8. S. P. Acharya and H. C. Brown, J. Am. Chem. ;Soc., 89, 1925 (1967). 9. D. A. Lidhtner and D. E. Jackman, Tetrahedron Lett., 35, 3051 (1975).

i0. V. A. Naumov, Izv. Akad. Nauk SSSR, Ser. Khim., 2425 (1971). ii. A. N. Vereshchagin, Polarizability of Molecules [in Russian], Nauka, Moscow (1980), p.

177.

REACTIONS OF DIAZAPHOSPHOLES WITH ISOCYANATES

B. A. Arbuzov, E. N. Dianova, and E. Ya. Zabotina

UDC 542.91:547.1'118

Within the scope of studying cycloaddition to the C=P bond of the compounds with a two-coordinated P atom [i, 2] we studied the reactions of substituted diazaphospholes with

isocyanates.

2-Phenyl-5-methyl-l,2,3-diazaphosphole does not react with trichloroacetyl isocyanate at ~20~ or with benzoyl isocyanate when heated in CC14, whereas the reaction of 2-acetyl-5- methyl-l,2,3-diazaphosphole (I) with trichloroacetyl isocyanate without a solvent is com- pleted in 7 days at ~20~ A criterion of this is the disappearance of the vN=C=O band at 2258 cm -~ in the IR spectrum of the reaction mixture and of the signal of the starting dia- zaphosphole (I) at ~P 238 ppm in the 31p ~R spectrum. The presence of an intense band at the pulsation vibrations of the diazaphosphole ring at 1280 cm -I in the IR spectrum of the product, and of a signal at 6P 249 ppm in the 31p NMR spectrum, testifies to the fact that this is a new derivative of a two-coordinated P atom, and specifically 2-acetyl-4-trichloro-

acetamido-5-methyl-l,2,3-diazaphosphole (II).

MeCO--N ,N ~ MeCO--N N I I( - , / I II

P C--Me ~- CClaCO--N----C=O | P C--Me l / \ / ]CCIaCO--N C--H

MeCO--N -N I II

_. P C--Me

C I

C=O

(II) I-I--NI --COCCIa

The formation of (II) can be depicted by the [2 + 2]-cycloaddition scheme via the inter- mediate bicycle with the migration of H from the C 4 atom to the amide N atom and cleavage of the P--N bond of the azaphosphetidine ring. The structure of (II) was confirmed by elemental

analysis and via the IR and the IH and 3~p N>~ spectra.

EXPERIMENTAL

2--Acetyl-4-trichloroacetamido-5-methyl-l,2,3-diazaphosphole (II). To 1.5 g of 2-phenyl- 5-methyl-l,2,3-diazaphosphole (I) in a Dry Box filled with N= was added 2 g of trichloroacetyl isocyanate. On standing the reaction mixture congealed to a viscous oil. After 7 days the mass was rubbed to give a bright yellow, exceedingly hygroscopic powder, from which by wash- ing with abs. pentane in a dry N2 atmosphere we obtained 3.3 g (100% yield) of product (II). Found: C 28.62; H 2.47; N 12.50; P 8,95%. C3HTN3PO3CI3. Calculated: C 29.05; H 2.13, N

12.70, P. 9.37%.

Infrared spectrum (UR-10, Nujol, v, cm-1): 1720, 1680 sh (C=O); 1280 (pulsation vibra- tions of diazaphosphole ring); 3280 (N--H). PMR spectrum (CHCI3, TMS, Varian-60, 6, ppm): 2.32

s (Me--C=), 2.73 s (MeCO), ~31P(CH2CI2) + 249 ppm.

CONCLUSIONS

A new derivative of a two-coordinated phosphorus atom, and specifically 2-acetyl-4-tri- chloroacetamido-5-methyl-l,2,3-diazaphosphole, was obtained by the reaction of 2-acetyl-5-

methyl-l,2,3-diazaphosphole with trichloroacetyl isocyanate.

A. M. Butlerov Chemical Institute, V. I. Ul'yanov-Lenin Kazan State University. Trans- lated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1182-1183, May,

1984. Original article submitted June 28, 1983.

1086 0568-5230/84/3305-1086508-50 �9 1984 Plenum Publishing Corporation

1.

2.

LITERATURE CITED I

B. A. Arbuzov, E. N. Dianova, and Yu. Yu. Samitov, Dokl. Akad. Nauk SSSR, 244, 1117 (1979).

i

B. A. Arbuzov, E. N. Dianova, and S. Z. Sharipova, Izv. Akad. Nauk SSSR, Ser. Khim., ii13 (1981).

PREPARATION OF BIS(I-R-o-CARBORANYL)MERCURY BY DIRECT MERCURATION

OF I-R-o-CARBORANES WITH MERCURY SALTS IN ALKALINE SOLUTION

L. I. Zakharkin and N. Yu. Krainova UDC 54Z.91:547.254.9'127

The reaction of either l-R-o-carboranyllithium [i] or l-R-o-carboranylmagnesium bromides [2] with mercuric chloride is usually used to obtain bis(l-R-o-carboranyl)mercury. For this purpose it is necessary to run the metallation of the l-R-o-carboranes using either n-butyl- lithium in benzene or ether, or EtMgBr in THF [3]. A method is described for the direct mer- curation of the l-R-o-carboranes with organomercury hydroxides [4]. It is known that acetyl- enes are mercurated by mercury halides in alkaline solution to give (RC-C) 2Hg [5]. Since the CH acidity of the l-R-o-carboranes is close to that of the acetylenes, it could be ex- pected that the l-R-o-carboranes will also be mercurated under similar conditions. The direct mercuration of C6FsH by mercury salts in alkaline solution to give (C~F~)2Hg was re- ported recently [6]. Similarly we found that the l-R-o-carboranes when treated with HgBr~- ions in alkaline aqueous DMF solution undergo direct mercuration to give bis(l-R-p-carboranyl) mercury by the scheme

DMF

BloHlo \ BloHlo/~ R = Me, Ph, C1CH~.

The reaction was run on the example of the 1-methyl-, l-phenyl-, and l-chloromethyl-o- carboranes. In harmony with [6], we postulate that the direct mercuration of the 1-R-o-car- boranes proceeds by the mechanism of the nucleophilic substitution of the halogen on the Hg

]~C CH + OH- ~_ RC C- + H~O \ / \ /

BloHlo B1oHlo HgBr~- ~_ HgBrz + 2Br-

B - ----> RC C- + HgBr~. ~ RC. CHg rz ~. RC CHgBr + Br- \ / \ / \ /

BloHlo BloHlo BloHlo RC C-+RC CHgBr~_(RC,--~C t H g B r - ~ / R C - - C \ H g + B r -

/ ~ / i BioHlo) 2 BloHxo BxoHlo \ BloHlo/'2 ~ /

atom by the carbanion particle. The direct m~ercuration of the l-R-o-carboranes with mercury salts in alkaline solution is a more convenient method than the reaction of the C-lithium and C-MgBr carboranes with HgCI2.

EXPERIMENTAL

General Method for Direct Mercuration of l-R-o-Carboranes. The reaction was run in 10% (by volume) aqueous DMF solution using HgCI2, LiBr, the l-R-o-carborane, and NaOH in a mole ratio of 0.56:2.5:1:2.5. The reagents were added in the enumerated order with vigorous stir- ring, in which connection cooling was necessary after adding the LiBr. After stirring at 20~ for 0.5-1 h the mixture was poured into satd. NaCI solution. The obtained product was extracted with ether and the extract was washed with water and dried over Na2S04.

From 1 g of l-methyl-o-carborane we obtained 0.59 g (34%) of bis(l-methyl-o-carboranyl)- mercury, mp 253-255~ (cyclohexane) [I]; from 2 g of l-phenyl-o-carborane we obtained 0.5 g

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1184- 1185, May, 1984. Original article submitted June 28, 1983.

0568-5230/84/3305- 1087508.50 �9 1984 Plenum Publishing Corporation 1087