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

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001549920001-0
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: August 9, 2001
• Sequence Number: 1
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

SpeCLI'OSCODiC InvestuigatElon of N-Vinyllactams -77C62
and Anilides
Card 2/3
ISP-51 and PRK mercury lamp were used to obtain Raman
spectra, and specturograph SF-4 to obtain UV-spectra.
Spectra of vinyllactams in the double bonds region
showed lines characteristic for C=C and C=O bonds.
It was found that the presence of the N-atom at the
double bund Influenced con3lderably the spectral
characteristics: the frequency of the C=O bond was
lowered nearly as much as in molecules contalninZ
>N-C---O bonds. Values of the extincticin , coefficient
of C~O bond line in vinylpiperidone and vin-yl6dp-ro
lactam were quite high, and close to those of.' vinylamine.
The intensity of C--C line of vinylpyrrolidone was
substantially higher, and that of C=O line in all
three vinyllactams was many times higher than in com-
pounds with > DT- C==O bonds. This anomaly in the
intensity of the C==O bond in Raman spectrum was the
most peculiar characteristic of vinylaact-ams which
distinguished them from molecules with C=C-N-< and
>N-C=O bonds. It can be explained by the influence
of the C-C bond, through the 14-atom, on the carbonyl
group (in the bond system C=C-N-C=O). Similar

Spectroscopic Inves-u-ilgation of N-Vinyllactams 77C82
and Anilides sov/62-59-12-20-/4-,-z
ASSOCIATION:
SUBMITTED:
Card 3/3
relationships were also observed in anilide spectra.
It wa3 noted that the alkylation of N in anilides
weakened the indications of conjugation of N with the
benzene ring, and strengthened those of conjugation
with the carbonyl group. It can be assumed, therefore,
that a C6 H5NRCO-X molecule loses the coplanarity of the
system C611 5- N-C arid the system C-N-COX becomes more
planar. There are 3 tables; 1 figure; and 6 references,
I U.S., 1 U.K., I German, 3 Soviet. The U.S. and U.K.
references are R. Bowden, E. Braude, E. Jones, J. Chem.
Soc., 1946, 948; E. Corey, J. Amer. Chem. SOC., 75, 2301
(1953).
N. D. Zelinskiy Institute of Organic Chemistry, Academy
of Sciences, USSR (Institut organicheskoy khimil imeni
N. D. Zel-inslcogo Akademii nauk SSSR)
April 7, 1958

5.3620 77089
sov/62-59-12-33/43
AUTHORS: Shostako]v~kl Prilezhayeva, Ye. N-, Tsymbal,
zovskaya, V. A., Starova, N. G.
TITLE: Brief Communication. Concerning Addition of Nucleophil-
1c Reagents to CL , /3,, -Unsaturated Sulfones in
Presence of "Triton B
PERIODICAL: Izvest-1ya Akademii nauk SSSR. Otdeleniye khJ-micheskikh
nau1c, 1959, Nr 12, pp 2239-2241 (USSR)
ABSTRACT: Addition of nucleophilic reagents (alcohols, mercap-
tans hydrogen sulfide, dialkyldithiophosphoric acids,
etc.~ to 0-,13 -unsaturated sulfones of various
structures is catalyzed to a great extent by "Triton
B11 (benzyltrimethylammonium hydroxide). The addition
reaction starts upon addition of a few drops of "Tri-
ton B" (40-60% aqueous solution, 0.2-0 .5% by weight)to
an equimolar mixture of reacting substances. In Tnost
cases the reaction is exothermic (temperature rises up
to 8o-iooo) and is completed wi in 2-3 hr, with a
Card 1/5 nearly quantitative yield. a tp_~ -Unsaturated sulfones,

Brief Communication. Concerning Addition 77089
of Nucleophilic Reagents to Ct, f-; - SOV/62-59-12-33/43
Unsaturated Sulfones in Presence of "Triton
B"
having other unsaturated bonds in the molecule (e.g.,
endo- and exovinyl bicycloheptenyl sulfones, obtained
by reaction of cyclopentadiene with divinyl sulfone),
add alcohol or mercaptan under these conditions only
at the unsaturated bond activated by sulfone Sroup:
SoCH=CH, + C,H, (~1 ICHICHzSCaHir
I -SH so
(C311,0H) iOC,H,)
>
- II OH, .11
(Pndo t exo) (endo + exo)
DJI-.,~ulfones, havlnr~ two unsaturated bonds, add two
mercaptan irtolecu'le3. TaI)Ie 1 litits the yields and
physical constants of the addition product3 (eight of
Card 2/5 them prepared to the first time) obtained by the authom.

Brief Communication. Concerning Addition
of Nucleophilic Reagents to a, /3 -
Unsaturated Sulfones in Presence of "Triton
B"
77089
sov/62-59-12-33/43
Ylew
% bp tw "t
(PI-eSSURE /A/
C
85,/, 147-148,5(3) 35-36 39,82 7,75 34,93 39, M 7,74 35, V
99 32-93 42,93 8,2-') 32,42 42,82 8,21 32,66
,8
40-41
45,44
8,62
30,57
45,68
8,62
30,4b
90 - 5G 54,W, G,(V, 26,10 54,06 6,60 26,24
90 124-195 (0,04) 30-40 6,0:1 27,68 52,14 6,12 27,M
90 - A 2) - 4: 1 311,78 7,46 22,94 34,76 7,49 23,2C
91 125-130 (4) - 4:1,40 8,42 19,30 43,3!) 8,49 19,20
116-116,5 (0,5) - 49,37 9,37 10,41, 49,45 9,34 t6,5C
114-1w (0,03) - xt, 1;1 7,77 17,66 39,54 7,74 17,60
Clymm. 85.4 188-190 (0,03) - 3U,55 7,:j:1 2t,10 39,71 7,13 21,221
85 - 108-109 35,/,() 6,79 : A, 8 2 35,01 6,61 35,05
34-4,3 133 - 137 (0, 31,46 6,18 3t,43 31,35- M,4C

Card

13)V r -1 - (6,L14 77089, SOV 2 -59-3-2-33/43

0 C
-
p
I
t 1 0/, /xz 6 ~
FOR ~1111_4 ~/, X / -1
1 - w S
-,
0
,
4
em 6 U /7 .5 C
S02CJ140C I H5 ~ )

/ I
it 815-85,5
C
1
5G 95
8
06 I
13
93
1

0 ymm. 9
,
i , ,
5-1 . 36 7,88
1 13.92
1 95-97 (0,03)
t 5 7
8,01 1
14
0i
01lao + ~Ipol ,
SO,C,H,SC,H,
86 X11
I
-
-
I

6, 13

'1,74
(~IUO + 3X30) 47 3,
6,27
21.71)
C.11'soxilic,11 - C11C1;_,0x.11..)
Card 4/5
112-113 56, 53 6, 66 24,81 55,99 6,66 24,92
Notes: Obtained for the first time. ** In the litera-
ture [Lorenz, W., Pat. FRG (Federal Republic of
Germany'), 876691 (5/18/1953); Referat Zhur. Khim., Nr
32864 (1955)3 , it is described as a compound, liquid
at room temperature, bp 127-1290 (2 mm). *** Literature
[Moore, A. H. Ford, J. Chem. Soc., 1949, 2433-7, MP 36-
380. **** Found: P 9.62; 10.00%. Calculated: P. 10.11%.
In the literature EThompgon, R. B., Cheniceck J. A.,
Symon, T., J. Ind. Eng. Chem,., 50,, 797 (1958~~ it is
described as "nonvolatile re idue .

P -I ):wilt I 1, 1 (!.rit, If), iw Add I I; I-oil
of Nucleophilic Reagent;s to CL J M -
Unsaturaced Sulfones in Presence Of "Triton
B11
ASSOCIATION:
SUBMITTED:
77089
"0
0 11/62-59-12-32/4-3)
There Is 1 table; and 6 references, 2 Soviet, I German,
1 U.K., 2 U.S. The U.K. and U.S. references are: A. H.
Ford, Moore, J. Chem. Soc. 1949, 2433; J. L. Szabo,
E. T. Stiller, J. Amer. Chem. Soc. 70, 3667 (1948); Ch.
D. EUrd, L. L. Gershbein, J. Amer. Chem. Soc. 69,
2328 (1911-'(); R. B. Thompson, J. A. Cheniceck, T.
Symon, J. Industr. and Engng. Chem., 50,797 (1958).
N. D. Zelinalciy Institute of Organic Chemistry of the
Academy of Sciences, USSR (Institut orl,,anicheskoy
Ichiniii imeni N. D. Zelinskogo Akademii nauk SSSR)
May 4, 1959
Card 5/5

KOGIIKIN, D.A.; KOTRELEV, V.N.; WOST"AK
,~OVSKIY, M.F.;,XALINIIIA, S.P.;
KlTZIIETSOVA, G.I.; BORISSENIr
Tin organic polymers. Vysokom. soed. 1 no.3:482-484 Mr 159.
(MA 12:10)
l.Nauchno-issledovatellskiy institut promyshlennosti plasticheakikh
mass.
(Polymers) (Tin organic compounds)

SHOSTAKOVSKIY, R.F., PRILEZILAYEVA, T6.N.-, KARAVAYEVA, V.M.
Synthesis of sulfur compounds from virql ethers and acetylene.
Part 19: Role of thionic complexes in the ionic polynerization
of sulfur-containing vinyl compounds. Vysokori.soed. 1 no.4:582-
582-589 Ap '59. (MIRA 12:9)
1. Institut organichesko khimij AN SSSR im. N.D.Zelinskogo.
(Polymerizationi (vinyl compounds)

SHOSTAKOVSKIY, KARAVAYEVA, V.M.
I '' - .
Synthesis of sulfur compounds from vinyl ethers and acetylene.
Part 20: Interaction of jercaptals with vinyl sulfides and vinyl
ethers. Vysokom.soed. 1 no.4:590-593 Ap 159. 04IR& 12:9)
1. Inatitut organichaskay khimit AN SSSR im. H.D.Zelinskogo.
(Sulfur compounds) (Vinyl compounds)

PRILEMYEVA, Ye.N.; KARVAYNVA, Y.M.
Synthesis of sulfur compounds from vIT71 etbers and acetylene.
Part 21: Ionic copolymerization of vinyl sulfides witb styrene
and vinylbutyl other. Vysokom soed. I no.4:594-596 Ap '59.
NIRA 12:9)
1. In.--titut organicbet3koy khimii AN SSSR im. IT.D.Zelinskogo.
(Polyalarization) (Sulfur compounds)

~zHAT~a , T a. N. ; UAVATNVA, V.)t.
_~4PRIIXZRATSVA
,.q~T ~ 4~&
Detex-mination of relative activity coefficients in capol7-!er',-
zation of vinyletblaulfide witb styrene and nethy-Imethacrylate.
Vysoko,n.soad. 1 no.5:781-783 YT '59. (MIRA 12:10)
~. Institut organichpsi-my kh1mii in. N.D.Zelinskogo.
(Sulfide) (Styrene) (Kethacrylic acid)

,6-, 3 37
670
AUTHORS: __S_h&atakovskiY,,X.,_Y-, Prilezhayeva2 Ye. N.~ SOV/153-2-5-22/31
Karavayevag V. X.
TITLE: Synthesis and Polnerization of Vinyl Sulfideal
PERIODICAL: Izvestiya vysehikh uchebnykh zavedeniy. Khimiya i khimieheskaya
tekhnologiya, 1959, Vol 2, Nr 5, PP 761 - 768 (USSR)
ABSTRACT- At the Laboratory for Vinyl Compounds of the Institute in which
the authors work, the synthesis methods and the chemical chWes
of vinyl compounds, which contain, besides double bonds such
hetero atoms as 0,8,92Si, etc, have been studied for several
years. The preoent paper gives a review on the studies of the
synthesis of monomers of this group containing sulfur, some of
their reaotions, the polymerization and the copolymerization.
A general method of synthesis was developed (Ref 5) based on a
modification of the vinylization reaction according to A. Ye.
Favorskiy and X. F. Shostakovskiy (1) (Ref 6). An excess of
acetyls still remains -to be a necessary condition. The vinyliza-
tion of mercaptanes yields several advantages (Refs 7p9,lO)-
From alkyl-mercaptanes and di-acetyle (Refs 11,12) it is possible
to obtain the corresponding aD71-thio-butenine (Equation (3),
Card 1/3 Table 1) at 30-500C,in a methanol medium and in the presence of

67037
Synthesis and Polymerization of Vinyl Sulfides SOV/153-2-5-22/31
Card 2/3
2-3~ of KOH. The authors developed, instead of the acid hydro-
lysis to the acetaldehyde and a titration of the latter, the
splitting of the vinyl sulfides by an alcoholic sublimate solu-
tion as a method for quan ,titative determination (Refs 7,8) (4).
This reaction (4) is also suited for alkyl-thio-butenines
(Refs 11,12). The authors also established the conditions of
the selective sulfur oxidation in vinyl-alkyl sulfides in which
vinyl sulfoxides or vinyl sulfones form (Table 2). These can be
used as starting substances for polymerization (5). The intro-
duction of the sulfur increases ihe dielectric properties of
the polymer (Ref 19) and its thermoplasticity (Ref 16). By in-
troducing tho sulfone groups, the benzo-resistance increases
(Ref 20). It was obser-fed that vinyl sulfides have less inclina-
tion to kationic polymerization under the influence of metal
halides, but they easily form polymers under the influence of a
DU;;'!able freo-radical initiator. The best yield of ionic poly-
ma"Is was obtained in the presence of tri-,boron-fluoride-ethyrate
(Ref 21). The polymers are viscous oils. For the determination
of their molecular weight, titration of the thio-vinyl terainal'
groups by sublimate was used besides cryoscopy (see also abo-fe).
Good accordance confirms the structure of the terminal groups

67037
Synthesis and Polymerization of Vinyl Sulfides SOV/153-2-5-22/31
to be -CH%--CHBR. Table 3 shows the fractionation of a sample
of polyvinyl-ethyl sulfide. Tables 4 and 5 illustrate the condi-
tions of polymerization of vinyl sulfides in the presence of
free-radical initiators and the properties of the pclymers ob-
tained. The beat yieldo were obtained with dinitrile of the azo-
isobutyrio acid. Benzoyl-peroxide cannot be used in this case
(Ref 23). No thione groups form on introduction of a free radi-
cal and the terminal groups of the polymers have also the cha-
racter of a thio-vinyl (7). 12 pairs of monomers containing
vinyl sulfides were-studied on copolymerization.-The properties
of the copolymers are also studied. Table 6 shows the polymeriza-
tion of the vinyl-ethyl sulfone. The rules establiihed can be ex-
plained in view of the reciprocal influence of the C.-C linkage
and the sulfur atom in the vinyl-sulfide molecule. There are
6 tables and 31 references, 24 of which are Soviet.
ASSOCILTION: Institut organicheskoy khimii AN SSSR im. N. D. Zelinskogo
(Institute of Organic Chemistry of the Academy of Sciencesi
USSR-imeni-N. D. Zelinski
Card 3/3

,57 3 ePJ
_5_~' ~ 617038
AUTHORS: Bogdanova~ A. V., SOV/i53-2-5-23/31
Chekulayevaq I. A.
"I
TITLE; Synthesis of New Monomers on the Basis of Acetylene
and
Diacetylene
PERIODICAL: Izvestiya vyashikh uchebnykh zavedeniy. Khimiya i khimicheakaya
tekhnologiya, 1959, Vol 29 Nr 5, PP 769 - 775 (USSR)
t
l
ABSTRACT: as from compounds con-
From acetylene and diace
ylene, as wel
taining a mobile hydrogeng monomers (ether and thioether) with
a vinyl-ethyl-vinyl- and a diene group can be obtained. The com-
pounds with mobile hydrogen eiein particular: alcohols of various
structure, amino alcohols, mercaptanes, phenols; silanols~ etc.
According to the method of A. Ye. Favorskly and M. F. Shostakov-
skiy different types of vinyl compounds with a total formula
CH2-CH-XR can be obtained where X - OqN,S,Siq and R is an alkyl,
aromatic, hydroaromatio, or other radical 'Ref 1). The most in-
teresting among the recently obtained unsaturated compounds on
acetylene basis, is the vinyl-ether of the amino alcohols
(Refs 5,6). They may be used as initial raw materials for several
Card 1/3 nitrogen-containing macromolecular products including some with

67038
Synthesis of New Monomers on the Basis of Acetylene SOV/153-2-5-23/31
and Diacetylene
a three-dimensional structure (to be used as ion-exchangerre-
sins). At present diacetylene becomes interesting because it may
serve as a starting raw material for various syntheses, and be-
cause it has both a scientific and a practical significance. In
the laboratory for vinyl compounds of the Institute in which
the authors work, the hitherto neglected chemistry of the di-
acetylenes concerning the interaction with compounds containing
mobile hydrogen has been systematically studied. By the reaction
of diacetyleae with alcohols (Ref 8) and mercaptanes (Ref 10)
(constants of the reaction products in Table 1), as well as with
amino alcohols (Ref 10) organic compounds with a simple other
(also containing nitrogen)and with a thio-ether-group in the
conjugated system of the double and triple linkages (I) can be
obtained. Additionally, butadiene-a-sther (II), a,b-di-thio-
ether (III) and mixed a96-thio-ether are obtained. The synthesis
method of the 1-alkoxy-butadienes-1,3 on the diacetylene and the
alcohol basis makes possible the production of several repre-
sentatives of this class which contain alkyl- and cyclic radi-
cals (Ref 16). The alcohols react with diacetylene under the in-
Card 2/3 fluence of alkali and on heating. In this reaction, ethyl-vinyl-

67038
Synthesis of New Monomers on the Basis of Acetylene SOV/i53-2-5-23/31
and Diacetylene
ether (I) and acetals of butin-2-&1-4(see Scheme) are formed.
The reaction of the diacetylene with mercaptanes occurs gradual-
ly. Unlike the reaction with alcohols, the 2-mercaptane molecule
adds itself to the threefold linkage and di-thio-alkyl (or
phenyl) of the butadiene-1,3 is formed (Schome). The compounds pro-
duced are highly reactive. The authors recommended a new method
of synthesis for the 1-alkoxy-butadiene-1,3 based on partial
hydration of the ethyl-vinyl-ether (Table 4). Tables 2.3,5,
and 6 list the constants of additional products synthesized.
Finally, they established the conditions of the synthesis of
vinyl ether of ethanol amines~of various structures, and ex-
amined their properties. There are 6 tables and 16 references9
13 of which are Soviet.
ASSOCIATION: Institut organicheskoy khimii AN SSSR im. N. D. Zelinskogo
(Institute of Organic Chemistry of the Academy of Sciences,
USSR imeni N. D. Zelinski
Card 3/3

SHIKHIYEV, I.A.; SHOSTAKOVSKIY, M.P.; KAYUTFINKO, L.A.
Investigations in the field of the synthesis and transformation of un-
saturated silicon organic compounds. Dokj.AII Azerb.SSR 15 no.1:21-23
59. (MIRA 12:3)
1, Institut organicheskoy khimii AN SSSR i Institut nefti AN AzerSSR.
Prodstavlono akademikom AN AzsrSSR Yu.G.Mamadallyevy-m.
(Silicon organic compounds)

5-.-S-100
27214
S/06 61/000/014/011/030
B103YB217
AUTHORst Shostakovskiy, M. F., Vlasov, V. M.
TITLE: Synthesis of some trialkyl silanols
PERIODICAL: Referativnyy zhurnal. Khimiya, no. 14, 1961, 257,
abstract 14yf289 (3b. nauchn. rabot Yaroslavsk. med.
in-ta, 1959, vyp. 22, 511-514)
TEXT: Pure R2R'SiOH (Ia-b; here and in the following ~ R = CH 37
R' = C2 H5; b)R = C2H51 R- = CH 3) suited for optical studies were
synthesized as follows: R 2R'SiCl (II) + ethylene oxide (III)
- R 2R'SiOCH 2 CH2Cl (IV) )I + HOCH2CH2 OH (V). A weak stream of III is
conducted through the ethereal solution of 0.1 mole of IT4 up to the
required overweight (20 - 250C) and (here and in the following, the y1eld
is given in %, and .the boiling point in 0C/mm, n 2o D, d42o ) 93, 71-;.-;y2/"39,
1.4260, 0.9469 of IVa are isolated. Similarly 91.8, 67-66/132 1.4.5!6~
Card 1/2

2 7 211t
S10811611000101410111050
BI03/B217
Synthesis of some trialkyl silanols
0.9478 of IV`b were obtained from 0.1 mole of IIb and 111- 5 % NaOH and
3-4 drops of phenoI phthalein are added to the ethereal solution of 18 g
of IVb, and the mixture is vigorously stirred for 1 hr- 72~ 61-062/30,
1.4204, 0.8456 of Ib are isolated from the ethereal luyer by the usual
treatment after 3 hr when the color of the indicator has vanished).
V was separated from the aqueous layer in a yield of 66.1 %. 86, 58/50,
1.40702 0.8335 of Ia were obtained from 0.1 mole of IVa under similar
conditions. [Abstracter's note: Complete translation3 VY
Card 2/2

5 (3)
AUTHORS: Shoztakovskiy, 14. F., Komarov, 11. V. SOV/74-28-6-4/5
___~~_hikhfyev, I. A.
TITLE: Silanols (Silanoly)
PERIODICAL: Uspekhi khimii, 1959, Vol 28, Nr 6, PP 741 - 771 (USSR)
ABSTRACT: The present paper describes the methods of synthesis and the
properties of silanols. Silanols are compounds containing hy-
droxyl groups directly bound to the silicon atom. Owing to
particular affinity of the silicon atom to oxygen, there are
silicon-organic compounds with one, two and three hydroxyl
&roups with the silicon atom. In this connection, they are
classified into alkyl (aryl) silanols aith the common formula
R3SiOH, silandiols R 2S'(OH)2 , and silantriols RSi (OH)3' Of the
mentioned compounds, the trialkyl (aryl) silanols are best in-
vestigated. They are highly reactive cormpounds and have Great
practical and theoretical importance. In contrast to silicon-
-organic alcohols, there are a number of common methods of
synthesis for silanols. For some representatives of this class,
there are quitespecial methods of synthesis peculiar to them.
Card 1A Of the methodsiof synthesis, the following were described:

Silartols
SCV/74-28-~-4/5
the hydrolysis of haloGen silanes (Refs 8, 10-63), of alcox~--
silanes (Refs 25,35,64-75), Of acetovailanes (Refs
of aminosilanes (Refs 10,21,82-90), the maj3nesium-oi-Eanic
thesis (Refs 91-95), the cleav--,-e of siloxanes (Refs _95-1o=),
.1
the cleavage of tetrasubstitut~-d silanes (Refs 102,104-12'),
and the hydrolysis of hydride silanes (Refs 35,60,8?j,128-112,
Besides the mentioned general methods of obtainino- silariols,
special publications describe many other methods which are
suitable for the synthesis of compounds with a certain struc-
ture (Refs 5,24,31,102,103,111,124',l',A3-147). The physical pro-
perties of many silanols have not yet been fully characterized
(Table). For sorme representatives, the physical constants are
contradictory. In spite of this, certain rules referring to
their physico-chemical properties cart be determined fron. the
da'-a indIcated in the table of the compounds of this class
(Refs 32,148-155). Trialkyl (aryl) silanols remind of tertiary
alcohols as to theIr structure. Silandiols and silantriols
have no analoga among organic compounds. Silanols are, in
general, similar to the corresponding organic alcohols, but by
the presence of the silicon atom their properties attain a
Card 2/4 character peculiar to them. This brings about that in many ca-

Silanols
SOV/74-28-6-4/5
ses they react diffcrently from alcohols. Some of these react-
ions were considered closely and compared with the correspond-
in,g reactions of or[;a-aic analo6a: action of metals and lyes
(Refs 8,12,31,43,6o,6a,Qi,c)6-103,203,205-222), dehydration of si-
lanols (Refs 4,24,26,33,35,37f46,41",60,63,6a,190,224-226), in-
teraction wi 'th halogen silanes (Refs 11,21,128,227,230,231),
action of mineral acids (Refs 31,62,228,232,233), interaction
with acid anhydrides and halo.-en anhydrides (Refs 22,31,41,61,
223,227 324,235), interaction with alcoxysilanes (Refs 21,230,
-230 , reaction with vinyl ether (Refs 52,80,87-90,226,240-
2
3~ 1~
244), action a-f Fischer's reagent (Refs 169,245), interaction
with isocyanat'es (Refs 37,51,183,246), hydration of silanols
(Refs 37,247). As mentioned-before, SilLnOls are highly react-
ive substances which are capable of underlgoinC various react-
ions. Some of these reactions were described (Refs 37,21,49,53,
81,102,139,167,169,172,2o6-209,223,2?~ll-'~164).Sil'l~iols are used
in industry for the production of Various resin3 (Refs 257-265),
heat-resistinG coats (Refs 203,20?-), bactericide substances
Ref 265), adhesives (Refs 267,2GE), water-repellent agents
,ief 210,268), for impre~natir- pa-pox (Ref 27r,"), as diffl'sion
Card 31,

3CV/714
liquids (Ref 237)j for lub---4c-~t-'nl-- o-i13 (Ref 237)
0, !7,'2-r substamce3. Tl,,cre t~T!I(, LI-ld 27C i-fr-:en;,,
arc Soviet.
ASSOCT ATTCN; Tn_t organich -skoy 10. D. Zelinsko~;o A:T SSI-~~
(Ills'u--; Lilt C, of C:t,~;.:j-,,j
c D.
Cal--l

5 (3)
a
K
UTHORS: Shost'Wrovsk F Bogdanova, A. V., SOY/74-28-9-3/7
TIME: Diace-uylene and Its Derivatives
PERIODICAL: Uspekbi khimii, 1959, Vol 28~ 'TTr 9, P.-P 1052-1085 (USSR)
ABSTRACT: In the present, paper the authors give a survey on the actual
state of the chemistry of acetylene and its derivatives.
First, the methods of obtaining these substances are described:
the synthesis of the diacetylene derivatives from acetylene
and other substituents among them dimerisation of mono-
substituents, acety-lenes,"kRefs 1-27); magnesium-organic
synthesis (Refs 28-31); dehalogenation of halogen derivatives
(Refs 32-37). The methods for obtaining diacetylene can be
subdivided into three groups: The syntheses of the first group
based on the oxidative dimerisation of metallic salts of the
acetylene have, at present, only a historical value (Refs 34,
38-41). The second group comprises methods using the effect
of an electric discharge on various bydrocarbons (Refs 42-48).
The third group comprises the syntheses based on a gradual
splitting-off of elements of the halcgen hydracl,--, from the
Card 1/4 halogen derivatives of the butane series (Refs 4~f-71). The

Diacetylene and Its Derivatives SOY/74-28-9-3/7
physical properties of diacetylene are treated according to
references 31, 32, 39, 40, 45, 75-90, and its explosive
properties according to references 39, 42, 47, 91-95. The
purification and the analytical determination of acetylene are
described according to the references 45, 48, 57, 59, 60, 72,
97-100. Then follows the description of the chemical properties
of diacetylene and its derivatives. Diacetylene is the first
member of t1B homologous p6lyine series with conjugated triple
bonds. The separation of first acetylene compounds from
vegetable prod-acts stems from the year 1892 (Ref 101). Since
that time about 50 of such compounds have been obtained.
References 17, 18, 102-107 are devoted to a close investigation
of the separation and of the synthesis. The informations
contained in publications on the properties of diacetylene
and its derivatives chiefly refer to the reactions of
substitution and addition. Among the substitutions we find the
reactions with magnesi~tm-organic compounds (Re* 29, 31-34, 49,
55, 98, 108-115); with metals (Refs 51, 544 57 :9' 1009 ill) 116),
with halogens (Ref 31) with carbonyl compounds (Refs 7, 10, 46,
48,' 117-122), and with methyl olamines. The field of additions
Card 2/4

Diacetylene rmd Its Derivatives
c
~OV74-26-9-3/7
to diacetylene covers: t', _e addition of hydrogen (Refs 123-127,
29, 32, 55), of halogens (Refs 29-32, 128-132); of nitrogen
dioxido (Refs 133-135); of water (Refs 66, 99, 136); of alcohols
(Refs 46, 57-59. 62, 65-67, 137-140), Of Glycols (Ref 137); of
rorcaptans (Refs 62, 141), of amino alcohols (Refs 48, 63, 122);
of acryllonitrile (Refs 142-144); of HUT Ref 145), of thio-
cyanogen (Ref 146) and of dialkylamines Ref 48). Marthermore,
the oxidative dimerisation of the diacetylenes is described
(Refs 1, 4, 6, 7, 17, 16, 29, 3'21, 101, 105-107, 147, 148)- The
follorring section of the paper is devoted to the ethinyl
compounds. The physical properties a-ad the spectra of the
ethinyl vinyl ester axe described, as ascertained by the
authors. limong the chemical reactions of the ethinyl vinyl
ester the substitutions of acetylene hydrogen and the addition
are the most investigated. Substitutions were investigated in
reactions with metal (Refs 57, 11), with ketones (Ref 149), and
with the magnesium-organic compounds (Refs 150-151). Additions
to ethinyl vinyl ester were investigated in reactions with -
alcohols (Refs 56, 59, 62, 65, 66, 91, 137, 136, 150-153) with
mercaptans (Refs 62, 156-158); with water (Refs 57-60, 64, 159);
Card 3A with carbonyl-compounds (Refs 48, 57, 124, 150, 160-162); with

Diacetylene and Its Derivatives
SOV/74-28-9-3/7
acetAls of acetaldehyde (Refs 163, 164); with bromine
(Ref 59)- Furthermore, the addition of hydro~gen (Refs 59, 158,
165-173) and the dimeriBation of ethinyl vinyl ester (Refs 17,
219 148, 174) were investigated. Finallyethinyl vinyl
thioester (Refs 62, 156-156, 175); ethyl vinyl ester,
containing N (Refs 63, 67) and ethinyl vinyl ester, containing
Si were produced. The table contains a list of some of the
functional diacetylene derivatives. The following Soviet
authors are mentioned: V. I. Yegorova, 0. M. Kuznetsova,
G. I. Plotnikov, 1. A. Chekulayeva, L. V. Kondrattyev, I. I.
Strizhevskiy, M. D. 0hekhovich, Zh. I. Iotsich, E. S. Shapiro,
and L. i.,.Shmonino*'TbeZeEm,ltable.,Mxl",'1.76 references. 33 of which are
Soviet.
ASSOCIATION: In-t orgimichoskoy khimii AN SSSR9 im. N. D. Zelinskogo
(Institufia of Organic Chemistry AS USSR imeni N. D. Zelinskiy)
Card 4/4

Synthesis and Transformations of Organosilicon SOV/79-29-2-5/71
Vinyl Ethars
The affiliation of alcohols, silanols, and organic acids to
the y-silicon-containing vinyl ethers takes place under the
influence of 'acid catalysts according to the ion mechanism,
in agreement with Markovnikov's rule. On their reaction with
organosilicon alcohols and silanols, hitherto unknown acetals
were obtained, containing silicon atoms in both alcohol radi-
cals. The reaction of these ethers with organic acids can serve
as a basis for the synthesis of a new class of organosilicon
compounds, i.e. organosilicon acylates. Hydrogenation, chlori-
nation, and hydrochlorination of the y-siliccn-containing vinyl
ethers were investigated. There are 3 tables and 12 Soviet
references.
ASSOCIATION: Institut organicheskoy khimii Ak-ademii nauk SSSR (Institute
for Organic Chemistry of the Academy of Sciences, USSR)
SUBMITTED: November 5, 1957
Card 2/2

SOV/79-29-5-30/75
Investigation in the Field of the Synthesis and Transformation of Substituted
Vinyl Ethers. 9. Formation and Nature of Resin-like Products Obtained in
the Vinylation of Phenols
on the ratio methyl acetylene : phenol. The yield in resin
increases with rising methyl acetylene content. The investi-
gation of the distilled resin fractionsby the aid of chemical
and spectroscopic methods has shown that they are mixtux-es
of the products (I - III).
CH3 H3 OH3
-O-C=CH2 0- C= CIR
,--cff -
C=CH2 2
1 1
CH3 CH3
M (II) (III)
The fraction boiling at 110-1150 ~3mm) represents the o-iso-
propenyl-isopropenylphenyl ether II). This was confirmed by
olementary anulysis, hydrolysis, by the determination of the
Card 2/3 molecular fraction and by spectral analysia. Fractions that

SOV/79-29-5-30/75
Investigation in the Field of the Synthesis and Transformation of Substituted
Vinyl Ethers. 9. Formation and Nature of Resin-like Products Obtained in
the Vinylation of Phenols
are distilled at higher temperat 'pres are mixtures of the poly-
mer (III) of different polymerization degrees with the mono-
mer. Ultraviolet and infrared spectra were taken at the
opticheskaya laboratoriya IOKh AN SSSR (Optical Laboratory
IOKh AS USSR) by B. V. Lopatin. There are 13 references,
3 of which are Soviet.
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR
(Institute of Organic Chemistry of the Academy of Sciences,
USSR)
SUBMITTED; March 12, 1958
Card 3/3

5 (3)
itU, T 11 C. !. A., 3hostakovskiy, 'f. P., 307/79-2c'-:5-71
Shikhiyev
,
Komarov, ". V. Aslanov,
T I T L F"' investigtitions in the Field of r3ynthesis and Transf orma t ions
of Unsaturated Organo-germaniun Compounds (Issledovaniya- v
obl7isLi sinteza i nr:)vrashcheniy nerro-lelInykh
germnnLyorganicheskikh soyedineniy). I. 3ynthesis of -.ono-,
Di-, -Ln(-' Tri subs titu ted Tertiary jr-Cerrizaniura Acetylene
Alcohols (Antozz odno-, dvukh- i trckhnto;.Qny!:h trotichnykh
7.--iirrlrLrti-:fiitsetLIenovyl~h spirtov)
PE_.~~IODICAL: 2hurnal ob3hchey khimii, Vol 29, '~r 5,
1)D 1549-1551 (U33R)'
ABSTRACT: In a previous paper (Ref 1) the reaction of di-magnesium-
ca::bincl tTotSich Rr~agent) 7ith
various ~.7,js inva:~,tigated. In
orler to explain 'Aur4,11er thG reaction Drocess wit4 this
reagent, its influence upon methyl-, dimethyl-, and trimethyl

. _ - ed. The renction was found
germanium brormi,~es tras
to proceed with the formation 01' tertiary 1-garmanium
containing acetylene alcoholu -.ccordiing to the following
scheme:

Investigation!3 in the Field of Synthezis and 30V/79-201 -5-3 1 /75
Transf Qrriat ions of Unsaturated Organo-germaniii-i Crripounda. 1. Synthesis of
Eono-, Di-, and Trieubstituted Tertiary r-Ge-rminium ~cctylene Al-:!ohola
(Cii ce!i7o
(C11 ) GeC=C-COTT(CI: 3 3 c-T 3
3 3 3 2
CH3G er'=_C-M':( 01, 3') 2
13
(cu Go =-C-011(cl, 2 Go C-C
3)2 IC 3) 2] 2 2 -C.-C '-3]2
I y catic
The occurronce of hydroxyl groups was confirnv?,11 b,
acid derivative of bis-(2-mathyl.butin-3-01-2)-Oiriei:)lvI
germanium. Furthqr reactions of organo-german-Jum alco'-,cls
and their derivatives will.be described in later papers. The
experimental part presents the physical data of the initial
substances, the details of the synthesis, and'the analysis
of the co7,pounds obtained. The ~Luthors prepared: (2-mothyl-
butin-3-ol-2)-4-trimethyl germanium, bis-(2-nothyl-butin-3-01-2)-
!I-dimethyl germanium, tri-(2-methyl-butin-3-al-2)-4-methy1
Card. 2/7d germanium, and bis-(2-methyl-butine-3-acetoxy-2)'-4-di-,Lethyl

in th~-. ~%Iiold oi' -;yntJcsir~ --.,.n,,i QC)V
of Unsiturated, Compounds. I. of
"-picu'rsIitui,cd Tertiaryr-f'ermanium Pcotylene Alcohols
rI,-Qrmr,niv-r1. There are " Soviet references.
95 1,)5'1
Card 3/13

5(3)' SOII/79-29-7-7/63
AUTHORS: Shikhiyev, 1. A., Shostakovskiy, 1,11. F., Kayutenlko, L.A.
TITLE; Investigations in the Field of the Syntheois and the Treawfor-
mations of Unsaturated Organo-sil-icoa Compounds (Issledovaniya
v oblasti sinteza i prevrashcheniy- nepredellnykh kremneorga-
nicheskikh soyedinepiy).
II. Synthesis of the Silicon Hydrocarbons of the Vinyl Acetylene
Series (II. Sintez kremneuglevodo,.-odov vinilatset-'Ll2novoCo ryado
PERIODICAL: Zhurnal obshchey khimii, 1959, Vol '29f Nr 7, pp 2137-21719 (USSR)
.1
ABSTRACT: The synthesis of acetylene alcohols (Ref 1), their hydrogenation
and dehydration (Refs 2, 3) as Trell as the affiliation of
various compounds to the triple bond (Refs 1, 4, 5) is of high
theoretical and practical interest. Similar conversions of the
organo-silicon acetylene alcoho!13 Yvere carried out for a
comparative investigation of their properties. Earlier, the
authors elaborated the synthesis of mono- (Ref 6), bi- (Ref 7),
and trivalent (Ref 8) r-silicon and a---ermanium substituted
(Ref 9) acetylene alcohols. In the present paper the dehydration
conditions of somp r-silicon sultstituted ditertiary acetylene
Card 1/3 glycols as well as the catalytic hydrogenation of the

Irivestigations in the Field of the Synthesis and the SOV/710-29-7-7/-93
Transformations of Unsaturated OrGano-silicon Cwmpounds. II. Synthesis of the
Silicon Hydrocarbons of the Vinyl Acetylene Serf'-es
silicon hydrocarbons obtained -,.Te r('~ 4nvestigated according to the
afore mentioned scheme. Thus, the synthesis of vinyl acetylene
silicon hydrocarbons was elaborated by the dehydration of the
corresponding ditertiary r-silicon substituted acet,,lene
glycols in the presence of UMO 4* The followinp.- compounds were
obtained and characterized: bi s- (2-me thyl-butene-1 -i n-3) -ethyl
silane; bis-(2-methyl butenc-l-in-3)-diethyl silane;
bis-(2-methyl butene-l-in-3)-dimethyl silane; bis-(2-methyl
butene-l-in-3)-methylethyl silane, and bis-(2-methyl butene-1-
in-3)-methyl propyl silane. By catalytic hydrogenation of
bis-(2-methyl butene-l-in-3)-diethyl silane the corresponding
saturated silicon hydrocarbon, diethyl diisoamyl silane, was
Card 2/3

Investigations in the Field of the Synthesis and the SOV/79-29-7-7/83
Transformations of Unsaturated Organo-silicon Compounds. H. Synthesis of the
Silicon Fydrocarbons of the Vinyl Acetylene Series
synthesized. The silicon hydrocarbons synthesized are more
exactly characterized in the table. There are 2 tables and
9 references, 8 of which are Soviet.
ASSOCIATION: Institut organicheskoy khimii Akadeirdi nauk SSSR i Institut
neftel:himicheskikh protsessov Akademii nauk AzerbaydzhanskoySSR
(Institute of Organic Chemistry of the Academy of Sciences USSR
and Institute of Petrochemical Processes of the Academy of
Sciences of the Azerbaydzhanskaya SSR)
SUBMITTED: July 3, 1958
Card 3/3

SHOSTAKOVSKIY, M.F.,doktor khim.nauk
-
Lariv chemicals industry of Irkutsk Province. Znan.sila 34
n0-3:22-23 Mr 159. (KIRA 12:4)
1. Direktor Irkqitskogo instituta organichaskoy khimii.
(Irkutsk Province-Chemicale industry)

50)
AUTHORS: Shostakovskiy, M. F. ogdanova, A. V., SOV/2o-124-1-30/69
Pl~tnikova, G. 1.
TITLE: Investin-ation in the Field of Diacetylene Derivatives (Issle-
dovaniye V oblasti proizvodnykh diatsetilena) Interaction
Between Diacetylene and Phenols, Thiophenol and Benzyl Alcohol
(Vzaimodeystviye diatsetilena s fenola-ai, tiofenolom i benzilo-
vym spirtom)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 124, Ur 1,
PP 107 - 110 (USSR)
ABSTRACT: The authors had earlier reDorted on syntheses based on di-
acetylene with aliphatic and hydro-~iromatic alcohols as well
as with ethyl mercaptan (Refs 1,2). In order to introduce the
corresponding aryl derivatives into the substances available
the authors tried to add phenol to the diacetylene. These two
substances, however, did not react together according to the
usual scheme under conditions suitable for alcohols. The
authors wanted to investigate the reaction mentioned in the
subtitle. They wanted to eliminate the influence of the
Card 1113 benzene nucleus which is caused by the oxygen atom. This

Invest ig-at ion in the Field of Diacetuylene Derivatives. SOV/2o-124-1-3o/69
Interaction Between Diacetylene and Phenols, Thiophenol and Benzyl Alcohol
was expected to be changed by means of the sulfur atom in
thiophenol and by the distance of the benzene nucleus from
the oxy.r,en. In fact, both reactions proceeded smoothly under
gentle conditions (1). The junction of the second molecule
of the benzyl alcohol or of thiophenol forms the next stage
of the reaction and can also proceed independently. In the
case of benzyl alcohol, this stage proceeds according to
the ionic mechanism. Butinal-dibenzyl-acetal
CH 3- CSMM C-CH(OCH2C6H5)2 (111) is formed. In the case of
thiophenol the second stage of the interaction with di-
acetylene proceeds mainly under the influence of radical
initiators. Dithio derivatives of butadiene-1,3 are formed.
Thus.either thiophenol or ethyl mercaptan is added to
eth-1 vinyl thiophenyl ether yielding dithiophenyl- and
thiophonyl-thioethyl-butadiene-1,3 (2), respectively. This
reaction is accelerated by KOH, a-zo-isobutyric acid-nitrile
or by increased teriperature. The yield of the end products
depends on the temperature and on the initiator. Dithiophenyl-
and thi-ophenyl-thioetliyl-butadiene-1,3 undergo the diene
Card 2/13 synthesis .-,,ith maleic acid anhydride, forming adducts that
I-

Investir-ation in the Field of Diacetylene Derivatives. SOV/2o-124-1-3o/69
Interaction Between Diacetylene and Phenols, Thiophenol and Benzyl Alcohol
lose two mercaptan molecules and forming phthalic anhydride
(I'lefs 2,6). An experimental section (not designed as such)
ent-iies. There are 3 tables and 6 references, 4 of .-;hich are
Soviet.
ASSOCIATION: Institut organichOskoy khimii ifr,. N. D. Zelinskogo Akademii
nauk SSSR (Institute of Or,,,,anic Chemistry imeni N. D. Zelinskiy
of the Academy of Sciences USSR)
PRESENTED: May 17, 1958, by B. A. Kazanskiy, Academician
SUBMITTED: May 15, 1958
Card 3/3

F1 -,V
PHASE I BOOK EXPLOITATION SOV/4989
ShIkhIyev, Ibragim AbasovIch, Professor, Doctor of Chemical Sciences,
Mikhail Fedorovich Shostakovskiy, Professor, Doctor of Chemical
Sciences, Nikolay 7a_`s11Ty_&Vicfi k6marov, Candidate of Chemical
Sciences
Novyye, kislorodsoderzhashchiye kremneorganicheskiye soyedineniyya
(New Oxygen-Containing Silicon Organic Compounds) Baku,
Azerneftneshr, 1960. 190 p. Errata slip inserted. 1,000 copies
printed.
Ed. (Title page): Yu. G. Mamedaliyev, Academician of the Academy of
Sciences Azerbaydzhanskeya SSR, Professor; Ed. of Publishing House:
A. S. Shteyngell.
PURPOSE: This book Is intended for persons working with organosilicon
compounds, and for students in schools of higher education.
COVERAGE: The book deals with the chemistry of organosilicon com-
pounds, including their synthesis and conversion. It describes
the use of organosilicon compounds in the manufacture of heat-
resistant and electric insulating materials, anticorrosive
Card, _7
~~ V

New Oxygen-Containing Silicon (cont.) SOV/4989
coatings, silicon rubber, lubricants, and hydrophobic and gluing
materials. The book also describes the new oxygen-containing
organosilicon compounds such as organosilicon alcohols and
silanols, simple vinyl ethers and their derivatives, and organo-
silicon acetals and acylals. The production and properties of
chlorosilanes are described briefly. B. N. Dolgov,
K. A. Andrianov, and A. P. Kreshkov are cited as Soviet writers
on the chemistry of organosilicon compounds. References accompany
each chapter.
TABLE OF CONTENTS:
Introduction 3
Ch. I. Alkyl (Aryl) Chlorosilanes 4
1. Production of alkyl (aryl) chlorosilanes 4
A. Organometallic synthesis of saturated alkyl (aryl)
chlorosilanes "ntaining chlorine directly at the
silicon atom 4
Card~~

SOV/4962
International gysposium on maernmclocular, chamistr7, !,zoom, 1960.
HesMunarodayy simpozium po makromol6kuly4mor khImIL SSSR~ ftbakva, 14-16
Iyunya 1960 g.; doklAdy I avtomf4raty. Sektalyn 1. (International Si-opos-
Ium an Maercaolecular Chemistry lidld In Vzscow,, June 14-18, 1W; PAW& and
-vo AN S55Rt 19601 An P. 5v500 cOPisv
Summaries. SactLnn I [Ma3cow, Izd
printed.
SpoosoriAg Agencyl The International Union of Pure aml Applied Chemistry,
Consission an Yacrocolecalar Chemistry
Tech. Ed.v T. V. Poly.kova.
PURPCSZi This collection of articles Is intended for chemists arJ researchers
intorsaUd im macromolocular chemistry.
COVER41i This is Sactica I of a multivolume work containing scientific papers
on morconlocular chemistry In Moscow. The material Includ%3 data Qo the
synthesis and properties of polymers, and on the procesaaa of polymerization,
copolymerization, polycondensation, and poly7-somcbicstion. Each text in
presented In full or sc;mari%4d in French, English, and Russian. Them am
4.7 papers; 28 of which were presented by Soviet, Rumanian, Hungarian, and
C%achoslovaklaa scientists. No personalities am mentioned. References
accompany individual articles.
TiArskovA, I.. I., B. A. Dolgoploak, T. G. Zbura'l
I . ____rs -cC14 ne
and I M I USSR). The Sitthes
a Study of Their Structure and Properties
d
Synt he. Is
0. V. F2_LV' T.. fi: 'czcv A.11
xQ
Polyn.ritation,of Z3tor!Xi Folyacryr~-tl..- 47
J. W-qzl.a A. St.ruschus. and 7 Z-,cr4r (Czochoslo~&kl.).
T. R~.'.M-of Harden.1 AsaturA 01T.statLL":~
(U551q). Nov
k. 41! 64
VAthd of PrapAratica esters md
Lbdasaij, X.. and A. St.rnschuaa (Czachoslovakis). ArAlysia of Cross-
L.Inked Polyesters -_ . 72
L V K!,!hhatmu-
of Crystal-
'mc b;t 90
r. (WIR). Cycilc Foly-rit.Ll- Cul
-XvID'y1sc stela
?...
Synthesis or Crystailina rol;41.1orn-1 116
and 11. R I -v USSI) . Polyr,rizatiqn of Poly-
Solomon. 0. 7, M Divani. 1. imbruah, and hjD=ja1cL. (Itumani.).
- 7i _Lho Press=& of Dutylllthium and
Polymerization ohinyle asoT
Titanium Chloride TnA Catalysts 131
L,.-.i AM_YEA1_-_kMML (USSR)- On the Pre-
combl"tion low Types of Linear Polymers by the Reaction of Polyre- 141
S v A. V r-Topchiyev, and 3. G. Durrar I a n (UMR) . The
SyUth4.ij ono4ilicon Polymers an A Complex catalyst (CH,)., Al+TICl, 152
""Fnk" a S I D-Iydl- Lod Z
oatajnjaC'Foi7;;. Gr" i%n- 2~6
.71.
stv..
T. 11salev, and Y s n iw. -iffct
."..:rA1.nEs1
of Chemical Structure on the Polyn Ity of the Unsaturated
~r tallia CompourAo 67
yollk-MhL4~m V (Usa). _1__.
tra-4or Bl,,,I,, era Comparative PrOO-01-4 1A the P01yamulax,...
C&M 6/9

~:'ILOO 78083
sov/62-6o-1-29/37
AUTHORS: Shostakovskiy, M. F., Gladyshevskiy, V. A., Baykova,
TITLE: Brief Communications. StepTiftse Synth-sis of Poly(Vinyl
13opropyl Ether)
PERIODICAL: 1:-,vesLly'a Akademl.l. nauk S01'3R. Otdelenlye khimicheskikh
nau1c, J.960, Nr J, pt) 1-30-139 (m.,,sri)
ABSTRACT: Stepwise polymerization of vinyl isopropyl ether was
studled. The reacLlon proceeds as follows:
'P /OR
Cll,,(~Ii(' +(~-~I)CII,7-Cli-OR-~-CttiClilCl4x-CH4CHICH
\OR I I -OP
on OR
1~.,here 11 .0111,11,76 etc. 1,1,3-TriisopropoYybutane M
C,;, rd (-25%). bj) 77-5-78 (4 mm), d20 o.86oo was obtained at

B--,,ief Co-aim,,i.nications. Stepwise Synthesis
Of FQ!Y(',,f1ny1 IsoprDpyl. ;:er)
sov/62-6o-i-29/37
0 ,
4
5 from diisopropyl acetal and viny-l isopropy-1 --ther
in the pre.,3ence of 5% alcoholic FeCl 3-1311 5-Tatlra-
isopropoxyhexane (H) (15%), bp 1.15 0 2 mm), n20. 1.4220,
00 D
(111 0-8'(87, was obtained Linder the same conditions as
I, 1'rom I and vin,y]. isopropyl. ether. 1 1,3,5, Pentaiso-
lane (111) (12'/,/), bP If---7-16
propoxyoct. 6
20
11D J.4,QOO, CILt 0.8940., was also obtained under the
same condi-tions as I, from II and vinyl isoprou),vl ethle!'-
The FLbOV(J polyethers acre hydrolyzed with NaOlf. Tile
e -.- 'j I
n of' hydrolysis wras There are 1 1) 1 e,;
reCerences.
Institiite of Organic Chemistry, Acade,~-,iy
14 D. " I -
r) ~Q USSR (Imstitut organiche.-,ko,", k1li-mij imeni
ul, ~'S"R)

a-HOSTAKOVSKIY, M.F.; SHIKHIYEV, I.k.; KOMkROV, N.V.
A.E. Favorskii; on the centennial of his birth. Azerb.khim.
zhur. no.2:69-73 160. (MDU 14:8)
(Favorskii, Aleksei Efgrafovtch,, 1860-1945)

~H'~S-TgVUUY-V--
A.B. Favorskii's contributions to thecbvelopment. of the
chemistry of high molecular weight compounds (on the 100th
anniversary of A.3. Favorakii's birth), Iisv*AN SSSR.Otd.khim.
nauk no.5:769-778 MY 160. (MIRA 13:6)
(lavorskii, Aleksei Bvgrafovich, 1.560-1945)
(Yaoromolecular compounds)

3/362'/6o'/000'/006/020/025,/XY
B020/BO60
AUTHORS. Shcsta! P- Khrmenkc. A, Kh,
TITLE Acetylene-dieae Isomerization of ',,4-D.oh1.oro Butane-2 and
,")'Ynti~eses Performed on Its Basis~ Communiration 1, A~~-~ion
of Mqier-we0ianol- and Methanoll-Sclutions of Potassium
Hydroxide on 1,4-D.Jr~hloro Buz-yae-2
PERIODICAL: Izvestiya Akadeff,4-i na,,;k SSSR, Otdol0niya khimicheskikh nauk.~
!9060, Ne, 6, pp. 1098-11103
TEXT. The authors oxidized !,,4-dichlcro butyne-2 with permanganate and
obtained monochloroaceti~, acid as the only reaction product, Proceeding
from the assumption that -~n the dehydrcchlor-4nation.of I,.4-dichloro
butyne-2 by means of an alco-holio. KOH soluiticr. the separation of hydrogen
chloride from one and the same carbon atorr. is improbable ', the attempt was
made to prove the course of an isomerizat-en on the basis of the reaction
products. From among the compounds produced by the reaction mentioned in
the title. the fc1lowing were identified and described, 2-c-hioro-buten-1--
Card 1/4

Acetylene-diene Isomerization of S/062/60/000/006/020/025AX
!A-Diohloro Butane-.2 and Syntheses B02O./BO6O
Performed on Its BasiS. Communication 1,
Action of Water-methanel- and Methancl.
Solutions of Potassium Hydroxide on 1,4--
Dichloro Butyne-2
methanol to -1.4-dichloro butyne.-2 (I in the presence of KOH at a
temperature below 500C was likewise cbservel, When an aqueous KOH solution
is added to a methanol solution of (I) at about 650Ci diacetylene is
obtained as the main productt The structure of the resulting
2-ch1orobuten--1--ine 3 was confirmed by the spectroscopic analysis made by
Lopatin. A description is given of the methods applied to confirm the
structure of the remaining isolated compounds. Production., oharacteristic
reactions, and identification of compounds (I) to (VIII) are also
discussed, On the strength of results obtained, a mechanism of
acetylene-allene-diene isomerization of 1,4-dichloro butyne-.2 in water-
methanol- and methanol KOH solution is suggested. V. R. Skorarchenko
(Ref. 7), Yu, S. Zalkind, and M. L. Ayzikc-vich (Ref. 9). as well as V. I~
Yei7orcva and 0, V1, Kuznet3ova (Ref, 10) are mentioned. There are 13
references-, a 3oviet, 4 German, and 1 Brltish~
Card 5/4

Acetylene-diene Isomeriza-ion of S/062/60/000/006/020/025/XX
!,,4-Dichloro Butane-2 and Synthese!i D020/BO60
Performed on Its Basis, Communication
Action of' Water-methanoll - and Methan--i
SOILItions of fl,:!ta:;~;ium Hydroxid-i cn
Di~~hjorc, Butync- --
ASSOCIATTON. Institut or-anicheskoy khimii im. N~ ). Zelinsko-o Akademii
0 n
nalik SSSR (Institite of Organic. CheMiOtry imeni N.. D~
Zeli.nskiy of the Alz~adqmy of 3c;ipn~es USSR)
SUBMITTED: ffoup-mbe- 18., '95e
Card 4/4

Studies in the Field of Chemical Transformations
of Unsaturated and High-molecular Compounds.
14, Copolymerization of Trivinylglycerol Ether
With Methkcrylic Acid and Its Methyl Ester
81935
S./062/60/000/06/06/011
BD20/W61
methacrylic acid and its methyl ester were used. On the examination of the
conditions of copolymerization of trivinylglycerol ether with methacrylic
acid., the following reactions may be expected: a) formation of copolymers
containing free vinyl groups, b) formation of branched copolymers, and
c) formation of three-dimensional copolymers insoluble in organic solvents.
From this it follows that the copolymerization of trivinylglycerol ether
and methacrylic acid takes place in several directions, and a complicated
mixture of copolymers is formed. No formation of three-dimensional
copolymers was found on the copolymerization of trivinylglycerol ether
with the methyl ester of methacrylic acid. The copolymerization of tri-
vinylglycerol ether with methacrylic acid and its methyl ester is precisely
described in the experimental part. The yield and composi ion of the
copolymers of trivinylglycerol ether and methacrylic acidi(Table 1), and
.->f methylmetha
crylatel(Table 2), are given. There are 2 tables and
Soviet references.
Card 2/13

3/1062/60/000/007/014/017AX
B004/B064
AUTHORS: _~hg-sta -cLY-%k-1:-, -JI,_~F-, Bogdano,.ra, A V~ , and
k j-
Ushakova, T. M
TITLE: Vinyl Compounds in the Diene Synthesis Communica-,-.on 3,
Synthesis and Properties of the Ethers of the Series
of Bicycloheptene and Di-endome"hylene Octahydro-
naphthalene Containing Aromatic Radicals I
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh
Tiauk, -1960,; No~ 7, PP, 1286 -- 1290
TEXT: The present paper rontinues the authors' investigations on the
diene synthesis by means of vinyl compounds of the CH 2=CH-XR type. The
authors report n the reactions of cyclopentadieneJand hexachloro
cyclopentadiene~with vinyl-p-naphthyl-, viniriphenyl-, and v--;'.nyl-p-tert-
b-utyl phenyl ether, The condensation of the vinyl aryl ethers- ith
syclopentadiene proceeds according to the sc
Card 1/5

Vinyl Compounds in the Diene Synthesis. S/062/60/000/007/014/017/XX
Communication 3. Synthesis and B004/BO64
Properties of the Ethers of the Series
of Bicycloheptene and Di-er-domethylene 0,~tahydronaphthaleiie Containing
Aromatlc Radicals
The ratio between the forming adducts may be varled by the initial
ratify cf the oomponents As in the case- of the vinyl alkyl ethers
also with the vinyl aryl ethers the second stage of reaction may be
carr-Jed out by means of hexachlorc cyclopentadiene; ether and di-
hydraldine result from th-.s react-c.-,: (2) W.Ith h-xachl,.Dro cyclo-
pentadiene the reaction prcce ds under "he formation of et-hers of
hexachloro bicycloheptene: (3), These -,-om-pounds could be easily
hydrogenated on the platinum oxide catalyst; the saturated compounds
of bicycloheptanp or di-endomethylpne-di-cal-ine r~suited The autho!7S
describe the syntheses of: III and VI (2-p-naphtho-,~xy-bi-cyclo-(2,2.1)-
heptene--5 ard I 4;5,8-tl~-'--endomethylene--2,p-naphthoxy-1,2-3,,',Aa-5,'8,8a-
octa-hydro narhthalene) by reacti,~n of vinyl-P-aph-thvi. ether w.4-.h
cys-lopentadiene in the a.-;toolas,~ a' ;700C; II and V (2-p-tert-butyl-
pheTioxybicyc-,o-(2,2. 1) ~heptene--5 arld
tert butylphenoxy-1, , 2;3, 4~ 4a, 5 8., 8 a -a ctahyd--rC!naphtha'-,e-r-? in I ~: the
Cazd '~,A

Vin,, 1 Compounds in the Diene Synt'---s.'s. S/062/60/000/007/0-1 4101, 7 IYA
Communication 5~ Synthesis and Proper- BOOL/BO64
ties of the Ethers of the Series of
B-'cy.--loheptene and DI-endomethylene Octahydronaphthalene Containing
Aromatic Radicals
same conditions by reacting vin.T! -p-tPrt-b-jty1 phenyl ether with cyclo-
pentadiene XI., X. and IX (2-0-naphthoxy-1.4,5,6 7,-7-hexaoh1,1=
yclo -~,.2.- 2.. --heptene.-'--.. and 2 -p-tert -butyl phencxy -1. 4,5, 6 ~ 7..
7 h~xachlcro and 2-pY..eno-ty-*,..4:5,6-7,
bicyclo-(2,2,*,)-hepten~-5 by reacting the :;crresp3nding
eth~r,s with hexachloro cyciopentad3.ene at 110 -- 1200C in
. the test glas--,
with reflux condenser ~ VIII 4.,5, 8--di-endom-zhyl ens-2 ~P -naphth.--xy -
i, 5~ 8, tahydr--naphthal -
5 6,..8.9,9 hexa.--hloro-1,2,3,4:,4a -ne
(-~Iihydraldine)) was obtained from compound III and hexachloro cyci-o-
pentadiene at 120 - 1350C. Crystalline derivatives of these compounds
we.re obtained by means of phenyl azide, There are 2 tabie~, ani
9 referen,:~es: ~:, Soviet. I US, and .3 German
Card 3/5

Vinyl Compounds in the Dlene Synth-e-Sl-s 3/06 '60/000/007' 144/017'Xx
Communi cation 3, Synthesis and ProFe-:- B 0 0
I B0164
tie-= of the Ethers of the Series of
Bicycloheptene
and Dil-endomethylene Octahyd.ron:qh~haLene Containing
Aromatic Radicals
ASSOCIATION: Inst'-tut organ-4cheskoy khimii im- N, D- Zelinskogo
Akademi-i nauk SSSR
(Tns+4~utp of rganic Chemistry im=pi N. D. Z-Iinqk-;L
0
cf tha- A-,ade-my of Sciences USSR)
SUBMITTED; December 29, lgq,8
Ca-rd 4/5

/00-/60/000/007/0-116/017/XY
()0 0
B004/BO0'4
AUTHORS. Komarov, N. V- and Shostakovskiy, hl, F.
TITLE: Synthesis of Primaryf-Orgar-o Silicon Acetylene Alcoholsl
C
PERIODICAL: Izvestiya Akademii nauk SSSR.. Otdeleniye khimicheskikh
nauk., 1.960, No~ 7j pp, 1300 1302
TEXT. The authors studied the synthesis of acetylene alcoholA
containing silicon or germanium'VRefs- I 3).--f-n -this paper, they
report cn the synthes:.s of primary r-organo silicon acetylene alcohols,
The reaction proceeded according tG the followirg equation:
R,S~'C! t BrMgC5C-CH OlJgBr----~ R SiCIC-CH OH; (R= alkyl or aryl).
2 3 2
The str~i--tu~7e of the alcohols was confi-rmed by hyd::ogenation or
acetaliZation The a,-ithors describe: ') The synth-sis of 5-trimethyl
silyl propin-2-~1-1, (A); (CH 3)3 Sic~--C-CH2OH in the water bath by means
of ethyl magnesium bromide --n etheric solution, droprise addition of
provargy! and., finally, addition of CuCl 2 and trimethyl ::hloro
Card

85666
Synthesis of Primary f-Organo
Silicon Acetylene Alcohols
3/062/'0/000/007/0!6/017/XX
B004/BO64
silane, After sr-roiing down the reaction mixture is diluted with ether,
5% HCI is added, and the compound extracted with ether; the yield -~S
40,2%, 3-1,7-~-thy~' sily! propin-2-1-1 and dimethy! pheryl sily'l
propin.-2-r---, were synthesized in the same way, 2) The synthesis of
~rimethyl silyl prop,-ne-2--butyl acetal
-OC H
CH 3-C-H- 4 9
~-OCH 2C---CSi(CH3)3
origina-,ed from a mixture of vinyl butyl ether and compound A to which
1 drop of concentrated HC1 was added., Then the substance was heated to
790C., Vacuum distillation is carried out after neutralization with
anhydrous potash; the yi.e-)d is 7!~~ 3) 3-trimethy- silyl propanol-I.,
whose physical data are in agreement with the p-ablish~-d ones, was
Gbtained from A by hydrogenat~c- Jn ethanolic solution on the Raney
nick,~,! --atalyst- There are 1 tabIe and 5 Soviet referenc-?s
Card 21/3

85666
Synthesis of Primary,~-Organo
Silicon Acetylene Alcohols
5/06216010001007101610171XX
B004/BO64
ASSOCIATION: Irkutskiy institut organicheskoy khimii,
Vostochno-Sibirskiy filial Sibirskogo otdeleniya
kkademii nauk SSSR
(Irkutsk Institute of Organic Chemistry,
E~stern Siberian branch of the Brian DFp-arTment
of the Academv of Sciences USSR
SUBMITTED* December 15, 1959
V~
Card 3/3

C z0
AUTHORS:
TITLE:
11S3 1106 z2 o5
864
s/o62/60N1OO/006/030/033/XX
F013/BO55
Bogdanova, A. V., and Plotnikova, G.L.
PERIODICAL:
On the Diene Synthesis of 1,4-Dithioethyl 1,3-Butadiene
With Cyclopentadiene
Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk,
1960, No. 8, pp. 1514-1516
TEXT: This is a brief communication on the diene synthesis of 1,4-di-
thioethyl 1,3-butadiene with cyclopentadiene. the ratio of the initial
substances and the time or reaction were varied in the experiments. The
synthesis proceeds by stages, addition products being formed which con-
tain varying numbers of cyclopentadiene molecules per dithioethyl-buta-
diene molecule. The ratio of these addition -products depends on the
ratio of the initial substances and duration of heating. Three addition
products were separated from the reaction mixture. The first, formed by
reaction of one cyclopentadiene molecule with one molecule of the diene
investigated, reacted readily with an alcoholic sublimate solution with
quantitative formation of ethylmercapto mercury chloride and HCI, which
Card 1/2

86415
On the Diene Synthesis of 1,4-Dithioethyl 1,3- S/062/60/000/008/030/033/XX
Butadiene With Cyclopentadiene B013/BO515
can be easily titrated with 0.1 N NaOH. This indicates the presence of a
vinylthioethyl group. (I) may therefore be assigned the structure of a
2-thioethyl 3-vinylthioethyl bicyclo(2,1,2)-5-heptene. The second product
(II) contains two cyclopentadiene molecules per dithioethyl-butadiene
molecule. Neither it nor the third product react with alcoholic sublimate
solution. The second product may be regarded as bisE2-thioethyl-bicyclo
(2,1,2)-5-heptenej. According to its composition and constants, compound
(III) is [1,4,5,8-diendomethylene-2-thioethyl-3-(21-thioethyl)-bicyclo
(21,11,21)-51-heptene]. The preparation of analYtically pure samples was
rendered very difficult owing to the formation of cyclopentadiene polymers
which are very soluble in the addition products. The 1,4-dithioalkyl(aryl)
1,3-butadienes prepared from diacetylene, which give the typical diene
reaction with maleic anhydride, exhibit dienophilic properties in the
diene synthesis with cyclopentadiene. There are 1 table and 6 Soviet
references.
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: January 19, 1960
Card 2/2

S/06 &) "boo/0091o I ~J/U2 I
B 0 2 3 YB 0 64
AUTHORS: Shostakovski_y, 14. F. and Khomutc-v, A. hl.
TITLE; Studies --;ri the Field of the Chemical Conversions of
Unsaturated and Highmolecular 'Co-mpounds. Communication 15.
Copolymerization of Some Di"inyl Ether,- With Metha-crylic
Acid
PERIODICAL: Izvestiya Akademii nauk SSSR, Otdeleniye lchimicheskikh
nauk, 1960, No, Q., pp 1168,,--16~36
TEXT: In continuation of their previous papers (Refs- I and 2), the
authors studied the behavior of some representatives of vinyl ethers in
the nornlymerization with methacrylic acid. The following two compounds
were used: CH CHOCH ~ CH2 (I), CH = CHOCH,CH OCH = CH (II), The ether
2 2 1 2 2
(I) rather tends to reactions with radical mechanism (Ref. 3)~ It
polymerizes readily when stored and in the Dre-sence of initiators (benzoyl
peroxide and dinitrile of azoisobutyr-ic acid). The ester (II) does not
polymerize under the action of the mentioned initiatcrsj but does so
Card 114

Studies -in the Field of the Chemical Conversion3 S/'C)0'2/C'O/OOC)//009/0-,O'/021
of Unsaturated and Hig'hmolecular Compound3, B023,'BO64
Communication 15. Copolymerization of Some Divinf,
Ethers With Methacrylic Acid
readily in the presence of iron chloride (Ref. 4), The aiai~hors assume that
these divinyl others, like the vinyl alky! ethers, enter a copolymerization-
reaction with methicrylir acid and form acylals at the same time. The
first experimental serie!, of tho copolymerization of (I) -Nith mpthanrylic
acid was carried out in the presence of benzoyl peroxide. A". an increast~
of the amount of divinyl ether in the reaction medium, the copolymer
yields decrease, while the number of the chain links in the ether rises
(Fig. 1). The second experimental series was carried ou-~ in the presence
of dinitrile of azoisobutyric acid. Fig., 1 shows the data on the depen-
dence between Yields, compositions, and molar concentraticn of the initial
monomers. At an increase of the d,.v---r-.yl ell-her concentration ir. the rteact-IC-1.
medium, the copolymer yields decrease first. then increase, and the
number of the chain 1,nks of d-;,riny! Esher increases. Acylals (III) were
found in the copolymer forming in consequence of competing reactions,
When comparing the copolymerizat,ion of the divinyl P-3ter with methacrylic
acid in the presence of benzoyl peroxide and the dinitrile of azoisobuty-ric
acid, the authors found that the kind of the initia~.-r exerts a considerable
Card 214

Studies in the Field of the Chemical Conversions S/062/60/000/009/0-16/02-
of Unsaturated and Highmolecular Compounds. B023/BO64
Communication 15. Copolymerization of Some Divinyl
Ethers With Methacrylic Acid
influence upon the yield and the composition of the copolymers (Fig.
The copolymers have in both cases a three-dimensional structure and the
number of the chain links of divinyl ether (I) amounts to more than
50 mole%. The vinyl alkyl ethers, forming linear 3opolymers with meth-
acrylic acid, give, however, a maximum of 50 mole% of the chain links.
The copolymerization under the participation of ethylene glycol divinyl
ether (II) with methacrylic acid takes a course different from case M,
and is similar to the reactions with vinyl alkyl ethers, Copolymers with
more than 150 chain link5 of divinyl ethylene glyool, have a three-
dimensional structure. A relation exists between the composition of the
copolymers, the yields and concentrations of the init-i-al monomers (Ref.7).
This dependence is linear (Fig- 2). The copolymers were subjected to
hydrolysis to determine their composition, The --ontent of acylals in
these copolymers is considerably higher than in copolymers with (I). ThIs
may be explained by the fact that (II) tends less toward reactions of the
type of a radical mechanism than (I), There are 2 figures, 4 tables, and
7 references: 6 Soviet and 1 US~
Card 3/4

Studies in the Field cf the Chf~mi t-,;Ll 0910'.6/021
of Unsaturated and Highmoiecular Compounds B025/EO6,,'
Communication 15. Copolymerization of Some
Divinyl Ethers With Methacrylic A--'Ld
ASSOCIATION,4 institut !~rganichezkoy khimii im, IT~ D. Zelinskogc Akadem.,
n-auk SSSR (Inst4Ltut- of Organi c Chem--5try 1:---,:n~. N, D,
Zelinskiy- cf the Academy of Sc ien:.~s USSR)
SUBMITTED: April 14,
Card 4/4

SHOSTAKOVSKIY, M.P.; BOGDANOVA, A-V-; PLOTNIKOVA, G.I.,,, DOIGIKEI, A.N.
Method of synthesizing merdaptoles and tritiated asters of orthoformic
acid. Izv. AN SSSR Otd. khim. nauk no.10:1901 0 160. (MIRA 13'-10)
1. Institut organicheskoy khimii im. N.D.Zelinskogo, Akademii nauk
SSSR.
(OrthoformAe acid)

S/1 90/60/002/012/006/0, 9
B01 YB055
AUTHORS: Shostakovskiy, M. F., Sidelikovskaya, F. P., Kolodkin, F. L.
--1 ................ .. .
TITLE: Synthesis cnd Polymerization of 11-Allyl Lactams
PERIODICAL: Vysokcmolekulyarnyye soyedineniya, 1960, Vol. 2, No. 12,
pp. 1794-1800
TEXT: The preparation -and properties of N-allyl q-pyrrolidone, N-allyl
E-caprolactam and N-sllyl X-piperidone are described. N-Allyl ~-capro-
lactam was prepared by reacting sodium derlvatives of the lactams with a
small excess of ally! br=ide in xylene at 100-11300C. N-allyl E-capro-
lactam is a very mobile liquid with a weak amine smell and a density of
approximately 1. It is miscible with water, alcohol and ether. The infra-
-red-, ultraviolet-, and Raman spectra of the compound were taken. The results
are listed in Tables 1 and 2. The presence of a carbonyl group and a
terminal vinyl group was established by these spectra. In their studies on
radical-initiated N-allyl pyrrolidone and N-allyl caprolactam polymeri-
zation, the authors found that N-allyl lactam is not activated by benzoyl
peroxide, but that 5 - 10% azodiisobutyronit:rile causes stepwise poly-
Card 112

Synthesis and Polymerization of N-Allyl S/19~60/002/012/oo6/oiq
Lactams B017 B055
merization with formation of dimei,s and trimers in low yield. Table 3
gives a survey of the synthesis of N -* all 1 lactams. The ultimate analybis
and properties of N-allyl pyrrolidone (I~, N-allyl pi-peridone (II), and
N-allyl caprolactam (III) are given in Table 4. The authors investigated
the copolymeTization of N-allyl pyrrolidone with vinyl acetate, methy-1
methacrylate and methyl acrylate, obtaining copolymer yields of up to 69~-
The spectroscopic analysis was Parried out by B. V. Lopatin and T. N.
Shkurina, collaborators at the optical laboratory of the authors'
institute. There are 6 tables and 14 references: 5 Soviet.
ASSOCIATION: Institut organicheskoy khim-ii im. N. D. Zelinskogo AN SSSR
(Institute of organic Chemistry imeni N. D. Zelinskiy of the
Academy of Sciences USSR)
SUBMITTED: May 13, 1960
Card 2/2

5 - K)rj 77351
S ov""79 - -JO-'-' - 1. ~'/(8
AUTHORS: Shostalcovsk-ly, M. P. , Ra'Anovich, M. S. , Preobrazhen2kaya,
7 e -ov- a 7-0 -. N .
TITLE: )OL the gynthe.,As of Precursors and
Structural Parto o[' AnLiblotle.,;. 1. 0. -Am~lnoadlnLc
Ac id
FERIODICAL, Diurnal obsticbey khimil, 1.960, Vol 30, Mr 1, pp 67-71
(USSR)
ABSTRACT: The c~-aminoadipic acid can be synthesized by the
following two methods: (1) by condensation of
Y-bromobutyronitrile with 1.1-acetyl-aminotna-lonic ester
followed by hydrolysis and decarboxylation; and
(2) by amination of diethyl ester of CL-bromoadipic
acid with subsequent hydrolysis. The yield of
CL-aminoadipic acic! prepared by the first and second
methods is 44% (based on starting '/-bromobutyronitrile)
and 82-11" (based on diethyl e3ter of CL-bromoadipic acid),
respectively. The technical a-aminoadipic acid is
Card 1/4 purified by dissolving in 1 M NaOH and treatment with

Investigation of the Synthesis oC T(351
Precursors and Structural Parts of SOV/79-30-1-12/78
Antibiotics. i. a -Aminoadinic Acid
activated charcoal (pFI 8.0). Upon acidification
(pH 3-3.5) of the colorless filtrate crystalline
(j. -amincadipic acid precipitates (yield 94,,,,"-), mp
17!" (decom). Heating of diethyl ester of a -bromo-
adipic acid in absolute alcohol saturated ~-,,ith gaseous
ammonia in the autoclave at 100-1100 (pressure 7 atum)
.Lor 12 hr yields amide of C1 '-pineridonecarboxy-
lic acid, inp 168-1690. When a -aminoadiDic acid is
recrystallize~l from water, about 50A of it is converted
Into CL , U -piperidonecarboxylic acid. Ester-IfIca-
Lion of' CL -axiinoadiple acid I)y heating i,.-ith isopropyl
alcohol in the presence of I[Cl yields isoprop,-l ester
of a , 1- 6
a piperidonecarboxylic acid, mp 6~.6-66-50-
This -v,,as verified by parallel synthesis of this ester
1rom piperidonecarboxylic acid. The cl -aminoadipic
acid .-;as also synthesized in the follol.%rin- .-Gay:
Z-1
Card 2/11

1nv.ej'L1--igatiori of t1rie Synthesis of
Precursors and Structlural Parts of
Antibiotics. I. Ci-Aminoadipic Acid
Card 3/4
77351
SOV/79-30-1-12/(8
Mir N.W.
C1f2-=C11GH211r -- 13rC11X11,.-C11?.Br -- ~- BrC11.-C1f2.C11XN----3-
0 1)
1.),(NIN ILCOC ll~ COO(,.211., lick
Ito,
C \N CALIC11CO011
I I
CoOG, I I.-, N112 - 11C1
(I V) (V)
cjl'~CINGOOII
I
C I I C I I CO 0 11
1
Nik
(VI)
The authors wish to thank A. S. Faiokhlov and Ye. M.
Kleyner for samples of Ct-amirkoadipic acid, and F. M.
Meller for performing elemental analysis. There are
10 references, 2 Soviet, 5 U.S., 3 German. The U.S.
references are: Schwenk, E., Papa, D., J. Am. Chem.
Soc., 70, 3626 (1948); Bun Hof, Demorsman, J. Org. Ch.,
18, 649 (1953); Waalkes, T. P., Fones, W. S., White, J.,

Investigation of the Syntheols of
Pre~ursors and Struct-uwal Parts of
Antibiotics. I. a -Aminoadipic Acid
J. Am. Chem. Soc., 72, 576o (1950);
Hess, R. W., J. Ain. Chem. Soc..,
G. B.
J , Baker, B. R., Bernstein,
Orr,. Ch. , 12, 162 (1947).
3
77351
3011/79-30-1-12/78
Derick, 0. G.,
'to, 547 (1918); Broi,,,n,,
S., Safir, S., J,
ASSOCIATION: All-Union Scientific Research Institute of Antibiotics
(vsesoyuznyy nauchno-issledovattlellskiy institut,
antibiotikov)
SM8MITTED: December 29, 1958
Card 1t/4'

5.3900 773152
SOV/79-30-1-13/78
AUTHORS: Rabinovich, M. S., hostakov:j.~r, M. F. , Preobrazhen-
sk.aya, Ye. V. 1~~~
TITLE: Investigation of the Synthesis of' Precursors and StrUC-
tural Part's of Antibiotics. Separation of (I -
Aminoadipic Acid Into Optically Active Forms
PERIODICAL: Zhurnal obshchey Ichimii, 1960, Vol 30, Nr 1, PP 71-75
(USSR)
ABSTRACT: Acyl derivatives were used in *~-his work for separation
of optically active forms of CL -aminoadipic acid.
N-benzoyl- L , d , CL -aminoadipic acid, not described
in literaLure, was synthesized in the following way:
To the mixture of 7, j (i , CL -aminoadipic acid (16 g),
sodium bicarbonate ( 90 g), and water (300 ml), after
heating for 1.5 hr, add benzoyl chloride (42 g) with
vigorous stirring. Continue stirring for another 4
hr, remove excess sodium bicarbonate by filtration,
acidify filtrate with HC1 up to --., pH 2.0. Recrystallize
Card 1/4 tne obtained acid from water., yield 18 g (68%),

Investigation of the Synthesis of Precursors 717352
and Structural Parts of Antibiotics. II . SOV/79-'30-1 -13/78
Separation of OL -Aminoadiple Acid Into
Optically Active Forms
0. -benzoyl-
mP 183-181' Separation of N d , CL
aminoadipic acid into optically active forms was carried
out v;lth brucine, I -threo-l-p--nitrophenyl-2-amino-
proparie-1,3-diol, and d,l-threo--l-p-nitrophenyl-2-amino-
propane-1,3-diol. In all cases the following optically
CD
active forms of N-benzoyl- a -aminoadipic acid
were obtained: N-benzoyl- 'L,CL -aminodipic acid, mp
177-1790 ' E: CL D + 17.2-1y .3"; N-benzoyl- d , CL
0
-16.o to 18.6
aminoadipic acid, RIP 178-18oJ, F a D
.
P
The I -form of amine produces a crystalline salt of
d N-benzoyl derivative, and the d-form_, the crystal-
I'Li,,e salt of I , N-benzoylaminoadipic acid. li~rdrolysis
of optically active forms of N-benzoyl- a -aminoadi
acid fields U_ -aminoadipic
acid, li,P 184-1850,T&I
.
+2~7.5 N; FICI) and (Y_ -aminoadiplc acid,,
-
2. " L 0
~j -1 .1
-"-,-c) (w i t h 6 N HC1). The
EC

a'l' nors, o, ,,ii~h P. Verkhovtsevoy (V~IIIA)'
T.

Card 2/4 e3tablished that 'F,he microor-anism ft-t-dr-i-11-taticlu-isop-,isaaL-ates
U I -

investigation of the Synthesis of Precursors 77352
and Structural Parts of Antibiotics. II. SOII/79-30-1-13/78
Separation of CL -Aminoadipic Acid Into
Optically Active Forms
1, d , CL -aminoadipic acid Into two optically active
forms. During Its life it cons',unes only the -L-form
of CL -arninoadipic acid. The authors succeded in obtain-
ing cl -f orm of CL -aminoadipic acid ( E a D p -25-90)
from the racemate in which the above microorganism was
cultivated for 5-6 days. The work devoted to the
separation of racemic amino acids with optically active
forms of 7- -threo-l-p-nitrophenyl-2-aminopropyl-1,3-
diol is to be continued. The authors thank M. A.
Guberniyev for his interest in this work. There are
8 references, 3 U.S., 1 German, 1 French, 1 Italian,
1 Swedish' 1 Belgian. The U.S. references are: Borsoon,
H., Deasy, C. L., Haagen-Smith, A. L., et al., J. Biol.
Ch., 176, 1386 (1948); Greenstein, P., Birnbaum, S. M.,
et al., J. Am. Chem. Soc., 75, 1994 (1953); Adams, R.,
So',., 6 , 27
Binder. L. 0., J. Am. Chem. 3 J73 (1941).
Card 3/4

Investigation of the Synthesis of Precursors 77352
and Structural Parts of Antibiotics. II. SO-11/79-30-1-13/78
Separation of CL -Aminoadipic Acid Into
Optically Active Forms
ASSOCIATION: All-Union Scientific Research Institute of Antibiotics
(Vsesoyuznyy nauchno-isoledovatellskiy institut anti-
1) Lotilcov)
SUBMITTED: Dec(-qber 29, 1958
Card 41)t

-3
7 7.3 _5j -j
S071/70/-30-1-14/78
AUTHORS* ho3 akovoiciy, M. F., Chelk-ulayeva., I. A., Kond--at 1yeva,
TITLE: React-lon. of Butadiyne With Amino Alcohols and Amines.
I. S~' nt;,esis and Conversions o-,-' 1-( 13- Di e t hy lam -J no
e ti,~ o,---.y bu t - 1 - e i i - 3 - Y n e
PERIODICAL: Z-'nu-(,1,,a1 obs~iche,-,, ichimiti, 1960, Vol 30. Nr 1, pp
7~----l (USSR)
A'!-'STRACT- Rea----tlion of butadiyne with (diethylamino)-ethanal
at room temperatUre witil ~c-atalyst yields (80-90%~
y -yne (I b-p cig
-dieth-lamino) -et, oxybut -1 -en-3
1 nam, n20 1 .4832 . Vl*qen cornpound I is hydrolyzed
D
t'r 10% H SO it yields 1,3,")-triacety-lbenzene (yield
2 4
0
I' -,d I viit,~i aliphatlc
Z) m. p,62-163 Reaction ,)- - npoui t. -L
a I. c, co 1 sunder ri-orous condit,'Lono (bc11inL:-- under vacuum
Cal-rd 0 (10 mm) for 6 hr in the prese.,.-ice of ca-ua!7 sL, po-tassi.-Lim

'7'7
R ea t 4B, a 'J W km' in o A -1, 1
aiid kmi!tes i and Convc-PL~ic)ii_~ S 0 9 - 3 0 - I - 1417 8
Of 1-( D.*,-e~u-ii,,-,lutiiii-lo)-et:,'!io;.~yb~it-i-e"-3-Y'le
e de e 'i d s , a lone, i t'.-i t l-, e ac, e ta 11 2 1,1:: f 'bu, t - I
i-al,also adid*Ltion products ot' c,,,.e molec-le ol' alcohoi
- r, " i ~ o' et~'i-Flvln-l These additlon
rlio i e c ~, -, 1 1, - d
pi~odl_ictls ~iave bot',, a dierLe a!-ld at-: al lene struct-,ure.
1~ea-.*~_ 0.~ of I with ieldo
d dl et~i-lam 1noetiio;~-
0 1 Y) -dJ eiie
20
1:5 10 4 mdr, n 1.4819. Compound II can also contain
D - '
some i,4-d-i-( d-Leti-iylamincet'~-I(Dxy)-buta--,-,3-di-ene (lia).
I
CH~=C-CH--CHOCF2 CH2N(C2H, /2
1
OCH 2 CH 2 l""C 2H5)2 (11)
-CH=CHOCH CH H (iIa)
(CO NCH CH OCH=CH 11(c
I - 2 2 2 2 2 2 5)2
Reaction of I with butanol yielded (50-60%) t"ne aCetal
of butu-l-yn-4-al (III), bp 1~~8-14oo (lo M. n 20 1.4-42,
Card 2/ 7 D - D

Rea c-z 10- E--_~, -I a d L,-?-ne IJ Am i-o A 1coil ols 7 T 3
and Amines. 1. Synthesis and Conversions S 0 V1 ~_( S9 - 3 0 - I - 14/7 8'
11 -
04 1 Die -L'Iy1amino) -eti-ioxybut-l-en-3-yne
13-
containizng an admi:,%,ture, a product with an allene
.-I-tructure. The yield of b,,itcxy-(/g-diet,iylanii~ic)-
ethoxlybuta-1,3-diene (IV), br- 153-1550 (7 mm), 11 20
D
.4-.(0, in this case, was otily 10-25%.
CH3 C~_CCH IOCJJ Hk) H9C.4 C1c1-1=cH_c1~=c I loci 12c 1 112N(C2H5)2
OCH2 cli2~T (C2it 5).~,
(III)
Card 3/ (7
(IV)
Dur_in.~* the reaction of e-Uhyl vinyl ether with alcohols
thei~e occurs, evidently, not only the isomerization that
causes mi --ration of the triule bond, but- ace-uylene-allene-
dienic isomerization of reaction prod-acts as well, w1nich
leads to t,~~e formation of di-alllcoxybuta-1,3-dienes.

Reaction of Butad~'Yne Wit', Amino Alcolnois 77 3 53
and Amines. I. Syntnes-Is and Conversions SOV/79-30--t-'14
of !-(/3-D~---',.-,ylamino)-ethoy~,Tbut-i-en-3-yne
OR
HC~C-CHL--CHOCH 2CH2 N(C2H 5)2 -i- HOR--->HCMC-CH2CH -Z
OCH CH N(C)H-
2 '2 2 2
OR CH CSC-CH(OR)OCH CH N(C H
> CH~=C=CH-CH / ___~ -3 2 2 2 5)2
\OCH2CH 2N(C2 H5)2 ('1 H~=C (OR) C-H=CHOCH2CH2N(C 2H5)2
R=C4H9 and CH2 CH 2N(C2H5)2
When the reaction of I with /g-(diethylamino)-ethanol
is extended from 6 to 22 hr,'-the addition product of' two
Card 4/7 molecules of am-no alcohol with one molecule of et'ayl

Re;a :-I o f E,-, a a
a-i
viii,yi ot;iei~ is obtained. The s'-,r-ucture of this Compound
V-, (based on, spectval analys.L;) and its physIcal
at it ~~ a ve c- rp, 1"7C -Y T Cio 'I -,o -I . ~,, ~ o (~!,
-/ I f D D.
C-:i.-~=C-CHDCH CH CH,~MIC
10 2 ;) H.
~ - -" il 2) 2
C H- CHI~) F C , H;~
2
c H 3 C '--l H-C H CH IIH 1,1(c H-)
1 10 2' p 2]
OCH2CH 2N(C~)H 5))
(va)
Re a,,; ', i o i i o w -1 tk~i ethylmercapta.n a, 70 800 ~'or hr
-Ieldecl ((30-70%) eti-iy1mercaptc-' diethylaminoethoxy)-
Card

7
SOV/7,cj-~0- I
a .1 Sl-i:~-.-e~3 -'s
D 1 i, I
0
(VI) or, (VIa), bf 1-20 (7 D
k D n
0 T~-,e aztempt ro pi,epare V! by paral"el
e S 6 fr~.jm 1-c-l~',,,yiiiiet-caLtobut-',--eri-3-yt-ie and 1-
L
failed. Only di-(#-diethylam4n~D-
z -.,-)-butla-i,3-dJ_en (H) vias cb aine The l'o-rmaton
!.o, Y e t
e
Of Tj in this case can be explained by disproportlona-
tici~ of butoxy-( -diene
,,(3-dieth~rlam4noethoxy)-buta-1,3
(IV) into symmetric diallcoxybuta-1,3-dienes.
2C'H-=C-CH--CHOGL'HO + 2HOCH CH N(C j=C-CH=CHCC H
2 2 4 Q
uuh2uh2N(C 2H 5)]2
(IV)
(!I) + CH,=CIOCL~;-7-.)CH==(-,HO,3,,H,.
Card r./T

Reac-ti--r- C7' 1~~ita-yre -Co-o"s
I, Z OV., 7 ~' ~7;:~
and Amines. I, S Iy z- e S -1, s a.- 'Ji C o:~ v e r s ~f 3 , s
of 1_(/3-Diethy amino -et'noxybut-l-en -yne
~t j -3
ASSOCIATION-
SUBMTTTEDt
T.,.,e author~3 wrisi-i to tihank B. V. Lz)patin l'or spectral
--,alysls c" ti-,e prepared compcunds. T"ere ar~- Il
n
Soviet, -3 Gei-irian, I U.S. De U.S,
L z3 CopeiihaveL~, j. W. , Blo-elot,. M. H.,
d Carbon Mono.*~ide Che-iii3trl' 305 (194~~) -
A c e ty I e ne an III I -
Institute of Organic Chemistry of t-le Academy of
Sciences, USSR (Institut or--aniches*loy Alademii
t5
nauk SSSR)
October 15,
(lard

p S
'%UTHO-RS: Ku!''bovol.--la-L., N. K.,
T -ITLE: Lon of S~,,nthc-As imcl Corive-ion-s oil Sulbst-!-tutE~a
L ! , "', I-,Irjn;, of ?- , -
X. tile s i.; Liml 3 r,
~I C)I) POJ)O I IPhen-I ~I
:y
PERIODICAL:
Reaction of th-lopet-101 .-;IAh Tile thy lace t yiene in alle:aline
ABSTRACT:
rae-d'.1-1111 -Leli-11:11 a rnL-,,-,tu-L,e of isopropenyl phenyl ~3u!..",Ldc (I)
I h n.-I sulfl-de
Q
D (j
22 0
D
+
(2)
Card 1/0

of Syrit'heols aml convepsions of -If 7 _`15 1 J-
I ' sov/-,iq - 70-
,:)~; c-'3 " it tit ed V I nyl E ther sX Synthesis and
ConveL-Ions of' Lsopvopenyl Phienyl Sulfides
The reactions (1) and (2) are nucleophilic additions.
Sterically directecl i(ldlltion of' trio! in reaction (2)
PeOUItS Ln only one stereoisomer. This was conf`irme~d by
oxiclation of' propenyl phenyl sult'lde y1eldIng only one
pi-openyl phenyl sull"one, C11_1CH=cHSO,C6*1-7~ (II')
0 :; -
~yield W%), mr) 69-5-70 Iso,,wopenyl phenyl SUlfide
converted into isopropyl phenyl sulf'one (IV) _`01. idlen-
tification. C112=C-SC,llr, Cl12=c--SO2cSl1S 1!t (CH02CIfSO'CO117,
I I
C113 Gil., ([Vl
O-X.idation of isopt-openyl phenyl s-a~flde yields (55%)
i~,,onro~)enyl henyl 1
sulfone, 42 (4.5 mm), n`0
b
1 - 5 21,Y0 In contrast to crystalline sulfones obtained
I
li-om -p,--o:)cn,,1 phenyl sulifide, the isopropenyl- and,
J 0
izzopcopyi phenyl :;L1lfLOt1eS ape oLl-likc substances. The
`bsorptio~n ri,xirna o!' isopropenyl phenyl and !.wopenyl
p 1, 2 plienyl suilides ave at I 212b cm,-"and 9-70-960 -e-
:I- e cI v f2 1 y. 11y"11-olysio of' propen""I anti,

Ll H 11(2 1 't' L ,3 at i o -I - 1:
convel'sion-- of ISoi~,"'.0perlyl Phenyl Sulfide:-;
pholly! Sulcides, y1olds
t ille 7r
. Decomposition of ti--,j obtalne- ol lfide,,;
-IlcollO'I'JC 301LIti-01-1 01- MO,-'CUT.~iC 2.hloL~idc ind"cated,
'Gliat this t-eaction can be used fotl t-he quzantlt-l'ive
determinat'Ll-,ion of lsopropenyl phew, 1 oulll.'Lde only. Upon
mixinc- of isooconowul nhen~,l sulficle a n
chlo-icle SOILItiOn.. phcnylrriePCLIPI.(.' chloi"ide precip!Lates in
~O seconds and 95% IICI IS Vecovei~ed by tLtratior: in 21'
hoiu~~3 . Renction ct' pi,openyll and isopt~opcnyl phenyl sul-
fLkles 'wlth thiophenol in t;he pvcz3ence of a ft-ec -adical
catalyst yields tlae sarne compound in both clasc~
(V), b:)
0~
mm) ri:~ -captain is used,
D ..6rj et1l,rImer
j
it reacts with fI) and (II) to form COMOOLInd (VI), yle-ld
L)1%, bu (5 m~), n'-,0)1
1.571r and compound, (VII),
':20
vicld 82%,
- bu PIM
i,eo,,lec 'L ive lir
C' n r 0. 3

~5
Investigation of Synthesis and Conversions of' 7-7 ) -
Substituted Vin,ri Ethers. X. Synthe-,is and SOV/79-30-1-15/13
Conversions of' Isopropenyl Phenyl Sulfides
(1) + C211.~,SH - C2H5SCHj-CHSCeH5
I
U113
(VI)
(11) + C~H,SH - C2H5SGH--G]12SC6H5
I
GH3
(VID
Isopropenyl phenyl sulfide
analog, isopropenyl phenyl
catalyst (SO 2) it reacts with
isopropenyl ethyl sulfide,
SOL G1:3 Sc(Ill'-'-
M+C2115SH I>C<
sc,11.5.
behaves similarly to its
ether. In the presence of
ethylmercaptan yielding
0 20
bp 112-114 , n 1.4755.
D
I CHI=C-SC211T, + C6115S11
I
C11:1
Hydrochlorination of"isopropenyl phenyl Sulfide yfelds
CL-chloroisopropyl phenyl sulfide. Sit-ice CL -chloroiso-
pt,opyl phenyl sulfide is an unstable compound, it was
Card 4/6 converted into tertiary-amyl phenyl sulfide, bp 96-930

InvestiL,,,Lation of Synthesis and Conversions of 7(354
Substituted Vinyl Ethers. X. Synthesis and SOVr()---`/O-l-l5/(8
Conversions of Isopropenyl Phenyl Sulfides
mm), n 1.5387.
D
_Lwqr (Cjj.),CSC.jj,
(1) (CI13)2 C-SC6115 4. 1
R
1,1-Dirnethylbutyl phenyl SLIlfiJe (yLeld 19%), bp
Qj~o (2 mm), n20 1.5312, was synthesized in an analogous
U D
way. There are 16 references, 6 Soviet, 6 U.S., 1 U.K.,
7 German. The 5 most recent U.S. reference3 ave: Tarbell,
D. C ., Lovet't, W. E. , J. Ain. Chem. Soc -, 78, 2267, (1956);
Bopdwell, F. G., Anderson, H. M., Pitt, B. M., J. Am. Cheiii.
soc., -(6, 10-85 (1954); TCLIC0, 111. E., Simms, J. A., J. Am.
Chem. Soc., -(08, 2(56 (1956); T.-uce, W. E.,gSiMmo, J. A.,
Boudakian, M. M., J. Ain. Chem. Soc., 78, 1/ (1956);
Tarbell, D. C., McCall, M. A., J. Am. Chem. Soc., 714, 48
Ca~~d 5/6 (1952).
ASSOCIATION: Institute of Organic Chemistry of the Academy off Sciences

5.3620 77856
SOV/79-30-2-7/78
AUTHORS: -Shostalcovskly, M. F., Gracilm va, Ye. P., Kullbovskaya,
TITLE: Study In the Field of' Synthesis and Conversions of'
Substituted Vinyl Ethers. XI. Synthesis and Properties
of' Isopropenyl Alkyl Sulfides
PERIODICAL: ZhUrnal obskichey Ichimii, 196c1, Vol 30, Nr 2, pp
383-388 (USSR)
ABSTRACT: The authors synthesized Isopropeny! ethyl sulfide,
isopropenyl bUtyl sulfide an6. isopropenyl propyl sulfide
by reactini., mcthylacetylene with mercaptans in an
alkaline med-LUM:
11S11+G11,C=-Cjj C112=C-SR (1)
t-t16.
The reactions were performed usir, the method described
earlier (Zhur. obshchey khim,., 28, 1253 (1958)). Kxperi-
Ca!,A. 1/8 mental conditions are 21riven in Table 1.

Stud,j in the Field of Synthesis and 77856
Conversions of Substituted Vinyl Ethers. SOV/79-30-2-7/78
xi
Table 1.
Key to Table 1. (1) Synthesized compound; (2) quantity;
(3) mercaptan (in moles); (4) methylacety" ene (in moles);
(5) KOH (in moles); (6) dioxan (in ml); (7) conditions
of' reaction; (8) temperature; (9) duration of heating
In hr); (10) yields of reaction products (in %);
) isopropenyl alkyl sulfide; (12) 1,2-dialkyl-
M
mercaptopropane; (13) isopropenyl ethyl sulfide;
(14) isopropenyl propyl sulfide; (15) isopropenyl
butyl sulfide.
Card 2/8
-2- 1 7
3 1 Z/- 5- 6 -47
13 L5 3 0.3 - 170-1800 2 44 9
/4 0.47 0.94 0.09 - ItO-120 1.5 49 15
/-61 0.34 0.68 0.068 30 120-U0 1.5 51

Stj,cjy ill t1ile Field of S.-ynul-riesis and 778;7~6
Co,,jVC-_,,jjojjS ()I' Substituted Vj*Lnyl Ethers. SOV/~9-30-2-~i/7_~,
xi
The pressure in the autoclave varied between 32 and 45 atm.
(Dio,xaii was added to minimize tarring.) By mixin- the
tD
obtained Isopropenyl alkyl sulfides with additional
I -rcaptopropanes
,jUaiititics of mercaptan, the 1,2-dialky1mc
ave obtained (reaction ("))..
I-
+
The reaction wa-, exothermic (temperature rose to ~~,0-600;
s,;nthe3io of' 1, 2 -die t1hy line rcapt opropane and 1,2-dipropyl-
rile v cap t- opropane). Lithe case of 1,2-dibutylinercap'Lopropane
and 1-1)ut,,/I-mei,cap'L-,o-2-etiiyl,mc-reaptopropane, the MIXtUre
iiad to be heated to 800 In presence of 0.01 .~ of azoiso-
bi.ityroniti-ile. Table 2 'iVE~S the yields and physical
COIIS'tant~~ ol' the synthesized compounds.
CLI,'Ci 3/6

S t u dy _1 I t t! ic- F _1 e i d ci I * Sy , -1, t - i e L; I s a t ld
Collvevf"J' oill.-, 0 f Sti 1)~; t i tu t ed Vill-I Et Jhero
X I
77856
S OV/7 9 - 3 0 -2 -7/~
c ti
I "S 5s.75 !67

7 :;7.j;l 7. 62. 11. 1

_ c'; I I is (;-,.0j IOAO
13 Li.57 .7.55
.7
0."'; ".
f; ~1.52
10.82

c_ I I 51.1's 9.8L
-,G)
10
:1:1.17'
c!' I I S
"~i;. 11;
1 (ul S
3108

.5'1.70 VUI:~ 218

o.!? if N
r)! 7 ~',
1.
A.70 i.4 I 11.1 33.01 1:1) 11 "S F19. I f; 10.118

in c a. i c u I 'at 10! 1 ') f MR the aut hors have u sed
D

re -i-
r~ -'
t lon of sl
_L I
ilfur,
fo-und 1'~)r
diall
yl sul
fi de
by
Card T. S. Prise arid D. F. Twi so (j. Chem. Soc., 101,
5
:J L' 3
27.57
2 1.1;o
33.3/1
2 q. to
33.3

c. I C1,Z 1 3 and 7 T~~ 5
I, t ed E i e S C, 11,,`7 9 - 3 0 - 2 -
(19112)) and equal to 8.011.
*~Atomic vefraction of 6ulfur was taken as equal
to 7.921 (Vo~~,-el, A. I., J. Chem. Soc., IgLi8, 1820).
In acid med'Um Isopropenyl alky'L s~zlfides react witil
raercaptanz (afte-c dropwise addition of' isopropenyl
to eqLilmolar qLtantity ol' mercaptan
containinL-,, 5-8 drops of HCI, the mixtu--e was heated
to 500 Cor 5 min and left, overnight; it was then
neulturalized, dried over K 2CC) 3j and distilled ) b,-,"-
an ionic mechani6m, the reaction obeyin4,~ Markownilco,,L'T 13
(P,la-1,11covnikov1~3) rLi1c., yie.IdJ.n,;,-, 2,2-diali.:,,lmerea-otcp.,opatics.
1-
Tia,- 2 decornpose on ?ieaI,-Lzi,,!-
the initial Passing hydro~Zen. cl,Llor-ide

Study in the Field of Synthesis and 77856
onversions o-L' Substituted Vinyl Ethers. SC:7/79 -30-2 -7/78
XI
throurrh isopropenyl alkyl Sulfides at -200 resulted
it, formation of a -chloroisopropyl alkyl sulfide, which
ea6ily decomposes on raisln6 temperature to 00, giving
off HC.1 and a complex MIXtUre of producto, Acid
hydrolyslo of Isopropen)~l alkyl sulfides yields acetone
as one of the products. Quantitative decomposition
of loopropenyl alkyl sulfides and 2,2-dialicylmercapto-
propanes bly exceso of alcoholic solution of' mercuric
chloride (reaction 5)(with Bubsequent titration ot'
HC1 b,1r blaOH):
GIL- -(I.-Sit +I- 2C2117.011 - IISI19CI + 110 +(Gll,)2C(Or_.,l1,,)2 (5)
,Gil,
can be used for estimation ot' purity of these compounds.
In the case of sulfides, the reaction mixture (0.1-0.2 6
of sulfide and 5 ml of 20% solution of' HgC1 2 In
alcohol) was heated at 700 in a sealed ampoule for 3
Card 7/10 hr, tranL;fecred quantitatively into a flask, and

St;jdy in the Field of'SyiithesiL; and 77856
ConverL;Iutis of Subotituted Vinyl Ethers. SOV/~9-30-2-7/~8
YT
titvatcd with 0.1N NaOll to methyloranee end point.
La
In the case of 2,2-dialky1mercaptopropanes, the
reaction mixture (-( ml of HgC12 solution was used
for 0.1-0.2 sample) was simply left overnight
in a stoppered conical flask. There are 3 tables;
and 12 references, 2 Soviet, 4 German, 2 U.K.,
3 U.S., 1 Polish. The U.S. and U.K. references
are. P. I. Wiezevi-lch, L. B. Turner, P. K.
Florich, Ind. Eng. Ch., 2", 295 (1933); U.S. Patent
2o66191, Ch. A., 31, 1038~ (1937), Ch. S., 32, 8359
(1938); T. S. Prise, D. F. Twiss, J. Chem. Soc.,
.101, 1259 (1912); A. I. Vogel, J. Chem. Soc., 1948,
1820; F. L. Cairus, G. L. Evans, A. W. Larchar, B. C.
McKusick, J. Am. Chem. Soc., 74, 3988 (1952); T. C.
Whitner, E. E. Reid, J. Am. Chem. Soc., 43, 639 (1921).
SUBMITTED: February 20, 1959
card 8/8

S/079J60/050/04/ ', 3/ObO
5"SSSI BOO1/BO1 6
AUTHORS: Shostakovski.~ri M. F., Prilezhayevag Ye. N.,
-A-z-o-vskaya, T;-~. . Dmitr1yeva, M, V.
TITLE: Investigations in the Field of Sulfones and Sulfcxides.
I. Synthesis of Vinyl Ethyl Sulfone and Some of It,
Transformations
PERIODICAL% Zhurnal obshchey khimiiq 1960, Vol~ 30, No- 4,
pp. 1123-1130
TEXT: The data available on the reactivity of low vinyl alkyl
(Refs. 1-10) -under the influence of ionic and free-radical init..'L-a-1-cs
are not clear. In order to clarify this problem, vinyl ethy-1 SUI-fcj-r-cr
was taken as initial product, It was synthesized by dehydration o.-^ 2-
hydroxy-diethyl- sulfone (I) with phosphoric acid at 260-2700 ill the
vacuum (Ref. 11) according to the scheme
H202. H3PO 4 , CH
HOCH2CH 2SC PH5 HOCH 2CH2so2C 2H5 2= CHSO2 C2H5'
M (II)
Card 1/3

Investigations in the Field of Sulfones and S/079/60/030/04/1 3/080
Sulfoxides. I. Synthesis of Vinyl Ethyl Booi/.Boi6
Sulfone and Some of Its Transformations
The yield in pure sulfane (II) was 70-75%; it contained no sulfoxides~
The dehydration method is far more convenient than the widely -used de-
hydrochlorination method (Refs. 1,2a,3,4,6910) (Scheme 2)~ "Triton B"
was used as the initiator of the ionic reactiona of vinyl ethyl. sulfons
(II); the reaction proceeded smoothly and quantitatively on intense
heating (Scheme 3):
C H SH
6 5
C2H5oil
C2H5so2CH=CH
~20> M.
The attempt of polymerizing vinyl ethyl sulfone under the influence of
free-.radical initiators gave polymers in fair yield on prolonged heating
(Polymerization Schemes). Vinyl ethyl sulfone shows a high dienophilic
activity, and yields adducts with cyclopentadieneg hexachloro cyclopenta.-
diene, and chloroprene. The table shows the polymerization of vinyl ethyl.
sulfone at 600 for 60 h. There are I table and 20 references.- 4 of which
Card 2/3

Investigations in the Field of Sulfones and S/079/60/030/04/13/060
Sulfoxides, I. Synthesis of Vinyl Ethy; BOO1/BO16
Sulfone and Some of Its Transformations
are Soviet.
ASSOCIATIONi Institut organicheskoy khimii Akademii nauk SSSR
(Institute of Organic Chemistry ol the Academy of
Sciences, USSR)
SUBDIITTEDt June 229 1959
Card 3/3

.SHOSTAKOVSKIY, M.F.; GUSEYI-I,--,V, I.I.; VASILIYEV, G.S.
- --------
Synthesis of compounds of the type of 1-all--ylthio-2-ox7chlorophosphine-
3-chloro-1,3-butadienes. Zhur. ob. khim. 30 no.9:2832-2835 S 160.
(MIU 13:9)
1. Institut organicheskoy khimii Akademii matd-, SSSR.
(Butadiene)