1 - E t h y n y l - 3 - p i p e r i d i n o m e t h y l t e t r a m e t h y l d i s i l o x a n e (XII) was ob ta ined the s a m e as (XI) f r o m 3,5 g of

(I) and 2.9 g of p i p e r i d i n e in 25 m l of benzene in 76.5% yieId (3.31 g).

C O N C L U S I O N S

The cohydrolysis of CH - CSi(CH3)2OC2H 5 with CISi(CH3)2CH2CI gave the previously unknown l-ethynyl- 3-ehloromethyltetramethyldisiloxane. The bromomagnesium derivatives of the latter were reacted with CH20 , CH3COCH3, Br2, and CISi(CH3) 3. In addition, the compound was subjected to hydrosilylation, entered into the diene condensation with hexach10rocyc lopentadiene, and reacted with Nal, morpholine, and piperidine.

i.

2.

3.

4.

5.

LITERATURE CITED

N. V. Komarov, O. G. Yarosh, and Z. G. Ivanova, Izv. Akad. Nauk SSSR, Ser. Khim., 698 (1972). O. G. Yarosh, V. 13. Pukhnarevich, Z. G. Ivanova, and N. V. Komarov, Zh. Obshch. Khim., 4__22,

1371 (1972). O. G. Yarosh, N. V. Komarov, and Z. G. Ivanova, Izv. Akad. Nauk SSSR, Ser. Khim., 2122 (1972). O. G. Yarosh, N. V. Komarov, N. I. Shergina, and Z. G. Ivanova, Izv. Akad. Nauk SSSR, Ser. Khim., 2541 (1972). K. A. Andrianov and M. A. Golubenko, Dokl. Akad. Nauk SSSR, 104, 725 (1955).

CONFORMATION OF P(O)SCH 3 AND P(S)OSi(CH3) a

GROUPS IN 1, 3, 2-DIOXAPHOSPHOLANES

E. A. Ishmaeva, M. Vitehak, M. Mikolaichik, and A. N. Pudovik

UDC 541.6 :547 .1 '118

As a continuation of studying the rotation around the exocyclic bonds of phosphorus, attached to a hetero- atom, we determined the dipole moments (DM) of some i, 3,2-dioxaphospholanes, whose synthesis was de- scribed in [I]. These compounds are geometric isomers of the 2-oxo-2-methylthio- and 2-thiono-2-trimethyl- siloxy-4-methyl-l, 3,2-dioxaphospholanes, which differ in the mutual arrangement of the CH 3 and P = O or P = S groups [an exception is compound (Ill), which is contaminated with 10% of (IV)].

Using the equation #2..~, = #~. 0.9 + Pb" 0.I, we calculated for (Ill) the experimental DM of the pure 2-thiono-2-trimethylsiloxy:~4~-~met~yl-l, 3,2-dioxaphospholane with a cis arrangement of the P = S and CH 3 groups in the ring, which was equal to 4.40 D.

Me ,~4e / | O \ ~ , c , S,~le

SM.e 0

Me Me

/ . - o / , I ,l OSiMe a S

(:\3

Me .\~.e

?--o,i 5_o , (v) at .\~e \ i i (V~) meso //-o/; , TD 473D

SiM% OSi~te a Me

V. I. Ul'yanov-Lenin Kazan State University Center of Molecular and Ivlacromolecular Studies, Polish Academy of Sciences, Lodz. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1880-1883, August, 1976. Original article submitted December 8, 1975.

I This material is protected by copyrigt t registered in the name o f Plenum Publishing Corporation 227 West 1 7th Street, N e w York N. Y. 10011. No part | o f this publication may be reproduced, stored in a retrieval system or transmitted in any form' or by any means electronic mect~anical photocopying,

lmicrofilming, recording or otherwise, wi thout written permission o f the publisher A copy o f this article is available from the publisher for $ 7150. I 1771

)I.R Y Y

p

~ D 5.50L

4 .f ~50 ~ (.ZEJ

0 sO lZO lag ~deg

Fig. i Fig. 2

Fig. 1. Poss ib le conformations of exocyclic bonds in 1 , 3 , 2 - d i - oxaphospholanes.

Fig. 2. Conformational dependence of dipole moments of com- pounds {IID {upper) and (IV) (lower).

TABLE 1. Exper imental and Ca l - culated Dipole Moments of 1 , 3 , 2 - Dioxaphospholanes

Compound ia Dxpt

(1) 3,87 (II) 4,07

(lII) 4,40 (IV) 4,t7

}~calc,D

cis gauch I trans

4,04 ] 4,57 6,,8 4,i8 I 4,50 5,46

TABLE 2. Coefficients of Calculation Equa- tions and Exper imenta l DM of Compounds (I)- (IV)

Compound a y p,, cm 3 laexpt, D

(I) (n)

(IIIt (Iv) (v)

(vI)

i8,288 i9,304 t6,687 i5,604 t6,937 i8,242

0,12i 0,ii8 0,087 0,067 0,038 0,072

3i0,235 342,574 397,t02 359,575 43i,238 462,603

3,87 4,07 4,38 4,i7 4,57 4,73

The s te r ic s t ruc ture of the 1 ,3 ,2-dioxaphospholanes has received little study [1]. In calculating the DM of the investigated compounds by the additive scheme we used the x - r a y s t ruc ture data for the cyclic f ragment of the molecule , which were obtained for the imidazolium salt of c i s -2 - th iono-2 -hydroxy-4 -me thy l - 1 ,3 ,2-dioxaphospholane [1]. It was established that the f ive -membered phosphorus heterocycle represents a d is tor ted a r m c h a i r with a phosphorus in t raeycl ic angle of 97.5 ~ This c is , gauche, or t rans forms are the possible conformat ions when rotation is around the P--O or P--S bonds (Fig. 1). The exocyclic angles at the phosphorus atom were taken to be the same as in [2-4]. The DM of the bonds involving the phosphorus atom are given in [5,6]. The group moment of (CH3)aSi ~ O (1.10 D) was calculated f rom the experimental DM of hexamethyldisi loxane (0.68 D) using an Si--O--Si valence angle of 144 ~ [7]. The group moment of CH 3 ~ S (1, 12D) was calculated f rom the exper imenta l DM of dimethyl sulfide [8] with a C--S--C valence angle of 99 ~ [9]. The experimental DM of compounds (I)-(IV) and the calculated DM of all of the conformers are given in Table 1. Since the additive scheme does not take into account the contribution made by the CH 3 group in the r ing to the calculated moment , the calculated moments for compounds (I) and (II), the same as for compounds (III) and (IV), are identical in pa i rs .

F rom Table I it can be seen that the p r e f e r r ed conformation in compounds (I) and (H) is the conforma- tion with a cis orientation of the P = O and CH 3 groups. An analogous conformation was previously observed in S-methyl pinacol dithiophosphate [10]. It is obvious that for {HI) and (IV) it is possible to speak only of a conformation of the "cisoid" type, s i n c e the graph express ing the DM of these compounds as a function of the angle of rotat ion around the P--O bond in the region f rom 0 to 60 ~ represen ts a gentle curve (Fig. 2). We also determined the DM of two 1 ,3 ,2-dioxaphospholanes with two CH 3 groups in the r ing, and specifically (V) and (VI). The attention is a t t racted to the increase in the experimental DM of these compounds when compared with (III) and {IV). A s imi la r increase in the DM of f ive -membered heterocycles as they accumulate more CH 3 groups was observed in [11-13]. The found DM of compounds (V) and (VI) are close to those calculated for the gauche orientation of the P = S and Si(CH3) 3 groups (see Table 1). However, we believe that important reasons are lacking for such change in the conformation of the exocyclic port ion of the molecule. A change in the rIng s t ruc tu re can probably occur here , or else the nonadditive contribution made by the dipoles of the CH 3 groups to the ring becomes substantial. This problem requi res fur ther study. Poss ib ly , by select ing the appropria te model compounds, the group moment of the f ive -membered ring can be used, thus reducing to a minimum the e r r o r s associa ted with the indicated fac tors .

1772

E X P E R I M E N T A L

The DM were determined in CC14 solution at 25~ the same as descr ibed in [8]. The coefficients of the calculation equations and the resul t ing data are given in Table 2.

The authors are indebted to A. N. Vereshchagin and V. A. Naumov for their valuable counsel.

C O N C L U S I O N S

Based on the dipole moment data, ei ther a cis or nea r - c i s orientat ion of the phosphoryl and methyl groups, or of the thiophosphoryl and t r imethyls i ly l groups, is real ized in the 2-oxo-2-methyl th io- and the 2 - th iono-2- t r imethy ls i loxy-4-methy l - and -4 , 5-d imethyl -1 ,3 ,2-d ioxaphospholanes .

LITERATURE CITED

I. M. Ivlikolajczyk, M. Witczak, M. Wieczorek, N. G. Bokij, and Yu. T. Struchkov, J. Chem. Soc. Perkin Trans., i, 371 (1976).

2. T.A. Steitz and W. N. Lipscomb, J. Am. Chem. Soc., 8__77, 2488 (1965). 3. H. Chiu and W. N. Lipscomb, J. Am. Chem. Soc., 91, 4150 (1969). 4. D. Swank, C. N. Caughlan, F. Ramirez, and O. P. Madan, J. Am. Chem. Soc., 89, 6503 (1967). 5. E.A. Ishmaeva, A. N. Vereshchagin, N. A. Bondarenko, G. E. Yastrebova, and A. N. Pudovik, Izv.

Akad. Nauk SSSR, Ser. Khim., 2695 (1970). 6. E.A. Ishmaeva, O. A. Raevskii, V. V. Ovchinnikov, F. G. Khalitov, Ro A. Cherkasov, and A. N.

Pudovik, Dokl. Akad. Nauk SSSR, 197, 862 (1971). 7. A. Almenningem, O. Bast iansen, V. Ewing, K. Hedberg, and M. Trae t teberg , Acta Chem. Scand. ,

1_!, 2455 (1963). 8. O . A . Osipov, V. I. Minkin, and A. D. Garnovstdi , Handbook on Dipole Moments [in Russian], Vyssha-

ya Shkola (1971). 9. L. P ie rce and M. Hayashi, J . Chem. P h y s . , 3__55, 479 (1961).

10. E . A . Ishmaeva, V. V. Ovchinnikov, R. A. Cherkasov, and A. B. Remizov, Zh. Obshch. Khimo ~ 4._55, 946 (1975).

11. B . A . Arbuzov, L. K. Yuldasheva, and I. Vo Anonimova, Izv. Akad. Nank SSSR, Ser. Khim. , 2712 (1969).

12. E . A . Ishmaeva, M. A. Pudovik, S. A. Teren t ' eva , and A. N. Pudovik, Dokl. Akad. Nauk SSSR, 19__~6, 630 (1971).

13. B . A . Arbuzov, L. K. Yuldasheva, I. V. Anonimova, N. A. Chadaeva, and A. N. Vereshchagin, Lzv. Akad. Nauk SSSR, Set. Khim. , 1512 (1974).

S Y N T H E S I S O F O - E T H Y L O - ( f i - A L K Y L M E R C A P T O E T H Y L )

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

N. N. G o d o v i k o v , V. M. K u z a m y s h e v , M. Kh~ B e r k h a m o v , a n d M. I . K a b a c h n i k

UDC 542.91:547.1'118

In [1] it was shown that the O-(fi-alkylmercaptoethyl) diphenylphosphinates-, and the methiodides co r - responding to them, are powerful revers ib le butyrylchol ines terase inhibitors, whereas the compounds with one phenyl group, namely, the O-ethyl O-(fl-alkylmercaptoethyl) phenylphosphonates, are weaker revers ib le chol ines terase inhibitors [2].

Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Transla ted f rom Izvest iya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1883-1884, August, 1976. Original ar t ic le submitted December 24, 1975.

1 This material is protected by copyright registered in the name o f Plenum Publishing Corporation 227 West 1 7th Street N e w York iV. Y. 10011. No part | o f this publican'on may be reproduced, stored in a retrieval system or transmitted in any form ~ or by any means electronic 'mec'hanical, pl~otocopying,

I micro]'ilming, recording or otherwise , wi thout written permission o f the publisher. A "copy o f this article is available f rom the publisher for $ 7. 50. l 1773