SCIENTIFIC ABSTRACT SHOSTAKOVSKIY, M.F. - SHOSTAKOVSKIY, M.F.

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001549920003-8
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: August 9, 2001
• Sequence Number: 3
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

S-HOSTAKOVSKIY, M.F.; BOGDANOVA, A.V.; VOLKOV, A.N.
Vinyl compounds in diene synthesis. Part 7: Diene synthesis
of vinyl ethers and thioethers with 2,3-dimethyl-1,3-butadiene.
Zhur.ob.khim. 31 no.7:2096-2100 Jl 161. (MIRA 14:7)
1. Institut organicheskoy khimii imeni N.D. Zelinskogo AN SSSR.
(Vinyl compounds) (Butp-diene)

24421
S/079/61/031/007/003/0-08
D229/D305
AUTHORS: Komarov, N.V., Shostakovskiy, M.F.p and Astaflyeva,
L.N.
TITLE: Interaction of y-silicon acetylenic alcohols with
thionyl chloride
PERIODICAL: Zhurnal obahchey khimii, V. 31, no. 7, 1961t
2100 - 2102
TEXT: This is a report on the syntheses and properties of new si-
lico-organic compounds. The present work is a continuation of an
earlier investigation concerning the syntheses and substitution
reactions of numerous acetylenic alcohols containing inorganic
elements. It was found in this work that y-silicon acetylenic al-
cohols reacted with thionyl chloride to form corresponding chlori-
des:
R3SiC _= C - CH20H + SOC12 ---,)R3SiC C - CH2C1 + H01 + S029
Card 1/4

24h2l
S/079/61/031/007/003/008
Interaction of y-silicon ... D229/D305
R = CH 3P C2H5f 06H 5'
Thus, new compounds were synthesized: 3-chloropropyne-1 - trimethyl-
silane, 3-chloropropyne-l-triethylsilane and 3-chloropropyne-l-
dimethylphenylsilane. The reactivity of the above chlorides was
studied by the following reaction:
(CH 3)3 SiC =_ 0 - CH2CHOHCH3+ CH 2 = CHOC 4H9--> CH 3 -CH(OC4H9
OCHCH2C = CSi(CH 3 )3&
CH3
named (4-trimethy"Lsilyl-l-methyl-butyne-3) - butylacetal. The syn-
thesis of (CH3) SiC C_CH2Cl, designated 3-chloropropyne-l-trime-
thylsilane is tL ~O described
b.P. 500/17 mm, n 1.4546, ~2 Sharacteristics of the product are;
D 4 0.9295, MRD 42-87; calc. 42-77 [Ab-
stractorb note; MR D not defined]. Found percent: Si 18.84, C6H 11 Si
Cl. Calculated percent: Si 19.14. The synthesis of (C 2H5)3 sic C_
Card 2/4

24h21
S/07 61/031/007/003/008
Interaction Of 7-silicOn D229YI)305
CH2C', named 3-chloropropyne-l-triethylsilane, was analogous to
that of 3-chloropropyne-l-trimethylsilane. Quantities used: 6.92 gr.
of thionyl chloride, lgr. of pyridine, 9.51 gr. of 3-triethylsilyl-
propyne-2-ol-1 (b.p. 109-1100/6 mm, n 20 1.4670, d20 0.8932). The
D 4 0
yield was 8.95 gr. (95 %). Characteristics of products b.p. 72 /6
20 20
mm, nD 1.4698, d 4 0.9262, MR D 57-03: calculated 56.66. Found per-
cent: Si 15-16. 09H17 SiCl. Calculated percent Si 14.84. Synthesis
of (CH ) - SiC E C-CH Cl named 3-chloropropyne-l-dimethylDhaylsila-
3 2 2
C6H5
ne was analogous to that of 3-chloropropyne-l-trimethylsilane
20
Characteristics of product: b.p. 1180/6 mm, n D 1.5345, MRC 62-39;
--alculated 62.44. Found percent: Si 13.54. C11H 13 SiCl. Calculated
f,ercent: Si 1j.42. The authors then describe the synthesis of 5-tri-
Card 3/4

21
S/o7q 61*T3. 1/007/003/008
Interaction of y-silicon ... D229YDD305
methy'Lsilypentyne-4-ol-2. The yield was 3.5 gr. (16.4 %). The cha-
racteristics of the product; b.p. 95-97'/2 mm, n 20 1.4748t d 20
D 4
0.9101. Found IM D 48.46; calculated 48-74. Found percent:.Si 17-90
C8H16 OSi. Calculated percent Si 17-9. Finally the synthesis of 4-
trimethylsilyl-l-methylbutyne-3/butylacetyl is examined. The yield
,aas 4.68 gr. (97.5 %). Characteristics of the product: b.p. 1530/
3 mm, n 20 1.4655, d20 0.8925, MR 2 79-12; calculated 78-51. Found
D 4 D
percent: Si 11-52. 0 14H2602Si. Calculated percent: Si 11.00. There
are 2 Sov-.Let-bloc references.
ASSOCIATION: Irkutskiy institut organicheskoy khimii Sibirskogo ot-
deleniya akademii nauk SSSR (Irkutsk Institute of Or-
.vanic Chemistry, Siberian Division, Academy of Scien-
ces USSR)
SUB".ITTED: July 27, 1960
Card 4/4

PRILLSIUMVA., Ye.N.; TS)MBAL, L.V.; SHOSTAKOVSKIY. M.F
Sulfoxides and sulfones. Part 2: Stereochemistry of the
addition of thiols to-triple bonds of dia~etylene and
1-aLkyl-l-thiobuten-3-ynes and properties of isomeric 1..4-
dialkylsulfonyl-1,3-outadienes. Zhur.ob.khim. 31 no.8:2487-
2496 Ag 161. (MIM 14:8)
I. Institut organicheskoy khimii im. N.D. Zelinskogo Akademii
naul-- SSSR.
(8utadiyne) (Butenyne) (Butadiene)

SHOSTAKOVSKIYI M.F.; PRILEZHAYEVA, Ye.N.; TSDMAL, L.V.;
TOWRINSKAYA, R.Ya.; STAROVA, N.G.
Sulfones and sulfoxides. Part 3: Comparative reactivity
ofo~./9-unsaturated sulfoxides and sulfones to nucleophilic reagents.
Zh,--.ob.khim. 31 no.8:2496-2503 Ag 161, (141RA 14:8)
1. Inatitut organirheskoy khimii im. N.D.Zelinakogo AN SSSR.
(Sulfoxide) (Sulfone)

25365
S/079/61/031/008/003/009
SJOD D215/D3O4
AUTHORS: Shostakovskiy, M.F., Kuznetsova, V.P., and Komarov, N.V.
TITLE': Study of synthesis and transformations of unsaturated'
organo-silicon compounds: interaction of r -silicon-
-acetylene chlorides with sodium-acetoacetic and sodium-
-malonic esters
PERIODICAL. Zhurnal obshchey khimii, 1961, v. 31, no. 8, 2504-250?
TEXT: This paper studies reactions of Y -Sl-acetylene chlorides of the
propargyl type with Na acetoacetic and Na malanic esters and the prospects
of obtaining Si-acetylene carbonyl compounds from these reactions. The
reaction is smooth and the yield of keto-esters. reaches 40-50%:
R3SiC_~~fC-CH2cl + CH COCHNaCOOC,H5
(R is CH C H or C H
3 2 5 6
R3SiC!tC-CH2__~H-CO0C2H5 + NaCl
Card 1/3 OCH3

25365
S/079/61/031/008/003/009
Study of synthesis... D215/D304
A Si-acetylene acid was obtained by the following reaction
(C.2 H5)3 SfCz.-C -CH_Cl + NaGH(COOG2H-5)2
.1 -,
(C2H5)3 SiC,=-7CCH 2CH(COOC2H5)2
I~H20
J~ *
(C H ) SICI~~C-Cfl -CH -COOH + GO + 2C. H OH The presence of the
2 5 3 ~=- 2 2 2 2 5
carboxyl group in the product of this reaction was established by reaction
with vinylbutyl ester forming - OC4H 9
CH--CH
00CC,H2C112C Cs i (C 91f5)3
Card 2/3

Study of synthesis...
_25365
5/079/61/031/008/003/009
D215/D304
The acylal formed hydrolyzes to form the original Si--acetylene acid
together with butyl alcohol and acetaldehyde. The stages in which the
original Si-acetylebe keto-ester is converted into the acid are two,
i.e. formation of a Si-acetylene keto-acid which then breaks down with
fission of the Si=--'C bond. Synthesis of the following new compounds is
described: 6-trimethylsilyl--3-carbetoxyhexene-5-on-2,6-trisethylsilyl-
-3-carbetoxyhexene-5-on-2;6-dimetliylphenylsilyl-3-carbetoxyhexene-
-5-on-2,6-triethylsilyi-3-carboxyliexene,5-on-2,4-tr4~e'vhylsilyi.-l-
--carboxybutenc--3, 1-butoxyethyl ester (4-triethylsilyl-i-carboxybutene-3).
There are 3 Soviet-bloc references.
ASSOCIATION4, IrkUtskiy institut organicheskoy khimii Sibirskogo
otdeleniya akademiy nauk SSSR (Irkutsk Institute of
Organic Chemistry, Siberian Division, Academy of Sciences,
us'~R)
SUBMITTED- July 25, 1960
Card 3/3

0 S-6
27904
S/079/61/031/010/004/010
D227/ D304
AUTHORS: Shostakovskiy, M,F., Skvortsova, G.G., Samoylova,
M. Ya., ana-tay-er-s-hteyn, Yu. M.
TITLE. Synthesis of vinyl ethers of o-., m-, and p-amino-
phenols
PERIODICAL: Zhurnal abshchey khimii, v. 31, no. 10, 19619
3226-323v
TEXT: The authors discuss the preparation of vinyl ethers of
aminophenols by direct acetylation, and investigate the dependence
of yields of the products on the quantity of alkali and water,
and the temperature. It has been found that the para-isomer vinyl-
ated at 170-1800C, while the ortho-isomer 'gav(! the highest yield
of ether at 1900C. m-aminophenol, the most stable isomer, vinyla-
ted at 210-22000. The re~Lctions were carried out in aqueous media
and the optimum quantity of water was found to correspond to 15-
20%. Larger quantitieo had no effect on the yield while smaller
caused tarring of the reaction mixture. The amount of KOH required
Card 1/ 4

279%
S/0-9/61/031/010/004/010
Synthesis of vinyl ethers ... D227/ D304
in the reaction was 40% (15-20% for alkylphenols) which corres-
ponds to the molar ratio of catalyst to aminophenol. The reaction
can be represented as follows:
C6H4NH 2OH + KOH - C6H 4 NH2OK + H20
C6H4NH 20K + CH a CH to H20 C6H 4NH 2OCH = CH 2 3 KOH
The yield of ethers was 30-60%. Their structure was studied by
hydrogenation to the corresponding phenetidines. Experimental
procedure: The quantities used were 20 g. aminophenol, I - 10 g.
KOH and 3 - 25 9. water. Vinylation was carried out in a rotating
autoclaveusing 30-35 atm. acetylene pressure at a temperature op-
timum for the particular aminophenol. After attaining calculated
absorption of acetylene the product was treated with benzene and
Card 214 1

27904
S/079/61,/031/010/004/010
Synthesis of vinyl ethers ... D227/ D304
the solution distilled in vacuum. Vinyl-o-aminophenyl ether sepa-
rated in the form of yellow oil b.pt. 900C/10 mm, nD 1.5700 which
on redistillation yielded 508 9. of colorless liquid b.pt. 66.5 -
680 C/1-2 mm nD 20 1.5715, d420 1.0677 MRD 41.9'; MRcalc* 42.06. The
pure meta isomer bjiled at 92.5 - 930C/2mm. nD 20 1.5820, d420
1.0759, MRD 41.9', MRcalc 42.06 and the yield corresponded to
63.6 g. of colorless., odorless liquid. The pure para-isomer boiled
at 11B'C/10mm, nD 20 1.5765, d420 1.0759 MRD 41-54 and its yield
was 52.0 g. The ether was in the form of a colorless oil which
darkened on exposure to air. Hydrogenation of the ethers on Raney
nickel in alcoholic solution yielded corresponding phenetidines.
o-aminophenol polymerises in the presence of ethereal boron tri-
fuloride forming a solid mass with shiny black crystals. With the
same catalyst, p-aminophenol forms a white, crystalline solid
which on standing changes to a solid, dark yellow and opaque resin.
Card 3/4

27904
S//079/61/031/010/004/010
Synthesis of vinyl ethers ... D227/D304
There are 4 figures and 7 referencesg 5 Soviet-bloc and 2 non-
Soviet-bloc.
ASSOCIATION.-, Irkutskiy institut organicheskoy khimii Sibirskogo
otdeleniya Akademii nauk SSSR (Irkutsk Institute of
Organic Chemistry, Siberian Division of the Aca-
demy of Sciences, USSR)
SUBMITTED: October 4, 1960
Card 4/4

31192
S/079/61/031/012/011/011
D204/D301
AUTHORS: Sidellkovskaya, F. P., Zelenskaya, M. G., and.Shosta-
kovskiy, M. P.
TITLE-. The preparation of acrylone - and methacrylone pyrro-
lidones
PERIODICAL: Zhurnal obshchey khimii, v. 31, no. 12, 1961, 4060
4061
TEXT: The work was carried out in view of the recent interest in
the amides of acrylic and methacrylic acids as potential starting
materials for the synthesis of new polymerB. CH2 = CH.CON(CH 2)3 CO
CH3
I
(I) and CH = C.CON(CH ) CO (II) were prepared in 20 and 40% yields
2 1 2 3j
respectively by the action of the appropriate acid chlorides on Na
pyrrolidons at _100-->-1500. Propyl gallate was used as an inhibitor
and structures of the products were confirmed by infrared spectro-
scopy. kcrylone pyrrolidone (I) polymerizes very readily, forming a
Card 1/2

3n92
S/07 61/031/012/011/011
The preparation of acrylone D204YD301
hard polymer, insoluble in water or organic solvents, during its
preparation and distillation. Monomer (II) polymerizes in 20% yield
on heating --for 30 hours at 600C, in the presence of 5% azo-iso-
butyric dinitrile, to form a white powder (m.p.--27000) soluble in
dimethyl formamide. Properties of the above two monomers and the
preparation of acrylone and methycrylone lactrams based on piperi-
done and caprolactam. are now being investigated.
ASSOCIATION: Institut organicheskoy khimii imeni N. D. Zelinskogo,
Akademii nauk SSSR (Institute of Organic Chemistry im.
N. D. Zelinskiy, Academy of Sciences USSR)
SUBMITTED: July 10, 1961
Card 2,12

88407
lot S/020/61/136/004/016/026
Bo16/B075
AUTHORS: Shostakovskijr, M. F., Corresponding Member AS USSR, Komarov,
-U. V'., and Pukhnarev'ich, V. B.
TITLE* Synthesis and Some Conversions of Secondary y-Sllicon-
containing Acetylene Alcohols
PERIODICAL; Dolclady Akademii nauk SSSR, 1961, Volo 136, No. 4,
PP. 646-848
TEXT: Proceeding from the reaction of chlorosilanes with dimagnesium
bromine derivatives of secondary acetylene alcohols the authors elaborated
a synthesis method of secondary y-silicon-containing acetylene alcohols:
R3SiCl + RICH - C ft CMgBr OR 3SiC ~ C - CHOH -RI, where R and R'
I
OMgBr
denote CH 39 C2H51 and other organic radicals. Furthermore, the reaction
of the synthesized alcohols has been studied 1) with thionyl chloride
Card 1/3

88407
Synthesis and Some Conversions of Secondary S/020/61/136/004/010'/026
7-Silicon-containing Acetylene Alcohols B016/BO75
and 2) with vinyl ethers. To I)t Substitution of hydroxyl by a chlorine
atom proceeds under relatively mild conditions and results in the
corresponding siliconacet ylene chlorides. The Si-C bond is not ruptured.
R3Sic -.A- C --CHOHC2H5+ SOCI2 R3sic -AE C - CHcl C2H5+ SO2 + HC1, where
R = CH 3 and C2H5' To 2): Reaction with vinyl ethers proceeds easily and
leads to the corresponding acetals: 0 CH
R 3Sic ~- C-- CHOHC2H5 + CH 2 = CHOC4R 9-;~cn 3 - CH
~'~OCH - c ~CsiR
3
2A5
where R = CH 3 and C2H5' The following compounds were synthesized
according to (1): 5-trimethyl-silyl-pentin-4-01-3, 5-triethyl-silyl-
pentin-4-01-3, 3-chloro 5-trimethyl-ailyl-pentine-4, and 3-chloro
5-triethyl-silyl-pentine-4; reaction 2 led to: butyl-(3-trime'uhyl-silyl-
Card 2/3

88407
Synthesis and Some Conversions of Secondary S/020/61/136/004/016/026
y-Silicon-containing Acetylene Alcohols BO16/BO75
I-ethyl-propine-2)-acetal and butyl-(3-triethyl-silyl-l-ethyl-propine-2)-
acetal. There are 3 Soviet references.
ASSOCIATION: Irkutskiy institut organicheskoy khimii Sibirskogo
otdeleniya Akademii nauk SSSR (Irkutsk Institute of Organic
Chemistry of the Siberian Branch, Academy of Sciences USSR)
SUBMITTED: October 12, 1960
Card 3/3

A-V-; PLOTIIIKOVX, G.I.
Stereo-oriented s7rithese.9 based on diacetyleney and Isomeric
conversions of l.,4-bls (arylthio)-11-3-butadienes and their
disulfones. Dokl. AN SSSR 136 no. 3:595-598 Ja 161. (Iff-RA 14:2)
1. Institut organicheskoy khimii imeni N.D. Zelinskogo AN SSSR.
2. Chlen-korrespondent AN SSSR (for'Shostakovskiy).
(Butadiyne) (Butadiene) (Sulfones)

- SHOSTAKOVM 9 M.F. KOMAROV9 N.V.,; FUMNAUMCE9 V,B.
%mthesis amdL some couversions of secondary rr-smcom~-eontginimg
acetulenic alcohols. DAL AN SM 3.36 no.4:84&-48 F 16.1.
(KMA 14: 1)
-1. lrkutsk~7 !nBt:LtUt orgiwicheakoy.kbimil SIbIrakogo otdeknjjva
AN SSW,. 2. Chleu-korrespondent AN SSSR (for Shostakovdk*1
kziupm orrvamle COMPOUMCIS)

S/020/61/138/005/018/025
253i8 B!03/B220
1-0
AUTHORS: Prilezhayeva, Ye, N., Tsymbal, L. V., and ShostakovskiyM.F.,
Corresponding blember AS USSR
TITLE: Comparative dienophilic reactivity -,.n the series: vinyl
sulfide -vinyl sulfoxide -vinyl sulfone
PERIODICAL: Akademiya nauk SSSR, Doklady, v. 13B, no. 5. 1961, 1122-1125
TEXT; In previous papers, it was proved by the authors that the electro-
philic nature cf the double bond in the ~_;eries of sulfor-containing vinyl
compounds increases from uLnyl sulf-Lde over vinyl sulfrixide to vinyl
sulfone. in ionic, reactions, reagents add to vinyl-alkyl sulfides in the
presence of acid catalysts in strict accordance with Markovnikov's rule
(14~ F. Shostaki:-vakiy et al. Ref, 1; izv AIT SSSR, OKhN. 1955, 154;
Sintez' i rePctcryy-2 s,,,(-vstva -Lrj1-1.nilovykh efirov Isynth is and me
k es I So
propertie's of t!ji~)virvl estar). 11 1. Uvarcva, Kani,
(cand idn 10K-i AN SSSR, 1955). Therefrcm the ~_-_lthoro nonc.Dide
that fi- ~_lztJ!jr :0--ri i!- fl-,e~ie ~.-tnvi ;:-_.i electr~~r
CH,
Ca rd '/ 5

S/10220/6 11/ 1 -',9/009//0 ! C/02 5
C()MP,31.!f t 1 "t, fi ~ ~.rcfjh 1 i I C. D _~ 2 G
;arl~i e
I h., 1 i r a e r uo t 1 i k i n
oxygen '.-'nvi ejtero- Tn- 'IX .~iilt'i7.xides -,:'!f(,neq
merely ur.Jer th~, , nt of -,i] k.il i ne oatalys ts., Thereb cnl~r
RSOCH 20H 2 X or RSO 2 CH 2 CH 2 Z com.noiinds are f,jrmed, ~jnd the associative
activ t I ~
i y of the nucleGphiiix reagent and, consequently, the electrophilic
nature of the doubie bond ircrease from sul-foxide to sulforie, This
indicates that the sul.fonyl group is a much better electron acoeptor than
the sulfinyl greup, Tne authcrs stud Led the variations of the reactivity
of this ier_ie" :i' wh'~.ri used as dienoulliii.es .,iith cne and the same
diene. C,.- lcoe,- ad iere CF) ar,~.' ii.- -.,La;-,h oi ~~at fad ~Eccp) were
c 11 o s e n as d e, n e,~ Ul~ pre;_z~,n reK t no i-.Ilg nas been 1, about
the reac~Lvi-c- of --inyi.~tltyl .-lulfoxicle arvi, abcif ti,,e reactions
occurrin- -.n :r;e z
Z' - ... I ~- r ta c t' In the presen-e c f a, P-unga turat ed
sulfinyl com~,.ound.-. The _.~itixr.= effected reactions bet"'ieen viny,'-.ethyl
sulfide, s,_ilfoxide, and 3-utif~ane on rhe one hand, and CP or HCCF on the
other, the oond-illions being as comT:Prative as pcssible. They concluded
from the results that the dienophiles mentioned from t-fic reverse series
with Cu and HGCP. Ls CP contains electropositive H atoms besides a diene
system, reacts exofterniudIly w:Lth vinyl-ethyl sulfone, and requires a
Card 2/5

S/02 61/1
-250 38/005/018/025
Com arative dienophilic reactivity... B103%220
p
longer heating with vinyl-e'uhyl sulfide, it may be-seen that the activity
for CH =CHX increases in the order X-RS-,*"RSORSO>RSO 2 ; here, vinyl-ethyl sulfide exhibits the
highest reactivity. It is concluded that the activity.of there synthesis
depends on the interrelations between the polarization of the double bonds
of diene and dienoDhile rather than on the character of polarization'of
the double bond of 'the dienophile. Thus, HCCP is bound to be active for
dienophiles having electrori donor substituents, whereas CP is active for
dienophiles having electron acceptor substituents. The au,thors obtained
only monoadducts of-vinyl-ethyl aulfoxide (IJI) with both HCCP and CP
01,-CH-Soc,ff,
0
SOCA C'Gror""
C1
C1
Card 3/5

S/020/61/138/005/018/025
Comnarative dienophilic rqactivil-,17-A B103/B220
On reaction vith CP a mixture of crystalline and liquid (1).is forimed at a
ratio of about 3:1. Apparently, the higher melting product has an endo-
configuration, ard Alder's rule is folloved in this reaction. (II) is
formed on reaction with HCCP; it has a definite mp.1ting point thich is not
changed by recrystallization. This indicates a steric homogeneity of (II).
The adducts obtained from HCCP and vinyl-e'uhyl sulfide (III) as wdll as
sulfoxide (H) gLve the same product (IV) as obtained from HCCP and vinyl-
ethyl sulfone, un,3er conditions excluding isomeriz-ation
C1 a 0
cj,,,`N._ 02Q15 2cfficoootf C1 SCA
tj SoQ15 c1l,ccoott
C~
C.,
C1
a (VI
a (11) C1 (IV) 0 (1111
M- MY) ll-;2*)
't ... P.77P.)
(where a) melting point; b) liquid at room temperature). Recently, it- has
been proved by the authors, and V. A. Azovskaya et al. (Ref. 11: ZhOKh, 3i,
No-. 6 (1961)) that the reaction of divinyl sulfone -with HCCP-results in an
exoadduct as primary product. In their opinion, the reason for this
deviation from Alder's rule is the thermal izomerization of the corre-
Card 4/5

25. 8 S/020/61/138/005/018/025
. '-11
Comparative dienophilic reactivi-Gy... B1031B220
sponding endo-monoadduct to an exo-monoadduct. Apparently, the same rule
holds in the present case. The adduct of vinyl-ethyl sulfide (III)
(synthesized at room temperature) undergoes complete isomerization during
fractionaticri of the reaction mixture. There are 1 table and 11 refer-
ences: 8 Soviet-bloc arid 3 non-Soviet-bloo. The two references to
English-lancluage publications read as follows: Ref. 7: K. Alder,
C)
XIV Intern. Congr. of Pure and Applied Chemistry,1955; Ref. 9: Aileri.
J. Am. Chem. Soc., 62, 656 (1940),
ASSOCIATION: 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: February 14, 1961
Card 5/5

6HOSTAK.OV6KIY, M.F.; KOMAROV, N.V.; ~LIVZOSHIN, Yu.V.
Synthesis and some transformations of silanols in the vinylacetylene
series. Ijokl. All SSSR 13c; no.4:913-915 Ag 161. (MIRA 14:7)
1. Irkutokiy institut organicheskoy khimii Sibirskogo otdeleniya
AN SSSR. 2. Chlen-korreapondent AN 88SH (for Shostakovskiy).
(Silanol) I

-k L V -I-\- I
23676
S/020/61/11,0/002/021/02x
B130/BlIO
AUTHORS: Shi~orin, D. N., Smirnova, V. I., Zburavleva, G. S.,
and Shontakov3kiy, III. F., Correnpoad4ng
AS USSR
TITLF. Epr rpnctra of y-irradiated acetylene and its derivatives
?ERIODICAL: Akademiya nauk SSSR. Doklady, v. 1~101 no. 21 19161
419-422
T--YT: To dctcrm4ne the relationship betucen the structure of the initial
moleculea "he structure of the resulting radical, the authors studied
the er, pectrs~ of 7-irradiated acetylene, methyl acetylene, methyl
r s
deutero acctylene, ethyl- and butyl acetylrne, as well as phonyl- and
mothyl-phenyl rcetylnne at 770
K. The compounds were irradiqted in
special-61aoo ampulo giving no epr spectrum with the used dose of 7-radia-
tion. Be f o r,~ the tests ' the ampule wore alacuated to 10-3 m~., jig. Ir a-
diation wrta csn(luctod with C060. A superheterodyne radiospectroscope
was uo-nd for taking the epr spectra. The zagnatic f'eld was calibrated
with the opr spectra of the pyroxylamine disulfone ion, ["0(S03 )22 -1 in
Card 1/1

28676
3/020/61/140/002/02'./023
Zpr 3i~ectra cf y-irradia-,cd ... B130/3110
chlorofor7, C,)ppcIr chloride mcnocry~talo were used f)r determining the
conceritz-LLti :r. of the radicals obtained. The relative error vhen
as ~20,~
determining the yirld 0~ radicals 'r - Tes~ reaults are Given in
Tableo I ara 4. The 3poctru.~ of 0.--2utero --ethyl acetylene obtained from
n-.eraction of t
heavy -xat~.r- a:,.,! Li-methyl acet,..Ienide sug,,ests an i,
unrcLir,~d ~~I,c~ron in the radical with the protons of -.he CD and CH2
triplet of methyl-phenyi acetylene may be
0) the interaction of the unpaired oloctron with the
Protons of ths~ nethylene group in the radical 4ZQ CzC-(.H2, or (2) by the
fact that zpcctrum has to be ascribed to the radical of the phony!
ring k comnarison -sith the spectra of bonzone and methyl-
pheny', ac,.,tyI,~nr, with benzene indicates that explication (1) in applicable.
An intensiv- t~;~r spectrum of C 2H2 in only obtained by hig4-doae irradia-
tian, whi,~h ou;,c;e-at3 a considerable redistribution of energy in the
system. Thi~i is even more distinct with phenyl acetylene which gives no
epr spectra ,,.'-'th hiGh-do;aQ irradiation either. The redistribution of the
er,er&y abz3orb-i may be explained by the formation-of conplexes betwocn the
moloculeu. In fac', polymerio compounds wore found on the ampul walls
A
Card 2/5

'76
Epr spectra of -1-irrLdiated
dui-::-.-;: 'OiL exp?rim,~nto Th-re nr.-? 1 2 tablea, vmd
2 Tho ttn r f,i,--iro.,i tj
r.-ad as :ollova: C. 11. S. And~roon, J. Chcl.
2 - 3,*,6 (1959), R. Wast , Ch. J . ",.M. C~'G-"'. So C.
7~,
5 (19-
C T,%'I 10:.: Fiziko-khimIcheokiy in. in
-i titut L. Ya. 7'arpova (Fhynicn-
chomical Inatituto imeni L. Tn. Karpov)
Yay 25, 1961
TrCo I., I .intjErai inte-naity of -1-1--radiation ~ 107 rad
~c-~-cind ;(u) ini tial compounds (boilinis Point, 00 W, radical pze3uacd,
(c) nz;nber of lines, (d)'total width, olOrptnea, (c~ the number of liniI3
duL to ouPerporition witli the spectrum of CII CzC-H cannot be drterminpd.
Card 315

SHOSTAKOVSKIY, M.F.; SKVORTSOVA, G.G.; SAMOYLOVA, M.Ya.; WONAYA, K.V.
Vinyl compounds. Report No.3: Refractometric investigation of the
copolymerization of vinyl cresyl, esters and acrolein in the presence
ot cation catalysts. Izv.Sib.otd.AN SSSR no.12:37-41 161.
(141RA 1-5:3)
1. Irkutskiy institut organicheskoy khimii Sibirskogo otdeleniya
AN SSSR.
(Vinyl compound polymers)

SHOSTAKOVSKIY, M.F.; CHEKULAYEVA, YJGALKINA, E,V.
Vinyl ethers of ethanolamines in diene synthesis. Report No.l:
Interaction of vinyl ethers of A -(dialkylamino)-ethanols and
monoethanolamine with cyclopenthdiene. Izv. All SSSR Otd.khim.nauk
no.1%152-155 Ja 162. (MIRA 15:1)
1. Institut organicheskoy khimii im. N.D.Zelinskogo AN SSSH.
(Ethanol) (Ethers) (Cyclopentadiene)

S/062/62/000/001/009/015
B117/BlOl
AUTHORS: Shostakovzkiy,_11__F__, Sidellkovskaira, F. P,, and Kolodkin,
F~ L.
TITLE; Study of lactones and lactama. Communication 21. Addition
of mercapto compounds to N-alkenyl lactams
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Otdeleniye khimiclieskikh
nauk, no. 1, 1962, 155 - 162
TEXT: N-alkenyl lactams are systematically szudied in the laboratoriya
vinilovykh soyedineniy Instituta organicheskoy khimii AN SSSR Laboratory
for Vinyl Compounds of the Institute of Organic Chemistry AS USSR).. In
the present paper, the free radical addition of mercaptano to N-alkenyl
lactams was studied:(,N-vinyl pyrrolidone (I), N-vinyl caprolactam (II)~
N-allyl pyrrolidone II), N-allyl caprolactam (IV). Ethyl, n-butyl
mercaptans, and ethyl mercaDto acetate were used for this reaction. Pre-
liminary results of this study have been published (Zh. obshch. khimii
50, 4108 (1960)). - The addition of mercaptans to N-vinyl and N allyl
lactams was conducted by heating equimolecular amounts of the initial
Card 1/0 q.

S/062/62'/000/001/009/015
Study of lactones and lactams... B110101
component in closed ampuls at 70 - 800C for 18 hrs. Azoisobutyrodinitrile
was used as initiator. When adding mercaptans to N-vinyl lactams, P- 1~
addition products are obtained, when adding it to N-allyl lactams, 7-alkyl
thio derivatives are obtained (70 - 95~ yields) : N-P-alkyl thioethyl-a-
pyi-rolidones, N-0-alkyl thioethyl-E-caprolactams, N-y-alkyl thiopropyl-a-
pyrrolidones, and N-y-alkyl thiopropyl-L-caprolactams. N-vinyl lactams
proved to be more reactive than N-allyl lactams. In both groups the acti-
vity of caprolactam derivatives was somewhat hiE;her than the activity of
other lactam derivatives. The reactivity of mercaptans decreases as
follows: HSCH COOC H n-C H H SH. With pyrrolidone derivatives,
2 2 0 4 9SH /C2 5
the structure of adducts was croved by a synthesis from N-p-chloro-ethyl
pyrrolidone (IX) and the corresponding sodium thiolates. The structure of
N-allyl lactam adducts was confirmed by N-P-alkyl thiopropyl pyrrolidones
(XVII) and (XVIII) syntheses: The reaction of N-P-chloro propyl pyrroli-
done (XVI) with the corresponding sodium thiolates yielded N-P-ethyl thio-
proDyl-a-pyrrolidone and N-p-carbethoxy-methyl thioproDyl-a-Dyrrolidone.
The effect'of the position of the lactam ring in substituted S-alkyl
mercapto acetic acids on the biosynth~a-is of penicillins was studied wi--,h
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S/062/62/000/001/009/015
Study of lactones and lactams... B110101
N-7-carbethoxy-inethyl thiopropyl lactams (XII, XV), N-p-arbethoxy-methyl
thioethyl lactams (VI, VIII), and N-carbethoxy-methyl thiomethyl lactqms
synthesized later (M. F. Shostakovskiy, T. IM. Voronkina, F. P. Sidel'-
kovskaya, Zh. obshch. khimii 31, 1463 (1961)). After their intro-
duction into the nutrient of Penicillium chrysogenum, the compounds in
question proved to cause the formation of new penicillins. As to their
activity in fungus fermentation, these compounds may be set up as follo'.'Vs.
CO if - CH2SR