PHOSHONOETHYLATION

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000700070185-8
• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 5
• Document Creation Date: December 22, 2016
• Document Release Date: August 19, 2011
• Sequence Number: 185
• Publication Date: July 10, 1952
• Content Type: REPORT

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CLASSIFICATION S-E-C-R-E-T
SECURE INFORMATION
CENTRAL INTELLIGENCE AGENCY
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS
COUNTRY USSR
SUBJECT Scientific - Chemistry
HOW
PUBLISHED Thrice-monthly periodical
WHERE
PUBLISHED Moscow/Leningrad
DATE
PUBLISHED 1 Sep 1951
LANGUAGE Russian
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REPORT
CD NO.
DATE OF
SUPPLEMENT TO
REPORT NO.
Doklady Akademii Nauk SSSR, Vol LXXX, No 1, 1951, pp 65-68.
A. N. Pudovik, Kazan' Sta`,e University imeni Ulyanov-Lenin
Submitted by Academician A. Ye. Arbuzov, 27 Jun 1951
In previously published reports (1) we described a new method of synthe-
sizing derivatives of phosphoric esters. This method consists of the addition
of dialkyl phosphorous acids to unsaturated electrophilic reagents such as un-
saturated ketones, aldehydes, acids and their esters, and esters of vinyl alco-
hols. The method we described is extremely simple to carry out, is practicable
in regard to the starting materials used, and, in most cases, supplies a high
yield of addition products. During the past few years, we have synthesized
with the aid of this method a large number of heretofore unknown esters of
ketophosphonic, unsaturated bydroxyphosphonic, cyanophosphonic, phosphono-
carboxylic acids, and some others. In the expansion and development of these
investigations in this report, it is shown that the simplest of the few previ-
ously known ocls-unsaturated phosphonic esters -- the ethyl ester of vinyl-
phosphonic acid -- car, be used successfully as the electrophilic unsaturated
reagent. It must be pointed out that vinylphosphonic esters and their deriva-
tives have been studied only very little up to now, and that, in particular,
the addition reactions with them have not been investigated at all.
In the course of the work, it was established that vinylphosphonic ester
is sufficiently available and -- another important feature -- is a sufficiently
stable compound which will not polymerize if left standing for several days at
room temperature, or during vacuum distillation, or during heating over a water
bath for several hours. Even the firs experiments conducted with vinylphosphonic
ester showed that it is an extremely active compound which Hill easily combine
not only w_th dialky7nhosphorous acids, but also with a number of other nucleo-
/philic reagents such as ammonia,?mines, the esters of malonic, cyanoacetic, and
acetoacetic acid, their homologs, benzyl cyanide, and others. We have discovered
a new addition reaction between nucleophilic reagents and vinylphosphonic aciC.,
which, in addition to being of theoretical interest, has definite significance
in the synthesis of various phosphonic ester derivatives.
DISTRIBUTION
I I
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To clarify the nature of the process, we found it expedient to call the re-
acti% we discovered phosphonoethylatlon, in analogy to the well-known and widely
_,usedlyanoethylation, since a phosphonoethyl group is introduced into various
organic compounds.
The addition of dialkylphosphorous acid to vinylphosphonic ester was carried
out in the presence of alcoholates of alkali metals. To prevent an exchange of
radicals between alcoholate and diaikylphosphorous acid, both these reagents
were taken with the same radical, as in previous work. The reaction proceeded
very easily. The following addition products of dimethylphosphorous, diethyl-
phosphorous, di-isobutylphosphorous, and dibutylphoephorous acid with vinyl-
phosphonic ester were obtained in yields of approximately 60% of the theoretical:
1-dimethylphosphono-2-diethylphosphonoethane (b 158-160?Cl2mm, n2D .1.4430,
dg0 . 1.2075)
1,2-di(diethylpbosphono)ethane (bp 164-165?C/2 mm, n20' 4_ 1.4410, d20
D _l.1376)
1-dl-isobutylphosphono-2-diethylphoephonoethane (bp 183-184?C/2 mm, n201.4391,
d40 : 1.0471) D
1-dibutylphosphono-2-diethylphosphonoethane (b0197-199'C/2 mm,
1,4430, d40: 1.0681
l,2 i(diethylphosphono) ethane which we obtained is completely identical,
according to its constants, with the prod-ut obtained by Ford-Moore (2) in the
action of triethyl phosphite on dibromoethane. The mechanism of the addition
reaction can be represented by the following general scheme:
(R0
)POH + ROHa (RO)
POF
2
2
a + ROH
Na 0
{{.. 0 /
H
r
CH .C
P
+ (OR) ---~
2 I 2
10/11
(0C2H5)2 0 (OC2H5)2
' (0R)
0
(R02)POH
C 2-CHaP
0
P
""~OR)
2
(OC H5 )
. Where R __ CH3, C2H5, i-C4H9, or n-C. 4H
9 .
P.CH2-CH2-P
(RO), \
(OCA )
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Ammonia and amines usually add to vlnylphosphonic ester in the presence of
sodium ethylate; in some cases, the reaction also proceeds very successfully in
the absence of catalysts. The addition of ammonia in an alcohol solution and
in the presence of sodium ethylate furnishe 0a 67% yield of_ diethylphosphono-
P 93-950c/4 mm, aD - 1.4270, d4 , 1.0515.
Dlmethylamiae is added-to vinylphosphonic ester in the absence of a catalyst.
Already during the mixing of the reagents a fairly considerable warming up of
the reaction mixture can be observed. The yield of the addition product, the
ethyl ester ofa- dimethylphosphono ethyldimethylamine, after letting the mix-
ture stand at oom temperaaare for 24 hr, was 83%. The product has a bp of 103-
lo4?C/4 mm, n2~- 1.4345, d4 - 1.0157. Analogously, upon the addition of piperidine
to inylphosp8nic ester,_ diethylphosphonoethylpiperidine with a bp of 135-
1370, /3 mm, nD ^ 1.0514, d - 1.0154 was obtained in a yield of 52.6%. Upon the
a4 ition of aniline, -. digthylphosphonoethylaniline, bp ^ 145-150?C/6 mm,
nD . 14910, d4?, 1.0947 was obtained. However, the yield of the latter was
insignificant. The formation of a large quantity of low-boiling fractions was
observed. The reaction can be expreset 'y the following general scheme:
0
R
R
0
C2 r CH - P +
RH___
H- CH - CH
- p
2 2
\
(OC2H5)2
R
R
(OC2R5)2
where R ^ H,CH3, C 6 H 5 , or others.
We further showed that malonic, cyanoacetic, and acetoacetic esters, their
homologs, and also benzyl cyanide, in most cases very easily add to vinyl-
phosphonic ester in the presence of alcoholates of basic metals. The esters
of the following compounds were obtained, with yields of 78-86%, as a result
of the addition of malonic ester, methyl-, ethyl-, propyl-, and n-butylmalonic
eater-, respectively:
13 -diethylphosphonoethylmalonic acid (bp 158-159OC/I mm, n20 = 1.4420,
20 D
d 4 1.1316)
13 -diethylphosphonoethylmethyl:atonic acid (bg0175-177?C/4 mm, n2D _ 1.4400,
d 1.1021)
-diethilphosphonoethylethylmalonic acid (bp 162?C/2.5 mm, n20 r 1.4423,
20 D
d 4 _ 1.09251
-diethylphosphonoethylpropylmalonic acid (bp 175-176?C/2 mm, n2D _ 1.4425,
d20 = 1.0782)
-diethylphosphonoethyl-n-butylmalonic acid (bp 185-186?C/2.5 mm, n2D c 1.4432,
d 4 ., ,1.0640)
Addition to vinylphosphonic ester of cyanoacetic acid in equimolecular
quantity yielded two products:
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13 -diethylphosphonoethylcyanoacetic ester (bp 166-167?C/2 mm, n20 : 1.4430
d t, 20 = 1.0740` D
~
di( f3-diethylphosphono ethyl) cyanoacetic ester (bp 227?C/2 mm, n20 - 1.4540,
= 1.3830)
D
d ,
The total yield. of these two products was 63%.
The addition of cyanoacetic ester homologs to vinylphosphonic ester pro-
ceeded more smoothly. Theethyl eaters of the following compounds were obtained
in yields between 75 and
-diethyipho.:honoetbylmethylcyanoacetic acid (bp 165-166?C/3.5 mm, n20 - - 1.4430,
20 _ 1.0989) D
4-
P -diethylphospbonoetbylethylcyanoacetic acid (bp 173-174?C/2 mm, n20 1 443,
24 D
d
= 1.0702)
0
P -diethylphosphonoetbyl n-butylcyanoacetic acid (bp 177-178?c/3 mm, n2D
d , 1.4460,
24 = 1.0564)
Addition o:^ acetoacetic eater and its homologs to vinylphosphonic eater pro-
ceeds considerably less smoothly than the addition of malonic and cyanoacetic
eaters and their homologs. Besides the addition products, a large quantity of
low-boiling fractions, with yields of 20-25%, was obtained. /3 -diethylphoaphono-
etbylcyanoaeetic and /3 -diethylphosphonoethylpropylacetoacetic ester were iso-
lated. Upon addition of benzyl cyanide to vinylphosphonic ester, the basic re-
N8ion product was di(/3-diethylpboaphonoethyl)benzyl cyanide (bp 247-248?C/2 mm,
D a 1.4940). /3 -diethylphosphonoethylbenzylcyanide was formed only in very small
quantities.
All reactions discussed above can be described by the following general
scheme:
x
R -CH +
C
i
2
CH0Na
5
CHCR
P
_
H-C - CE
- CH
- P
2
1 2
2
000C2H
5
(CC 2 H )
OOC H
(OC H )
5 2
2 5
252
where X . cooc2H5, CH3CO, CN, or C6H5, and R . H, CH3, C2H5, n-C3H7, or n-C4H9.
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BIBLIOGRAPHY
1. A. N. Podoyik, Teziey Doklada na Sesii OKhN AN SSSR (Theses of Report at the
Ses on of the Department of Chemical Sciences, Academy of Sciences USSR),
947; Dok Ak IIauk SSSR, Vol LUIII, No 3, P 499, 1950. A. N. Pudovik
and B. A. Arbuzov, Iz- AN SSSR, OKhN, P 525, 1949; Dok Ak Nauk SSSR, Vol
I XIII, No 2, p 327, 1950.
2. A. Ford-J(oore and I. H. Williams, Journ. Chem. Soc., 1947, p 1465.
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