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Phosphorus-containing polymers—XII. Synthesis of polymeric analogues of phosphorus-containing insecticides
Phosphorus-containing polymers-- XII
1025
(3) It was found that diallylamides of acids polymerize only in the presence of radical initiators w i t h a low degree of conversion, forming soluble p o l y m e r s of low m o l e c u l a r weight ( ~ 1 5 0 0 ) , containing cyclic s t r u c t u r e of N - s u b s t i t u t e d piperidines. T e r t i a r y diallylamines do not p o l y m e r i z e in practice.
Translated by E. SEMERE REFERENCES
1. G. S. KOLESNIKOV and S. L. DAVYDOVA, Uspekhi khimii 29: 1474, 1960; G. BUTLER and R. ANGELO, Amer. Chem. Soc. 79: 3128, 1957; G. BUTLER, A. CRAWSHAW and L. MILLER, J. Amer. Chem. Soc. 80: 3615, 1958 2. W. GIBBS and R. van DEUSEN, J. Polymer Sei. 54: 51, 1961 3. S. G. MATSOYAN, G. M. POGOSYAN, R. K. SKRIPNIKOVA and A. V. MUSHEGYAN,
Vysokomol. soyed. 5: 183, 1963 4. M. MARTIN and N. JENSEN, J. Organ. Chem. 27: 1201, 1962 5. W. SCHNEIDER, Liebigs Ann. Chem. 590: 165, 1954 6. S. G. MATSOYAN, G. M. POGOSYAN, A. O. DZHAGALYAN and A. V. MUSHEGYAN,
Vysokomo]. soyed. 5: 854, 1963 7. G. BUTLER and R. BUNCH, J. Amer. Chem. Soe. 71: 3121, 1949 8. Sintezy organieheskikh preparatov. Sb. 1. (Syntheses of Organic Compounds), Symp. 1, Izd. in. lit. 180, 1949
PHOSPHORUS-CONTAINING POLYMERS--XH. SYNTHESIS OF POLYMERIC ANALOGUES OF PHOSPHORUS-CONTAINING INSECTICIDES* K. A. PETROV, E. YE. NIFANT'YEV, R. G. GOL'TSOVA a n d S. M. KORNEYEV
(Received 1 July 1963) I T IS well k n o w n t h a t certain s y n t h e t i c p o l y m e r substances h a v e a physiological activity. Thus, h y d r o x y e t h y l cellulose is used as an antiseptic [1], an ester of p o l y v i n y l alcohol a n d di-(4-oxycoumarinile-3-) acetic acid (vinyl P K ) is rec o m m e n d e d for the medical t r e a t m e n t a n d p r e v e n t i o n of t h r o m b o s i s a n d o t h e r complaints [2]. T h e r e are indications t h a t alkyl esters of polyphosphonitrile h a v e an insecticidal action [3], which is m u c h less effective t h a n t h a t of widely k n o w n low-molecular weight insecticides. D a t a are p r e s e n t e d in this p a p e r on the synthesis of p h o s p h o r u s - c o n t a i n i n g polyesters with c o n s t i t u e n t s of m o d e r n insecticides. I~esidues of n - n i t r o p h e n o l , 2,4,5-trichlorophenol, m e r c a p t a n s , tri-fl-chloroethanol were used as constituents. These residues were i n c o r p o r a t e d in the p o l y p h o s p h a t e s as side chains (I, H ) : * Vysokomol. soyed. 6: No. 5, 929-933, 1964.
K. A. PETI~OVet
1026 O(S)
It [--P--O(CH2)eO--]. I
I
al.
o(s)
II
[--P--OCH3CH~OCI-I2CI-I20--]n, I II
X
X
where
x:--o/~_>No.;
C1 ; -o,f-\--Cl; \~
--SC*H9;
C1 OH I --SCH~CH~SC2Hs; CHCC13. Substances of types I and II according to X are polymer analogues of wellknown insecticides and parasitocides (paraoxane, oxotrolene, trolene, thiophos, isisystox, chlorophos). Apparently, all these are inhibitors of esterases and will have toxic properties particularly on insects. However, unlike the low-molecular weight analogues, they will persist for a longer period in the object protected as on its surface which opens up new possibilities in the fight against a~oTicultural pests. To obtain substances of types I and II, polyphosphites (molecular weight 50-70,000) and their oligomers made by re-esterification of diethylphosphite with hexamethyleneglyeol or diethyleneglycol, were used as phosphorus components. In the case of synthesis of polymer analogues of paraoxane and oxotrolene (A), polyphosphite was chlorinated, the polychlorophosphate formed was then treated with n-nitrophenol, or 2,4,5-trichlorophenol in the presence of a tertiary amine. In the synthesis of polymer analogues of thiophos and trolene (B,) polyphosphite was converted into polythiophosphate [4]. which, when treated with phosgene in 4ioxane at 30-40°C was converted into polychlorothiot~hosphate which reacted with n-nitrophenol, or 2,4,5-trichlorophenol. It should be noted that, during chlorination of polythiophosphates, the reaction takes place in two directions: with formation of polychlorothiophosphates and polychlorophosphates which was confirmed by elementary analysis. Hovewer, we have not studied this problem in closer detail. When preparing polymer analogues of isosystox (C) and chlorophos (D), polyphosphites were treated with sulphenchlorides or thiocyano compounds in one case, and chloral, in the other, i.e. the same reactions were used as for the synthesis of low-molecular weight insecticides. It should also be noted that the reaction of phosphites with sulphenchlorides, particularly with the simplest forms, takes place more readily than with thiocyano compounds and dees not take place at all with disulphides even at 160°C. The formation of substances of types I and II can be represented by the following schemes
Phosphorus-containing polymers-- XlI O
O
I!
Ih
1027
[--PO (CH2)+O--]. [--P--O (HC~)~--O]+ I
I
(B)
SR
CH(OH)CC1 a (G) / -
z-
== I
t°
[
OH 48
0
tl " > [--P--O(CH2)+O--],+ I
J
[--P--O(CH2)60--]~
S
CCIaCHOT
~ J O
C1
O
I
t
C1
I
C1
i[ [--PO(CH~)+O--],, I OAr
S
tl coc~+, il tP [--PO(CH,)+O--I,, " [--PO(CHm)6OPO(CH,)+O--],, OH
I~0Ar
Ho~r
(A)
O
S
!1
tl
" • [--PO(CH2)aOPO(CH2)60--]+
I
OAr
!
OAr
(B)
01igomers of types I and I I were obtained as indicated above. The oligomer analogues of high molecular weight pol3~hosphites were synthesized by interaction of diethylphosphite with glycols [4] which were used in excess of the amount calculated for obtaining polymers. At the same time it was noted that the viscosities of the oligomers markedly decrease with increased glycol excess (see Table). The synthesized polyphosphates, polythiophosphates and polyphosphonates are lightly eoloured elastic or glass-like substances, mostly insoluble in water and organic solvents; alkyl esters of polyalkylenethiophosphoric acids and polyalkylene-fl,fl,fl-trichloroethylolphosphonates are soluble in alcohol tetrahydrofuran and certain other organic solvents. The oligomer products are more freeflowing and soluble than their high molecular weight analogues. This paper presents the first results of investigations of the anticholinesterase activity of one of the compounds obtained: polyhexamethylene-fl,fi,fl-trichloroethylolphosphonate [5]. With five minutes exposure of pseudo-cholinesterases of horse serum to inhibitor, pI*5o appeared to be 6.66 which in close to values pIao of modern insecticides. EXPERIMENTAL Polyhexamethylene-n-~itrophenylphosphate. D r y c h l o r i n e is p a s s e d t h r o u g h t h e m i x t u r e of 2.6 g p o l y h e x a m e t h y l e n e p h o s p h i t e a n d 5 nfl CCla for a n h o u r a t 5-7 °C (until t h e a p p e a r a n c e of a p e r m a n e n t g r e e n colour) t h e n t h e p r o d u c t is k e p t in vacuo (30 r a m ) for 1 h o u r w i t h o u t e l i m i n a t i o n of t h e s o l v e n t . A s o l u t i o n of 2.2 g n - n i t r o p h e n o l in 5 m l e t h e r a n d 1.7 g t r i e t h y l a m i n e are s i m u l t a n e o u s l y a d d e d d r o p w i s e t o t h e r e a c t i o n m a s s ; t h e m i x t u r e is c a r e f u l l y m i x e d a n d h e a t e d for 1 h o u r at. 80°C, t r e a t e d w i t h 40 m l c h l o r o f o r m a n d w a s h e d w i t h w a t e r u n t i l t h e c h l o r i d e ion d i s a p p e a r s . A f t e r e l i m i n a t i o n of t h e s o l v e n t a n d r e t e n t i o n of t h e p r o d u c t for 1 h o u r a t 80°C (5 m m ) , 3'1 g (65"0Oo) n - n i t r o p h e n y l e s t e r of p o l y h e x a m e t h y l e n e p h o s p h o r i c acid, a n elastic, s l i g h t l y c o l o u r e d p r o d u c t , was o b t a i n e d .
F o u n d , % : P 10.14; 10.25; N 3.99; 4.05. C~2Ht606PN C a l c u l a t e d , °~o: P 10.01; N 4.65. * pIso is t h e n e g a t i v e l o g a r i t h m o f t h e m o l a r c o n c e n t r a t i o n of t-he i n h i b i t o r c a u s i n g 50O/o s u p p r e s s i o n o f c h o l i n c s t e r a s e .
K . A . PETROV et al.
1028
POLYALKYLENE-~,~,~-TRICHLOROETHYLOLPHOSPHONATES Content, % Pol.vmer (oligomer) unit
P
C1
[ caleuf°und I lated
found
calculated
t/sp o f 1 % s o l u t i o n in dimethylform amide
Is dissolved in
0.08
Ethanol, benzene, t e t r a h y d r o furan, dimethylformamide
0.072
Ethanol, benzene, t e t r a h y d r o . furan, dimethylf o r m a m i d e , dioxane
0.041
Ethanol, benzene, d i o x a n e , chloroform, tetrahydrofllran
i
0
// - - P --O(CH2)eO --*
9.75! 9.87!
9.95
33.48 33.35
33.2
CH(OH)CC].~ O
//
--P -- 0(CHs)eO
-
-
i CH(0H)CCI
3*
0
// --P
-- O(CHs)sO
--
i
CH(OH)CCI 3 O
//
_ p _ OCI-ItCHsOCHsCHsO
-
-
i
10.84 11.07
10.35
35.71 35.85
35.6
0.071
E t h a n o l , dioxane, dimethyl formamide
CH(0H)CCIs*
0.063
E t h a n o l , dioxane, dimethylformamide, tetrahydro furan
0.028
W a t e r (warm), e t h a n o l , dio x a n e , chloroform, t e t r a hydrofuran
O
// _p
]
_
OCHsCH~OCH2CHsO --?
CH(OH)CC13 0
// -
-
p -- 0CH~CHs0CHsCHs0
- ~;
r CH(0H)CCI3
* The polymer was obtained at the molar ratio 1 : 1 o f the initial reagents. ~f The oligomer was obtained with a glycol excess of 10 moles -%. ;~ The oligomer was obtained with a glycol excess of 16.5 moles -%.
Poly-3-oxaamylene-n-nitrophenylphosphate is o b t a i n e d i n a m a n n e r described above. F o u n d , ~): P 9.06; 9.21; N 4-81; 4.57. CIoH12OTPN. C a l c u l a t e d , % : P 10.05; 1~ 4.85.
similar to that
Phosphorus-containing polymers-- X I I
1029
Polyhexamethylene-2,4,5-trichlorophenylphosphate. I n a method similar to t h a t described, from 3.3 g polyhexamethylene phosphite, 3-69 g 2,4,5-tricblorophenol in 7 ml CCI, and 2.0 g tricthylamine, 5.3 g (79.2°/O) 2,4,5-trichlorophenyl ester of polyhexamethylenephosphoric acid was obtained. Found, °/o: P 8.16; 8-45; C1 29.52; 29.61. C12H1404PC1 a. Calculated, °'o: P 8.82; C1 30.2. Poly-3-oxaamylene-S-ethylthiophosphate. A mixture of 3-47 g poly-3-oxaamylenephosphate and 2-42 g ethylthiocyano compound is heated in an inert atmosphere at l l 0 ° C for 6 hours so that hydrocyanic acid is distilled off and collected in a receiving vessel cooled to --15°C. The reaction mass is then heated for 4 hours at 110-125°C, followed by a gradual rise of temperature to 135°C in hours. The reaction mixture is kept for 40 minutes at 100110°C (5 mm); 3.8 g (77.0°/o) poly-3-oxaamylene-S-ethylthiophosphate is obtained, a dark-coIoured dense substance soluble in ethyl alcohol, dioxane and tetrahydrofuran. Found, ~o: P 18.04; i8.12; S 8.4; 3.2. Calculated, ~o: P 18.0; S 3.3 (calculated on the basic of 21.8°o conversion of phosphite groups into thiolphosphate groups).
Poly-3-oxaaraylene-S-butylthiophosphate. 0.94 g sulphuryl chloride is added dropwise ~o 1.24 g dibutyldisulphide at --30 to --20°C. The mixture is gradually heated to 20°C and kept at this temperature (200 ram) for 0-5 rain, then a solution of 1-95 g poly-3oxaamylenephosphite in 15 ml chloroform is added dropwise at --10°C and is allowed to stand overnight at 20°C. After the elimination of the solvent and keeping the substance for 1 hour at 100°C (5 min), 3.35 g ( ~ 100%) poly-3-oxaamylene-S-butylphosphate is obtained, a dark-coloured viscous mass which is soluble in ethanol, dioxane and tetrahydrofuran. Found, °/o: P 13.29; 13.26; S 13.98; 13.39; CsH1704PS. Calculated, o/o: p 12.9; S 13.3.
Poly-3-oxaamylene-S-(B-mercaptoethyl)ethyl thiophosphate. By a method s~nilar to t h a t described, 7.0 g (68O/o) poly-3-oxaamylene-S-(fl-mercaptoethyl), a dense dark product soluble in alcohol, dioxanc, tetrahydrofuran, is obtained from 1-45 g fl, B-diethylthioethyl disulphide and 5.59 g poly-3-oxaamylene phosphite. Found, ~o: P 14.75; 14.44; S 12.64; 12.32. Calculated, °/o: P 14-92; S 12.4 (calculated for groups into thiolphosphate groups).
53%
conversion of phosphite
Polyhexamethylene chlorothiophosphate. Phosgene is passed through a solution of 1 g polyhexamethylene-thiophosphate [4] in 2.5 ml dioxane at 30-40°C for 15-20 min and d ry nitrogen is passed through the apparatus for 30 minutes and the product kept for 2 hours at 50°C (12 ram) and 0.5 hour at 50-60°C (3 ram). 0-98 g (89.0O/o) polyhexamethylene chlorothiophosphate is obtained. Found, o,~: p 13.89; 13.69; C1 16.48; 16-34. S 8.49; 7.94. C6HlaO2PSC1. Calculated, ~o: P 14.4; C1 16.5; S 14.9.
Polyhexamethylene-n-nitrophenyl thiophosphate. To 5.2 g polyhexamethylene chlorothiophosphate, previously swollen in 25 ml chloroform, a solution of 4.0 g n-nitrophenol in 10 ml ether and 3.4 g triethylamine are added simultaneously at room temperature. Then, the mixtm'e is heated for 1 hour at 60-70°C and the solvent eliminated at 100°C (20 ram). The residue is washed with water until the chloride ion is eliminated, then with acetone and kept for 0.5 hour at 100°C (20 mm) and 0.5 hour at 100°C (1 ram). 7-4 g (94.00/o) polyhexamethylene-n-nitrophenyl thiophosphate is obbained.
1030
S.N. USHAKOV a n d P. TUDORIU Found, %; P 7-66; 7.81; N 5.76; 6,03; S 2.99; 2.77. Cl~H16OsPNS. Calculated, %: P 9-8; 1~ 4.4; S 10.1.
Polyallcylene-fl, B,B-trichloroethylolphosphonate. A n equimolecular mixture of polyalkylenephosphite and chloral is heated for 40 minutes at 80°C, 4 hours at 100°C, 1.5 hours at 100°C (10 r a m ) a n d 1 hour at 100°C (3 mm). ~ 100% polyalkylene-fl,fl,/?-trichloroethylolphosphonate is obtained, a light-coloured, vitreous mass. The properties of the polyphosphonates obtained are tabulated. CONCLUSIONS
(1) Methods of synthesis were developed for polyalkylenephosphates and phosphonates, analogues of insecticides. (2) It is shown that polyhexamethylene trichloroethylolphosphonates have a siginficant anticholinesterase activity. Translated by E. SEMERE REFERENCES 1. U. E. ALLER and J. A. NAEGELL, J. Econ. Entomol. 54: 511, 1961; RZhKhim, 2L364, 1962 2. S. N. USHAKOV, Tr. Leningr. tekhnol, in-ta im Lensoveta 45: 132, 1958 3. G. F. LUDVIK and G. S. DECKER, J, Econ. Entomol. 40: 97, 1947 4. K. A. PETROV, E. Ye. NIFANT'YEV, R. G. GOL'TSOVA and S. M. KORNEYEV, Sb. Geterotsepnyye vysokomolekulyarnyye soyedineniya. (Hetero-chain High-molecular Weight Compounds). Izd. ":Nauka", 1964 5. A. A. POKROVSKII, Voyen.-med. zh. No. 9, 61, 1953
SYNTHESIS OF THE ESTER OF POLYVINYL ALCOHOL AND DI-n-BUTYLBORIC ACID* S. N. U S H A K O V a n d P. T U D O R I U The Leningrad Technological Institute
(Received 1 July 1963)
THE authors demonstrated and studied [1] for the first time the possibility of obtaining esters of polyvinyl alcohol and di-substituted organic boric acids by the action of the acid chlorides of di-substituted organic boric acids on polyvinyl alcohol (PVA) in an electron-donor solvent medium and, in particular, described the method of synthesizing the ester of polyvinyl alcohol and diphenylboric acid and its properties. * Vysokomol. soyed. 6: :No. 5, 934-939, 1964.
1025
(3) It was found that diallylamides of acids polymerize only in the presence of radical initiators w i t h a low degree of conversion, forming soluble p o l y m e r s of low m o l e c u l a r weight ( ~ 1 5 0 0 ) , containing cyclic s t r u c t u r e of N - s u b s t i t u t e d piperidines. T e r t i a r y diallylamines do not p o l y m e r i z e in practice.
Translated by E. SEMERE REFERENCES
1. G. S. KOLESNIKOV and S. L. DAVYDOVA, Uspekhi khimii 29: 1474, 1960; G. BUTLER and R. ANGELO, Amer. Chem. Soc. 79: 3128, 1957; G. BUTLER, A. CRAWSHAW and L. MILLER, J. Amer. Chem. Soc. 80: 3615, 1958 2. W. GIBBS and R. van DEUSEN, J. Polymer Sei. 54: 51, 1961 3. S. G. MATSOYAN, G. M. POGOSYAN, R. K. SKRIPNIKOVA and A. V. MUSHEGYAN,
Vysokomol. soyed. 5: 183, 1963 4. M. MARTIN and N. JENSEN, J. Organ. Chem. 27: 1201, 1962 5. W. SCHNEIDER, Liebigs Ann. Chem. 590: 165, 1954 6. S. G. MATSOYAN, G. M. POGOSYAN, A. O. DZHAGALYAN and A. V. MUSHEGYAN,
Vysokomo]. soyed. 5: 854, 1963 7. G. BUTLER and R. BUNCH, J. Amer. Chem. Soe. 71: 3121, 1949 8. Sintezy organieheskikh preparatov. Sb. 1. (Syntheses of Organic Compounds), Symp. 1, Izd. in. lit. 180, 1949
PHOSPHORUS-CONTAINING POLYMERS--XH. SYNTHESIS OF POLYMERIC ANALOGUES OF PHOSPHORUS-CONTAINING INSECTICIDES* K. A. PETROV, E. YE. NIFANT'YEV, R. G. GOL'TSOVA a n d S. M. KORNEYEV
(Received 1 July 1963) I T IS well k n o w n t h a t certain s y n t h e t i c p o l y m e r substances h a v e a physiological activity. Thus, h y d r o x y e t h y l cellulose is used as an antiseptic [1], an ester of p o l y v i n y l alcohol a n d di-(4-oxycoumarinile-3-) acetic acid (vinyl P K ) is rec o m m e n d e d for the medical t r e a t m e n t a n d p r e v e n t i o n of t h r o m b o s i s a n d o t h e r complaints [2]. T h e r e are indications t h a t alkyl esters of polyphosphonitrile h a v e an insecticidal action [3], which is m u c h less effective t h a n t h a t of widely k n o w n low-molecular weight insecticides. D a t a are p r e s e n t e d in this p a p e r on the synthesis of p h o s p h o r u s - c o n t a i n i n g polyesters with c o n s t i t u e n t s of m o d e r n insecticides. I~esidues of n - n i t r o p h e n o l , 2,4,5-trichlorophenol, m e r c a p t a n s , tri-fl-chloroethanol were used as constituents. These residues were i n c o r p o r a t e d in the p o l y p h o s p h a t e s as side chains (I, H ) : * Vysokomol. soyed. 6: No. 5, 929-933, 1964.
K. A. PETI~OVet
1026 O(S)
It [--P--O(CH2)eO--]. I
I
al.
o(s)
II
[--P--OCH3CH~OCI-I2CI-I20--]n, I II
X
X
where
x:--o/~_>No.;
C1 ; -o,f-\--Cl; \~
--SC*H9;
C1 OH I --SCH~CH~SC2Hs; CHCC13. Substances of types I and II according to X are polymer analogues of wellknown insecticides and parasitocides (paraoxane, oxotrolene, trolene, thiophos, isisystox, chlorophos). Apparently, all these are inhibitors of esterases and will have toxic properties particularly on insects. However, unlike the low-molecular weight analogues, they will persist for a longer period in the object protected as on its surface which opens up new possibilities in the fight against a~oTicultural pests. To obtain substances of types I and II, polyphosphites (molecular weight 50-70,000) and their oligomers made by re-esterification of diethylphosphite with hexamethyleneglyeol or diethyleneglycol, were used as phosphorus components. In the case of synthesis of polymer analogues of paraoxane and oxotrolene (A), polyphosphite was chlorinated, the polychlorophosphate formed was then treated with n-nitrophenol, or 2,4,5-trichlorophenol in the presence of a tertiary amine. In the synthesis of polymer analogues of thiophos and trolene (B,) polyphosphite was converted into polythiophosphate [4]. which, when treated with phosgene in 4ioxane at 30-40°C was converted into polychlorothiot~hosphate which reacted with n-nitrophenol, or 2,4,5-trichlorophenol. It should be noted that, during chlorination of polythiophosphates, the reaction takes place in two directions: with formation of polychlorothiophosphates and polychlorophosphates which was confirmed by elementary analysis. Hovewer, we have not studied this problem in closer detail. When preparing polymer analogues of isosystox (C) and chlorophos (D), polyphosphites were treated with sulphenchlorides or thiocyano compounds in one case, and chloral, in the other, i.e. the same reactions were used as for the synthesis of low-molecular weight insecticides. It should also be noted that the reaction of phosphites with sulphenchlorides, particularly with the simplest forms, takes place more readily than with thiocyano compounds and dees not take place at all with disulphides even at 160°C. The formation of substances of types I and II can be represented by the following schemes
Phosphorus-containing polymers-- XlI O
O
I!
Ih
1027
[--PO (CH2)+O--]. [--P--O (HC~)~--O]+ I
I
(B)
SR
CH(OH)CC1 a (G) / -
z-
== I
t°
[
OH 48
0
tl " > [--P--O(CH2)+O--],+ I
J
[--P--O(CH2)60--]~
S
CCIaCHOT
~ J O
C1
O
I
t
C1
I
C1
i[ [--PO(CH~)+O--],, I OAr
S
tl coc~+, il tP [--PO(CH,)+O--I,, " [--PO(CHm)6OPO(CH,)+O--],, OH
I~0Ar
Ho~r
(A)
O
S
!1
tl
" • [--PO(CH2)aOPO(CH2)60--]+
I
OAr
!
OAr
(B)
01igomers of types I and I I were obtained as indicated above. The oligomer analogues of high molecular weight pol3~hosphites were synthesized by interaction of diethylphosphite with glycols [4] which were used in excess of the amount calculated for obtaining polymers. At the same time it was noted that the viscosities of the oligomers markedly decrease with increased glycol excess (see Table). The synthesized polyphosphates, polythiophosphates and polyphosphonates are lightly eoloured elastic or glass-like substances, mostly insoluble in water and organic solvents; alkyl esters of polyalkylenethiophosphoric acids and polyalkylene-fl,fl,fl-trichloroethylolphosphonates are soluble in alcohol tetrahydrofuran and certain other organic solvents. The oligomer products are more freeflowing and soluble than their high molecular weight analogues. This paper presents the first results of investigations of the anticholinesterase activity of one of the compounds obtained: polyhexamethylene-fl,fi,fl-trichloroethylolphosphonate [5]. With five minutes exposure of pseudo-cholinesterases of horse serum to inhibitor, pI*5o appeared to be 6.66 which in close to values pIao of modern insecticides. EXPERIMENTAL Polyhexamethylene-n-~itrophenylphosphate. D r y c h l o r i n e is p a s s e d t h r o u g h t h e m i x t u r e of 2.6 g p o l y h e x a m e t h y l e n e p h o s p h i t e a n d 5 nfl CCla for a n h o u r a t 5-7 °C (until t h e a p p e a r a n c e of a p e r m a n e n t g r e e n colour) t h e n t h e p r o d u c t is k e p t in vacuo (30 r a m ) for 1 h o u r w i t h o u t e l i m i n a t i o n of t h e s o l v e n t . A s o l u t i o n of 2.2 g n - n i t r o p h e n o l in 5 m l e t h e r a n d 1.7 g t r i e t h y l a m i n e are s i m u l t a n e o u s l y a d d e d d r o p w i s e t o t h e r e a c t i o n m a s s ; t h e m i x t u r e is c a r e f u l l y m i x e d a n d h e a t e d for 1 h o u r at. 80°C, t r e a t e d w i t h 40 m l c h l o r o f o r m a n d w a s h e d w i t h w a t e r u n t i l t h e c h l o r i d e ion d i s a p p e a r s . A f t e r e l i m i n a t i o n of t h e s o l v e n t a n d r e t e n t i o n of t h e p r o d u c t for 1 h o u r a t 80°C (5 m m ) , 3'1 g (65"0Oo) n - n i t r o p h e n y l e s t e r of p o l y h e x a m e t h y l e n e p h o s p h o r i c acid, a n elastic, s l i g h t l y c o l o u r e d p r o d u c t , was o b t a i n e d .
F o u n d , % : P 10.14; 10.25; N 3.99; 4.05. C~2Ht606PN C a l c u l a t e d , °~o: P 10.01; N 4.65. * pIso is t h e n e g a t i v e l o g a r i t h m o f t h e m o l a r c o n c e n t r a t i o n of t-he i n h i b i t o r c a u s i n g 50O/o s u p p r e s s i o n o f c h o l i n c s t e r a s e .
K . A . PETROV et al.
1028
POLYALKYLENE-~,~,~-TRICHLOROETHYLOLPHOSPHONATES Content, % Pol.vmer (oligomer) unit
P
C1
[ caleuf°und I lated
found
calculated
t/sp o f 1 % s o l u t i o n in dimethylform amide
Is dissolved in
0.08
Ethanol, benzene, t e t r a h y d r o furan, dimethylformamide
0.072
Ethanol, benzene, t e t r a h y d r o . furan, dimethylf o r m a m i d e , dioxane
0.041
Ethanol, benzene, d i o x a n e , chloroform, tetrahydrofllran
i
0
// - - P --O(CH2)eO --*
9.75! 9.87!
9.95
33.48 33.35
33.2
CH(OH)CC].~ O
//
--P -- 0(CHs)eO
-
-
i CH(0H)CCI
3*
0
// --P
-- O(CHs)sO
--
i
CH(OH)CCI 3 O
//
_ p _ OCI-ItCHsOCHsCHsO
-
-
i
10.84 11.07
10.35
35.71 35.85
35.6
0.071
E t h a n o l , dioxane, dimethyl formamide
CH(0H)CCIs*
0.063
E t h a n o l , dioxane, dimethylformamide, tetrahydro furan
0.028
W a t e r (warm), e t h a n o l , dio x a n e , chloroform, t e t r a hydrofuran
O
// _p
]
_
OCHsCH~OCH2CHsO --?
CH(OH)CC13 0
// -
-
p -- 0CH~CHs0CHsCHs0
- ~;
r CH(0H)CCI3
* The polymer was obtained at the molar ratio 1 : 1 o f the initial reagents. ~f The oligomer was obtained with a glycol excess of 10 moles -%. ;~ The oligomer was obtained with a glycol excess of 16.5 moles -%.
Poly-3-oxaamylene-n-nitrophenylphosphate is o b t a i n e d i n a m a n n e r described above. F o u n d , ~): P 9.06; 9.21; N 4-81; 4.57. CIoH12OTPN. C a l c u l a t e d , % : P 10.05; 1~ 4.85.
similar to that
Phosphorus-containing polymers-- X I I
1029
Polyhexamethylene-2,4,5-trichlorophenylphosphate. I n a method similar to t h a t described, from 3.3 g polyhexamethylene phosphite, 3-69 g 2,4,5-tricblorophenol in 7 ml CCI, and 2.0 g tricthylamine, 5.3 g (79.2°/O) 2,4,5-trichlorophenyl ester of polyhexamethylenephosphoric acid was obtained. Found, °/o: P 8.16; 8-45; C1 29.52; 29.61. C12H1404PC1 a. Calculated, °'o: P 8.82; C1 30.2. Poly-3-oxaamylene-S-ethylthiophosphate. A mixture of 3-47 g poly-3-oxaamylenephosphate and 2-42 g ethylthiocyano compound is heated in an inert atmosphere at l l 0 ° C for 6 hours so that hydrocyanic acid is distilled off and collected in a receiving vessel cooled to --15°C. The reaction mass is then heated for 4 hours at 110-125°C, followed by a gradual rise of temperature to 135°C in hours. The reaction mixture is kept for 40 minutes at 100110°C (5 mm); 3.8 g (77.0°/o) poly-3-oxaamylene-S-ethylthiophosphate is obtained, a dark-coIoured dense substance soluble in ethyl alcohol, dioxane and tetrahydrofuran. Found, ~o: P 18.04; i8.12; S 8.4; 3.2. Calculated, ~o: P 18.0; S 3.3 (calculated on the basic of 21.8°o conversion of phosphite groups into thiolphosphate groups).
Poly-3-oxaaraylene-S-butylthiophosphate. 0.94 g sulphuryl chloride is added dropwise ~o 1.24 g dibutyldisulphide at --30 to --20°C. The mixture is gradually heated to 20°C and kept at this temperature (200 ram) for 0-5 rain, then a solution of 1-95 g poly-3oxaamylenephosphite in 15 ml chloroform is added dropwise at --10°C and is allowed to stand overnight at 20°C. After the elimination of the solvent and keeping the substance for 1 hour at 100°C (5 min), 3.35 g ( ~ 100%) poly-3-oxaamylene-S-butylphosphate is obtained, a dark-coloured viscous mass which is soluble in ethanol, dioxane and tetrahydrofuran. Found, °/o: P 13.29; 13.26; S 13.98; 13.39; CsH1704PS. Calculated, o/o: p 12.9; S 13.3.
Poly-3-oxaamylene-S-(B-mercaptoethyl)ethyl thiophosphate. By a method s~nilar to t h a t described, 7.0 g (68O/o) poly-3-oxaamylene-S-(fl-mercaptoethyl), a dense dark product soluble in alcohol, dioxanc, tetrahydrofuran, is obtained from 1-45 g fl, B-diethylthioethyl disulphide and 5.59 g poly-3-oxaamylene phosphite. Found, ~o: P 14.75; 14.44; S 12.64; 12.32. Calculated, °/o: P 14-92; S 12.4 (calculated for groups into thiolphosphate groups).
53%
conversion of phosphite
Polyhexamethylene chlorothiophosphate. Phosgene is passed through a solution of 1 g polyhexamethylene-thiophosphate [4] in 2.5 ml dioxane at 30-40°C for 15-20 min and d ry nitrogen is passed through the apparatus for 30 minutes and the product kept for 2 hours at 50°C (12 ram) and 0.5 hour at 50-60°C (3 ram). 0-98 g (89.0O/o) polyhexamethylene chlorothiophosphate is obtained. Found, o,~: p 13.89; 13.69; C1 16.48; 16-34. S 8.49; 7.94. C6HlaO2PSC1. Calculated, ~o: P 14.4; C1 16.5; S 14.9.
Polyhexamethylene-n-nitrophenyl thiophosphate. To 5.2 g polyhexamethylene chlorothiophosphate, previously swollen in 25 ml chloroform, a solution of 4.0 g n-nitrophenol in 10 ml ether and 3.4 g triethylamine are added simultaneously at room temperature. Then, the mixtm'e is heated for 1 hour at 60-70°C and the solvent eliminated at 100°C (20 ram). The residue is washed with water until the chloride ion is eliminated, then with acetone and kept for 0.5 hour at 100°C (20 mm) and 0.5 hour at 100°C (1 ram). 7-4 g (94.00/o) polyhexamethylene-n-nitrophenyl thiophosphate is obbained.
1030
S.N. USHAKOV a n d P. TUDORIU Found, %; P 7-66; 7.81; N 5.76; 6,03; S 2.99; 2.77. Cl~H16OsPNS. Calculated, %: P 9-8; 1~ 4.4; S 10.1.
Polyallcylene-fl, B,B-trichloroethylolphosphonate. A n equimolecular mixture of polyalkylenephosphite and chloral is heated for 40 minutes at 80°C, 4 hours at 100°C, 1.5 hours at 100°C (10 r a m ) a n d 1 hour at 100°C (3 mm). ~ 100% polyalkylene-fl,fl,/?-trichloroethylolphosphonate is obtained, a light-coloured, vitreous mass. The properties of the polyphosphonates obtained are tabulated. CONCLUSIONS
(1) Methods of synthesis were developed for polyalkylenephosphates and phosphonates, analogues of insecticides. (2) It is shown that polyhexamethylene trichloroethylolphosphonates have a siginficant anticholinesterase activity. Translated by E. SEMERE REFERENCES 1. U. E. ALLER and J. A. NAEGELL, J. Econ. Entomol. 54: 511, 1961; RZhKhim, 2L364, 1962 2. S. N. USHAKOV, Tr. Leningr. tekhnol, in-ta im Lensoveta 45: 132, 1958 3. G. F. LUDVIK and G. S. DECKER, J, Econ. Entomol. 40: 97, 1947 4. K. A. PETROV, E. Ye. NIFANT'YEV, R. G. GOL'TSOVA and S. M. KORNEYEV, Sb. Geterotsepnyye vysokomolekulyarnyye soyedineniya. (Hetero-chain High-molecular Weight Compounds). Izd. ":Nauka", 1964 5. A. A. POKROVSKII, Voyen.-med. zh. No. 9, 61, 1953
SYNTHESIS OF THE ESTER OF POLYVINYL ALCOHOL AND DI-n-BUTYLBORIC ACID* S. N. U S H A K O V a n d P. T U D O R I U The Leningrad Technological Institute
(Received 1 July 1963)
THE authors demonstrated and studied [1] for the first time the possibility of obtaining esters of polyvinyl alcohol and di-substituted organic boric acids by the action of the acid chlorides of di-substituted organic boric acids on polyvinyl alcohol (PVA) in an electron-donor solvent medium and, in particular, described the method of synthesizing the ester of polyvinyl alcohol and diphenylboric acid and its properties. * Vysokomol. soyed. 6: :No. 5, 934-939, 1964.