2186
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
Krut´ko et al.
0.28 (s, SiMe3 (2c)); 0.29 (s, SiMe3 (2b)); 0.86 (s, MeC(5)
(2c)); 1.06 (s, MeC(5) (2b)); 1.17 (br.s, MeC(5) (2a)); 1.65
(br.s, MeC(3), MeC(4), (2b)); 1.69 (br.s, MeC(4) (2c));
1.79 (br.s, MeC(1), MeC(2), MeC(3), MeC(4) (2a)); 1.88
(br.s, MeC(3) (2c), MeC(2) (2b)); 1.89 (s, MeC(1) (2c)).
13C{1H} NMR (C6D6), δ: –2.70 (SiMe3 (2a)); 1.70 (SiMe3
(2b,c)); 9.78, 12.98, 14.55 (CH3C(1), CH3C(3), CH3C(4) (2c));
9.89, 10.96, 15.01 (CH3C(2), CH3C(3), CH3C(4) (2b)); 11.2,
12.5 (both br.s, CH3C(1), CH3C(2), CH3C(3), CH3C(4) (2a));
13.7 (br.s, CH3C(5) (2a)); 21.95 (CH3C(5) (2c)); 22.26
(CH3C(5) (2b)); 53.7 (br.s, C(5) (2a)); 55.51 (C(5) (2c)); 56.89
(C(5) (2b)); 132.94, 145.31, 150.37, 151.17 (C(1), C(2), C(3),
C(4) (2b)); 134.31, 135.05, 142.64, 162.19 (C(1), C(2), C(3),
C(4) (2c)); 134.7, 138.1 (both br.s, C(1), C(2), C(3), C(4) (2a)).
Trimethyl(tetramethyl(2ꢀchloroethyl)cyclopentadienyl)silane
(mixture of isomers 3a—c). A procedure of alkylation of lithium
salt 1 with 1ꢀbromoꢀ2ꢀchloroethane and 2ꢀchloroꢀ1ꢀiodoethane
in THF and an Et2O—THF (10 vol.%) mixture is similar to that
described above for alkylation with methyl iodide. 1H NMR
(C6D6), δ: –0.23, –0.17 (both br.s, SiMe3 (3a)); 0.19 (s, SiMe3
(3c)); 0.20 (s, SiMe3 (3b)); 0.72 (s, MeC(5) (3c)); 0.92 (s,
13C NMR spectra coincide with the previously published
spectra.7,8
References
1. D. P. Krut´ko, M. V. Borzov, E. N. Veksler, E. M.
Myshakin, and D. A. Lemenovskii, Izv. Akad. Nauk, Ser.
Khim., 1998, 986 [Russ. Chem. Bull., 1998, 47, 956 (Engl.
Transl.)].
2. P. Jutzi, Chem. Rev., 1986, 86, 983.
3. M. Szwarc, Ions and Ion Pairs in Organic Reactions,
WileyꢀInterscience, New York, 1972, 1, 399 pp.
4. J. C. Pando and E. A. Mintz, Tetrahedron Lett., 1989,
30, 4811.
5. P. Jutzi and A. Mix, Chem. Ber., 1992, 125, 951.
6. P. Jutzi, T. Heidemann, B. Newmann, and H. G. Stammler,
Synthesis, 1992, 1096.
7. H. Hashimoto, H. Tobita, and H. Ogino, Organometallics,
1993, 12, 2182.
8. S. Doring and G. Erker, Synthesis, 2001, 43.
9. C. Adamo and V. Barone, J. Chem. Phys., 1998, 108, 664.
10. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A.
Montgomery, Jr., R. E. Stratmann, J. C. Burant,
S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin,
M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi,
R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford,
J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui,
K. Morokuma, D. K. Malick, A. D. Rabuck,
K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz,
A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko,
P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J.
Fox, T. Keith, M. A. AlꢀLaham, C. Y. Peng, A. Nanayakkara,
M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, J. L. Andres, C. Gonzalez, M. HeadꢀGordon,
E. S. Replogle, and J. A. Pople, GAUSSIANꢀ98, Revision A.1,
Gaussian, Inc., Pittsburgh (PA), 1998.
11. R. F. W. Bader, Atoms in Molecules: A Quantum Theory,
Clarendon Press, Oxford, 1990, 438 pp.
12. F. W. BieglerꢀKonig, R. F. W. Bader, and T.ꢀH. Tang,
J. Comput. Chem., 1982, 3, 317.
13. C. M. Fendrick, L. D. Schertz, V. M. Day, and T. J. Marks,
Organometallics, 1988, 7, 1828.
14. N. S. Zefirov, G. A. Sereda, S. E. Sosonuk, N. V. Zyk, and
T. I. Likhomanova, Synthesis, 1995, 1359.
15. D. D. Perrin, W. L. F. Armarego, and D. N. Perrin, Purifiꢀ
cation of Laboratory Chemicals, Pergamon Press, Oxford,
1966, 362 pp.
16. M. Horácek, R. Gyepes, I. Cisarová, M. Polásek, V. Varga,
and K. Mach, Collect. Czech. Chem. Commun., 1996, 61, 1307.
5
MeC(5) (3b)); 1.43 (q, MeC(4), JH,H = 1.2 Hz (3b)); 1.47 (q,
MeC(4), 5JH,H = 1.2 Hz (3c)); 1.53 (q, MeC(3), 5JH,H = 1.2 Hz
5
(3b)); 1.67 (s, MeC(1) (3c)); 1.76 (q, MeC(3), JH,H = 1.2 Hz
(3c)); 1.78 (s, MeC(2) (3b)); 1.83 (m, CH2CH2Cl (3c)); 1.94,
2.27 (both m, CH2CH2Cl (3b)); 2.75 (m, CH2Cl (3c)); 2.77,
2.93 (both m, CH2Cl (3b)). 13C NMR (C6D6), δ: –2.9 (br.q,
1
1
SiMe3, JC,H = 120 Hz (3a)); 1.25 (q, SiMe3, JC,H = 118 Hz
1
(3b)); 1.49 (q, SiMe3, JC,H = 118 Hz (3c)); 9.56, 12.78, 14.37
(all q, CH3C(1), CH3C(3), CH3C(4), JC,H = 125 Hz (3c));
9.76, 10.76, 14.91 (all q, CH3C(2), CH3C(3), CH3C(4), 1JC,H
125 Hz (3b)); 21.87 (q, CH3C(5), JC,H = 127 Hz (3c)); 22.34
(q, CH3C(5), 1JC,H = 126 Hz (3b)); 38.40 (t, CH2CH2Cl, 1JC,H
1
=
1
=
129 Hz (3c)); 39.15 (t, CH2CH2Cl, 1JC,H = 129 Hz (3b)); 40.54
(t, CH2Cl, 1JC,H = 149 Hz (3c)); 41.03 (t, CH2Cl, 1JC,H = 149 Hz
(3b)); 58.80 (s, C(5) (3c)); 60.23 (s, C(5) (3b)); 135.33, 136.75,
139.22, 158.56 (all s, C(1), C(2), C(3), C(4) (3c)); 138.07,
142.08, 147.12, 153.26 (all s, C(1), C(2), C(3), C(4) (3b)).
1,2,3,4ꢀTetramethylfulvene (4). Paraform (3.50 g,
116.4 mmol), which was preliminarily stored for a long time
in vacuo above P2O5, was depolymerized in an argon flow on
heating, and the formed formaldehyde was trapped at –30 °C in
absolute THF (100 mL). A solution of salt 1 (7.77 g, 38.8 mmol)
in THF (80 mL) was added to the resulting solution under
stirring and cooling to –20 °C for 1 h. The temperature of the
reaction mixture was brought to room temperature (~20 °C).
The reaction mixture was left to stand for ~14 h. The resulting
orange solution was filtered through a column with silica gel
(0.063—0.200 mm, 10ꢀcm layer) under argon to separate side
lithium alkoxides, and the solvent was distilled off under reꢀ
duced pressure (120 Torr). The product (orangeꢀred oil) was
distilled in vacuo (35—40 °C, 1 Torr). Compound 4 was obꢀ
tained as an orangeꢀred oil in 60% yield (3.12 g). The 1H and
Received January 15, 2004;
in revised form April 7, 2004