N E W B I C Y C L I C P H O S P H O R A N E S W I T H A P - H B O N D

M. A. P u d o v i k , S. A . T e r e n t T e v a , a n d A. N. P u d o v i k

UDC 542.91:547.1,118

The p rope r t i e s of P -a lky la ted 4 ,5 -benzo- l , 3 ,2 -oxazaphospho lanes a r e quite dependent on the c h a r a c t e r of the subst i tut ion at the endocycl ic N atom. Thus, oxazaphospholanes, containing a s econda ry amino group, a re unstable and are eas i ly conver ted to the the rmodynamica l ly more s tab le sp i rophosphoranes and phosphetidines [1]. When reac ted with p ro ton-donor reagents they fo rm phosphoranes with a P - H bond [2]. The addition of an alkyl subst i tuent to the endocycl ic N a tom r a i s e s the i r s tabi l i ty , but h inders the fo rmat ion of the pentacovalent adducts [3]. React ion in this case goes with a rupture of the in t r acyc l i c P - O and P - N bonds.

In this connection we studied the p r o p e r t i e s of some 4 ,5 -benzo- l , 3 ,2 -oxazaphospho lanes with a hydroxy- alkyl grouping on the N a tom and made the assumpt ion that invo lvement of the OH group wilt faci l i ta te the s tabi l iza t ion of such sys t ems .

The s ta r t ing compounds in the synthes is were the d iamides of a lkyl(aryl)phosphonous acids and N-( f i - hydroxye thyI ) -o-aminophenol (I). Since the phenol and alcohol groupings in (I) a r e found fl to a secondary amino group, the format ion of oxazaphospholane de r iva t ives ffI) and fig) could be expected.

CH~CH~OH I

N

NH (II) N / ~ O

�9 Nit (~) (]v)--(vl)

- - =

o J (Hi)

R =Me (IV), Et (V), pit (VI)

However, on the example of the d iamides of the methyl- , e thyl - , and phenylphosphonous acids it can be seen that in alI cases the reac t ion products a re bicyclic phosphoranes with a P - H bond (IV)-(VI), whose f o r m a - tion occurs via the i n t r am o l ecu l a r addition of the f i-OH group to the t r i va l en t P atom.

The s t ruc tu re of (IV)-(VI) was conf i rmed by the e l ementa l ana lys i s and the 31p NMR, ill, and IR spec t r a l data. The values of the chemica l shifts , 6p = - 2 8 to 46 ppm, tes t i fy to the pentaeovalent s tate of the P atom. Due to s p i n - s p i n coupling with a proton the s ignals of the P nuclei r e p r e s e n t doublets with JPH = 680-720 Hz. In the IR spec t r a the s t re tch ing v ibra t ions of the P - H bond appear in the 2350-2410 em - I region. In the PMR spec t rum the protons of the CH 3 group of phosphorane (IV) have the f o r m of pa i r s of doublets due to spli t t ing f rom the phosphorus atom, 2JCH3P = 15 Hz, and the proton, 3JCH3Ptt = 2 Hz. The doublet with 5 5.80 ppm and IJHP = 690 Hz co r re sponds to the proton on the phosphorus . Condensed phosphoranes with a P - H bond, ob- tained f rom die thanol~nine and devoid of a romat ic subst i tuents in the cycl ic sys t em, we re desc r ibed in [4].

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

The 31p NMR spec t r a were taken on a KGU-4 NMR ins t rumen t at a f requency of 10.2 M/-Iz and using 85% H3PO 4 as the s tandard. The PMR spec t ra were recorded on a Var ian T-60 ins t rument , using TMS as the i n t e r -

nal s tandard.

A. E. Arbuzov Insti tute of Organic and Phys ica l Chemis t ry , Kazan Branch, Academy of Sciences of the USSR. Trans la t ed f r o m Izves t iya Akademii Nauk SSSR, Seriya Khimicheskaya , No. 6, pp. 1408-1409, June, 1982. Original a r t i c le submit ted October 27, 1981.

1256 0568-5230//82/3106-1256507.50 �9 1982 Plenum Publ ishing Corpora t ion

7, 8-Benzo-5-hydro-5-methyl-4,6-dioxa-l-aza-5-phosphabicyelo[3.3.0]octane (IV). A mix~dre of 4 g of (I) and-5 g of methylphosphonous acid tetraethyldiamide was heated at 130~ for 1 h until the ELzNH evolution ceased (yield 3 g, 79%). Fractional distillation in an argon s t ream gave 3.1 g (60%) of (IV), bp 93-96" (0.08 ram); nD 2~ 1.5830;d42~ 5 3 i p - 3 6 p p m , ~JpH=690 Hz. Found: C 54.61; H 6.29; N 7.25; P15.86%. C~H12NO2P. Calculatecll C 54.80; H 6.10; N 7.10; P 15.75%.

L 8-Benzo-5-hydro-5-ethyl-4, 6-dioxa-l-aza-5-phosphabicyclo[3.3.0__joctane (V). Obtained in 67% yield, bp 93 ~ (0.001 ram); nD 2~176 5 3 i p - 2 8 p p m , JpH=680 Hz. Found: C 56.54; H 7.15; P 14.29%. Ci0HiiNO2P. Calculated: C 56.80; H 6.65; P 14.69%.

L_8_Benzo_5_hydro-5-pheny!-4,6ndioxa-lraza-5-phosphabicyclo[__3.3.0joctane (VI). Obtained in 67%yield, bp 148-150 ~ (0.001 mm); bp 63-67 ~ 5 3~p_46 ppm, JpH=720 Hz. Found: C 64.80; H 6.18; P 11.99%o CI~H14NO2P. Calculated: C 64.75; H 5.39; P 11.97%.

C O N C L U S I O N

The reaction of N~(/3-hydroxyethyl)-o-aminophenol with the diar~Xdes of the methyl-, ethyls., and phenyI- phosphonous acids gave new bicyclic phosphoranes with a P - H bond.

I.

2. 3.

4.

LITERATURE CITED

A. N. Pudovik, M. A. Pudovik, S. A. Terent'eva, and E. I. GoPdfarb, Zh. Obsheh. Khim., 4_~2, 1901 (1972). M. A. Pudovik, S. A. Terent'eva, and A. N. P~dovik, Izv. Akad. Nauk SSSR, Ser. Khim,, 1976, 1897. M. A. Pudovik, S. A. Terent'eva, A. A. Karelov, ~. I. GoPdfarb, and A. N. Pudovik, Zh. Obsheh. Khim., 50, 740 (1980). D. Houalla, J. Brazier, M. Sanchez, and R. Wolf, Tetrahedron Lett., 1972, 2969.

P O L A R I T Y AND P O L A R I Z A B I L I T Y OF SOME

N - T H I O D E R I V A T I V E S

B. A. A r b u z o v , L. K. A l e k s a n d r o v a , V. A. M u l l i n , A. N. Z o l o t o v , a n d A. N. V e r e s h c h a g i n

PHTHA LI MI DE

UDC 541.G7 : 547.584'054.211

A determination of the electrical properties of the bonds that are formed by various heteroatoms makes it possible to study the nature of the bonds, the character of electron transfer, and the degree of their lability. To a large degree these properties depend on the valence state of the atoms. Consequently, the polarity and polarizability of the bonds that involve atoms with a variable valence are of greatest interest. One of the least studied from this standpoint is the N-S bond. The dipole moments (DM) of sulfamides were previously deter- mined and analyzed within the framework of an additive approximation [I]. It was established that the N-S bond in them is slightly polar and that its moment depends on the substituents on the S atom. rune DM of some N-

thiophthalimides with various substitnents on the S atom (1)-(IV) are discussed by us.

co

B =cyclo -C6H~, (I); (;6H~ (I~); p-C~,H~Ctta (iii); C[ (IV).

The imide ring is a regular dipole [2], and the polarity of the studied compounds is independent of the internal rotation around the N-S bond. This permits calculating the unknown bond moments m (N-S). The valence angle of the S atom is taken equal to 107 ~ [3]. In the calculations we used the dipole of the phthalimide fragment =3.52 D, with a direction from the aromatic ring to the N atom [4], while the moments of the bonds Csp3-S 1.20 and Csp2-S 0.69 d were calculated from the data for dialkyl sulfides, thioanisole, and its p-chloro

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch, Academy of Sciences of the USSR. Izhevsk State Medical Institute. Translated f rom Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1410-1412, June, 1982. Original art icle submitted November 2, 1981.

0568-5230/82/3106-1257507.50 �9 1982 Plenum Publishing Corporation 1257