THE SYNTHESIS OF ESTERS OF ALPHA-AMINOALKYLTHIOPHOSPHONIC ACIDS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000700190017-1
• Release Decision: RIPPUB
• Original Classification: U
• Document Page Count: 7
• Document Creation Date: December 22, 2016
• Document Release Date: August 24, 2011
• Sequence Number: 17
• Publication Date: June 10, 1954
• Content Type: REPORT

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STAT
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THE SYidTHESIS OF ESTERS UF' ALPHA_A~NOpLgyyTHIOPHOSPRONIC ACIDS
Doklady Al;ademii iJauk.SSSR M.I. Kabachnik, T. Ye. Medved.',
Moscow~'11.Oct 1953 s.nd T.A. Mastryukova
Inst of Organic Chem, Acad Sci USSR
In our w..rk (1) it was shown. that alehydes and ketones react with diall~yl-
phosphltes in alcohol-aimucnia"solutions to form esters of Q aminoalkylphosphonic
acids:
R H\ /OR R ~ /NH
j =. 0 -(' NH3 '(' / p \ --~ C p
R 0/ OR R./ \ p0(OR)2 + R2
The reaction is csrried out by heating the mixture to 100 degrees centi-
grade in sealed tubes for a period of several hours. The free acids are read-
ily obtained by saponifying the esters cf cz-aminoal3~yiphosphonie acids. This
reaction is simil.=r to the well-known reaction for the preparation of aminoni-
triles from aldehydes or ketones, a~a~ia, and hydrocyanic ecid (2); or accord-
ing to N.D.Lelinskiy (+), fx?om aldehydes or ke'.ones, ammonium chloride, and
:otassium cyanide:
R / C _ 0 -f- NH3 .~. HCN -~ R \C / ilH2 ~. H2O
R'/ ~ CN
The synthesis of Q-aminosulionic acids from aldehydes and ammonium bisul-
fate is also related to th?s type of reaction (4):
R R \ /~2
oC = 0 + IJ~ikHS03 ..~ C ~. g20
R ~
'~ ~
R
503H
V.M. Rodionov's reaction is eiso related, i.e., the synthesis of ~-aminoacids
"\ C = 0 /COOR R ~ /ilH2
R / f NH3 .~. C\ 2 _~ C .;. 920 .~ C0~
COOfj, R' / ~ CH2000R
A common characteristic of the above reactions is that the ammonium salts
participating in them are salts of acids which are capable of tautomeFic con=?
versions of either the ciiad or triad type;
H - C N ~ C A' _ II, H ~ Si0 HO\S - 0
If0/ e0 ~ H0/
H\p/OR ~ HO - p/OR ~ COOR ,000R
O~ FOR ~ OR ~ C\ COOR , ~ ~ ~ OR
~ OH
phites.also belo~ik and T. A. Mastryukova (6) pointed out that dislkylthiophos-
n$'to this category:.;:. ~
S j ~ ~ RS ~ P\OR
OR
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The tautameric equilibrium in these substances is strongly shifted tc the
side having the pentavalent phos
h
p
orus. However, under the action of sodium
alcoholate, for example, these substances form salts having,-trivalent phoaphorus:
RO" -~ g 7.,OR ROH ~ OR
t IPA '~ + t - p/
Na S~ OR NaS ~ ~ OR
Upon all~ylation, these salty form derivatives of ali~lphosphonic acid with a
pentavalerrt phosphorus atom:
k-~ .
I + RAP OR I- R' FOR
NuS~ FOR ~ Na ~ S%P~OR
These properties of dialkylthiophosphites permitted us to assume that in
reactions with carbonyl compounds and ammonia,- they must form esters of the
corresponding aminothiophosphonic acids:
_ \ i N}i
R /C 0 + ~~ + Si FOR ~ Ri C~PS(OR)2 + H2O
This assumption has been fully confirmed by experiment. The reaction of
dialkylthiophosphites with aldehydes or ketones and ammonia takes place more
smoothly than the reaction of dialkylphosphites. We accomplished it by tieat-
ing a mixture of equivalent amounts of aldehyde or ketone, dia]l~ylthiophoaphite,
and a 10~, ammonia soluticn in absolute alcohol (a 50~i excess of ammonia)~in
a sealed glass tube on a boiling water bath for a period of ~ fours. Then the
alcohol and the excess ammonia were iistilled off and the residue distilled
under vacuum. In the reaction with benzaldehyde or acetophenone, the heating
was continued for 6 hours; the reaction product was separated in the form of
its picrate. The initial dialkylthiophosphites xere synthesized through the re-
action of phosphorus hexasulfide with alcohols, according to the method pro-
posed by M.I. ICabacknik and T.A. Mastryukova (7)
Listed in tables 1 snd 2 ~ppended) are the substances synthesized by the re-
sction of dialkylthiophosphites with ammonia and aldehydes or ketones, together
xith their constants and the 3ata of analysis.
phosphonicoacidtas anrexample~f Saponification ofetheeesteruof th~saecidibypheatl
ing it with hydrochloric acid (1:1) in a sealed tube yielded Q-aminoisopropylphos-
phonic acid which was synthesized earlier by T. Ya. Medved' and M. I..Kabachnik.(8)
$o~h preparations proved to be~ideritical..
~3\ /~2 CH. NH2
C\ ( ) + 3H2O ~ j`C/ '~ H2S '~' 2C2HSG;i
CH3~ PS OC2H5 2 CH3~ ~p0(OH)2
In regard to the mechanism of the reaction, it may be assumed that the
dialkylthiophosphite forms the corresponding ammonium salt in the alcohol-asmionia
solution:
x3N: ~ H-y ioR
~ P ~ P, OR
S~ `OH ~~45~ FOR
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This :alt reacts with the carbonyl compound with a transfer of the reaction
center in a manner similar to that which tLkea p1RCe during the a]]Sylation of
sodium dialkylthiophocphite. nn exchange reaction with ammonia completes the
formation of the ester of q-amirothiophosphonic acid:
~ R ~ ~ OH R ~ /~3 R
3 + R''~O~P3(OR)2~R'/O~PS(oH)2~ ~ ~' R'~O~PS(oR) + H2o ~
2
The presence of an ammonites salt he.ving the structure NHkS-P(oR)2 in the
e.lcohol-ammonia solution of dialkylthiophosphite is proved by the fact that sul-
f'ur'is soluble it this solution afte it has been heated to lp0 degrees centi-
grade; ammonium salt o~ ~ialkyldithiophosphoric acid then forms, which has been
i olated and described:
c~tr5o P . sr+rR c?H5~ os__ rift c2H5o~ ~s
c2x5o' k+ s -~ czHSO~P~s~4 E--3P c2H5o~P~SH
We prepared this salt from dialkyldithiophosphate of known composition and
ammonia. In both cases, and in a mixed test, the melting point uas 162-163
degrees centigrade.
(Table follows on next page.)
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Tsble 1. Esters of alpha-Aminoalkylthiophosphonic Acids
Formals
Boiling
Point
(degrees)
Pressure
(~
H d
~
ncU
CH NH
.
-~
~
D
3\C/ 2
a~ o~.
_
.
CH3/ ~PS(UC2H~)2
r_g
3 C
cH3
PS(UC1Hr-i)2
CH3 CH3
C
~/ `~(UC4~)2
CH3 \C/ ~2
C2H5/ `~(~2H5)2
CH3 ~ /~2
c
c2H5 ~ Ps(oc3H7-i)z
cH3 ~ c ` H2
CkH9/ ~ (acpHS )2
CH3 ~ C/~2
C~H9i ~ pS(aC3x7-i)2
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H
Found Calculated
8.8
8.5
8.6
8.8
9.2
8.9
N
Found Calculated
-------------?14.2 _
12.9
____ 13. o
6.2
6.1
5.4
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Yield C
~~+) Found Calculated
39.8
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Table 2. Eaters of alpha-pminoalkylthiophosphonic Acids
Melting
Point Yield P Valves (~,) N Valves (~)
Formula de rees
( g ) ~L Found Calculated Found Cslcu]$ted
r
0685 ? / NH2HOC6H2(NO2)3
0
II ~ ~ PS(OC3H7-i)2
C6H5 ~C /NR2ROC6H2(Np2 )3
174
33
5.9;5.8
6.0
2.8;2.8
2.7
~
cR3 Ps(oc,xG)2
_,
c6R5 ~ / NR2ROC6R2(NO2)3
C
CH3 / ~ pS(OC3R7-i)2
169-171
170
42
31
6.2;6.3
5.6;5.6
6.2
5.8
2.7;2.9
---
2.8
---
B*BLIOGRA?RY
1. M.I. Kabachnik, T. YR. Medved', DAN SSR, Vol 83, No 5, 689 (1952);.
N,. I. Kabchnik, T.Ya. Medved', Iz Ak Nauk SSSR, OkhN, No 5, (195:1)?
2. A. Strecker, Ann., Vcl 75, 27 (1850).
3? N.D. Zelinskiy, Ber., Vol 39, 1722 (1906); Zhur Russ Fiz IO~im Obshch,'
Vol 38, 722 (1906); vol 40, 790, 792 (1908).
4? H. Backer, H. Mulder, Rec., Vol 52, 454 (1933); Vol 53, 1120 (1934)?
5? V.M. Rodionov,Ye.F. Malevinakaya, Ber., Voi 59, 2952 (1926); V.M.
Rodionov, Usp Khim, Vol 3, 373 (1951),
6. M.I. Kabacknik, T.A. Mastryukova, Iz Ak Nauk SSSR, GiihN, No 1, 163
(1953)?
7? M.I. Kabachnik, T.A. Mastryukova, ibid., No 4, 727 (1952).
8. T.Ya. Medved', M.I. Kabachnik, DAN SSSR, Vol 84, No 4, 717 (1952)?
.STAY
_. _~-,
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