RECENT WORK ON ORGANIC TIN COMPOUNDS, SIMILAR DERIVATIVES OF OTHER ELEMENTS, AND THE SYNTHESIS OF TIN-PHOSPHORUS COMPOUNDS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600330856-5
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 5
• Document Creation Date: December 22, 2016
• Document Release Date: August 26, 2011
• Sequence Number: 856
• Publication Date: August 18, 1950
• Content Type: REPORT

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CENTRAL INTELLIGENCE AGGVUtTIRkPORT
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
Scientific - Chemistry - Tin-phosphorus,
compounds,
Monthly periodicals
Moscow-Leningrad.
Jan, 1 May 1950
DATE OF
INFORMATION
DATE DIST. If Aug 1950
NO. OF PAGES 5
SUPPLEMENT TO
REPORT NO.
THIS DOCUMENT CONTAINS uroNNATION AFFECTING THE NATIONAL DEFENSE
OF INC UNITED STATES WITHIN THE MEANING O F ISFIONANI ACT GO
V. t . C.. D I Ano SEAN AWEROI D. ITS TRANS NISSIOM OA TMI NIVELATION
OF ITS CONTENTS IN ANT WANNER TO AN IINAUTHOAI.EO FENS ON IS IAO?
NINITID NT LAW. AEFAODUCTION OF THIS FORM IS FROMISITIO.
Zhurnal Ohahchey Khimii, Vol XX (LXXXII), No 1,1950. Doklady Akademii
Nauk SSSR Vol IXXII, No 1, 19;0
RECENT WORK ON ORGANIC TIN OOMPOUNDSL
SIMILAR DERIVATIVES OF OTHER ELEMENTS,
AND THE SYNTHESIS OF TI:N-PHOSPHORUS COMPOUNDS
LWhiie the toxicological properties of the newly synthesized tin-
phosphorus compounds mentioned below have not been published by the
Russian authors, it. may be assumed that some of these substances have
a strongly toxic effect. A st:ernutator.y effect combined with physio-
logical action, commonly ascribed to phosphorus derivatives of this
type, Is conceivable.
The tin-phosphoru=s compounds on which data has been published in
.,.T m_bly low vnlAtilitV
_.
this 1n!: C'SI1CC have iii Ali wciti upy y:i;t~ ::..,+ pr. -?"= -
However, if found to possess appropriate toxicological properties,
they can presumably be used as in the form of aerosols. No actual in-
tention to use compounds of this type in the manner mentioned above is
implied -- this is entirely conjectural.
In the May 1, 1950, issue of Doklad Akademii Natilc SSSR (Reports
of the Academy of Sciences of the USSR , Vol LXII, No 1, Aa Ya. Yaku-
bovich, S. P. Makarov, V. A. Ginsburg, G. I. Gavrilov) and E. N. Mer-
kulova published a paper on the synthesis of organic compounds of el-
ements of the IVth Group by usin.E the diazo method. The contents of
this paper are summarized below../
Previous work L 1_/ has demonstrated that aliphatic diazo compounds can
be used successfully for the synthesis of organic derivatives of Group V ele-
ments.. The current article describes results of investigating the reaction
of aliphatic diazo compounds with halides of.Group IV elements,
In the only previous work which has been published so far on the same
subject f27, it was noted that tin-organic compounds are not formed as a
result of the interaction of in tetrachloride with diazo acetic ester and
diazo methane. The present study shows that halides (chlorides and bromides)
of tin, lead, and silicon react with diazo aliphatic compounds to form corre-
sponding alpha-halogen-alkyl derivatives of these elements.. The reaction pro-
ceeds according to the scheme
- 1 - GOJF!EES TIfL
STATF_ NAYI NSRS
ARMY X AIR Fill
DISTRIBUTION
I
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^ONKDENTIAA -it
EX,, + RCHN2 -;-PC?iXEX 3 -}-NP
---(RCHX)2EX2 Id2, etc .
RCi-3CEX3?RCHNp
Tin tetrachloride or tetrabremide, at 0-5`C in benzene, readily interact
with aliphatic diazo compounds to form all poss=ible alpha-halogen-alkyl de-
rivatives of tin; In this reaction, it is evident that an increase in the num-
ber of radicals combined with the metal makes it more difficult to obtain fur-
ther introduction of the alkylene radical in this manner 'lalkylenization) so
that the formation of tetra-substituted derivatives, for example, generally
proceeds very slowly and only in the presence of a considerable excess of the
diazo compouna Forman, ou of primary, secondary, and tertiary derivatives oc-
curs simultaneously, the relative amounts of each compounds dependent on the
ratio of the diazo compound and The tin halide.
The alpha-halogen-alkyl hadides of ti.n as well as the diazo compounds
with other alkylene radicals or magnesium-organic compounds, all of which are
used as reagents in these reactions, can be synthesized from mixed alpha-
halogen-alkyl tin derivatives containing various alpha-halogen-alkyl radicals
or halogen substituted and nons:bstituted radicals Tin tetracluoride does
not react with diazo aliphatic compounds.
In contraST to Tin tetrachloride, stannous chloride reacts with diazo
methane in an unusual f ashicn to form various polystannic derivatives of tetra-
valent tin. A a result of conducting this reaction in ether, there was ob-
tained a substance the structure of which, according to its chemical properties
and conversion products, is represented by the. formula:
CH2 -SnC12
C12Sn <
0E2-SnC12
C2H5)20,
In benzene analagous higher molecular compounds are formed.. The interac-
tion of the reagents In this case proceeds, apparently, according to the scheme-
-N2
CH2NZ-0'-CH2+-SnC12+-CH2 = bnLi2
T t
C12Sn=CH2 -}- SnCl2+CH2 =SnCl2-*-- -Sn-CH2-Sn-CH2-SIIn-
y
C1 Cl C1
In this reaction polymerization is interrupted through the action of traces of
moisture which are present in the reaction medium..
In contrast to the tin halides, lead chloride and the ammonium salt of
lead chloride-hydrochloric acid do not react with diazo aliphatic compounds,
probably due to the fact that they are practically insoluble in the mediums
usually used in these reactions. On the other hand, soluble lead .tetraacetate
interacting with diazo methane causes an energetic evolution of nitrogen as
well as the formation of methylenediacetate and plumbous acetate;
CH2N2-}' Pb(OCOCH3)k-4-NO?CH2(000CH3)2? Fb{OCOCH3)2
G Fc I'AI
50X1-HUM
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C0JFIDENT1AL
Alkyleniza.ion along the Fb-X bond was observed under specific conditions
in reactions of diazo methane with triethyl and diethyl lead chlorides in the
presence of copper bronze Without the catalyst these reagents do not interact
even when heated.. Copper bronze as well as copper :alts cause decomposition of
the diazo compound, which leads to the formation of alky].ene radicals, and pro-
motes alkylenization with formation of alpha.-chloromethyl derivatives of lead.
Alpha-c:hloroethyl compounds were found to be unstable, and their preparation in
a pure form was unsuccessful,.
At ordinary temperatures aliphatic diazo compounds were very energetically
decomposed by silicon tetrachloride or tetr.ebromide; because of this, the for-
mation of silicon-orgenic compound: was no, observed, the reaction product in
this case being a high molecular compound (a polymethylene). That is why the
reaction to prepare silicon-organic compounds is conducted at temperatures of
_15 to -55?C in an ether solution, The nonsubstituted alkylsilicon halides
(CH,SiC13, !CH~)2SiCl2) react with aliphatic diazc compounds more slowly than
the inorganic r?alides of silicon or alpha-halogen-alkyl derivatives of silicon.
Since an increase in the reaction temperature in these cases decreases
the yields of silicon-organic compounds because of an increase in the quantity
of polyakylenes forming in a secondary reaction, a catalyst -- copper bronze or
anhydrous copper sulfate -- is used to accelerate the reaction by decomposing
the diazo compound at low temperatures and thereby increasing (10-15 times) the
formation of halogen-alkyl-silicon halides
Tetra -(halogen -methyl) -si lane s, decomposed by heating, could not be iso-
lated. Silicon tetra-fluoride, energetically interacting with aliphatic diazo
compounds with the formation of nitrogen and polymethylene, did not. form sili-
con-organic compound:. even at low temperatures. (See Table 1).,
Therefore, the interaction of aliphatic diazo compounds with halides of
Group IV elements, (aF well as with Group V elements) is a convenient new
method for the synthesis of elemento-organic compounds, which are difficult
to prepare in other ways. The results obtained in this investigation also
show that the applicability of the diazo method for the synthesis of elemento-
organic compounds of the aliphatic series is no lees general than that of the
analogous method for the aromatic series.
Eccrlcientai_ dA+n on the reactions of diazo compounds with halides of var-
ious elements ... e make it possible to consider these reactions as free radical re-
actions. The biradical formed in the decomposition of the diazo compound is
an alkylene group which is introduced along the E-X bond, this leading to the
formation of new elemento-carbon bonds.
Other possible processes in this reaction are- the solvent being attacked
by free radicals, the polymerization of alkylenes into polyalkylenes and a re-
action with halides of elements at the site of unshared valence electrons of
the element, leading to an increase in the valency and formation of new elemento-
organic compounds,
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Formula of the Compound
C1CH9Sic13
(C1CH2)2SiC12
(C1cH2)3SIC1
CH3(CH2C1)SiC12
CH3CHC1SiC13
BrCH2SiBr3
(BrCH2)2SiBr2
(BrCH2) 3SiBr
C (BrCH2)3Si_/20
C1CH2SnC13
(C1CH2)2SnC12
(01CH2)3SnC1
(C1CH2)ILSn
BrCHoSrBr 3
(BrCH2)2SnBr2
(BrCH2)4Sn
(CH3CHC1)2SnC12
(CH3CHC1)3Sn01
(CH3CHC1)4Sn
(cH3cHC1)2SnO
(CH3CH2CH2CHC1)2SnC12
C1CH2SnC1(CBC10H3)2
(C1CH2)2Sn(CHCICH3)2
(CH2CHC1)2Sn(C2H5)2
(c2H5)3PbCH2C1
(c2H5)2Pb(CH2C1)2
(02H5)3PbCHCiCH3
B.p. in ?C
20
320
116,5?/750 mm 1.4776
58.5?/16 mm 1,4624
700/4 mm 1.4377
121-1220/760 mm 1.2778
66?/75 mm 1=3919
700/6 mm 2:5730
107?19 mm 2.4614
123?/5 mm 2.3440
m.p, 69.5?
72.5-73?/5 mm
m.p: 89.5-?900
138-140?/5 mm
m.p. 49-49.5?
109?/5 mm
nip. 87?
m.p. 570
112?/4 mm, m.p.. 12?
130?/3 mm
1420/2 mm
m.p. 180?
134?/5 mm, m.p.
128?/3 mm
141-1420/5 mm
114-115?/5 mm
660/3 mm
96?/2 mm
decomposes at 200
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ND
D
2.03
--
3.251
--
--
1.829
1.5535
1.684
1.5450
1.568
1.5365
1.765
1.555
1.675
1.5478
1.414
1.5083
1.7917
1.5443
1.9890
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CONFIDE NPFJ N ? ML
]t will be noticed that organic tin halides have been synthesized
by the method described in the paper published by A. Ye.. Yakubovich et
al and summarized above. According to B. A. Arbuzov and N. P. Grech-
kin, Zhurnal Obshchey Khimii Journal of General Chemistry), Vol. XX
(LXXXII), No. 1, January 1950, pp, 107-15, analogous compounds (io-
dides in this case) react with esters of phenylphosphinous and di-
phenylphosphinoue acids, yielding the tin-phosphorus organic compounds
which are listed below together with data on their properties and de-
tails of the reactions leading to them]
Addition of 2,8 g PhP(OMe)2 to 4.7 g Me SnI and warming to 80?C gave a vio-
lent reaction (maximum temperature 240?C) which on subsidence gave 3.4 g PhPO(OMe)
(SnMe 3)' in. pt. 132-4?C (from EtOH). Similar reaction of 6.4 g PhP(OEt)2 with
10.8 g Et SnI preheated to 150?C gave insoluble colorless PhPO (OEt) (SnEtg),
in. pot- 294.7?C, in 1..6 g yield. The use of 4.3 g PhP'OEt)2 and 9..5 g (Bu3 nI) at
185 c gave 7.2% insoluble PhPO(OEt) (SnBu~), m.. Pt, 302-5?C (decomposition), al-
though 86% EtI was evolved, Heating PhPO(OMe) (SnMe3) 30 minutes with H2O gave
no change, but 15% HC1 at room temperature yields Me~SnCl rapidly, while 10% KOH
in three hours yields Me3Sn hydroxide, m, pt, 117-2000. Addition of 5.1 g
PhP(OMe)2 to Me2SnI2 (6 g) gave after a violent reaction 3,7 g, Me2Sn(B(0)
)2 , decomposing at 291-3?C,. Similarly 7 g Et SnI2 and 6.5 g PhP (OEt)2
after preheating to 150?C gave 2.8 g Et2Sn(P(0) (OEt5Ph)2, decomposing at 296-
300?C, while k,5 g Et2SnI2 and 5 g PhP(OPr)2 gave, at 1950C, 61.4% Et2Sn(P(0)
(OPr)Ph)2, decomposing at 245-8?C. All these products are insoluble in organic
solvents; they are stable to hot H20, but rapidly cleave in 15% HC1 yielding
R2SnC12, while 10% HaOH yields RoSnO; action of Cl in CHC13 also yields R2SnC12
at room temperature. Heating PhPC12 eight hours in sealed tube to 300?C gave 36%
Ph2PC1; this treated with McOH in presence ofMe2NPh have %Ph2POMe, b10P5E-5?C,
while EtOH gave 51% Ph0POEt, b10_61-3 C., Heating 7 g v3S53 and 2
170?C gave 5.1% Ph2P(O~SnEt , decomposing a. 346-8?C, while EtOH-Et20 washings
gave Ph2EtPO, m, pt. 121-4?C (1.4g). Likewise, 5.1 g Me3SnI and 4 g Ph2POEt gave
9.8% Ph2P(0)SnMe3, decomposing at 365-8?C, and 1.75 g Ph2 EtPO, while 4.6 g Et SnI
treated with 3 g Ph^FOMe and heated to 190?C gave Ph2MeP0, m.. pt. 108-10?C, and
4,2 g Et SnI (9l?5%~.. Me2SnI2 (6 g) and 6.9 g Ph2POEt heated at 140?C gave 2.2
g Me2Sn( (0)Ph2)o, decomposing at37,2-5?C, and 0.9 g Ph2EtPO, while 5.6Pg Et2SnI2
and g Ph20Et gave 17.3% Et2Sn(P(rO)Ph0)2, decomposing at 351-30C, and
These derivatives are stable to hot H20, while warm 156 HC1 yields Ph2PO2H,
m pt. 193-4?C, and R2SnC12, and hot 2C% NaOH similarly gives Ph2PO2H and R2SnO:
:_,do 0.enr1_ an presumahlV PhnPOC1. for aqueous treatment
action of Ci2 " Y-~.. -e --~ --- .- -- _
yields Ph2PO2H; the action of AcCl in benzene under reflex is similar, as R2SnC12
and Ph2PO2H are isolated.
he paper by A. Ya, Yakubovich et al was submitted for publica-
tion on 6 Dec 1949, and presented by Academician A. N. Nesmeyanov on
21 Feb 1950. The paper by B. A, Arbuzov and N. P., Grechkin, which
originated by the Chemical Institute of the Kazan Affiliate, Academy
of Sciences USSR, was submitted for publication on 8 Jul 1948, accord-
ing to the note under the published article, and published on the date
mentioned above,/
1. A. Ya Yakubovich, V. A, Ginsburg, and S. P. Makarov, Doklady Akademii Nauk
SSSR, LXXI, 2, 1950 (00-W Proj 5618).
2, A. Nesmeyanov and A. Segalevich, Izvestiya Akademii Nauk SSSR, Otdeleniye
Khimicheskikh Nauk, 6, 1942.
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