after which the mixture was worked up as described above and vacuum-distilled. From i0 mmoles of l-hexene we obtained 1.97 g (80%) of 2-ethyl-l-iodo-hexane (XIX) [9], bp 89 ~ (i0 mm). PMR spectrum (6, ppm): 0.9 m (6H, CH3), 1.28 m (9H, CH2), 3.17 d (2H, CH2I). M + 246. In a similar manner, from l-octene we obtained 2-ethyl-l-iodo-octane (XX) [9] in 78% yield, bp 115 ~ (i0 mm). PMR spectrum (6, ppm): 0.9 m (6H, CH3), 1.27 mm (IIH, CH2), 3.20d (2H, CH2I). M + 260. CONCLUSIONS Diethylmagnesium adds regiospecifically to a-olefins in the presence of catalytic amounts of Cp2ZrCI2 to give difficultly available higher dialkyl organomagnesium compounds. LITERATURE CITED i. 2. 3. 4. 5. 6. 7. w 9.

B. Snider, M. Karras, and R. Corm, J. Am. Chem. Soc., i00, 4624 (1978). L. Farady and L. Marko, J. Organometal. Chem., 28, 159 (1971). U . M . Dzhemilev and L. Yu. Gubaidullin, Izv. Akad. Nauk SSSR, Ser. Khim., 915 (1979). S.-H. Liu, J. Org. Chem., 42, 3209 (1977). F. Sato, H. Ishikawa, and M. Sato, Tetrahedron Lett., 365 (1981). H . L . Finkbeiner and G. Cooper, J. Org. Chem., 27, 3395 (1962). W. Strohmeier and F. Seifert, Chem. Bet., 94, 2356 (1961). U . M . Dzhemilev, A. G. Ibragimov, O. S. Vostrikova, G. A. Tolstikov, and L. M. Zelenova, Izv. Akad. Nauk SSSR, Ser. Khim., 361 (1981). P. Levena and F. Taylor, J. Biol. Chem., 54, 351 (1922).

REACTION OF BICYCLIC AMIDOPHOSPHITES WITH CARBOXYLIC ACIDS UDC 542.91:547.1'I18

S. A. Terent'eva, M. A. Pudovik, and A. N. Pudovik

1,3,2-Oxazaphospholanes with alkylene bridges in the ring react with carboxylic acids via the cleavage of the endocyclic P--N bond and the formation of acid phosphites [I]. The acidolysis of 2-alkyl-4,5-benzo-l,3,2-oxazaphospholanes proceeds with a retention of the cyclic fragment and leads to their oxidation products [2]. A study of the acidolysis of bicyclic amidophosphites with a trivalent phosphorous atom is of undoubted interest. We obtained compounds of this type by the reaction of N-(B-hydroxy. alkyl)-o-aminophenols with hexaethyltriaminophosphine.

J\/

NHCH~CHROH ~- P(NEt~)8

/

Oil (i), (IO R = H (I); Me (II).

However, it proved that the ring-unsubstituted bicycloamidophosphite (I) is unstable and immediately after formation it quickly oligomerizes. Consequently, in subsequent work we used compound (II), whose greater stability was caused by the presence of a methyl group in the ring. The reactions of bicycloamidophosphite (II) with the acetic, benzoic, trifluoroacetic, and methacrylic acids proceed with an exothermic effect and lead to the formation of eightmembered acid phosphites (VI)-(IX). A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch, Academy of Sciences of the USSR. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. I, pp. 221-222, January, 1983. Original article submitted June 4, 1982. 0568-5230/83/3201-0195507.50

9 1983 Plenum Publishing Corporation

195

/Me

,Me

r/ (iii)

(iv)

tlco

Si

o/ O (v)

(vD- (ix)

R = Me (VI); Ph (VII); CF8 (VIII); CH~ = C(Me) (IX). Compounds (VII) and (VIII) were isolated analytically pure. Their IR spectra have absorption bands at 2460 (P--H), and at 1650 (VII) and 1690 cm -~ (VIII) of the carbamide groups. In the ~IP NMR spectra the cyclic acids are characterized by the doublet signals: 6 3~p 6 ppm, JPH = 720 Hz (VI), 5 ppm, 4 7 0 H z (VII), 4 ppm, 740 Hz (VIII), and 4 ppm, 720 Hz, (IX). In the PMR spectrum of (VII) the methyl group is represented by the doublet ~ 1.38 ppm, JCH~-CH = 7 Hz, while the doublet ~ 6.80 ppm, JHP = 734 Hz, corresponds to the proton of the P--H bond. The reactions apparently proceed by the following scheme. The initial protonation of the phosphorus atom is accompanied by the formation of phosphoranes with a P--H bond (III). Such a structure was recorded using the 3~p NMR and IR spectra in the reaction of amidophosphite (II) with methacrylic acid , ~3~p--36 ppm, JpH = 880 Hz; v (P-H) 2400 cm -~ Due to transfer of a proton to the nitrogen atom, the (III) phosphoranes can be found to be in equilibrium with the trivalent form (IV) [3]. Acidolysis of the latter leads to the acid cyclic phosphite (V) and the isolation of the anhydride, which, reacting with each other, give the end products with a regeneration of the carboxylic acid. EXPERIMENTAL The 31p NMR spectra were taken on a KGU-4 NMR instrument at an operating frequency of 10.2 MHz, and using 85% H3P04 as the standard. The PMR spectra were recorded on a Varian T60 instrument using TMS as the internal standard. The IR spectra were taken on a UR-20 spectrometer as KBr pellets and in CC14 solution. 7,8-Benzo-3-methyl-4,6-dioxa-l-aza-5-%3-phosphabicyc!o[3.3.0]octane (II). A mixture of 18 g 0--f N-(B-hydroxyisopropyl)-o-aminophenol and 26.7 g of P(NEt2)3 was heated in benzene solution for 3 h. The solvent was removed and the residue was fractionally distilled to give 15.5 g (74%) of (I) with bp 82 ~ (0.008 mm), nD 2~ 1.5645, d4 2~ 1.0255; ~31p 152 ppm. Found: C 55.16; H 4.78; N 7.11; P 15.81%. CgHIoNO2P. Calculated: C 55.40; H 4.63; N 7.17; P 15.91%. 4,5-Benzo-6-benzoyl-8-methyl-2-oxo-l,3-dioxa-6-aza-2-%5-phosphocane (VII). A mixture of 3.4 g"0f (II) and 2.7 g of benzoic acid was kept in benzene solution for 24 h at 20oc. We obtained 1.8 g of crude product, the recrystallization of which from either hexane or CC14 gave i.i g (22%) of (VII), mp 139-140 ~ Found: C 60.75; H 5.15; N 4.47; P 10.11%. C~6H16' NO4P. Calculated: C 60.50; H 5.05; N 4.42; P 9.77%. 4,5-Benzo-8-methyl-2-oxo-trifluoroacetyl-l,3-dioxa-6-aza-2-%5-phosphocane (VIII). With cooling, 1 g of (II) was mixed with 0.6 g of CF3COOH. We obtained 0.5 g (32%) of (VIII), mp 136-139 ~ . Found: N 4.70; P 10.11%. C11H~IFNO4P. Calculated: N 4.52; P 10.05%. CONCLUSIONS When bicyclic amidophosphites are reacted with carboxylic tion and form acid cyclic phosphites. LITERATURE i.

196

M. A. Pudovik, A. S. Terent'eva,

acids they undergo protona-

CITED

and A. N. Pudovik,

Zh. Obshch.

Khim., 51, 518 (1981).

2.

3.

S. A. Terent'eva, M. A. Pudovik, and A~ N. Pudovik, Izv. Akad. Nauk SSSR, Ser. Khimo~ 1152 (1979). C. Bonningue, J. F. Brazier, D. Houalla, and F. H. Osman, Phosphorus and Sulfur, 5, 291 (1979).

STUDY OF ANION-RADICALS OF CARBORANES-12 IN THE GAS PHASE BY THE MASS SPECTROMETRY METHOD OF THE RESONANCE CAPTURE OF ELECTRONS V. A. Mazunov, Yu. S. Nekrasov, V. I. Khvostenko, and V. I. Stanko

UDC 543.51:541.515:547o1'127

The specific properties of the electron-deficient carborane systems was the reason for the appearance of a large number of theoretical and experimental papers, which deal with the electronic structure and the structure [i], the stability and reorganization of the skeleton of the molecule under excitation [2], and a study of the reactivity and characteristics of the physicochemical properties [3]. These studies relate mainly to the condensed phase, where the principal role is played by processes that include the step of forming the dianions. However, the mechanism of adding the electrons is still not clear, is the addition of two electrons stepwise or simultaneous, does the polyhedron open during one-electron addition, can the capture of one electron lead to isomerization, etc. To answer these questions a detailed analysis must be made of the elementary processes of the capture of electrons with low energies (resonance capture region = 0-i0 ev) by isolated molecules. One-electron addition in the gas phase was studied for several lower carboranes, which form only fragment ions under these conditions [4, 5]. In the present paper we used the mass spectrometry method of the resonance capture of electrons to study the gas-phase processes of one-electron addition by molecules by the icosahedral carboranes-12 (Table i), which possess the criteria that are characteristic for the formation of long-lived* negative molecular ions (under the conditions of a positive electron affinity): a high symmetry of the molecule, delocalization of the electrons, and a sufficiently large number of atoms. Of the three carborane-12 isomers only the o-carborane molecules capture electrons with thermal and epithermal energies to give molecular anion-radicals, which can spontaneously eject an electron with an average lifetime T that is characteristic for each state (see Table i). An increase in the ionization chamber temperature leads to a sharp change in the intensity ratios of the peaks of the negative molecular ions (N~I) from 0.5:1 at 350~ to 1:0.3 at 600~ A decrease in the lifetime of the NMI is observed here (from 130 to 80 ~sec in the first state, and from 45 to 30 ~sec in the second state) and a shift of the second resonance peak toward smaller energies (Fig. i). Two states of the NMI can correspond to two stable electronic configurations of the molecule-electron system, whose lifetimes exceed those of any other possible configurations. It is known that in carborane molecules the C atom bears an excess positive charge. In o-carborane-12 the icosahedron formally contains two types of electronic centers, attached to two C--C and six B--B triangles, while the m- and p-isomers do not contain triangles with

\/

\/

B

C

two C atoms and, as experiment shows, do not form long-lived h~I. *Negative ions that are recorded by mass spectrometry,

The reason for this could

i~e. with a lifetime > 1 ~sec.

Division of Physics and Mathematics, Bashkir Branch, Academy of Sciences of the USSR, Ufa, A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. i, pp~ 223225, January, 1983. Original article submitted June ii, 1982.

0568-5230/83/3201-0197507.50

9 1983 Plenum Publishing Corporation

197