SCIENTIFIC ABSTRACT AKHREM, A.A. - AKHREM, I. S.

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• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

of 2-Methyl-l-(11-acetoxy-ethylidene)-oyclo-
Osmium. Tetroxide and Peracetic Acid
SOV/62-59-4-35/42
because so far no case has been known where continually ro-
tating isomers were formed in a crystalline form (Refs 5 and
The compound (IV) was previously obtained (Ref 1) also by the
reduction of cis-dioxycarboxylic acid (VI) with lithium
aluminum hy4ride. Since with such a reduction of the
carbalcoxy group the configuration is usually maintained the
dioxyacid (VI) should have "cis-treo" configuration. Cis-
dioxyacid (VII) and cis-triol (VIII) have cis-erythro'con-
figuration. Upon oxidation of acetate (I.T) wM peracetic acid in
chloroform a normal oxidation product *Lb ~uriued - the liquid
acetate of glycide alcohol (IX). A direct transition of
acetate (II) to cis-2-methyl-l-(w -acetoxyacetyl)-cyclo-
hexanol (X) could not be achieved by oxidizing hydroxylation
by means of phenyliodosoacetate in the presence of osmium
tetroxide (Ref 7). In the experiment the initial acetate was
cbtained unchanged. There are 9 references, 3 of which are
Soviet.

oxidation of 2-Methyl-l-(11-acetoxy-ethylidene)-cyclo-
SOV/62-59-4-35/42
hexane by osmium Tetroxide and Peracetic Acid
ASSOCIATION: Institut organioheskoy khimii im. N. D.
Zelinskogo Akademii
nauk SSSR (institute of Organic Chemistry imeni N. D. Zelinskiy
of the Academy of Sciences, USSR)
SUBMITTED: August 8p 1958
Card 3/3

5M SOV/62-59-9-25/40
AUTHORS: Batuyev, M. 1.0 tkhrem, A. A., Matveyeva, A. D.
TITLE: Optical Investigation of Equatorial and Axial Carbonyl
Groups of
Some Substituted Cyclohexanes
PERIODICAL; Izvestiya Akademii nauk SSSR. Otdeleriiye
khimicheskikh naukv
1959p Nr 9? pp 1665-166a (USSR)
ABSTRACT: The Raman spectra of the following compounds in the
liquid phase,
taken by means of the ISP-51 spectrograph and the E-612 Hilger
spectrograph are investigated: Acetoxy-cyclohexand (I), acetyl-
oyclohexane (II)o I-acetoxy-l-acetyleyclohexane (III),
ois-2-mothyl-l-acotoxy-l-acetyloyclohexane (IV), and trans-2-
methyl-l-acetoxy-l-acetyloyclohexane (V). The pbysical data of the
compounds are given in the table. The frequencies obtaine4~ are
given in A-0 -.. cm-1. The configuration of the compounds (IV) and
M was determined from the results of special analysis. Taking
the largest substituent as basis, the conformation of (IV) was
found to be trans-ee and trans-aa, that of (V) cis-ae and cis-ea.
Card 1/2,

Optical Investigation of Equatcrial and Axial Carbonyl
SOV162-rl-9-9-2514-0
Groups of Some Substituted Cyclihexanes
The amounts of these isomers were found to be fairly equal in
both cases, as was also the case for-the two possible
conformations of compound (III), of which equal amounts are
formed. There are 4 tables and 2 Soviet references.
ASSOCIATION: Institut goryuchikh iskopayemykh Akademii nauk SSSR
(Institute
for Combustible Mineral Resources of the Academy of Sciencesp
USSR)*Institut organicheskoy khimii im. N.D. Zelinskogo Akademii
nauk SSSR (institute of Organic Chemistry imeni N.D. Zelinskiy
of the Academy of Sciences, USSR)
SUBMITTED: January 21, 1959
Card 2/2

5(3)- SOY/62-59-9-26/4()
AUTHORS: Batuyev, M. I., A rem.,A. A.., Kamernitskiy, A. V.,
Matveyevap A.D.
_' ~kh
TITLE; Optical Investigation of the Conformations of Cis and
Trans-10-dimethyleyclohexanols
PERIODICAL- Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh
naukt
1959P Nr 9, pp 1668-1670 (USSR)
ABSTRACT: A reaction scheme for the synthesis of the substances
investigatedf
(I) OH and (11) 0" is given from a previous paper,
CH3 CH3
The Auer-Skit transformation rule is valid for compounds (I) and
(II)(Table). The Raman spectra of the compounds were taken in the
liquid phase and in carbon tetrachloride solution. From the data
obtained, the following conclusions were drawn: The alcohols form
intermolecular hydrogen bonds in solution (bands split up into
Card 1/3 lines in the3160-3530 cm- I range). These hydrogen bonds
do not

Optical Investigation of the Conformations of SOV/62-59-9-26/40
Cis and Trans-10-dimethyloyclohexanols
stem from the hydroxyl group. In the_liquid phase complexes are
formed by hydrogen bonding of the OH group (continuous bands in -Uie
3600 and 3614 am-I region)o 'The hydroxyl groups generally have a
similar position (equatorial) in the associated complex. Thus, in
(I) their position is cis-la3a and in (11) trans-lale. Their
position was determined at cis-le3a in (1) and trans-la3e and
trans-le3a in (II) (equatorial and equatorial-axial), relative
to the CH -group outside the hydrogen bond as the largest
substitueRt. If one disregards the nomenclature of these
configurations and conformations by reason of their formation,
and regards solely their real structure, deduced from their
physical properties, as well as taking into account the
transformation rule by Barton and Hassel (the configuration is
determined by the position of the largest substituent) one would
have toredefine the cis-la3a conformation of (I), the form
predominant in associated molecules, of (I), and also the
Card 2/3

Optical Investigation of the Conformations of SOV/62-59-9-26/40
Cis and Trans-lt3-dimethylGyClohexanols
trans-la3e conformation of (II). The nomenclature of these
conformations would then be trans-le3a and cis-le3a
respectively. There are 1 table and 3 Soviet references.
ASSOCIATION: Institut goryuchikh iskopayemykh Akademii nauk SSSR
(Institute for Combustible Mineral Resources of the Academy of
Sciences, USSR) Institut organicheskoy khimii im. N.D. Zelinskogo
Akademii nauk S;SR (Institute of Organic Chemistry imeni
N.D. Zelinskiy of the Academy of Sciences, USSR)
SUBMITTED: January 21, 1959
Card 3/3

U.-
AKHRR4, A.A.; TITOV, Yu.A.
Chemistry of 19-norsteroids. Usp.kilim, 33
no.2:151-181 F 164.
1. Institut organicheskoy khimli irneni
N.D.Zelinskogo A' SSSR.
(MIRA 17:10)

5 (3)
SOV/79-29-3-14/61
AUTHORS:
Tishchenko, 1. G., Akhrem, A.
A., Nazarov, 1. 11. (Deceased)
TITLE;
a-Keto Oxides
(a-Ketookisi). IX. Oxides of Alkylidene Acetones

and Some Other
a,P-Unsaturated Ketones (IX. Okisi alkili-

denatuetonov i
nakotorykh drugikh a,P-nepredel'nykh ketonov)
PERIODICALz
Zhurnal obahchey khimiiq 1959, Vol 29, Nr 3, pp 809-820 (USSR)
ABSTRACT:
The authors carried on their earlier investigations
(Refs 1-3, 5)

and investigated-the oxidation with alkaline
hydrogen per-

oxide of the following compounds: ethylidene
acetone (penten-

2-one-4) Prop lidene acetone (hexen-3-one-2),
trans-n-butyli-

dene acetone ~hepten-3-one-2),
trans-isobutylidene acetone

(5-methylhexen-3-one-2), as well as
3-methylhepten-3-one-

2,1-methoxy-5-methylocten-4-one-3 and
5-methylociadiene-1,4-

one-3. It was established that in the
action of alkaline

hydrogen peroxide upon the alkylidene
acetones (I) in methanol

solution, the corresponding a-keto
oxides (II-VI) form in

cooling: R - CH R CH-,,,

if 1 0

CH3CO - CH
CH3CO CHZ
Card 1/3
M (II-VI)

SOV/79-29-3-14/61
a-Keto Oxides. IX. Oxides of Alkylidene Acetone5and Some
Other alp-Unsaturat-
ad Ketones
where in (II) R-CH3(V)R.iso-C 3H7
v (III) R=C 2H5 (VI)R=iso-C4H9
it (IV) R-n.-C3117 .
In the same way, compound (VIII) (Scheme 2) resulted from
VII) and compounds (XI) and (XII) (Scheme 3) from (IX) and'
. It was shown that under the influence of diluted sul-
M
phuric acid solutions, the alkylidene acetones and the oxide
of 3-methylhepten-3-one-2 isomerize into the a-diketones and
also hydrolize into the corresponding keto glycols. The
ultra-
violet absorption spectra of the oxides of ethylidene-,
propylidene-, trans-n- and trans-isobutylidene-,
isovalerylidene
acetone and of 3-methylhepten-3-one-2 were recorded. All
these
acetones have one and the same absorption band at 285-290 mg,
which refers to the carbonyl group (Figs 1-2). There are
2 figures and 27 references, 12 of which are Soviet.
Card 2/3

SOV/79-29-3-14/61
a-Keto Oxides. IX. Oxides of Alkylidene Acetonesand Some Other
a,P-Unsaturat-
ed Ketones
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR
i Belo-
russkiy gosudarstvennyy universitet
(Institute of Organic Chemistry of the Academy of Sciences,
USSR and Belorussian State University)
SUBMITTED: January 3, 1958
Card 3/3

5~ I? / 00 671,914
SOV/20-129-5-21/64
,~ZMWHS i Batuyev, M. I., Akhrem, A. A., Matvayeva, As D.
2ITLEt Optical Investigation of the Conformations of Aottyl
Cyclo-
hexene%nd Its Oxide
YERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 129, Nr 5,
PP 1038 - 1041 (USSR)
ABSTRAM Table 1 shows the physical properties of acetyl
cyclohexane
and its oxide which was produced by the aid of alkaline
hydrogen peroxide (Ref 1, see Scheme). The Raman spectra
of both these substances were taken by means of the Soviet
3 prism spectrograph ISP-51 with a central chamber and the
Hilger spectrograph Ye612 in the liquid phase. The exciting
frequency 4358 A stemmed from a mercury lamp. The measured
frequencies are specified. The presence of frequencies in the
region of the triple bond (2096, 2111 am-1) in the spectra
of both substances points to the fact that they still contained
residues of the athinyl compound utilized for their synthesis.
i - C frequencies showed that the oxidation of acetyl cyclo-
hexene was incomplete and that the oxidation product is a
Gard 1/4 mixture from acetyl Cyclohexene and its oxide. The
oxide, how-

67914
Optical Investigation of the Conformations of Aostyl
BOV/20-129-5-21/64
Cyclohexone and Its Oxide
over, is clearly predominant. It was electronographically
confirmed (Refe 2,3) that the carbon atoms of the double
bond C, and C2 are placed on or approximately on the same
planso The molecule exhibits half-chair-shaped (polukreelo-
vidnyy) conformations (Ref 4) (see Scheme). The vhlencies
are quasi-equatorial (e1) and quasi-axial ( at) at the atoms
C3 and CO whereas they are equatorial (e) and axial (a) at tK
C4 and 05. Since the half-chair-shaped confirmation of cyclo-
hoxene is energetically by 2-7 kcal/mol more advantageous and
since the rules established by Barton and Khaseell (Rof fl
are evidently still valid for substituted cyclohexenes, the
half-chair-shaped confirmation in acetyl cycloboxene is
apparently predominant. In this connection, the acetyl group
is placed on the plane of atoms C,C 2C3C6 or on an approximated
plane (see Scheme). There are no reasons for denying the con-
servation of the acetyl group position in the case of
conversion
(I)# (II). The carbonyl group frequency is divided into 1663
and 1672 cm-1. The ethylene bond frequency is practically not
Card 2/4 divided into a doublet. The authors are inclined to
assume that

67914
optical Investigation of the Conformations of Acetyl
BOV/20-129-5-21/64
Cycloh*xene and Its Oxide
the division of the oarbonyl frequency is to be explained
by the possible double position of carbonyl with respect to
the ethylene formation CaC of the ring, namelyg the ois-oid
position ((I)#(II)) and the trans-oid position ((14# (IV))
(see Scheme). The oscillation frequency of the ethylene bond
remains practibally unchanged. The oxidation of the acetyl
cyclohexene on the double bond leads to the formation of a
3-maimbered: oxide ring
/-\C, whose C-C-bond belongs to the 6-membered carbon ring. The
half-chair-shaped conformation of the 6-membered ring.is-oon-
served in the acetyl cyclohexene oxide (Ref 9). If the above-
mentioned position of the acetyl group is conserved, the oxygen
atom of the 3-membered ring (see above) is placed on a plans
which is peryendicular~-to the plane C 1C2C 3C6* The above con-
cepts were concreted by optical data supplied by the authors.'
It was finall confirmed that acetyl cyclohexene oxide exists
in cie oid (V~*ft(VI) and trans-oid (VII)V-:~(VIII)
conformations.
Card 3/4 The causes leading to the formation of both these forms
ara '

67914
Optical Investigation of the Conformations of Acetyl
SOV/20-129-5-21/64
Cyclohexene and Its Oxide
different in acetyl cyclohexene and in its oxide.There are I
table and 9 referencest 3 of which are Soviet.
ASSOCIATIONs Institu t goryuchikh iskopVemykh Akademii nauk
SSSA (Institute
of Mineral. Fuels of the Academy of Scie .ncea, USSR)
PRESENTEDt July 15, 1959, by B. A. Arbuzov, Academician
SUBMITTEDs July 3, 1559
Card 4/4

left'
L 9
C 11ji!f1i
1:
-j vp ~j- 32,
*1
vil
Olk

- -- -,- , - I - - ____ - _M
BATUTIT, M.I.-
., AKHR . A.A.; )UMTBVA, A.D.
Optical study of some acetylenic alcohols and their acetates.
Izv. AN SSSR.Otd. khim. nauk uo,12:2201-2207 D 160. (MA 13tl2)
1. Institut goryuchikh iskopayoxykh Ali SSSR I Institut orga-
nicheekoy khimii im.N.Z.Zelinekogo AN SSSR.
(Acetylene compounds-Optical properties)

BATUYLT, M.I.;_AKHRIM, A.A.,,KkXMMTSKIT, A.V.;
HATMITA, A.D.
Optical stud7 of the conformations of cyclohexanous
and some of
its derivatives. Dokl.AN SSSR 133 no-5:1077-1080 Ag
'60.
(MINA 13:8)
1. Institut goryuchikh iskopWomfth Akademii nauk SSR
i Institut
organichookoy kbimli in. N.D. Zelinskoga A W enii
nauk SSSR.
(Cycloboxanone)

MMER, Dzh. [Musher, -1.1.1; AMM A.A.
- tlltl~-
Nuclear magnetic resonance study of the configuration of
saturated
cyclic systems. 2-Methyl-l-hvdrozycycloboxylethylene oxides
and
some 1-hydroxydecalylethylene oxides. Dokl.AR SSSR 134 no.2:
354-357 S 16o. OURA 13:9)
1. lizicheskaya laboratoriya Garvardskogo universiteta, SShA
i Institut organioheskoy khimii im. N.D.Zelinakogo Akademii
nauk
SSSR. Predstavleno akad. B.A.Kazanakim.
(Xthylene oxide) (Nuclear magnetic resonance)

BATUM, M.I.; AUREM, A.A.; AMNITSKIY, Aj, MATV=A, A.D.
()ptiea study of conformations of cyclopen~aWne and
d--chloro-
oyalo~entanone. Izv*AN SSSR.Otdo'chim.nauk' no.6t1138-lUl
J;a 161.
(MA l4s6)
I* lastitut &'67uohikh iskopayamykh AN SWR i Institut
organicheskoy
kh'm4i ime Nb.Zelinakogo AN SSSR.
(Cyclopentanons) (Isomers)

BATUYEV, M.I.; !XHREM, A.A.L.KAMERNITSKIY, A.V.;
MATVEYEVA, A.D.
Optical investigation of conformations of cyanohydrims
of
some derivatives of cyclohexanone. Izv.AN
SSSR.Otd.Ichim.nauk
no.10:1813-1816 0 161. (MIRA 14:10)
1. Institut goryuchikh iskopayenykh AN SSSR i Institut
organicheskoy
khimii im. N.D.Zelinskogo AN SSSR.
(Cyanohydrins) (Cyclohexanone)

A:'~:: A. A.
'-'-ion to the carbonYl
c, ke 3 F f 61.
-1 L
-L lu, In I. oc ':Mmi I AN S38-K
Uk
(Carlbon',ri Z-10up)
t
R Vt

8/020/61/137/005/017/026.
B103/B208
AUTHORSt Batuyev, M*I*# Akhrem, A.A.# and Matveyevat A.B*
XY-
TITLEs Optical study of the conformations of 2-methyl-l-hydro
-cyolohexyl-ethylene oxides
PERIODICALs Boklady.Akademii nauk SSSRp v, 137, no. 51 1961, m3 1116
TEXT: It is the purpose of the present study to define~the structure
of.
the following glyoide alooholst
0
0 CHI CHI CH
CH CHI OPH CHI
H CH
\ 0
0
'OH (:rOH OH OH
(IV)
which had been obtained by-oxidation by peracetio acid in chloroform
from
card 1/

S/O~OJ61/137/005/017/026
.0ptical.study of the ... B103/B208
cis-2-methyl-l-vinyl oyclohexanolt (1) and (II); and trans-2-methyl-1-
vinyl-cyolohexanolt (111) and (IV); and which were assumed to have the
;
bove structural formulas. All four alcohols have different melting
points*
:..Their structures were studied by their Raman spectra recorded on
the 'USSR
speotrograph of the type ViCTI-51 (ISP-51), and on an E612 Hilger
spectro-
graph. It is concluded from the data (Table 1) that a hydrogen bond
exists
between the hydroxyl group of these alcohols in liquid state and the
oxygen
atom of the oxide ring. This is confirmed by the fact that the 0 - H
fre-
quency is a blurred narrow band_yhioh is quite different in the two
trans-.
-ib omers. It is narrow 45 0m ) in the low-melting isomer (IV) (40-5
m in the high-melting isomer (111).(7
- 410C), and broader (- 200 o -1) 5
0
- 75-5 C). Thi's is assumed to indicate a:predominanoe of the
intramolecu-
lar H-bond in (IV), whereas in (III) the intermolecular bond prevailse
-This difference seems to exert a considerable effect on the melting
points*
This fact was used for the identification of (III) and (rV). If the
dif-
nto of (1) and (II) have the same reasont the higher-
forent melting-poi
is that with intermolecular H-bondt
melting alcohol (1) (43 43-500)
Card,2/Y

S/020/61/137/005/017/026
Optical study of the ... B103/B208
while the liquid (II) has the intramolecular bond. This
assumption was
confirmed optically. In a considerable part of the molecules of
(II) in
the liquid phase the O-H group is released from the
intramolecular H-bond
and enters the intermolecular H-bond. The threo-isomer is thus
partly
converted to the erythro-isomer, or to an isomer having a
similar position
of the oxide ring as the erythro-isomer. The conversionof the
erythro.-
-isomer th the threo-isomer can hardly 6 confirmed op .tically
in the case
of'(I)., The authors conclude from these facts that the two
types of
H-boild represent the most important stabilizing factors in the
case of
erythro-threo-isomerism. The energy of the H-bond is not high
(- 3 kcal/mole). These bonds therefore cause a considerable
difference of
the mentioned isomerism in crystalline state, but not in liquid
or super-
cooled-liquid state. The intramolecular bonds are, as a rule, not
destroyed in 20% solutions of these alcohols in M 49 which was
also
optically confirmed. The complexes of (I) and (III) with several
members, which are associated by the intramolecular H-bond, are
destroyedt
while dimeric complexes are preserved, and monomers are formed.
The
authors conclude from the optical data that under their
experimental con-
Card 3/~

Optical study of the ...
S/020/61/137/005/017/026
B103/B208
ditions each of the four alcohols mentioned exists in two
conformations.
The prevalent conformation.are: in (I) - cis-ea (Fig. 1), in
(III) and
(IV) - trans-ee; in (II) both conformations'appear to about the
same
extent. There are 1 figure and 6 Soviet-bloc references.
ASSOCIATIONs Institut goryuchikh iskopayemykh Akademii nauk SS.SR
4 (Institute of Mineral Fuels of the Academy of Sciences
USSR)
Institut organicheskoy khimii im. N. D.,Zelinskogo
Akademii nauk SSSR (Institute of Organic Chemistry imeni
N. D.- Zelinskiy of the Academy'of Sciences USSR)
?RESENTED: November 28, 1960,.by B. A. Arbuzov, Academician
SUBMITTED: December 29, 1960
Card 4/

AKHREMt A.A4-KUZNETSOVA, A.I.; TITOV, Yu.A.; LEVINA,
I.S.
Separation of acetylenic alcohols and glycols by means
of thin
layer chromatography on aluminum oxide. Izv.AN SSSR
Otd.khim.-
nauk no.4:657-661 Ap 162. (MIRA 15:4)
1. Institut organicheskoy khimii im. N.D.Zelinskogo AN
SSSR.
(Alcohols) (Chromatographic analysis)

S/1062/63/000/001/009/025
B101/B186
AUTHORS. Bystrov, V.,F.f Pozdnyakova, T.-SYe.t Yelizarova, A.-N-v
and,Akhremi A--&.
TITLE; Structural analysis of chemical- compounds based on their..'
nuclear magnetic resonance spectra. Communication 2.
Determination.of the structure and conformation-of some
substituted cyclopbntenones
PERIODICAL: Akademiya nauk SSSR, Izvestiya. Otdeleniye
khimicheskikh nauk, no. 1, 1963, 66-74
TEXT: The synthesis of the erythro isomer IA and threo isomer IB o
f-3t5-'.
dimethi -acetoxyethyl)-&2-cyclopenten6ne by condensation of 3.,5-di-
, I.
(1-5-(a
methyl-.A2_cyclopentenone with vinyl acetate has already been
described
(Izv. AN SSSR, Otd. khim. n., in press). That reaction also produced
the.,
erythro and throo isomer of 3,5-dimethyl-5-(a-acqtoxyethyl)-A3-cyclo-
entenone (IIA, IIB) and the 2-e thyli done - 3, 5-dijnethyl-,&4 -
cyclopent enone
I). By analyzing the high resolution proton magnetic resonance
(P-M-r.)
M
spectra it was possible to dofine-the structure and conformation
of-IA,
Card 1/4

�/062/63/000/001/009/025
Structural analysis of chemical ... M01/B166
2
IB and III a~ well as of 3,57dimethyl- A -ciclopentenone (IV),
3,5-dimethyl-
A4-cyclopentenone M, 3,5-di-methyl-5-vinyl-k~-t)yd'Lopentenone (VI),
3,5-
dimethyl-5-(a-acetoxyethyl)-cyclopentazione (VUA~~ VIIB),
3,5-dimethYl-5-
a-hydroxyethyl'-6F-cyclopentenone (VIIIA, VIIIBj,cand 3,5-dimethyl-5-
a-hydroxyethyl)-cyclopentanoiie (IXA) which were-s~nthesized for
~
comparison. The p.m.r. spectra of 0.2-0-5 1-1 solutions in CCI were
-taken,
4
at room temperature and at 20.'529 Mo. Hexamethyl disiloxane was used
a6
internal standard. The spectra Were analyzed according to J. T. Arnold
and X. B. Packard (J. Chem.-Phys., 19, 1608 (1951)). The slight
difference
between the spectra of IA and It led to the conclusion that there is
no
structural difference but only a different.steric orientation of the
groups;
thi.s was confirmed by converting IA and-IB i7nto VI' Equally, IXA was
obtained by hydrogenation from! VIIIA as well as from VIIIB.
Conclusions:-
The isomerism i's based on a different position of the q-obstituents
at the
asymmetrid C atom.- Two steri'c series are possible with 3
conformations
6
each (Fig. 6). One of these conformations must outnumber the*two
other.
The IR spectra of VIIIA, VIIIB.and IXA showed thtit an intramolecular
H bond
exists at the hydroxy group of-VIIIA and IXAj which is absent.in
VIIIB.
C a r d 2 /'A

s/o62/63/ooo/ool/009/025
Structural analysis of chemical Bf01/ M1 66
Hences the compounds IA, VIIA, VIIIA and IXA have the structure a with
predominant conformation 3a, the isomer compound.s IB, VIIB and VIIIB
have*-~
the structure b with predominant conformation 3b. The structure of III
was confirmed by the p.m.r. spectrum. The.p.m.r. spectra of IfA and
IIB:,
were not taken, since these isomers could not bq separated. -There are
7, figures and I table.
ASSOCIATION: Institut khimicheakoy fiziki'Akademii naukV3,SR (Institute
of Chemical Physics of the-Adadamy of Sciences USSR);..
Institut okganicheskoy-khim~,~.-Akademii nauk SSSR
emi!i
-of the koademy ~of
Institute of Organic Ch st'ry
Sciences USSR),
SUJIMITTED: June 16, 1962
Fig. 6 Conformations of the rotation isomers'4 M-dimethyl-(a-~Ydroxy_
ethyl) A2-cycilopentenono (V11fA and V111B).
Al
Card 3/4

Structural analysis of chemic4l ...
s/962/63/000/001/009/025
B101/13180'
Fig. 6
-,t 0
Card 4/4

S/062/63/000/001/015/025
B1O1/B186
AUTORS: Yelizarova, A. N., Pozdnyakova, T. Ye., and Akhreml..A. A.
TITLEs Chemistry of cyclopentenones.. -Communication 6. Conversions
of er thro and threo-isomers of 3*,5-dimethyl-5-(,4-ace toxy-
ethyl~-6.yc_lopenltenones
PERIODICALi Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no. 1, 1963, 129 - 136
TEXT& To clarify the configuration of
erythro-3,.5-dimethyl-5-(O~-acetoxy-
2_
ethyl)-A cyclopentenone (IA), m.p. 69-70PC, and its threo-isomer(IB),
m.p...
-520C, and of the analogous compounds IIA, IIB)
of,63-cy'clopentenone,~
1
5
the following reactions were carried out: Hydrolysis of IA and IB
in.iq/
HCl at 1000Cyielded the
corresponding.3,5-dimethyl-5-(,k-hvdroxyethyl)_/A2_
cyclopentenones IIIA (yield 83%. b.p..92-93 0C/5mm-Hg,
crystallizea'.when
standing, m-P. 40-41 0C)-ELM -III-B (yield 87%,'m-P'-,'72-73 0C); IB
hydrolyzed
more readily than IA. Hydrolysis of IIA, IIB yielded the corresponding
Dc-hydroxyethyl derivatives IVA, IVB. IA and IB did not hydrolyEe in
2(Y/.
Card 1/3

s/o62/0/000/001/01 5/025
Chemistry of cyclopentenonds. B10J/B186
NaOH at,100 OC;' only sma 11 amqunjs of IIA, IIB were obtained,
in*40~- NaOR;
2-
the initial! 3,5-.:dimethyl-A ~-cyclopentenone form!&&,in 60~ yield.
Hydrogens
-dimethyl-5_ (->1,-acetoxy
tion of IA or IIA with plae catal st yieldea 3,5
ethyl)-cy6lopentanone (VIA),.M.P. 41oYG-j.-;1ike'wisi, 'the
corresponding epi'mer
20
VIB was formed from 1B.or I~B, yield 7M~, b.p. 84-85OC/4 mm H9, n
1-44461
20
d 1 0066.' Hydrogenation 'Of IIIA? IIIB, IVA, and IVB,only yielded
3,5-di-r
4
methyl-'5-((V-hy~roxyetbyl)-ey~~opentanone (VA), yield 81~-, b.p.
88-90OC/6mm.
20 20,
-by acidolysis of VIA,
Hg,- n 1.4604,1:cl o.986o,.which was formed also
D 4
this indicatingepimerization of the threo-Xetone alcohol IIIB. In
oxida
tion of IIIA and IIIB with CrO ahd acetic acid, one of the two
centers of
1~ 3 2_
asymmetry disappearb and only 3,5-dimethyl-5-acetyl-LA.
cyclopentanone (VI.I)
is formed, yield 60%, b.p. 9?-93'G/5 mm Hg,,n 20._ 1.14877, d20
1.0471. "Such..'.`.
D 4
isomerization also occurs in the formation of 2,4dinitrophenyl
hydrazone
(2,4-DNPH) of IB and IIIB. 'Both IA and IIIA, and IB and IIIB, form
the
0
same 2,4-DNPH, m.p. 158 C, i6ich, sa AhAU in acetone, gives
ponified wi
Card 2/.3

S/062/63/000/001/015/025
Chemistry of cyclopentenones. B101/B186-
'IIIA. Likewise, VIB and VA form only one type of 2,4-DNPH, m.p.
147.'50c,.,
.which forms VA by saponification. An isomerization similar to the
reaction.
de.scribed by B. Ellis (Mrs.) et al..(J. Chem. Soo., 1961, 4111)
is-assumed
for the asymmetric 06' The.higher stability of 'IA, as compared'with
IB,
indicates that the compounds of the A series have erythro-, and the
compounds,
of the B series threo-configurat~on. Reduction Pf VIA with.LiAlH in
ether
4
yielded a chromatographically'separable mixture of the two epimers of
3, 5-dime thy 1- 5- (c4-hydroxye t.hyl) -cyclopentan- 1 -o1, yield
90%, b.p. 107~109%44'
20 20
Hg, n 1.4708, d 0.9946, which was~'not further investigated. There
D $74.
are 3..f igures-.~
ASSOCIATION:~ ~.Institut.organichesk6y khlmii im. N. D. Zelinskogo
Akademil
r) a*uk SSSR (Insti*tute',of Organic.Chemisiry imeni N.DZelinody
of, the Academy of Sciences USSR)'
SUBMITTEDs June 18, 1962
Card 3/3

5~3 SOV/79-29-3-3/61
A &RS: Nazarov, I. N. (Deceased) Burmistrova, M. S.,
Akhr9-q,_A. A.
TITLE: Synthesis of the Simplest Analogues of
Corticosteraids (Sintez
prosteyshikh analogov kortikosteroidov). VII. Introduction
of the Dioxyacetone Side Chain bZ, HYdrmtiOa Of
Acetylene Alcohols (VII. Vvedeniye dioksiatsetonovoy bokovoy
tsepi metodom gidratatsii atsetilenovykh spirtov)
PERIODICAL: Zhurnal obshchey khimii, 1959, Vol 29, Nr 3, PP
735-744 (USSR)
ABSTRACT: The authors earlier described (Ref 1) the
bromohydrin-, di-
bromoketol- and glycide method of introducing the oxidized
side chains into the cyclic compounds. They were likewise
interested in the introduction of the dioxyacetone side
chaing
which is characteristic of some hormones, by the hydration
of acetylene alcohols. Although after the completion of their
investigations some reports appeared on the synthesis of the
simplest cortisone analogues, in which the same method of
introducing the above chain had been applied, their
investiga-
tion results still had to be published, inasmuch as the
yields
of the initial products obtained in the latter investigations
mare higher, than had been those published according to
Card 1/3 references 2-4. At first the dimethyl ethynyl
carbinol (1),

SOV/79-29-3-3/61
Synthesis of the Simplest Analogues of Corticosteroids. VII.
Introduction
of the Dioxyacetone Side Chain by the Hydration Method of
Acetylene Alcohols
which was obtained according to Favorskiy's reaction by conden-
sation of the acetylene with acetone (Ref 5), was used an
an initial product. In the hydration of carbinol (I) in the
presence of sulphurio mercury, the dimethyl acetyl carbinol
(H) (Ref 6), which is transformed into bromo acetyl dimethyl
carbinol (III) by dioxane bromidep results in a high yield.
In the action exerted upon this by alcoholic caustic potash
lye, dimethyloxyacetyl carbinol (IV) (Scheme 1) is formed.
On the reaction of the acetate of dimethyl acet 1 carbinol
(V)(Ref 6) with dioxane dibromide, compound (Vl~ is formed,
which in the action of alkaline caustic potash lye likewise
passes over to (IV) and in acetolysis forms diacetate of
(IV) - (VII) by the aid of potassium acetate in methanol.
Also the following compounds were used as further initial
products for this reaction: 1-ethynylcyclohexanol (VIII);
3,5-dimethyl-l-ethyn 1 clopentanol (XV); cis-2-methyl-1-
ethynyloyclohexanol ~Xcx~ and 3,8-dimethyl-l-ethynyi- A5-
tetrahydroindanol (XXVII). Their hydration with subsequent
bromination and saponification of the forming a-bromo ketols
Card 2/3 led to compoundsl which likewise contain the
dioxyacetone

SOV/79-29-3-3/61
Synthesis of the Simplest Analogues of Corticouteroids. VIL
Introduction
of the Dioxyacetone Side Chain by the Hydration Method of
Acetylene Alcohols
side chain..There are 10 references, 7 of which are Soviet.
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR
(Institute of Organic Chemistry of the Academy of Sciences,
USSR)
SUBMITTED: January 39 1956
Card 3/3

AURFAI, Afanasiy Andreyevich for Doe Cher.. Sci on the bosis
of diasertaLion defended
9 JHne 59 in Council of Inst of Orpnic Cher. im Zelinskiy,
Actad Sci USSR, entitled
4z
"St7idy in the field oftsynthasis and stereochemistry of
analogues of cortico-
steroids. Methods of Ibuilding and th,~ atereocheiaistry of
P cortiooid side chain ."
(BMViSSO USSR,1-61, 25)
-208-

AXHRM A.A.: GMZHNAMEK, S. [Hermanek, S.]; SYGOIRA, X.
[Svhora, KJ
New case of the closure of the 5c