CONCLUSIONS

A simple method was proposed for the synthesis of l,(E)6-alkadienes from the telomers of butadiene with phenol, methanol, and acetic acid and alkylmagnesium halides in the pres- ence of catalytic amounts of Cu(1).

i.

2. 3.

,

5. 6, 7.

LITERATURE CITED

B. Mundy, K. Lipowitz, and G. Dirks, Synth. Commun.~ ~, 7 (1975). N. Byron, R. Grigg, and B. Kongkathip, J. Chem. Soc. Chem. Commun., 1976, 216. A. Commereon, M. Bourgain, J. F. Normant, and J. Villieras, Tetrahedr0n Left., 197___~5, 3870. G. Fouguet and M. Schlosser, Angew. Chem. Int. Ed., 1~3, 82 (1974). E. J. Smutny, J. Am. Chem. Sot., 89, 6793 (1967)o S. Takahashi, T. Shibano, and N. Hagihara, Bull. Chem. Soc. Jpn., 41, 454 (1968). D. Rose and H. Lepper, J. Organomet. Chem., 49, 473 (1973).

4-BENZALPYRAZOLINES WITH bIETALLOCENYL SUBSTITUENTS

A. N. Nesmeyanov, A. M. Baran, S

L. Eggert, V. N. Postnov, and V. A. Sazonova

UDC 542.91:547. l'13:547. 772.2

It was shown by us recently that l-unsubstituted pyrazolines which contain ferrocenyl or cymantrenyl substituents are unstable in solution and decompose to give the starting chal- cones [i]. However, under conditions that exclude destruction of the pyrazolines, it is pos- sible to obtain their 4-benzal derivatives. Thus, condensation in the 4 position occurs when a 3,5-disubstituted pyrazoline is heated under argon in excess benzaldehyde at 200oC for 1 h.

- - R " C6HsCH - - R"

N --~ N 90--95% / \ / / \ /

R NH R NH R = R' : CbH4FeC~H5 (1); R = C~H4FeC~H~,

R ' = CsH4/vIn(CO)a (II); R ---- R' = C~H4Mn(CO)3 (III)

4-Benzalpyrazolines (I)-(III) are much more stable than the starting compounds. Besides the signals of olefinic proton and the protons of the phenyl and cyclopeuKadienyl rings, the PMR spectra of compounds (I)-(III) have a common signal for methine proton and the proton on the nitrogen atom. It is characteristic that the vibrations of the NH group do not appear in the IR spectra of (I)-(III) as a Nujol mull or in CHaCIa, CHCI,, or CCI~ solution. The char- acteristics of the compounds, the PMR spectral data, and the elemental analysis results are given in Table I.

TABLE 1

Co m pound

4- Benza [: 3, 5 -d i - f e r roceny lpyrazo- fine (I) 4- B e n z a l - 3 - c y - ma ntre nyl -5- ferro- ce ny lpyrazo line (II

4 - Benza l -3 , 5 -d i cy - m a n t r e ny [pyrazo- l ine (llI)

.rap, o C

t68

t21--123

ii9--121

PMR spectra (~, ppm)

C,H,

4,08)

4 ' I i I (i(

4,03 (5)

(]~H4

4,26 (~) ~,38 (2) 4,76 (2) 4,20~ 4,30} (~) 4 70 (2) 5:20 (2) /~,67 / 4,75~(6) 4,85) 5,27 (2)

=CH

653(0

6,33(I)

6,37(0

CH NH

5,5~(2)

5,~3(2)

5fli(2)

: o u n d / c a lcu la ted, %

i (3 ~ ] Fe Mn N

I

~s,5o i5,84 ; t , 5 t - ~,5:

Empixica I for mu [a

C ~oHz,FezN2

C,,Hz,FeMnNzOa

Cz,H,sMn,N.~Oe

M. V. Lomonosov Moscow State University. Translated from Izvestiya Akademii Nauk SSSR, Seriya K~himicheskaya, No. 6, p. 1402~ June, 1979. Original article submitted November 30, 1978.

0568-5230/79/2806-1313507.50 �9 1979 Plenum Publishing Corporation 1313

CONCLUSIONS

4-Benzal derivatives of pyrazolines that contain metallocenyl substituents in the 3 and 5 positions are described.

I.

LITERATUKE CITED

A. N. Nesmeyanov, V. A. Sazonova, V. N. Postnov, A. M. Baran, Ya. A. Angel}n/k, and B. A. Surkov, Dokl. Akad. Nauk SSSR, 241, 1099 (1978).

HEXAKIS(TEIMETHYLSILYLMETHYL)DITUNGSTEN AS CATALYST FOE METATHESIS

REACTIONS OF OLEFINS

N. B. Bespalova, E. D. Bablch, UDC 541.49:547.245:546.78:542.97:547.313 and V. M. Vdovin

Metal complexes that function as metathesis catalysts are obtained by coupling the reac- tion products of the W, Mo, or Re halides or oxyhalides with the organic derivatives of the nontransition metals of groups I-III and IV [i]. The active metathesis centers have a carbene nature [2] and usually contain electronegative CI, O, etc. atoms as ligands.

We established that hexakis(trimethylsilylmethyl)ditungsten W2[CH2Si(CH3)3]6 (I), which is devoid of electronegative heteroatoms, also catalyzes the metathesis reaction (Table i).

In benzene solution catalyst (I) causes the metathesis of cyclic olefins to give high- molecular-welght polymers. The yield of the polymer decreases with decrease in the cyclo- olefln:(I) ratio, which is apparently due to an increase in the yield of the low-molecular- weight fractions. The less active linear u- or 8-olefins fail to undergo metathesis under these conditions. The catalytic activity of (I) is increased substantially when coupled with WCI,. Here the polymerization of cycloolefins is accelerated substantially (see Table i, Expt. 7) and the metathesis of linear a-olefins is realized (Expt. 8).

Complex (I) has a cluster structure and a W~W multiple bond [3], and does not contain electronegative substituents on the transition metal atom. This has interest for elucidating the nature of active metathesis centers and, in particular, the ligand environment of this center.

EXPERIMENTAL

Synthesis of Hexakis(trimethylsilylmethyl)ditungsten (I). Compound (I) was obtained as described in [3] by reacting WCI, with (CHs)sSiCH~MgCl in diethyl ether. Recrystallization from pentane gave brown crystals with mp 109-110 ~

Metathesis of Cycloolefins. The reactions were run using benzene solutions of the catalysts in sealed glass ampuls at 20-50 ~ in an argon atmosphere. The yield of the high- molecular-weight products was determined gravimetrically, and here the polymers were precip- itated with methanol and evacuated to constant weight at 50 ~ (0.5-1 torr). The multiple bonds in the polymers were determined by the bromine number method [4] and by IR spectroscopy on the basis of the absorption bands at 967 and 1400 cm -~ [5].

Expt. i. A mixture of 0.27 g (0.00033 mole) of (I) and 5 ml of benzene, in an ampul that had been evacuated and then filled with argon, was frozen using liquid Na, evacuated to i'i0 -s torr, 1.90 g (0.028 mole) of cyclopentene was recondensed into the ampul, and the ampul was sealed and heated for I0 h at 50 ~ . The yield of the polymer was 0.40 g (21%) after a double reprecipitation and drying in vacuo. It was shown by IR spectroscopy that the ob- tained polypentenamer analyzes 45% of cis and 55% of trans units.

Expt. 2. A mixture of 1.15 g (0.017 mole) of cyclopentene and 1.02 ml (0.000017 mole) of a benzene solution of (I) was polymerized for 10 h at 50 ~ . The yield of the polymer,

A. V. Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow. Translated from Izvestlya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1403- 1404, June, 1979. Original article submitted December i, 1978.

1314 0568-5230/79/2806-1314507~ �9 1979 Plenum Publishing Corporation