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This is to certifg that the

thesis entitled

SYNTHESIS AND ATTEMPTED BECKMANN REARRANSEMENT
OF SOME 2-ALKYLTETRALONE OXIMES

presented by

 

MARTIN ROBERT LEVEN

has been accepted towards fulfillment

of the requirements for

‘Mfig degree in WY

Major professor

 

 

Date MAY 19. 19‘3‘1

 

\
\

0-169

SYNTHESIS AND ATTEMPTED BECKMANN REARRANGEMENT
OF SOME 29ALKYLTETRALONE OXIMES

By
martin Robert Leven

A THESIS

Submitted to the School of Graduate Studies or.Michigan
State College of Agriculture and Applied Science
in partial fulfillment of the requirements
for the degree of

‘MASTER OF SCIENCE

Department of Chemistry

1951

Cl‘lEMlSTRY DEPT.
7545fi
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ACKNOWLEDGMENT

The author wishes to express his
sincere appreciation to Dr. harold Hart
for his constant encouragement and'
advice during the course of this

research.

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TABLE OF CONTENTS

INTRODUCTION .....................................
HISTORICAL .......................................
EXPERIMENTAL
DISCUSSION or RESULTS ............................

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INTRODUCTION

In order to determine the configuration or
2-alkyl- Ok-tetralone oximes, the synthesis or 2-methyl,
Z—ethyl and 2-isopropyl- ak-tetralone oximes and a study
of their Beckmann rearrangement was undertaken. The
Beckmann rearrangement of 2-alkyl-ak-tetralone oximes may
lead to two possible structural isomers, ortho-
amino- (-phenylo oc-alkylbutyrolactam or ortho(3-amino-
pr0pyl)-benzoic acid lactam.

Ungnade and McLaren (2) were able to rearrange
a series or alkylcyclohexanone oximes in sulfuric acid
and round that the 2-alkyl compounds gave single products
on rearrangement. Isolation and identification or these
lactams indicated that the oximes were in all cases anti
to the alkyl group.

Schroeter's results on the Beckmann rearrange-
ment of fi-tetralone oximes were anomalous to those of
the cyclohexanone series (2). He reported the end
product of the rearrangement offi-tetralone oxime to be
eL-naphthylamine. However, Schroeter employed acetic
anhydride, acetic acid and gaseous hydrogen chloride to

bring about the rearrangement.

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Sulfuric acid and phosphorus pentachloride were
not cited in the literature as rearranging:mediums for
the 2-alkyl-ck-tetralone crimes. It is one of the pur-
poses of this investigation to report the results obtained

with these reagents.

HISTORICAL

Beckmann rearrangements of 2-alkylcyclanone
oximes have been studied extensively in the cyclohexanone
(l) and cyclopentanone (3) series. The rearrangement may

possibly lead to the formation of two structural isomers
(rise 1) e

CH—
(CH2)/ CHZ\C-NOH -—-> (CH2)/ 2 llH

1‘93/ xw‘mmcso

I II

Fig. l

Hildebrand and Bogert (3) studied the rearrange-
ment of 2-methyl, 2-ethyl and 2-nppr0pylcyclopentanone
crimes and 2-methylcyclohexanone oxime in a sulfuric acid
medium. In all cases, the rearranged product was found
to be represented by III in Fig. l.

Ungnade and McLaren (l) were able to rearrange
a series of mono-, di- and trialkylcyclohexanone othes.

The cyclohexanone oximes with one Ok-alkyl group gave

O b’fllr-

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single products on sulfuric acid rearrangement which had

the 2-keto-7-allcylhexamethyleneimine structure (Fig. 2).

u
0'“ ---> "

Fig. 2

R

' When other alkyl groups were substituted on
the OK-alkylcyclohexanone oxime, the Beckmann rearrange-
ment followed the same course as indicated in Fig. 2.
Unsymmetrical alkylcyclohexanone oximes that did not
contain, an ok-substituent were found to give a mixture of
the two possible isomers upon rearrangement. Rearrange-
ments were successfully carried out on 2-methyl-, u-methylo,
2,lp,6-trimethyl-, 2.3,5-trimethyl-, 2,t—dimethyl-, 2,5-
dimethyl-, 3,5-dimethyl- and 2-t-butyl—h-methylcyclohexanone
oximes. only one rearranged product was isolated in all
of these instances. With the unsymmetrically substituted
cyclohexanone oximes without the OC-substituent, both of
the possible isomers were isolated and identified.

The oximes ofak-tetralone should behave in a
manner similar to those of the cyclohexanone and cycle--
pentanone series. The work of Schroeter, however, showed
that X-tetralonc oximes gave unusual products when sub-

Jected to the Beclnnann rearrangement (2).

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Schroeter was able to treatcg otetralone oxime
or the acetyl ester of at-tetralone oxime with a Beclmann
reagent which consisted of acetic anhydride and acetic
acid saturated with gaseous hydrogen chloride. The end
product was found to be o(-naphthylamine. Schroeter was
also able to get an "cg-naphthylamine rearrangement" with
substituted OK-tetralone oximes such as 5- or 7-nitro-,
6- or 7-chloro- and 6-methoxy-ka-tetralcne oxine. The
proposed and rather unbelievable mechanism for the re-
arrangement has the title of "the gap molecular theory!
or "the univalent nitrogen hypothesis." ' (Fig. 3)

CJK/Nson 01‘ fifi-CHB

«>6 up M

N .;... L t-
”+- ® EEO

The oi onaphthylamine rearrangement was carried
out in an Open container. ' Schroeter also carried out a
rearrangement of 5,8-dimethyl-Ok-tetralone oxine acetate
using Beckmann's reagent in a closed systan. The lactam

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or (2,5-dimethyl-6-amino- Y-pheuyl)-n-butyric acid was
isolated (lie. I.)-

   

Fig. h

Since the end product was what might be expected
in a normal Beolmann rearrangement, the configuration or
the oxime was established. The normal Beckmann rearrange-
ment was also given with ct-tetralone oxime p-toluene-
sulronate. .
. °anith (h), using the Schmidt reaction onoQ-
tetralone, was able to isolate homodihydroearbostyryl
(ortho-anino- T-phenyl-n-butyrtlactalh) in 85% yield. The
solvent for the Sehmidt reaction was trichloroaoetio
acid. when the crime or ok-tetralone was warned to 60°
in trichloroaoetic aeid,-the trichloroacetate offl-
tetraloue crime was the only product isolated.

Smith also attempted the rearrangement of the
potassium ek-tetralone oxine-O-sulronate in a hydrogen
chloride solution or dioxane (5). The end product was
largely ak-tetralone, but he also reported 12$ ok-naphthyl-
amine. Small amounts or honodihydrocarbostyryl were formed
when the potassium ck-tetralone oxime-O-sulronate was
wamed in dry pyridine.

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In a 250-ml. flask there was placed 26 g.
(0.102 mole) of finely divided iodine in 60 ml. of glacial
acetic acid. After the addition of 5 ml. of bromine to
the solution, the flask was placed on a steam bath and
warned to 50'. when the solution was renewed from the
steam bath and cooled, ll. 5. (0.096 mole) of q-naphthol
in 1.5 ml. of glacial acetic acid was added. The contents
of the flask were mixed by shaking and then allowed to
stand at rou temperature for one hour. The solution was
then added to 16 g. of sodium bisulfate in 700 ml. of
water. The resulting crude precipitate of L-brono-ob
naphthcl was filtered, washed with water and air dried.
For each gram of compound, 1.5 ml. of 33% ethanol was
used for recrystallization. from this process, 20 g.
(93% yield) of colorless needles melting at 127-129.

(uncorrected) was obtained.

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.Attggpted ggepggation or 2-t- t 1- -brcmo- -nn hthol

 

Using the slkyleting vessel described uy
Stillson et el. (7), 20 g. (0.089 mole) of h-bromo- OK-
naphthol was dissolved in 3092ml. or p-xylene end 5 ml. or
concentrated sulfuric acid and elkylsted at 65-70° with
12 g. (0.21.mmle) or isobutylene. ‘After fifteen minutes
or slkyletion, the solution turned black. The entire
slkyletion took one and one-half hours. The black solu-
tion was then neutralized with sodium bicerbonste, washed
with water and dried over anhydrous sodiun.sultete. A
precipitate was formed in the organic layer during the
process or neutralization. The precipitate end solvent
were transferred to e Vigresux column.and the solvent was
removed in vacuo. The residue consisted of a black gummy
resinous material which could not be recrystallized to
give a sharp.melting point. Four to five grams or this

material was obtained.

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1- to-l 2 -tct dronaphthalcne»(gggtetralone)L81

 

five hundred grams of commercial tetralin
(3.78 moles) was placed in a one-liter round-bottomed
flask equipped with a fritted glass bubbler, thermometer
and a series of reflux condensers. The type of reflux
condensers used was a Liebig condenser surmounted by a
Freidrick and a Graham condenser. Since rubber stoppers
contaminate the subsequent reactions, only ground glass
equipment was used. A.rapid stream of air was drawn
through the tetralin by applying suction from.an.aspirator
pump attached to the uppermost condenser. The air current
was continued for fifty to fifty-five hours. The contents
of the flask was maintained at 78' by means of‘a Glas-col
heater.

at the end of this period, the warm partially
oxidized tetralin was poured into 500 ml. of 2 N sodium
hydroxide which had been placed in a two-liter flask.
During the addition of the partially oxidized tetralin,
vigorous mechanical stirring was maintained while the
temperature was kept below 70° by adding ice when neceso
sary. This temperature was maintained for at least ten

minutes. Tho mixture was then cooled to room.temperature

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and nearly neutralized with 6 N sulfuric acid (about

160 ml.). The upper tetralin.and aflrtetralone layer, which
was now colored dark orange, was separated and washed

with 100 ml. of .5 N sulfurioqacid and then with 100 mi.

of 1% ferrous sulfate. If an emulsion formed during the
ferrous sulfate addition, the solution was acidified,
followed by the addition of 25 to 60 g. of sodium chloride.
The lower layer was removed and the upper tetralin-Ofl-
tetralone layer was dried over 25 g. of anhydrous sodium
sulfate. It was then fractionally distilled through a
30-cm. column packed with #8 glass helices. The un-
changed tetralin distilled at 65-72° at 2 mm. (70-85°/h:mm.,
59-69°/l mm.). The temperature then rose and the fraction
distilling at 105-107“ at 2 mm. (115-118°/5 mm”),
(113.5-116°/l. mm.), (123-12v/9 mm.) was practically pure
6k-tetralone. If rubber-stoppered equipment was used, a
fraction distilling at 96-98°/3 mm. was obtained. This
material was not analyzed. - ‘

It was noted that if the recovered tetralin was
used in a future oxidation, the yield of'OKPtetralone
increased to as much as 80%. If the tetralin was oxidized
for the first time, the yield of'¢(-tetralone varied from
75-85 g. (us-55% of the theoretical amount based on the

tetralin not recovered).

-10-

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fitgxl-g-tetralone-2-glzoylate (51

"‘ (32-0.,

 

The equipment used in the procedure was a
SOC-ml. two-necked flask fitted with an addition tube, an
inlet for nitrogen gas, a reflux condenser and a separa-
tory funnel. Commercial sodium methoxide (17.28 g.,
0.32 mole) and 37.76 g. (0.32 mole) of methyl oxalate
was placed in the flask with 160 ml. of anhydrous benzene
and refluxed for fifteen minutes. An atmosphere of dry
nitrOgen was maintained from this point until the end of
the glyoxylation. At the-end of the fifteen minutes, not
all of the solid material had dissolved. After allowing
the mixture to cool to room temperature, a solution of
23.36 g. (0.16 mole) of K-tetralone in 80 ml. of dry
benzene was added. The flask was swirled until a defi-
nite yellow color formed throughout the mixture. The
flask was then immersed in a water bath which was main-
tained between l5-20° for four hours. During this four-
hour period the contents of the flask were shaken from
time to time.

At the end of the four-hour period 200 ml. of
water was added, and the sodium salt of the glyoxylate

was extracted into the water layer. The benzene was then

-11-

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extracted with 200 mi. of 20% sodium hydroxide and then
again with 200 ml. of water. Ice was added, and the
alkaline solution was then neutralized with cold 1:1
hydrochloric acid. The resulting yellow precipitate was
kept cold for three hours to facilitate the complete
precipitation. The yellow crystals were then filtered
and washed with water and while they were still wet,
recrystallized from aqueous methanol. Thirty-five grams
(82% yield based on the x-tetralone) of yellow plates
melting at 5h-56° were isolated. .

Ethyl-gs-tetralone-Z-glzoxxlate

a no...

 

To a 500-ml. two-necked flask equipped with a
mercury sealed stirrer and a reflux condenser surmounted
by a separatory funnel, 12 g. of sodium and 250 ml. of
absolute ethanol was added. When the mixture was cooled
to room temperature, a solution of 35 3. (0.23 mole) of
Ok-tetralone in 71 g. (0.36 mole) of cold ethyl oxalate
was poured into the flask. The resultant mixture was
stirred for one hour while the flask was immersed in an
ice bath. The ice bath was removed, and the stirring was
continued for an additional hour without application

-12-

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of heat. While the solution was kept cold, 150 ml. of
cold water was added followed by dilute sulfuric acid
until neutral to litmus. The yellow crystals were fil-
tered and recrystallized from methanol. Forty-four grams
(67%) of yellow crystals (plates) melting at 1.6-1.7" were
isolated.

Metgyl-cL-tetralone-2-carb3llate (91

“1...,

Twenty-four grams (0.10 mole) of methyl-og-
tetralone-z-glyoxylate was placed in an eight-inch Pyrex
test tube and heated on an oil bath to 150'. Powdered
glass (12 g.) was added,’ and the temperature was raised
to l80-l90° and kept there for thirty minutes. At the
end of this time carbon monoxide ceased to be evolved.
After the contents of the test tube had cooled to roan
temperature, the carboxylate was extracted from the glass
with acetone. The acetone extracts were then warmed and
treated with carbon black and filtered. The acetone was
evaporated, and the viscous material remaining was cooled
and scratched with low boiling petroleum other until
crystals famed. These crystals were recrystallized from
50 ml. of 60-70' petroleum ether and 5 ml. of acetone.

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5“.“ ‘ L ‘1 ‘ ,_vl .‘J«’. '7. t). D it. -- ”(-l
. . ’ 2 - - . _' 3 .. , r. 1-, 'L _
_. I . fl
’ '_ - . . L . . I \) « . \1 ‘4 __'. , 'r .5 '
' " — a - .
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- * 'I. » . . 'I .‘ .‘ 90b Ll ' b ’ *. l
' I
I . z ‘ ’ -' -~ .‘.'. ; . 2'
- , ,, ‘. , . b _ _"... a , J p e s . '
e > - . - . "' . L - .
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. -J .J a. .w‘ .. .L . . v0-)
. 4‘ . p . ' e. I l
- , -- y 1 .a '1 y .‘ . I-e_ . . . . .. ’. l - - n
. a .‘ (‘1‘ . ‘ 1 - | :J J J L ~: . n ’ ‘-- ‘4 - I i . J. “ m :' I
e e I .
. a ’.I t "'3 r‘ . r —' f ,9 J - ._ . .5
L o. ' ' K '. I' h' j d .‘. \ ‘1 1.“ I -- ' L.) .4 v 21
r 9. ' - 1 ~ I . ._
I ‘x ,‘ - ' I' (r ' r ~ ’ ‘. s -. i n
-. . J’s L-LJ”} “‘--w .L\? but J”: l‘.’v d. )'J
4 5'
. -. ' (w :3-\ 3.“ 3'" u-“"§ ,-" "
- J": ‘ ’ ‘- I 'J u . ‘. es -4 a; I Q ‘- l M.
, v- _ r L ‘ 2" . . '
. . . , r‘~' . r ,
1- .1»- .l.,-'.J."\"~ l‘x-‘ ‘ 6 0'
‘( ‘

\

a
A

A

Colorless plates melting at 83-8h° were obtained. The
yield was 15 3. (7h%).

Theélhylation or methyl:0(gtetralone-2-carbogzlate (2,101

N
<§~0°H3

Methyl iodide, ethyl iodide, isOpropyl iodide,
isopropyl bromide and isopropyl chloride were used in
the alkylation of the carboxylate. The following general
procedure applied to all or the alkylations:

To 5 g. (0.22 mole) of.sodium.and 95 ml. of
anhydrous methyl alcohol was added a solution or 18 g.
(0.09 mole) of methyl l-keto-l,2,3,h-tetrahydrOnaphthalene-
2-carboxylate in 50 ml. of anhydrous methyl alcohol and
50 ml. or dry benzene. The mixture, at this point, became
distinctly red in color..

To the red solution was added the appropriate
alkyl halide.

methyl iodide (38 3., 0.27 mole)

ethyl iodide (42 3., 0.27 mole)

isopropyl iodide (as 3.,026 moles)
After the addition or the alkyl iodides, the red solution
. was refluxed for three hours. In the case or the methyl
and ethyl iodides, the solutions gradually changed color
until they were practically yellow, but in the instance

-14-

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shown.- up. to.

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of isopropyl iodide, the solution remained red. At this.
point the procedure varies depending upon the alkyl halide
employed.

The methyl alkylated compound was treated as
follows:

After cooling, acetic acid was added until the
solution was neutral. The solvents were then removed in
w and the residue taken up in benzene and water. The
water layer was extracted twice with benzene, and the
combined benzene solutions were washed with sodium bi-
carbonate and then dried with anhydrous potassium carbo-
nate. The benzene was removed under reduced pressure.

The product that remained was recrystallized from 60-70°
petroleum ether acetone. Eleven grams (55%) of presumably.
methyl 2-methyl- 0(~tetralone-2-carboxylate was obtained

in rectangular prisms melting at Ste-56°.

The ethyl and isopropyl alkylated compounds
were treated as follows:

Acetic acid was added to the yellow solution
until it became neutral. The solvents were then removed
in vacuo until about 150 ml. of material remained. The
residue was taken up in benzene and water, and the water
was extracted twice with more benzene. The benzene ex-
tracts were combined, washed with sodium bicarbonate and
dried over anhydrous potassium carbonate. The benzene was

then removed in vacuo, and the red oil that remained was

 

vacuum distilled through a five-centimeter Vigreaux column.

-15-

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Thirteen grams (62%,yield) of presmmably methyl
2-ethyl-OQ-tetralone-z-carboxylate distilled at 135-138°/h
mm. When the oil was scratched with petroleum.ether
(60-70°), it crystallized in colorless prisms melting at
55-57°.

Eight grams (35%) of presumably methyl 2-iso-
propyl-OQ-tetralone-2-carboxylate was distilled at
155~160°/5 mm. .Arter repeated scratching of the oil with
petrolemm ether (30-h0’), a tan crystalline material was
obtained which melted at 62-63’.

The alkylated carboxylates obtained above were
hydrolyzed and decarboxylated as follows:

Eleven grams (0.05 mole) of methyl 2-methyl-ofl-
tetralone-Z-carboxylate, 11 g. (0.05 mmle) of methyl
2-ethyl-CK-tetralone-2-carboxylate and 8 g. (0.032 mole)
of methyl 2-isopropyl- d-tetralone-z-carboxylate were
hydrolyzed by refluxing with 80:m1. of 20% sodium.hydroxide
and 20 ml. of ethanol for three hours. The reaction
mixture underwent a color transition from.orange to red.
Acidification of the warm solution with 1:1 sulfuric acid
caused a vigorous evolution of carbon dioxide. To insure
complete decarboxylation, the acidified solution was
warmed on a steam bath for one hour. The ketones were
then extracted with benzene,and the benzene extracts were
washed twice with water, once with sodium.bicarbonate and

again with water. The benzene extracts were dried over

-16-

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anhydrous potassium.carbonate. vacuum.distillation yielded
8 g. of colorless 2~methyl-°(-tetralone, b.p.
lh5-lSO°/25 mm.; 9 g. of colorless 2-ethyl- X-tetralone,
b.p. 123—125°/5 mm. (the isolation of these compounds
was practically quantitative); 6 g. (96%) of colorless
2-isopropyl-€<rtetralone, b.p. 155-160°/5 mm.

When the alkylated aflgtetralones were allowed to
stand at room temperature for three to four days, they

became slightly yellow in color.

Oximation of the S bstituted CkrTetralones ll

HDH

 

H

To 2 g. of the substituted.°(-tetralones in a
50-ml. flask was added 2.5 g. of hydroxylamine hydrochloride
and 20 g. of redistilled pyridine. The flasks were fitted
with condensers and placed on a steam bath for ten hours.
The solution.was then poured on 35 g. of ice and stirred.
After standing at roem.temperature for two hours, the
heavy oil was extracted with ethyl ether. The ether exp
tracts were then combined, and the ether, as well as.most
of the pyridine, was removed by concentrating the solution
on a steam bath. The remaining viscous oil was cooled
and scratched until solidification occurred. The green

mass was recrystallized from.aqueous methanol and

-17-

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‘ ... V ‘ K .’ - ‘ ‘ ‘ ‘ ' o~ 2 - "T " ' I“ u .‘l
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r . L . .. n _ \J _ - F ‘ t' J n.‘ “ .r- 'w n! - d. . ’ ' ‘r
e
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a . - . x w
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\ I
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. ... \. ' L- : ‘ . . , O at) ”NJ . U .a ..
. ‘ ' 1 ' " ' ‘ (
I . _/ . . ' P‘ v , ; . " 7. ' I.“ ' I) ' -o‘s ‘ Q
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4. .. ._ ‘ ~‘t , . ._ -.§ .J. _.‘ '. -4 1 g. A .avc ’ J
as -

colorless plates were obtained. The yield was 2 g.

2-methyl- K-tetralone oxime melted at 96-98" (uncorrected)
Analysis for 0 75.I.O% H 7.1.876 N 8.00%
Calcd. for 0 75.68% H 7.63% N 8.03%

2-cthyl- K-tetralone oxime melted at 96-97° (uncorrected)
Analysis for C 76.15% H 7.99% N 740%
Calcd. for c 76.h7% H 7.98% N 7.g5%

2-isopropyloé-tetralone oxime melted at 84-86" (uncorrectedf’
Analysis for c 76.80% H 8.h3% N 6.89%
CEIOde for C 75.05% H 7eh3% N 7e97%

*The discrepancy in the analysis is discussed below.

Mixed melting point data:
2-methyl-o(-tetralone oxime
ok-tetralone oxime melted 82-87° (uncorrected)

2-ethyl-Ok-tetralone oxime
K-tetralone oxime melted 79-85" (uncorrected)

2-isopropyl-O( -tetralone oxime
“-tetralone oxime melted 76-81° (uncorrected)

Beckmann Rearrangements (22 2 :12: 13 )
I

Four grams ofofl-tetralone oxime was added to

15 ml. of 85% sulfuric acid. The warm solution was heated

-13-

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slowly to 185°, whereupon it turned light brown. At no
time was there a sudden increase in temperature which is
characteristic of Beckmann rearrangements. After cooling
the sulfuric acid solution to room temperature, ice was
added and a precipitate formed. Upon addition of cold
20% sodium hydroxide, no oil formed, and the solid still
remained. After filtration and recrystallization of the
solid material from aqueous methanol, colorless plates
were obtained. The plates melted at lOl-lO3°. No de-
pression in the melting point was noticed when these

crystals were mixed with d—tetralone oxime.

II

Alpha-tetralone oxime ( 3 g.) was added to 10 ml.
of hot (loo-110°) 85% sulfuric acid. This temperature
was maintained for fifteen minutes, and then the solution
was allowed to cool. Upon cooling, by addition of ice, a
' precipitate formed. After neutralizing with cold dilute
sodium hydroxide and filtering, the solution was extracted
with ethyl ether, and the ether extracts were concentrated.
A minute quantity of a black tarry material was recovered.
The precipitate (above) gave a melting point of loo-101°.
When it was mixed withok-tetralone oxime, it caused no
depression in the melting point.

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III

In a 500-ml. round-bottomed flask fitted with
an efficient condenser was placed 3 g. of OK-tetralone
oxime in 100 ml. of anhydrous ethyl ether. Three grams
of phosphorus pentachloride was added. The solution was
allowed to stand at room temperature for three hours.
Upon distilling the ether, a yellowish white solid which
consisted in part of some unreacted phosphorus penta-
chloride remained. water was added to dissolve the
phosphorus pentachloride, and a white flaky precipitate
remained. The precipitate was filtered and recrystallized
from aqueous methanol. The melting point of 101-103“
indicated that the recovered material was K-tetralone

crime e
Iv

Z-Methyl-Ok-tetralone oxime (l g.) was added to
5 m1. of hot (130') 85% sulfuric acid. No temperature rise
was noted during the addition. The temperature was main-
teined at 130° for ten minutes. Upon dilution with ice
water, pink crystals formed. The crystals were filtered,
and the filtrate was neutralized with cold 2 N sodium
hydroxide and then extracted with benzene. The benzene
extracts were concentrated, and only a minute quantity of
black tarry material remained. The pink crystals were
recrystallized from aqueous methanol and melted at 96-98°

(the melting point of 2-methyl-OQ-tetralone oxime).

-20-

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V

Schroeter's technique was attempted in the
”Beckmann rearrangement" using gaseous hydrOgen chloride,
glacial acetic acid and acetic anhydride. Alpha-tetralone
oxime (5 g.) was treated with no ml. of glacial acetic
acid and b g. of acetic anhydride. While the above solu-
tion was heated on a steam.bath for three hours, a stream
or hydrogen chloride gas was bubbled through it. During
the course of this treatment, the solvents evaporated and
left a brown crystalline mess on the bottom.or the cpen
beaker. Dilute hydrochloric acid (1:1) was used for re-
crystallization and 4-5 g. or colorless needles were ob-
tained. The needles were placed in 200 ml. or hot water
and dissolved. As soon as the solution cooled to h0—50°,
sodium.bicarbonate was added until the evolution or carbon
dioxide was no longer apparent. The neutralized solution
was warned on a steam.bath for thirty minutes. After
cooling, ethyl ether was added,and the oil that formed
following the bicarbonate treatment was extracted. Upon
removal of the ethyl ether, a brown viscous liquid re-
mained. A sample or the liquid gave a positive coupling
reaction with 6 -naphthol. It also reacted with acetic
anhydride and glacial acetic acid to give colorless plates
melting at 155-157°. The acetate or ogrnaphthylamine was
reported as melting at 159' (1A).

-21-

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’ II.

Eemration of Semicarbazonesm

The semicarbazones of the substituted tetralones
were prepared by refluxing one gram of the ketone with
one gram of semicarbazide hydrochloride in 5 ml. of
pyridine and 10 ml. of absolute ethanol. The refluxing
required from twelve to fifteen hours. At the end of
this time, the solutions containing the semicarbazones
were poured on 50 g. of ice and the semicarbazones crystal-
lized out as colorless needles. Z-Methyl-OQ-tetralone
semicarbazone melted at 203-205". Z-sthyl-og-tetralone

semicarbazone melted at ZOO-201°.

Mixed melting point data:
2-methyl- og—tetralone semicarbazone
dq-tetralone semicarbazone

melted 161,-173' (uncorrected)

2-ethyl- d—tetralone semi carbazone
OK-tetralone semi carbazone

melted l6?-l77° (uncorrected)

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- 22a-

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C4

DISCUSSION OF RESULTS

A. Preparation of 2-Alkyl-Gkrtetralones and Their Oximes

The two principal methods for the preparation
or 2-alkyl-ckotetralones are cyclization of Yrephenyl-a&-
alkylbutyric acids and the direct alkylation of ck-tetralone-
2-glyoxylate. Krollpfeiffer (15) and Alexander (16) em?
ployed the method or cyclization for 2-methyl-OQ-tetralone
as indicated in Fig. 5. The over-all yield of h7% was

8

reported by Alexander.

‘5 03333—010 A1012 |.\/ ‘an
/ Hz-Cgf / cog-C}-13
Mo
1
CE
I” «new 152%
/ -CHB n It / c OHCH.GH3

8

Fig. 5

The second method, developed by Bachmann (9).

Kloetzel (10) and codworkers, involved the preparation or

Zemethyl-Z-cerbomethoxy-cflrtetralone followed by the

-23-

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hydrolysis of the keto ester and subsequent decarboxyla-
tion (Fig. 6). The overball yield of 75% was reported by

c o

u g R

-c- -ocn3 soft mw-ocn3
glass
68.

Kloetzel and Close.

 

-02H5

ézdrolxsis

decarboxylation

 

Fig. 6

Cole, in a personal cummunication, indicated
that the first step in the above reaction is a very
critical one. The yield of the glyoxylate is dependent
upon the amount or starting material used. In all cases,
where the amount or OQ-tetralone exceeded 5.81. g., the
yield of the glyoxylate was lowered. .Since this occurred,
Cole suggested that in preparing a large quantity or the
glyoxylate, a series or small runs, using ag-tetralone and
dimethyl oxalate, should be employed.

In the experimental portion describing the syn?
thesis of’methyl~Oflttetrelone-Z-glyozylate, the amount
or‘ok-tetralone used was four times the quantity suggested

II."

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by Bachmann. Bachmann's yield was 91%, whereas the
maximmm yield in this work was 82%. It is possible that
the extent of obtaining an intimate mixture with large
amounts of starting material could be facilitated by con-
tinuous stirring throughout the glyoxylation, thus imp
proving the yield.

The ethyl o( -tetralone-2-glyoxylate was prepared
by using a combination of the procedures described by
Bachmann (9) and Snyder (17). In an attempt to eliminate
carbon monoxide by heating the compound with ground glass,
only decomposition took place. The methyl ester was,
therefore, employed in the remaining experiments.

The alkylation of methylwc‘3tetralone-2e
carboxylate was accompanied by color changes. At the
beginning of the alkylation, using methyl and ethyl iodide,
the color of the reaction mixture was red and later changed
to yellow toward the end of the refluxing period. In
the instance where isopropyl iodide, isoprOpyl bromide, or
isopropyl chloride was used, this color change was not
evident. This was probably an indication of'a small
amount of alkylation or no alkylation at all. The carbon-
hydrogenpnitrogen values for the oxime of the isOprOpyl
alkylatech‘-tetralone suggests that the oxime may have
been a mixture of the isoprOpyl substituted and un-
substituted o(-tetralone. Nevertheless, repeated re-
crystallizetions and subsequent analysis showed no change

in the melting point or percentage composition.

-25-

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The oximation technique presented in this report
follows the procedure described by Siggia (18) and
Sengupta (11). Normal methods of preparing oximes were
not applicable to 2-alkyl cyclic ketonee, since steric
hindrance prevents oximation. Specifically, Sengupta
found that the best conditions for converting 2,2-dimathyl-
cketetralone into the oxime was by treating the ketone with
hydroxylamdne hydrochloride and pyridine at 100° from.ten
to twelve hours. This procedure was followed and the

yields were practically quantitative.
B. Attempted Bookmann Rearrangements of the Crimes

The Beckmann rearrangements attempted in this
report followed the methods described by.Marvel (12),
Hildebrand (3) and Blatt (13). It was noticed that when
sulfuric acid was used, a definite temperature rise was
effected upon the addition of the crime. It has been
reported that this rise in temperature is not due to a
rearrangement but to a salt-like complex that is formed
between the crime and the rearranging agent (Step 1 in
Fig. 7) (19).

The steps in Fig. 7 illustrate the mechanism.of
the rearrangement as reported by Chapman and Kuhara and
verified by Pearson (19).

In Step 2 of the reaction we find the formation
of an ester that is potentially capable of ionizing (this

~26-

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Fig. 7

can be seen in Step 3). Step 3 is the rate determining
step. The ease of the ionization of the ester partially
determines the rate and ease of rearrangement. The
polarity of the solvents also determines the rate of re-
arrangement (20). The migrating group which attaches
itself to the nitrogen atom is anti to the hydroxyl group
in the original oxime (Step 3).

Jones (20), in reviewing the work of Chapman
and Kuhara, indicated that Step 3 (Fig. 7) determines
whether a rearrangement will or will not occur. Specifi-
cally, if the ionization cannot occur, in the case of the
oQ-tetralone ozimb-O-sulfonate, then the Beckmann re-
arrangement cannot take place. There are a number of

factors which may influence ionization of this ester,

-27-

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including the effect or groups which exert a dipole

moment.

The group UK is the ester part of the crime, and
’according to Chapmann and Kuhara, a rearrangement will
occur when 0X exerts a sufficient attraction for elec-
trons to cause the electrons at the R-C bond to be dis-
placed and thereby set up a state or stress within the
molecule. If, however, group R.has associated with it a
dipole in the opposite direction or 01, electron displace-
ment cannot occur, and the rearrangement will either by
retarded or stopped completely.

To warrant the lack of a rearrangement in the
o(-tetralone oxime series, any combination or the factors
discussed could conceivably prevent a rearrangement. The
reason for luck or rearrangement in this series is not

yet understood.

-23-

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SUMMARY

1. Z-Methyl-akrtetralone and 2-ethyl-afir
tetralone were prepared from.ok-tetralone in h0% over-all
yield.

The steps included glyoxylation of aK-tetralone
(82%); decarbonylation (74%); alkylation (methyl 55%,
ethyl 62%); hydrolysis and decarboxylation.

2. The 2-methyl and 2-ethyl-0k-tetralones were
characterized through semicarbazone formation.

3. Alkylation using isoprOpyl halides was not
complete under the conditions employed and 2-isopropyl-
ek-tetralone crime was not isolated in pure form.

h. The oximes of Okgtetralone, 2-methyl-e(-
tetralone and 2-ethyl-ak-tetralone did not undergo the
Beckmann rearrangement under a variety of conditions.

The oximes were in all cases recovered.

5. The conversion of x-tetralone oxime to
ofi-naphthylamine reported by Schroeter (2) was verified.

6. The following new compounds were prepared:

2-methyl-o(-tetralone oxime
Z-ethyl~ oQ-tetralone oxime .

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BIBLIOGRAEHY

H. F. Ungnade and A. D. hicLaren, J. Org. Chem., 12,
29 (1945).

G. Schroeter, A. Gluschke, S. Gotzky, J. Huang, G.
Irmisch, E. Laves, 0. Schrader, G. Stier, Ber., _62,
1308 (1930).

J. G. Hildebrand and M. T. Bogert, J. Am. Chem. Soc.,
2%. 650 (1936).

P. A. 3. Smith, ibid., o, 320 (1948).
P. A. s. Smith, ibid., 19, 323 (1918).
W. Militzer, ibid., .62, 256 (1938).

G. H. Stillson, D. W. Sawyer and C. K. Hunt, ibid.,
913 303 (19h5)e

Be Be Thdmpson, Org. syntheses, COlle vOle 20) 9h (19h0)e

W. E. Bachmann and D. G. Thomas, J. Am. Chem. Soc.,
9;, 598 (191.1) .

“M. C. Kloetzel and W. Close, J. Org. Chem.,.11, 395

(19u6).
c. Seagupta, J. Prakt. Chem., 1 1, 82 (1938).

C. 3. marvel and W. Eck, Org. Syntheses, Vol. 17, 60
(1937).

A. H. Blatt and J. F. Stone, Jr., J. Am. Chem. Soc.,
.22, “13h (193l)e

N. D. Cheronis and J. B. Entriken, "Semimicro Qualita-
tive Organic Analysis,” T. Y. Crowell 00., New York,
1917, p. h06.

F. Krollpfeiffer and W. Schafer, Ber., 26, 631 (1923).

E. R. Alexander and A. Mhdrak, J. Am. Chem. Soc.,‘zg,
3194 (1950).

-39-

i.

5

(N

e[

0....

( OJ»

OIe

. .e\) . a.

I
\

17.

18.

19.

20.
21.

He Re Snyder, Le He BrOOKS and Se He Shapiro, Org.
Syntheses, Coll. Vol. II, 391 (19h3).

S. Siggia, "Quantitative Organic Analysis via Func-
tional Groups," John Wiley and Sons, New York,
19t9, p. 16.

D. E. Pearson and F. Ball, J. Org. Chem., 13, 118
(1969).

B. Jones, Chem. Reviews, 22, 335 (19th).
a. Levy, Ann. cum. (11), 3, 69 (1938).

-31-

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