparation
of sufficient quantities of some tertiary dimethwl
m1 carbinole to make possible the further study of
their condensation with phenol, and with benzene, in
the presence of alumimm chloride.

REVIEW OF THE HTWTURB

2.15m, 3mm PENTANOLZ

In preparing this Carbinol in 1908, Clark (2)
need Conrad's method for the preparation of ethyl
diethylacstoacetate which, upon hydrolysis with 10%
non, game the ketone 3.,ethy1 pentanone.2 in a 60%
yield (bop. 158° c. at 760 m). This ketone was
converted to the carbine]. by the use of the methyl
iodide Grignard reagent in an approximate 15% yield.
2,3, smmmm. PEIJTANOLQ

Vmitnore and Laughlin (3) prepared this oarbinol
in 1932. Methyl, tertiary amyl ketone (13.1). 129°.
131° 6.) was prepared from acetyl chloride and tertiary
m1 mgnesim chloride. This ketone was changed to
the cortisol by a Grignard reaction with methyl
magnesium chloride in a 65$ yield.

The above authors (4) also reported this carbinol
in 1953. Ethyl dinethyl ethylacetate (up. 140°.
140.8° C. at 730 m.) was prepared in a 37% yield
from tertiary amyl magnesium chloride and ethyl chloro-
carbonate. This ester was converted to the carbine}.
by means of a Grignard reaction with methyl magiesium
chloride. The reported yield was 78%.

In 19:56 Huston and Seulati produced this carbine].
from tertiary amyl chloride and acetone by the
Grignard reaction. A yield of. about 55 was reported.

This carbine]. was prepared in 1936, also, by
Horton and Haas. It was obtained through the action
of diethyl magnesium upon 2,3..didnethyl 2,3..epoxybutane
which forms an addition product that upon hydrolysis
gives the carbinol. The reported yield was 34.6%.
2,3,LTRIMETHYL PHITANOLQ

The preparation of this carbinol was reported
in 1959 by Huston and Guile ('7). The ketone 5,4...
dimethyl pentanone (mp. 135°-14o° c. at 744 m.)
was prepared in a 9.3% yield mm acetyl chloride
and 2.1mm, 3.31er butane. The sarbinol was
obtained in a 58.1% yield through the usual methyl
iodide Grignard reaction.
2,4,LTRIMETHLEL PENTANOLz

Butlerow (17) reported the preparation of this
carbinol in 187?. Diisobutylene vies prepared from
tertiary butyl alcohol and sulphuric acid. This,
in turn. was converted to the halide Liedo, 2,4,4.
trimethql pentane by the addition or dry hydrogen
iodide. Treatment of the halide with silver hydroxide
(moist silver oxide) yields the carbinol.

EXPERIMENTAL DATA

MATERLXLS .

Tertiary butyl alcohol was Eastman's "practical“,
M.P. 25°-25°C., and was used without further purification
to prepare diisobutylene.

The bromides of diethyl carbinol, tertiary amyl.
and isopropyl were prepared from the corresponding
alcohols; Eastman's”technical" without further pur-
ificetion.

Acetone was the C.P. grade dried over sodium
sulfate and twice distilled before using.

Ether used for Grignsrds was anhydrous dried
over metallic sodium.

Acetyl chloride was Baker's G.P.. used without
further purification.

lmgnesium turnings prepared for Grignard reactions
were dried over calcium chloride in a desiccator
before using.

Acetaldehyde was Eastman‘s "practical," distilled
once through a colmsn and used imediately.

PRELIsmm PREPAliATIONS
3.3mm) PENTAHE

Diethyl carbinol was added to an excess of 48%
fwdrobromic acid and a bromination reaction was carried
out by refluxing for 8-10 hours. ms reaction mixture
was then distilled and the bromide layer was separated,
and washed twice with water; then dried over CaCIQ. The
dried bromide was then distilled, collecting a LEI-action
over a four degree range. 114-1180 0.

Isa-propyl bromide (8) was prepared in a similar
manner with the one exception that sulfuric acid
was also used in the bromination. A fraction from
58.50-60°0. was collected for this halide.

Tertiary ml bromide was prepared in a similar
manner to 5.bromo pentane, collecting a fraction boiling
at 105-1080 c. '

Tertiary any]. chloride (9) was prepared by slow-
ly adding an excess of 0.19.. concentrated hydrochloric
acid to tertiary m1 alcohol. After shaking. the
layers were allowed to separate and the upper layer
was drawn off, and washed first with a dilute sodium
carbonate solutioa, then twice with water. The halide
was dried with calcium chloride and then distilled.
comecting the fraction‘boiling at 54.5-56" 0.

Methyl iso-propyl oarbinol (19) was prepared
from the Grignard reagent of ice-prowl bromide and

aceteldehyde, the reaction being carried out at 05°C.
The fraction boiling from 110-11206. was collected
as the products

The preparation. of the bromide of methyl inc-w
prowl carbiml was carried out as follows: To
mam: zeo-pmpyi carbincl. at a «10°C. was added,
while stirring, a calculated summit of phosmorcue
tribromide necessary for a molecular etguivalent bro-v
£11116.th After the addition was completed, the
reaction mixture was allowed to earn up to 25°C. and
remain at that texzqaerature over night. The next day
the too layer was secreted and washed with water
and a dilute sodim carbonate solution... After W
with (:3ch chloride, the halide was fractionated
with the main fraction distilling at ins-108%. ms
boiling point am not corresporxi” to that ”corded
in the literature {11) (114.1169 0.). but rather. to
the boiling; point of tertiary any}. bromide. In W
to so: mrs definitely shat compound was formal by
this bromimtion, a portion of the product was treated
with mist silver oxide in order to convert the We
back to an alcohol. The product obtained had a definite
boiling point of loo-102° 0., the highest Water-c
reached being 104°C. this indicated that the tun-wide
formed was that of tertiary ml and not the expected
2m. mthyl butane.

Bothy]. bromide Grim reagent. A modification

of the mthyl chloride preparation (12) was used.
A methyl bromide generator (five-liter, round bottom
flask) was charged with a cooled solution of 67 ml.
of water, 400 ml. of concentrated sulfuric acid, 687
m1. of methyl alcohol, and 1410 grams of sodium bromide
(a theoretical 15 moles). The generator flask was
fitted with a reflux condenser, on the tOp of mick
was placed a delivery tube. Generation of the gas
was started by warming 'a sand bath under the flask.
The methyl bromide was passed through a nine bottle
washing train consisting of three safety flasks (1,5,9),
three bottles of reagent sodium hydroxide solution
(2,3, as 4) to remove any free acid fended. and three
bottles (6,? s s) of sulfuric acid for drying. After
drying, the gas was passed into the Grignard reaction
flask containing magnesium turnings and other. It is
advisable to initially start the reaction with a
small cilantity of some reactive halide, such as ethyl
bromide. It was necessary to add anhydrous other
to the flask throughout the reaction to keep the
temperature down. Addition of methyl bromide was
stopped when most of the magnesium disappeared.
Phosphorous tribromide (13) was prepared by acid..-
ing bromine to a stirred suspension of red phosphorous
in carbon tetrachloride. After all the bromine was
added, the carbon tetrachloride was removed by
distillation and the phosphorous tribromide was

fractionated, collecting the portion boiling
1699173000

ALCOHOLS PREPARED
I 2.1nethy1, 3.eth'y1 pentanoLg
II 2,5,5-trimcthyl pentanoLg
III 2,3,4-trimethyl pentanoLg e
IV 2,4,4.tr1methy1 pentanol.2
I Emethyl, (Lethyl pentanol-2

0115
633.cag-cn-cwa
0,112 $33
£35

12113 octane]. was prepared by two methods: (1) me
treatment of the Grignard reagent of 3.brom pentene
with acetone, forming the octane]. directly. (23) the
treatment of acetyl chloride with the Grignard reagent
of 3.bromo pentane giving the ketone, :5-ethyl pentanom.2,
and then the reaction of this ketone with a methyl
bromide Grignard to give the octanol.

(1) In the first preparation a modification or both
the following methods was used: the $2111er (14)
procedure for preparing, the Grigxard reagent, and the
Edgar (15) procedure for the reaction of the reagent

m.

4* Preparation reaction completed, but the alcohol was
not obtained because of a rearrangement that took place

in the preparation of the bromide, 2.bromo, 3...le butane.

with a ketone and subsequent hydrolysis of the result-
ing compelmd. Because of these modifications, the
procedure used willbgiven in detail.

A dry} tweeliter. three-neck, round bottom flask
was fitted with a reflux condenser (with drying tube),
on efficient glycerine seal stirrer. and a 500 ml.
drOpping funnel (with drying tube). A small crystal
of iodine was placed in the flask; the flask was
then heated until the iodine began to vaporize. When
the vapor had condensed. 48.5 grams (2 moles) of
fresh, dry ammonium turnings were placed in the
flask. 60 ml. of anhydrous ether, sufficient to
contact all the magnesium turninge present, were added.
500 ml. of anhydrous other were added to 352 grams
(2.2 moles) of 3-bromo pentane. (.2 mole excess was
used to insure complete reaction with all the magnesimn
turnings present.) 15 ml. of this solution were
added directly to the magnesium turnings and the stirrer
was started as soon as there was definite evidence of
reaction; (external cooling was applied when necessary).
The remainder of the halide-ether solution was placed
in the dropping ftmnel and added at such a rate (drape
nice) that the reflux did not exceed one drop per

second. After approximately one-half the halide-ether

4* It is essential that all apparatus and chemicals
used be dry, and that the reaction be protected frmn
moisture throughout.

solution was added an additional 50 ml. of anhydrous
other were placed in the separatory fimnel. After

the halide-ether addition was completed, the reaction
mixture was stirred at least five hours before continuing.
At this point the Grignard reagent was black in color.

To complete the reaction a mixture of 116 grams
(B‘moles) of purified acetone and 100 m1. of anhydrous
ether was added, (imp-wise, to the Grignard reagent,
at such a rate that the reflux did not exceed one
droy per second. The Grignard complex was stirred a
few hours and let stand overnight before decomposing.

The Grignard complex at this point should be white
in color, and mostly in the precipitated form.

The next day the decomposition was carried out
by slowly pouring the complex on ice and water while
stirring. The other layer was decanted off into a.
separatory funnel and the remaining precipitated magmaium
compounds were dissolved by slowly adding, while stirring,
concentrated hydrochloric acid (kept cool with sufficient
ice during the addition). The other layer was separated
and added to the first ether portion. The water layer
was twice extracted with 60 ml. of ether. The combined
ether portion was washed with a small volume of dilute
sodium carbonate Solution, followed by a washing with
a small volume of distilled water. The other solution
was then dried over anhydrous sodium sulfate. The

ether was removed by distillation at atmospheric pressure

until the temperature reached 45°C. The remainder
of the fractionation was oarriefi out at a reduced
pressure. Three, two mole runs wider these conditions
gave an average yield of 13.5% carbinol b.p. 46-47.5° C.
at 6 mm.

The other fractions were:

28 grems b.p. 55 ~ 580 C. at 18 Iran.

5 grams 13.13.. 48 - 59.50 C. at 6 ms.

Y‘ihen the some quentities were used in a similar
preparation with increased rate of addition of the
I halide-ether solution and of the acetoneuether solution,
to maintain a gentle reflux throughout, the yield was
decreased to 10% carbinol. With the increased temperature
there was an increase in the amount of low boiling fraction.

(2) In the second preparation of the octenol,
through the ketone synthesis, a modification or the
method of Idinitmore and Badertscher (14) was used.
Because this method for preparing the carbinols was
found to be the most satisfactory, it will be given here
in detail.
Preparation of 3-ethyl pentanonc-2. Using; the same
apparatus and procedure just described, a 3 mole
Grignard reagent was prepared from: 73 grams (3 moles)
of magnesium turnings, “100 m1. of axfilydrcus ether (added
to the tunings), a solution of 500 grams (5.3 moles) of
3~bromo pentane and 500 ml. of anhydrous other, plus
an additional 100 m1. of anhydrous ether as the reaction
progressed. The yield of Grignerd as determined by the

Gilman method (16) was found to be approxizmtely 50%.

An epgeretus similai' to that just described to:-
he preparation of the Grime-mi reagent, was next
used; the two-liter flesh being replaced by a three-
liter, hreeuneck flask. Into this three-liter flask
was placed 157 grams (1.5 moles) of acetyl chloride
and 200 ml. of anhydrous ether. The stirrer was
started and the Grigerd reagent was added through the
separatory funnel at such a rate that a reflux of
two to three drops a second was maintainers}. When all
but approximately 200 m1. of the reagent solution was
added, an additional '25 ml. cf acetyl chloride was
slowly added to the reaction flask through the condenser,
to insure an excess. During the reaction a mu
precipitate was formed which turned light orange on
completion. The reaction mixture was allowed to stir
at least five hours before decmnycsing. The decomposing
was carried. out in the some I? more as that of the previous
method except that an addition of hydrochloric acid
was unnecessary because of the acetic acid formed when
the excess acetyl chloride was hydrolyzed. The other
solution in this case can be dried with either anhydrous
potassium carbonete or sodium sulfate before distilling
at atmosgfiloric pressure. After the other was rmed,
the residue was placed in a one-liter distilling flask

with 300 ml. of water and a smell Lguontit‘y of sodium

or potassium carbonate, and distilled. In this way
the kotone was eteem.dietilled away from.the higher
boiling impurities. It wee found unnecessary to

salt out the kotone. Therefore, it was separated

from the water and dried with.enhydrous sodium.sulfete.
After drying. the ketone was vecuum.dietilled, collecting
a small irst end last fraction whiCh were discarded.
Rent, the middle fraction was distilled, at atmospheric

pressure, three times until a main frection.waa collected.
A 50% yield of kotone was obtained within boiling range
of 135-14000 at 742 mm.

Preparation of Semethyl, S-ethyl pentenol. An

8 mole quantity of methyl bromide Grignerd (preliminary
preparations) was prepared and the hetone in a 131.5
dilution with.ether (anhydrous) was added to it not
faster than one drOp every two seconds. The Grignard
reaction mixture was stirred at least five hours before
decomposing in the usual manner. In this case, the

precipitated magnesium.compounds were dissolved with
dilute hydrochloric acid rather than the concentrated,
When the carbinol was fractionated at reduced pressure
78% yield of product b.p. 4.6 - 47.60 c. at 6 m. was
obtained from the kotone.

This second preparation of the cerbinol was by

far the better of the two methods. The final product

was quite pure, as shown by its eesy separation

during the distillation.

II 2,3,3-trimethyl pentanol-z

OHS ({HS
“5-032” ,0 '- IC “OH
CH5 CHS

Several attempts were made to prepare this octanol
following the methods given by Whitmore and Laughlin;
((5 6: 4), but the preparations met with very little
success. Trouble was encountered, in the preparation
of the Grignerd reagent, by the precipitation.of
magnesium.dhleride which.hindered the formation.ef the
msgnesium.Grignsrd complex. Varying the conditions
of the reaction gave no appearance of ingrovements
Seven attempts to prepare the Grigncrd reagent were
made. Of these, all but one solidified before the
calculated amount of halide could be added and this
contained umch.precipitute. The reaction mixture was
divided into two portions, one was used to prepare
the octsnol directly by he reaction with acetone,
the other used to prepare the kctcne 3,3~dimethy1
pentsnone-g by the methods already described. Upon
fractionstlon.no trace of product could be found:
only lower boiling products were recovered, indicating
that no Grignard reagent had been fozned in the original
preparatien.

The writer carried out a trial (.25 mole) Grignard

on.tho bromide of tertiary smyl instead of the

Chloride as described.by'Whitmore and Badertscher (l4).

This yielded a black Grignard reagent that was without
the presence of a precipitate. The Grignard reaction
was completed using acetone to prepare the carbine}.
directly. Upon fractionation a small amount (4 grams),
of product was collected in the boiling range of the
carbinol.

A 2 mole Grignard was carried out using 532 grams
(2.2 moles) of halide and 87 grams (1.5 moles)of acetone
which yielded upon fractionation a 12 percent yield
of the carbinol. boning at 45° - 47° 0. at 6 mm.

A similar Grignard reagent (2 moles) was also
made and was used to pmparc the ketone 5,3-dimethyl
permanency-.2. This gave a {50 percent yield of the
ketone, boiling at 46-490 a. at :50 m.

This .5 mole of ketone was added to a one mole
methyl bromide Grignard which, in turn. gave a 50
percent yield of the carbinol boiling at 45.54.70 0.
at 6 m.

A 81:: mole run carried out under similar conditions
gave a 38% yield of the ketone from tertiary emyl
bromide, which, in turn, gave a 59 percent yield
of the carbine]. from the ketone.

III 2 ,3, Ltrimethyl pentamLz

CH3
(ms-CH «- OK -\c ~- OH
('33; £333 ('333

In this preparation the bromide prepared tron
methyl iso propy’l carbinol and phosphorous tribrmnide
did, not have the correct boiling point for 2-bromo,
Wthyl butane as stated in the preliminary
preparations. . .

A ketoneoalcohol synthesis was carried out starting
with this bromide and following the above ontlimd
procedure. The yield of ketone obtained was 32%. From
this an 81% yield of the alcohol (believed to be
2,3,3-trimethyl pentamLz) was obtained, boiling at
45 - «5.5" c. at 6 m.

IV 2 ,4,4.trimethy1 pentanoLz

as as
CHS" [C *- CHz. lCtOH

CH3 035

The method originally described by Butlerow (17)
was used with some modifications for the preparation
of this carbinol. The procedure consisted essentially
of fonning the iodide, 2.,Iodo, 2.4,4_trimethyl pentane
from diiscbutylene and then changing the iodide to
the alcohol by means of silver hydroxide (moist
silver oxide).

The best method for preparing diisobutylene
which is a modification of the procedure by Panels:
and coworkers (19) was described by Whitmoreua).

In a one-liter round bottom flask a cooled mixture

of 500 m1. of cm. sulfuric acid and 500 ml. of

water Was slowly added to 700 ml. of tertiary butyl
alcohol while stirring. This solution was heated

on the steam bath for three hours, then allowed to
cool. then cool, the two layers were separated and
the top layer washed with a dilute solution of sodium
carbonate until neutral. then it was very slowly and
carefully separated and placed in a distilling flask
with a very small quantity of metallic sodium. Suction
was then applied to remove a considerable quantity

of dissolved isobutylene. The rest of the solution

was vacuum distilled, keeping the temperature near

60°C., the first small fraction and the last high
fraction being discarded. A second fractionation
was carried out at ordinary pressure which gave
a 54.5 percent yield of diisobutylene collected, at
loo-105° c.

The iodide, 2-iodo,2,4,4-trimethyl pentane,
was prepared by passing dry gaseous hydrogen iodide
(preliminary preparations) into the diisobutylene
until it was completely saturated. In order to
have the addition of RI start. an initial temperature
of looc'was used. As soon as there was evidence
of adsorption, the temperature was decreased to
below 0°C. by means of an ice salt bath. This crude
iodide (at 0°C.) was then washed with 200 ml. of
distilled water (at 2°C.), which contained one crystal
of sodium thiosulfate, to remove any dissolved
hydrogen iodide or any free iodine .2resent. (This
iodide is quite unstable at. room. temperature; there-
fore it is advisable to keep it at least below 5°C.)
After a careful separation. the tap layer was dram
off and dried over calcimn chloride in the refrigerator.
To the dried iodide was added (at 0°C.) the moist
silver oxide in small quantities, while vigorously
stirring. (Sufficient silver oxide has been added
when the black silver oxide no longer changes to the
yellow iodide upon addition). The resulting mixture

was then allowed to come to room temperature and all

the liquid was removed from the precipitated silver
iodide by filtering with vacuum. The filtrate

was separated and dried while the water from the
filtrate was extract-ed twice with ether, dried and
distilled. The precipitate was placed in a flask and
the adsorbed carblnol was removed by vacxmm distillation.
The distillate consisted of two layers which were
separatei and treated in a manner similar to the
filtrate. Upon the final distillation 12 percent

of the diisobutylene was recovered, while a 44 percent
yield of the carbine]. was obtained.

TABLE OF RESULTS
BOILING POINT REFRAC IVE INDEX SPECIFIC SURFACE*

 

 

ALCOHOL T3318. Press. n GRAVITY TENS ION
M. f
I 151.2 742 1.4308200 .8268260 22.12128°
II 155.5 740 1.44072°° .8595260 22.45528°
III 155.5 740 1.4406200 .8563260 22.387280
17’ 146 740 1.42909°° .319025° 20.9119 °

* Du Nouy Tensiometer

éLCO QLS

I 2.METHYL, 5-ETHYL PEHTANOL.2
II 2,3,3-TRIMETHYL PENTAHOL.2
111* 2,5,4-TRIsETHYL PENTAHOL.2
IV’ 2,4,4.TRIhETHYL PENTANQL.2

DIoCUSSION

In the study of the preparation of these tertiary
dimethyl amyl carbinols, the best synthesis was through
the initial preparation of the corresponding heptanone.
This ketone, then allowed to react with a methyl bromide
Grignard reagent, gave a good yield in every instance.

The methyl bromide Grignard reagent was found more
suitable than the methyl iodide reagent, because an ex—
cess of the bromide reagent could be used without the
loss of product by dehydration, as Would be the case if
an excess of the iodide rare used.

2~methyl butsnol-5, the prs“iminary compound in the
preparation of h,o,4-trimethyl pentanol-d,did not yield
z-bromo,e-msthyl butane, as EXPcctcd, when bromdnated
with phosphorous tribromide. a rearrangement, which gav e

tertiary amyl bromide, tCOA place during the bromination.

S US$5.91. BY

The three tertiary aimethyl amyl carbinols:
2—methyl,o-ethyl pentanol-g;2,5,o-trimethyl pentanol-2;
and 2,4,4-trimethyl pentanoi-2 wane prepared. These
products will be used, in this laboratory, for the study
of their condensation with benzene in the presence of
aluminin.chloride.

Preliminary work on the preparation of 2,o,4-tri—
methyl pentanol-2 indicated that a method for bromine
ating 3-methyl butanol-g must be found before the ketone

synthesis can.be used to obtain this carbinol.

BIBLIOGRAPHY'

lo HUSton 81m 1131911 JOAOCOS. 58 439 1936

Master’s Thesis,
Michigan State College 1936

JvoCo 3o 59 2001 1937

Huston and Anderson

Huston and Rodrick

Rheton and Guile J.A.C.3c 61 69 1939
2 9 Clark J. A00 0 So 39 574 1917
(or) Chemisohes Zentralblett 2 51 1908

5. Whitmore and Laughltn J.A.G.S. 54 4013 1932

4. Whitnore and Lenghlin :.A.c.s. 55 5753 19:53

Master's Thesis
{ichigan State college 1936

58 2148 1936

5. Huston and Souleti

6. Norton and Haas 308.003.

7. Huston and Guile J.A.C.S. 61 69 1959
8. Gilman, Organic Synthesis 0011. Vol. Pg. 25

9. Gilmsn, Organic Synthesis 0011. Vol. Pg. 138

10. Drake and Cook, Organic Synthesis Vol. 12 Pg. 48
. 11. Mulliken. V01. I? # 4605 Pg. 88

12. Organic Synthesis Vol. 10 Pg.32

13. Gilman, Organic Synthesis Coll. Vol. I Pg. 419

14. Whitmore and Bedertscher'J.A.C.S. 55 1561 1933
15. Edgar ’0' A00. 3. 51 1485 1929
16. Gilmen 3.11.0 .S. 45 150 1923
17. Butlerow Annalen 189 53 1877
18. Tonfiberg, Fensko
Pickens, Whitmoro J.A.C.3. 54 570? 1932
19. Fensko & co~workers Ind. & Chem.
24 408 1932

      

 

   

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