SCIENTIFIC ABSTRACT NESMEYANOV, A.N. - NESMEYANOV, A.N.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001136620018-3
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: January 3, 2017
• Document Release Date: August 1, 2000
• Sequence Number: 18
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

- IVznYAKQ7, _4.Nt, akademik; KR&VTSOV, D.N.
,p Zimethylaminopheny1mercury derivatives of nitrosoanflinne
nitrosona hylamineo. Dokl. AN SWR 137 nO-3t614,617 Ifr 161-
. . Pkt
(HOA .14:2)
1. Institut elementoorKanicheskikh isoyedineniy AN SSSR.
(Mercury organic compounds) (Aniline)
(NaphtIVITine)

811H 2zoq~jOzj 1407 .31020/6111371004/024/031
B105/B208
AUTRORSt Froydlinxq It,Kh. tOorrospondin'e Neabor AS USSRv
Chukovskaya, Yo&Ts## Tsao-re'ani Issmoyanov# Aaf.t
koademician
TITLEs Tolomerization and polymerization of ethylene with stliaon
hydrides in the Presence of titanium-tetraohlorider
PERIODICALt Doklady Akadomii nauk SSSZq v, 13Tt no- 4# 1961t 885 - 888
TEM The authors studied the tolomerization. of ethylene witht 1) sili-
oo-chlorofora# 11) asthyl diohloro-silinap and III) triethyl silano in
the presence of TiOl4 which catalyzes (initiates) those reactions accord-
ing,to the formula al 3sial2a + ILOK2- C'M--vQff3 U012(052CM) a1. They used
a steel au,toolave in which the reaction was carried out under pressure and
by hoatingo Zthylons was found to be tolomerized smoothly and with a gof
degree of conversion in oases Z and IX* In case I# some tolomer homologov
with. the structure SiOl 3 enR2n+1# where n = 2# 4# 6p Sp were isolated from
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570201611137100410241031
folomerization and polymerization of ... 3103/B208
tht mixture of tolomerization products. The constants of these substances
(Table 2) and of their nothylation products (Table 3) are in good Wee-
seat with those previously obtained by the author* (Rof*2# DANp 1139 1209
1957)o The noratl structure of their alkyl.g'roups was confirmed by in-
frared spoitra# Ad M A mixture of teloaor hosologs with a structure
ON)Sial ?-%'2n+l was formed at 180 - 20000 and at a maximum pressure of
280 atm: This reaction is complicated by the -formation of liquid hydro-
carbons duo to ethylene polymerizations Table 4 given the constants of
some mothyl-alkyl diahlora'silenes with a w 29 40 6g 8. Ad M. At 130 0,
ethylene is polymerized to polyethylene with no tolomers being formed.
This difference in the course of the reaction in said to be due to a dif-
ferent reducing power of the individual silicon hydrides studied$ Tri-
ethyl silanop e.gog contains sleatroaLdonor groups bound to silicon# and
is therefore a more powerful reducing agent than trichloro-silane and me-
thyl-diohloro-silanso This night be the reason why-thess, silicon hydrides
with TICI4yield products that are reduced to a different extent. X-ray
structure analysis (performed at laboratoriya, rentgonostrukturnogo analiza
(Laboratory of X-Ray Structural Analysis) and laboratoriya fiziki polimerov
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S/020161/13
7/004/024/031
band o2ymerization of 3103/B205*
p
8) of the :rA titut Oldfi*ntaor~inich6sklkk ~1,
G$
tuts"df Elemental solosed t a
t~':soyedinenly,-: (Insti ounds)).di h ~t
-organic Camp
f'poljethyl w. , I
on* -obtained by the, authors is identical 4ith la'' ir
,po2
q
ethylens~,and. the odiat obtained by dissomethane decaspositia
(jC
pictures bf the two letter Polymers were.made available by 1'*A, ffergeyev
-Ther'momeahanioal analysis showed. a melting point of 155*0 for the authorst
polyethylene which also'corrshponds to low-pressure'polyethylonoo Its
m a I a cul ar weight was 26670# deteizine4 from the viscosity in tetrahydro-_.':f;.
oThthalone at 13506. This indicates that tfi'e authors' polyethylene is
loned (an& asous dstai~~`
identical with the two,polystbylones ment I
ih Ref.'4? So Niteshe, Xhimiya i t6khnologlys pollmerove 19609 Pe 54),
There.are 2 figures,, 4'tab2os and 6 r's,ferencest 5 Soviet-blog "d. 1. non-,
viet-blooo-
December S' 1960
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W76
J,-70 ID 2205 1155 11(04 S/020/61/137/005/020/026
B103/B208
ADTHORS& Preydiina, R.Khq Corresponding Member AS USSRO
Martirosyanq G.T. and Resmeyanov, A.-Usp Academician
TITLEt Addition of trichlorabromomethane to compounds of the
structure R(C 6H5)2 ECH w CH 2 (where R -.a6H51 CH3t
F. - Sn, Sig 0)
PERIODICALt Doklady Akademii nauk SSSR, v. 137p no. 5, 1961, 1129 - 1132
TMt Thi stuthorB studied the capability of rearrangement of the radicals$
(a H SnCHCH eel and (CJ)2CdHCH2CCl3 in solution
6 5)3 2 31 (C6H,5)3SidHCH2_0Cl3 5 1
UJI3
and in the presence of benzoyl peroxidep where the phenyl is subjected to
a 1.2-migration from the metal atom to a carbon atom. For this purpose
the authors investigated the addition of trichlorobromomethane to 1) vi-
nyl triphenyl sta=.ane# 9~ vinyl triphenyl silane, and 3) 3,3-diphenyl-
butane-I* In the cases 1) and 2)q the addition takes place very smoothly*
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Addition of trichlorobzemomethane B103/B208
Not rearranged addition products are formed in nearly quantitative yield
according to the formulav Bz202
(a6H 5)3 ECH~CR2 + BrCCI 3 tP(C 6H 5)3 ECHB__CH2CCl3*
%he structure of the reaultant oompounds is confirmed by the missing
E-Br bond (negative test with AgV0 3) and by the behavior of the re-
sultant adducts with respeot to alcoholic alkali. The organotin compound
is not hydrolyzedp but, dehydrobrominated according to the formulas
(06H 5)3 SnCHBrfwH 2CC2,3 JU'Lt(c6a5)3 SuCH -CHCC1 30
Ad 1). After distilling off the excess BrCCl 3 14-3 g of a dense oil were
left from uhich crystalline tjrt-trichlorc-A -bromo-propyl triphenyl
stannene was isolated by diouolution in absolute alcohol and cooling to
-4000, This was completely neutralized over night with KOH in ethanol
at room temperature " Crystals of rvrslr-trictiloropropen-l-triphenyl-
stannane precipitated. Ad 2). tl-tr-trichloro-cg-bromo-propyl triphenyl
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Addition of trichlorabramomethane ... B103YB208
silane was obtained in an analogous manner, which did not react with
AgKO 3 and remained unchanged when treated for 20 hr with alcoholic alkali.
Ad 3). The addition is difficult. 66% of the initial diphenyl butene
were recovered in unchanged state after boiling of the reaction mixture
for 20 hr and repeated addition of benzoyl peroxide. As the principal
product yielded an unsaturated compound with the empirical formula
C 17H15C13 (5,5,5-trichloro-2,3-diphenyl pe 'nt'ene-1). The following re-
sulted by ozonolysiss Formaldehyde and a keto~e C 1_6H 1'3 Ol30 from the
crystals of which.a 294-dinitrophenyl hydrazone C.2",7 al31404 was formed
with 2,4-dinitrophenyl hydrazineo These data correspond to a compound:
CH-C(C H ) CH Ccl (III) which may be formed according to
2 6 ~) CH (C6H5 2 3
the formulat
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Addition of trichlorobromomethane..,. B103/B2013
CH3a (C6H 5)20H~--CH2 + 6C'~~CH3C (06H 5)28HCH2CO13 rear-
'Breal range-
del + IfBr +'CHZ~C H ) CH (a H CH CC1 3
3 (C6 5 6b5) 1 2 a (C I) CH ment.
CH 3 (06HO C 6H5 2CC'3~_
Simultaneously with 1119 a saturated adduct (bromide) was formed in low
yidldq' whose structure has not been studied, The authors summarize that
radicals (C6H 03 E15HCH2M 3 (z - Sn ISi) are not rearranged under com-
parable coAditions, whereas radicals (C6 H 5).2C (CH 3) allca2ccl3were re-
arranged. The reasons for this different behavior may be a) a low
stAbIlity of the first radical, as compared wtth the initial radicals
06H 51.3 idwa2ccl,v or b) the Sn- and Si-atoms are less able to impart
the affect caused by an odd electron at the adjacent carbon atom to the
phenyl groupe There are 9 referencest I Soviet-bloc and 8 non-Soviet-
-bloc. The 3 most'recent references to English language publications
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Addition of trichlorobromomethane so* MOONS
read as followat Do 3eyferth (Ref. 2t J*Org.Chera*Soc*v 22p 1252P 1957),
R.A. Bankellerp.NoVo, Bennetp R.A.Iudkner (Ref. 3t J.Am.Ohem.Socot 79,
6253, 1957)t S.D. Rosenberg, A.lo Gibbons et.al. (Refs 7t J.Am.Chem*Soc.g
791 21379 1957).
SUBMITTEDt Decem6r 24P 1960
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157,9114 2 7- S/02 IfWY7/006/013/020
-36 B1 030YB217
AUTHORS: Ifesmeyanovi A* N., Academician, Korshak, V. V.,Corresponding
I&emYe-~-A-9-Ug-SY,--Voyevodakiy, V. V., Corresponding Member "
AS USSR, Kochetkova, N. S., Sosin, S. L., Materikova, R. B:,
Bolotnikova, T. N., Chibrikin, V. M., and Bazhin, N. M.
TITLE: Synthesis and some optical-magnetic properties of poly-
ferrocenes
PERIODICAL: Doklady kkademii nauk SSSR, v. 137, no. 6, 1961, 1370-1373
TEXT: The authors studied the magnetic properties of ferrocene derivativea:31--
11) of the polyferrocenylenes (Table 1, nos. 1-6), 2) the polydiisopropyl-
ferrocene (Table 1, nos. 7-8), 3) the polymethano- and 4) the polyethano-
polyferrocenes (Table 1, nos. 9-13). They were synthetized by: A) Poly-
recombination. To 1). and 2). 1 mole ferrocene (or of its diisopropyl
homolog) was tre4ted with 1 mole tertiary butyl peroxide in nitrogen
atmosphere at 2000C.1 1) and 2) are assumed to be formed as follows: the
Butoxyl and methyl radicals formed during peroxide decomposition separate
the hydrogen from ferrocene (or the a-hydrogen). The radicals thus formed
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Synthesis and some
S/020 VYf37/0006/01 3/020
~1!
B103/B217
recombine and form linear 1) or 2), easily soluble in benzene. An in-
soluble polymer (Table 1, nos- 5-6) with a two- or tridimensional network
struc~.ture is formed simultaneously. The conversion of ferrocene to high-
molecular products amounted to 2%. Nos. 1-3 have a softening temperature
of 290-3000C and are a dark-red powder, whereas nos. 5-6 had their softening
temperature at about 4000C and were light-yellow. B) Polyalkylenation of
ferrocene by methylene chloride and 1,2-dichloroethane in the presence of
anhydrous aluminum chloride. Aluminum chloride solution in 50 ml of di-
halogen alkane was added gradually to 40 gferrocene dissolved in 250 ml dry
dihalogen alkane. The mixture was stirred for 6 hr at the boiling tempera-
ture of the solvent. The next day, 10 g aluminum chloride in 25 ml dihalo-
gen alkane were added and treated for 6 hr as above. The mixture was
decomposed by ice and HCl and treated with sodium sulfite. The obtained 3)
and 4) were well soluble in benzene, differed, however, by their solubility
in ether. Table I shows the molecular weights, the always equal g-factor
and the magnetic characteristics of all substances produced. The decomposi-
tion temperature of 9-13 was 115-1200C. All substances are amorphous
powders, nos. 9 and 10 light-yellow, no. 11 grey-brown. Nos. 10 and 11 are
of a chemical composition similar to that of no. 9 (pontaethanodifferrocene).
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Synthesis and some ... B103~B217
They consist possibly of 2 and 4 molecules similar to the latter, connected
by ethane bridges. 4-5 methyleaea in the molecule of nos. 12 and 13 belong
to 2 ferrocene radicals. They do not contain halogen. The infrared spectra
of nos. 9-13 have frequencies within the range 1000-1100 cm-1. To I).
Derivatives 1) having a x-conjugation between the ferrocene links give a
signal the electron paramagnetic resonance (a-p-r), similarly to the poly-
aromatic hydrocarbons. This cannot be explained by the presence of a
corresponding quantity of the oxidized form of the forricinium'cation.
Table 1 shows that also polymers in which the ferrocene links are separated
by the -CH2-CH27 group give an e. p. r. signal. It is known that the
delocalization of the unpaired electrons between the two phenyl rings is not
prevented by this group. In the substances described here, which give an
a. p. r. signal, this signal is the smaller, the smaller the number of
ferrocene links is. This signal vanishes in 2). Polymers with a low
molecular weight give no e. p. r. signal in the solution (benzene), but in
solid state. This is explained by the fact that the intramolecular
interactions cause in solid state a conjugation of the adjacent polymer
molecules. This causes for its part an e. p. r. signal. All polymers
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Synthesis and some ... B103YB21T
giving this signal show a single symmetrical line of.the e. p. r. of the
Lorenz type. The 1) obtained from the reaction A yields a wide e. p. r.
line of 120-160 oersteds, its width being dependent on the polymer structure.
This line becomes broader on reducing the measuring temperature. Its width
is changed most considerably in low-molecular polymers. The authors
believe the nature of the measured signals to be unclarified, they cannot
maintain that the number N of the unpaired electrons per 1 member, deter-
mined by a comparison with the standard, corresponds to their actual number.
X may, however, be a certain characteristic of the magnetic properties of
the system,, (nos. 2-4).- N reaches an anomalous size in the insoluble
..ri-polymer no. 5. This is assumed to be connected with a collective effect of
the ferromagnetic type. The ultraviolet (UV-) spectra of 1) dissolved in
n-octane, which give an e. p. r. signal in solid state, differ from the
ultraviolet spectra of such thatgive no signal in solid stated. In the
first.case the UV-speotrum agrees completely with that of ferrocene dis-
solved in M 4 . It was proved for these spectra (Ref. 7) that the charge
transfer takes place here under formation of an ion pair Fer +ccl- On the
4*
contrary, the UY-opectrum of such 1) that give no e. p. r. signal is similar
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Synthesis and some ...
23,954
S/020/61/137/CD6/013/020
B103/B217
to,that of fer;oce'ne in a neutral.solvent (n-actane), i. e. under conditions*
under which the charge is not transferred. Finally, the authors point out
that their results concerning.the UV-spectra apparently confirm the
11pseudoferromagnetism" of the polynucleotides and of the polyaroma tic
hydrocarbons (Refs- 5 and 8). There are I figure, 1 table, and 8 references,
7 Soviet-bloc and 1 non-Soviet-bloc. The-only reference to English-language
publication reads as follows: J. C. D. Brand, Ref. 7:* Trans. Farad. Soc.,
53, 894, 1957.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akademii nauk SSSR
(Institute of Elemental-organic Compounds of the Academy of
Sci6nces, USSR)
SUBMITTED: December 20, 1960
Legend to Table'l. I) Current number, 1-4) linear polyferrocenylene,
5-6) insoluble pol forrocanylener 7) polydiisopropylferrocene, linear, 8) .!7
like 7, insoluble, 9-11) condensation products of ferrocene with Di-1,2-
1~-13) with methylene chloride, 14) ferricinium cation
ohloroethane, ;h, t44.
II) Substance, mofecular weight, IV) g-factor, V-VI) line wid oers
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FREMLIn,, R.Kh.; KOST, V.N.; VASIIIYEVA, T.T.; NESKEYAROV, A.H., akademik
ffmolytic isomerization of 'l-fluoro-lp 1-