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REPRINTS
314
ZHONG, XIONG, AND HUANG
General Procedure for the Synthesis of 3a–g
Under nitrogen atmosphere, to a suspension of Cp2Zr(H)Cl (1.5 mmol) in
CH2Cl2 (10 mL) was added acetylenic stannane 1 (1.5 mmol) and the mixture was
stirred at room temperature for 30 min to yield a clear solution. After the mixture
had been stirred under an atmosphere of CO for 2 h, a solution of Br2 (1.5 mmol)
in 2 mL alcohol was added at room temperature, and the mixture was stirred for
1 h. The solvent was removed by rotary evaporator under reduced pressure to give
a crude oil, which was purified by preparative TLC (silica gel, hexane: AcOEt =
20:1) to give 3.
3a: a pale yellow solid, mp 106◦–108◦C (from methanol). 1H NMR:
==
δ = 3.60 (s, 3H), 7.00–7.60 (m, 21H, Ph, CH ); IR (KBr) ν = 3095, 3080, 2980,
2960, 1735, 1495, 1440 cm−1; EIMS m/z = 512 (M+, 4.1), 481 (M–CH3O, 9.5),
435 (M–Ph, 100), 351 (SnPh3, 23.5%). Anal. for C28H24O2Sn, calc. %C 65.79,
H 4.73; found C 65.55, H 4.70.
3b: a pale yellow solid, mp 108◦–110◦C (from methanol). 1H NMR:
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δ = 0.60–1.55 (m, 7H, C3 H7), 2.00 (m, 2H, CH2CH ), 3.48 (s, 3H, OCH3),
==
6.33 (t, J = 6.5 Hz, 1H, CH ), 7.00–7.70 (m, 15H, Ph); IR (KBr): ν = 3095,
2990, 2880, 1735 cm−1; EIMS m/z = 492 (M+, 3.2), 461 (M–CH3O, 12.9),
415 (M–Ph, 100), 351 (SnPh3, 14.8%). Anal. for C26H28O2Sn, calc. %C 63.58,
H 5.75; found C 63.65, H 5.77.
3c: a pale yellow solid, mp 112◦–114◦C (from methanol). 1H NMR:
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δ = 0.60–1.60 (m, 9H, C4 H9), 2.10 (m, 2H, CH2CH ), 3.47 (s, 3H, OCH3),
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6.25 (t, J = 6.5 Hz, 1H, CH ), 7.00–7.70 (m, 15H, Ph); IR (KBr) ν = 3095, 2950,
2880, 1750 cm−1; EIMS m/z = 506 (M+, 1.0), 475 (M–CH3O, 8.6), 429 (M–Ph,
100), 351 (SnPh3, 24.6%). Anal. for C27H30O2Sn, calc. %C 64.19, H 5.99; found
C 64.35, H 6.02.
1
3d: oil. H NMR: δ = 0.65–1.65 (m, 27H, C4 H9), 3.65 (s, 3H, OCH3),
−1
==
7.00–7.60 (m, 6H, Ph, CH ); IR (film) ν = 3065, 2985, 2950, 2870, 1740 cm
;
EIMS m/z = 452 (M+, 23.5), 421 (M–CH3O, 4.7), 291 (SnBu3, 100%). Anal. for
C22H36O2Sn, calc. %C 58.56, H 8.04; found: C 58.74, H 8.02.
3e: a pale yellow solid, mp 103◦–105◦C (from methanol). 1H NMR:
δ = 1.30 (t, J = 8.0 Hz, 3H), 4.00 (q, J = 8.0 Hz, 2H, OCH2), 7.00–7.60 (m, 21H,
Ph, CH ); IR (KBr) ν = 3090, 2980, 2960, 1738, 1495, 1445 cm−1; EIMS
==
m/z = 526 (M+, 4.5), 481 (M–C2H5O, 10.0), 449 (M–Ph, 100), 351 (SnPh3,
25.5%). Anal. for C29H26O2Sn, calc. %C 66.32, H 4.99; found C 65.95,
H 4.78.
3f: a pale yellow solid, mp 110◦–112◦C (from methanol). 1H NMR:
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δ = 0.60–1.55 (m, 10H), 2.05 (m, 2H, CH2CH ), 3.95 (q, J = 8.0 Hz, 2H, OCH2),
==
6.35 (t, J = 6.5 Hz, 1H, CH ), 7.05–7.70 (m, 15H, Ph); IR (KBr) ν = 3090,
2995, 2885, 1735 cm−1; EIMS m/z = 506 (M+, 3.6), 461 (M–C2H5O, 15.2), 429
(M–Ph, 100), 351 (SnPh3, 18.5%). Anal. for C27H30O2Sn, calc. %C 64.19, H 5.99;
found C 63.85, H 5.87.