D I P O L E M O M E N T S OF C Y C L I C T H I O - A N D

D I T H I O P H O S P H O N A T E S

E . A . I s h m a e v a , R . A . C h e r k a s o v , V . V . O v c h i n n i k o v , a n d A . N . P u d o v i k

UDC 139.143.43:661.718.1

Informat ion is lacking in the l i t e r a tu r e on the dipole moment of the P - S single bond. A d e t e r m i n a - tion of the moment of this bond is of independent in te res t , and it also makes it poss ible to study compounds contaifling the p h o s p h o r u s - s u l f u r bond by the method of dipole moments , which, in turn, helps in e s t ab - l ishing the spat ia l s t ruc tu re of these compounds. Consequently, we de te rmined the dipole moments of the cycl ic thio- and dithiophosphonates:

X II (Y--CHs

R--P \Z__ ]CHz

(I)--(vn) (I) R=CH3, x = s , Y--Z=O; (11) R=CH3, x = y = z = s ;

(iiI) R=C~Hs, X~Y=Z=S; (IV) R=caH6s, X=S, Y=Z=O; (V) R=CH3, X~Y=S, Z=O; :(VI) R=CsHa, X=Y=S, Z----O; (VII)R=CHa, X=Z=O

Y=S

and also of:

Z

(VlII)--(X)

(VIII) R=CH~, X=Y--O, Z=tt; (IX) R=CH3; X=Y=O, Z=CH3; (X) R=CHs, X=u Z=H

The exper imen ta l dipole moments of these compounds, together with the coeff icients of the ca lcula- tion equations, are given in Table 1.

TABLE 1. Coefficients of Calculation Equations and Exper imenta l Dipole Moments of Cyclic Th io- and Dithiophosphonates

CoII1 - pound No Solvent

I C~Hs II CCI~

I I I CC14 IV CCI~ V CC14

VI CCla VII CCIa

VIII CC14 C6H6

IX C6H6 X CsH~

f ~ Y

48,62 9,086J 26,496 0,990J 24,776 0,703[ 16,036 0,324[ 9,417 0,330] 9,228 0,382]

12,838 0,322] t9,658 0,2t5] 12,308 0,080! 22,489 0,078 13,606 0,335

Po, c~ ~ ~exp , D

481,744 4,83 457~911 4,71 467,984 4,76 352,150 4,t3 147,731 2,67 156,920 2,76 182,461 2,97 3t2,538 3,89 350,207 4,t2 699,757 5,82 459,316 4,71

As can be seen f r o m Table 1, a noticeable dif- fe rence is obse rved in the dipole moments of c o m - pounds (I)-(IV) and (V)-(VII). It is poss ible to a s - sume that this dec r ea se of the dipole moments in the cycl ic thiophosphonates is due to changes in the con- fo rmat ion of the ring. The inser t ion of a methyl group into the s i x - m e m b e r e d he te rocyc le (IX), and also changing the solvent when de te rmin ing the dipole mo- ment of compound (VIII), both cause a noticeable change in the dipole moments of these c o m - pounds which tes t i f ies to the conformat ional labil i ty of the r ing. Work in this d i rec t ion is being con- tinued.

V. I . Ul 'yanov-Lenin Kazan State Universi ty . T rans la t ed f rom Izves t iya Akademii Nauk SSSR,

Ser iya Khimicheskaya , No. 6, pp. 1317-1318, June, 1971. Original a r t ic le submit ted June 21, 1970.

�9 1971 Consultants Bureau, a division of Plenum Publishing Corporation, 227 West 17th Street, New York, N. Y. 10011. All rights reserved. This article cannot be reproduced for any purpose whatsoever without permission of the publisher. A copy of this article is available from the publisher for $15.00.

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E X P E R I M E N T A L M E T H O D

Compounds (D, (III), (VII), and (IX) were synthesized by the procedure described in [1]. Compounds (IV), (VI), and (VIII) were obtained as described in [2]. Compounds (ID and (V) were obtained by the r e - action of the ammonium salt of methylethoxydithiophosphonic acid with ethylene chlorohydrin. The new cyclic thio- and dithiophosphonates had the following constants (bp; d42~ n~ calculated MR; found MR; cal- culated P, %; found P, %): (II) - 110-111 ~ (1 ram); 1.2264, 1.5430, 39.41, 39.55, 20.13, 19.65; (IV) - 92-94 ~ (0.7 ram); 1.3656, 1.5340, 31.91, 31.41, 22.45, 22.43; ( 1 0 - 114-116~ ram); 1.1912, 1.5340, 44.03, 43.83, 18.45, 18.51; (DO- 88-90 ~ (0.5 ram); 1.2495, 1.5210, 40.92, 40.44, 18.45, 18.59.

The dipole moments were determined in CC14 and benzene at 25~

The dielectric constants were determined on a IDM-2 instrument [4], and the refract ive indices were determined on a IRF-23 refractometer . The orientation polarization was calculated by the Guggenheim -Smith method [5].

C O N C L U S I O N S

The dipole moments of some cyclic thio- and dithiophosphonates were determined and it was postulated that the rings exhibit conformational lability.

le 2.

3. 4. 5.

LITERATURE CITED

M. Wieber and H. U. Werther, Monatsh. Chem., 99, 1153 (1968). N.K. Bliznyuk, P.S. Kholdllov, and L.A. Kalutskii, USSR Patent No. 239329 (1968); Byul. Izobr . , No. 11, 35 (1969). A.N. Pudovik, E.M. Faizullin, and G.I. Zhuravlev, Zh. Obshch. Khim., 36, 718 (1966). R. Sh. Nigmatullin, M.R. Vyaselev, and V.S. Shatunov, Zavod. Lab. , 3 0 , - ~ 0 (1964). E.A. Guggenheim and J .E. Prue, Physicoehemical Calculations [Russian translation], IL (1958), p. 100.

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