RESEARCH OF A. N. NEMEYANOV ON ORGANOMETALLIC COMPOUNDS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600270237-9
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 5
• Document Creation Date: December 22, 2016
• Document Release Date: September 19, 2011
• Sequence Number: 237
• Publication Date: December 22, 1949
• Content Type: REPORT

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INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
CLACEINTRALOINTELLIGENCE A NCY' ",,i ,'~~"i~. RI
Chemical - Organomotallic compounds
Bimonthly periodical
Moscow
Sep/Oct 1949
TMI. COCONINT COITAII. INPoII.ATIOA ATIICTIN. "I NATIONAL OIT(NII
TNI ONITIO ITATU ^ITNI^ TNI IIINNINO OF II.IONA1I ACT 50
.. .. c.. al 11110 $1, AN ANI1OI.. ITS TIANINIe11ON O. TNe ONr:LATION
OP ITI CONTINTN IN ANT %ANON* TO AN O.AOTOO.IIIO POTION tI I.O.
DATE OF
INFORMATION 1949
DATE DIST. ;,A Doc 1949
NO. OF PAGES 5
SUPPLEMENT TO
REPORT NO.
THIS IS UNEVALUATED INFORMATION
S. A. Socheehbov
I. F. Lateenbo
0. A. Reutov
Moscow
f-A Digest]
194-} l N02 --0 '- NO2+ H+ + w4 and
1! C
C6R5 :J:C6R Bl4 -}- :A - C P BF4 + - CWSJ proceed by virtue of an
into forme;tion of the post ve phenyl radical.
Reactions C6B5
The following is a review of research done by Academician Aleksandr Nibolaye-
vich Neemeyanov in the field of organometallic compounds. The introduction of
mercury into a definite position of the aromatic nucleus (over the diatoniumm salt--
mercuric chloride complex) Is discussed and the reactions Ar-N,9 000E+HgC ArKgC1
+N2 +C02 -1- V1 and 4CBN2.000C2H5.+ 3HgCl2-Y 2CH2Cl OOC2E5 ? 4152 + Hg J.--~Cl(HgCl)
COOC23i7 2 are mentioned in that connection.
Several reactions of the types (RN2C1)2.SnC14-- 2Zn-R2SnC + 232?2ZnC12i
C6H5N2Cl.1bC12+ Cu -;r (c )2PbC12, 4C62k+ 3Pb -i, (C6H5 )4Pb~ 432 -; 2Pb
(274)2, C62532Cl.SbCl33?Zn-+C6R5SbC12+N2+ZnC12i 3(XC6H432Cl)2.BiCl3
+4Bi-2(3C66 )3Bi+6N2?5BiC13, (C6R5'2Hg+4N2O3-;2C 23O34-Hg(NO a )
are listed, an the great number of conversions and variations based on thb ypioal
reactions is pointed out.
50-170 degNtriohloracetic acid reacts with naphthalene: C13C.C~
(yield 3 percent) "OR
I ` 1718-814
This is explained by the following scheme:
a. CC13: S Zo: R CC13: -}- C02+ H +
' Il IDt IirI Ii I G ~I.
STATE IX I RAW 1< NSRB I I DISTRIBUTION
I ARMY AIR IYI FSI
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i
50X1-HUM
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CC'.3: + h+-- :3aC=z
.. CC13: oxii5ticr_
02 (air) CCl3
d. CC13. + (\~ =r
(stage a) proceeds over the cupric ion, and is facilitated thereby.
The reaction RJO2 +HgO RH64" -I- J03 15 cceede with a yield of 8C-90
percent in the presence of silver oxide.
Mercuric chloride can be arylated in the following manner: (C6H5)kSn -
4-39CI2 --> (C6H5 )3SnCl+ C6R5HgCl; (C6H5 )2SnC12+ ?W12- 2C H gCl + SnCl4
C6H5SnCl3-1- HgC12 - 6H5W,,l + SnC14
This reaction has been applied extensively to organic compounds of lead,
arsenic, and antimony.
(C6R5 )23n0 +HgO -I- 2NaOH - 0002H9 + Na25n03 + H2O
Sia'"larly, organomercuric hydroxides can be arylated:
R R g O H + R `Sb0 ? N a OH - I ? -+ NaSb02 + H2O
Compounds RHgR? containing functional groups in the aromatic nuclei can be
obtained in this manner; this would be impossible if organomagnesium compounds
were used.
The reaction of a series of aymmetric organamercurio compounds (which became
available via the diazo compounds) with metallic zinc or aluminum proceeds in the
following manner:
(C1C6K1 )2Hg -1-" zn -" (a1C6H4 )2zn + Hg, /rCR3 )2NC6HlfJ2Hg + zn--o- /cCH3 )2NC6ffy72zn + Hg.
These reactions have been studied by Nesmeyanov?s collaborators. It is
essential to understand that while conversions of the type R2Hg + SnC12 --> R2SnCl2
+)Fg can be carried out with Grignard reagents, the latter are much more reactive
than mercuric compounds and affect the substituents in aromatic nuclei. In the
presence of certain radicals, the following variation occurs: R2Hg + SnX2?
+2C2H?0H -b 2RH+ Hg-}- (C2H50)2gnX2 .
The relative facility of this conversion enables one to measure the affinity
of various radicals to hydrogen, i. e., the eleotronegative strength of these
radicals. It could be ebown that organcmerouric salts react with anhydrous SnC12
in accordance with the equation 2RHgC1-1-23nCl2- R2SzCl2+2Bg"+SnCl4, chile
the conversion RHgX? Sn12----RSn%3 + Eg plays a subordinate role. With bromides
another variation occurs: 2RHg1 r-}- SnRr2 --s R2Sn&"2 -I-2HgHr.
Thus a whole aeries of compounds R28u12 and RSab3 (the latter after a reaction
with SnX4) containing halogen in the aromatic nucleus could be obtained, To
synthesize compounds containing a dimethylemino or hydroxyl group in the nucleus,
the variation expressed in the~.,--following equation was found useful:
5-(CH3)2Hc 2A+/Tc2A5)33J2 -'2p-(CH3)2HC6H4Sn 02E.03+99-
This method made possible the synthesis of compounds of the type ArSnAlg3 and
Ar2SnA1S2 containing any desired substituent in the aromatic nucleus.
L 1d 174'N5 i TIAl
C GtlF IDlNT1 I
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(c1cu'=cH)2ag
CiCH=CHC1+ HgC12
C]CH=CHI- + HgC1.Hr
C1CH-CHJ +HgC1.T
C1CH-CHJC12+ HgCle
l`> 2ClCH=CHHgCl
JC13
- ClCH--=CHJCl2+ C1CH.CHHgC1
c1CH=CHJC14 (C1CH=:CH)2JC1+ClCH=CHHgC1
&4 12 > (C1CH-. CH)2SnC12 -}- Hg
2b( 3co) (clcn-cH)2 + (CH3000)2Hg
(ocoCH3)2)
C12 C1CH=CHHgCl+C1CH=C1Ml
In another type of reaction, decomposition into acetylene and mercuric chloride
occurs. This deoomposition can be brought about by beating ebove the melting point
of the highest melting of the four compounds (124 degrees) (C1CH=CH)2Hg--a
C1CHCHHgC1-fC2H2, C1CH=CSHgCl --* HgC12-}- C2H2.
The action of reagents capable of binding mercuric chloride induces tha mum
type of decomposition even at roes, temperature CH2H8 I+ 3&7 -c2H2-i_ r
+221 L___~~3??? J _
Silver oxide in water converts trans- c-chlorovinyl mercuric chloride into
the soluble hydroxide C1CH-CHHgOS. The latter is capable of forming a number of
salts with various aside. Among these the phthalimide salt merits attention.
The salts in question could be also obtained in the following manner: (C1CH=CH)24
?BgJ2 `-1 2C1CH.CHHgJ.
Similar conditions obtain in a series of ehlorovinyl compounds of other metals.
Thus, cis and trans 01=-CH)3SbC12 and cis and trans (C1CH-CH)38b have been
syntheetaed and found to behave in the following manners
2J2 ?
3CICH=CHJ +SbCl2J
(clcH = CH)3sbcl2 38r2
3CleB=CHBr + SbCl.2Br3
Na2S204
(CICH=CH)3sb
(C1CH=CH)38b+ 3HgCl2 --k 3ClCH=CH1gCl? SbCl3
~7i 4LYS Y Sri..
' About 15 years ago Hesmeyancv and his group of workers- launched an extensive
investigation of addition compounds of metal halides and unsaturated compounds.
Compounds of this type behave either as molecular complexes or as products of
addition to a triple bond, I. e., Cl-CH~CH-HgCl. This dual character has led to
doubts and controversy on the subject of the actual constitution of substances of
this class. The work of Hesmeyanov and his collaborators has permitted a solution
of that question. The essential similarity of chemical behavior could be estab-
lished on the basis of accumulated data in the new field of quasi-addition com-
plexes. Trans-C1CH--CHHgCl, trans-(C1CH=CH)2Hg, cis-ClCH?= CLHgCl, and cis-(CINCH=
CH)B8 have been adequately characterized. se four substances are definitely
-ohlorovinyl organcaeerouric compounds, as the following reactions, which lead
to compounds containing the 6-ohlorovinyl group, show quite clearly.
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coff~c aW g s km~
The chlorovinyl compounds of tin, lead, and thallium react in an analogous
manner.
The producto of the addition of mercury salts to olefins or carbon monoxide
must be also regarded as belonging to the class of quasi-complex compounds. In
aU compounds of this class the mercury is exceptionally mobile, i.e., it
approaches the ionic state more clor,ly than in ordinary mercury compounds. This
is due to conjugation in which the mercury atom participates.
It could be sLovn that the transfer of the chlorovinyl group proceeds under
rigid retention of its sterio configuration in all reaction involving electrophilic
and radical substitution at the olefin carbon. This is illustrated by the following
scheme:
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G0i1nFi0i L8TIAL
Coffin TIAL
This retention of the configur,`tion is also observed in the reaction
H \ Cl R. Cl
Ar-15~' C=C ----~ rC=C + N2+ C02 -t- BS:l+ Rg
b-g C1Hg" A,/C=C
r/ H
Vh1eh leads to cis-omega-ohlorostiyrronee. The synthesis of these rather inac-
cessible ocmipounds has b^n facilitates by that reaction.
A general rule to the effect that alsotrophilic and radical substitutions
at a carbon bound by wane of a double bond to another carbon proceed under
retention of the gecmetc configuration has been formulated on the basis of the
experimental data obtained by Nesmeyanov and his collaborators. This rule is of
considerable theoretical interest and undoubtedly has an important beeri.*g on
substitutions in aromatic nuclei.
i., : i i.'41
L 1
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CWVFIIMIAL
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