2170
B.A. Bulgakov et al. / Tetrahedron 68 (2012) 2166e2171
ꢀ
pressure (2e5 mmHg, 20e90 C) to give the desired products as
residual viscous oils. Yields were calculated based on ethylene/
acetylene used.
(C(2), C(5)), 23.7, 23.1 (C(4)), 22.3, 21.4 (C(3)), ꢂ1.2, ꢂ4.3 (Ge(CH
IR:
¼3120, 3057, 1598, 1551, 1315, 1276, 1240, 1229, 830, 752, 710,
590, 580; m/z (EI): 238, M (2%), 119, Ge(CH
3 3
) );
n
þ
3
)
3
(100%). Elemental
analysis calculated for C12
H, 8.42.
H20Ge: C, 60.84; H, 8.51. Found: C, 60.70;
4
.2.1. 3-Trichlorogermyltricyclo[4.2.1.02,5]nonene-7 (9). To achieve
better conversion of the ethylene into the desired product 2.5-fold
excess of Q was used. The desired product was obtained as
4.3.2. 3-Trimethylsilyltricyclo[4.2.1.02,5]nona-3,7-diene
desired product was obtained as a colorless liquid. Yield 60%. H
NMR: ), 6.12e6.03 (m, 2H, CH]CH),
¼6.67 (s, 1H, CH]CSi(CH
2.43e2.30 (m, 4H), 1.42 (d, J¼8.7 Hz, 1H, CH
(16). The
1
1
a
moisture-sensitive colorless liquid. Yield 62%.
H NMR:
d
¼5.50e5.43 (m, 2H, CH]CH), 2.68 (br s, 0.4H, C(1)H, C(6)H),
d
3 3
)
2
2
2
.30e2.20 (m, 1.6H, C(1)H, C(6)H), 1.98e1.73 (m, 3.6H), 1.45e1.24
2
), 1.20 (d, J¼8.7 Hz,
¼156.4 (C(3)), 149.4
(C(4)), 135.5, 135.2 (C(7), C(8)), 46.6, 46.5 (C(1), C(6)), 39.4 (C(9)),
); IR:
1
3
13
(
1
3
(
m, 2.4H), 0.93e0.91 (m, 1H, C(9)H
34.9, 134.1 (C(7), C(8)), 44.5, 44.4, 43.8, 43.3, 41.6, 40.2, 38.8, 37.5,
7.2, 35.7 (C(1), C(2), C(3), C(5), C(6)), 40.5, 39.7 (C(9)), 24.9, 22.9
C(4)).
2
); C NMR:
d¼135.4, 135.0,
2 3 3
1H, CH ), 0.06 (s, 9H, Si(CH ) ); C NMR: d
38.6, 38.3 (C(2), C(5)), ꢂ1.7 (Si(CH
3
)
3
n
¼3127, 3059, 3011, 1604,
1562,1552,1364,1288,1248,1226,1199, 885, 837, 817, 746, 701, 676,
þ
6
29, 498, 484; m/z (EI): 190, M (1%), 73, Si(CH
3
)
3
(100%). Elemental
4
.2.2. 3-Trichlorolsilyltricyclo[4.2.1.02,5]nona-3,7-diene
(13). The
analysis calculated for C12
H, 9.62.
H18Si: C, 75.71; H, 9.53. Found: C, 75.85;
desired product was obtained as a moisture-sensitive colorless
1
liquid. Yield 75%. H NMR:
(
d
¼6.98 (s, 1H, CH]CSiCl
3
), 5.94e5.86
13
4.3.3. 3,4-Bis-(trimethylsilyl)tricyclo[4.2.1.02,5]nona-3,7-diene
m, 2H, CH]CH), 2.46e2.22 (m, 4H), 1.27e1.15 (m, 2H, CH
2
);
C
NMR:
d
¼158.9, 146.2, 135.5, 135.0 (C(3), C(4), C(7), C(8)), 47.4, 47.1,
(17). The desired product was obtained as a colorless liquid. Yield
1
3
8.3, 38.1 (C(1), C(2), C(5), C(6)), 39.2 (C(9)).
55%. H NMR:
d
¼6.07e6.02 (m, 2H, CH]CH), 2.35 (br s, 2H), 2.28
2
2
(
br s, 2H), 1.30 (d, J¼8.7 Hz, 1H, CH
2
), 1.13 (d, J¼8.7 Hz, 1H, CH
2
),
.2.3. 3,4-Bis-(Trichlorosilyl)tricyclo[4.2.1.02,5]nona-3,7-diene
0.10 (s, 18H, Si(CH
)
3
); C NMR:
13
d
¼167.8 (C(3), C(4)), 134.6 (C(7),
4
3
(14). The desired product was obtained as a moisture-sensitive
C(8)), 47.1 (C(1), C(6)), 39.1 (C(9)), 38.7 (C(2), C(5)), ꢂ0.6 (Si(CH
IR:
¼3125, 3058, 1607, 1562, 1524, 1320, 1281, 1248, 1192, 885, 833,
3 3
750, 703, 691, 625, 498, 485; m/z (EI): 262, M (2%), 73, Si(CH )
3 3
) );
1
colorless liquid. Yield 92%. H NMR:
d
¼5.80e5.77 (m, 2H, CH]
n
2
þ
CH), 2.36e2.23 (m, 4H), 1.08 (d, J¼9.7 Hz, 1H, CH ), 1.01 (d,
2
2
13
J¼9.7 Hz, 1H, CH
2
). C NMR:
d¼164.9, 134.8 (C(3), C(4), C(7), C(8)),
2
(100%). Elemental analysis calculated for C15H26Si : C, 68.62; H,
4
9.3, 38.3 (C(1), C(2), C(5), C(6)), 38.8 C(9).
9.98. Found: C, 68.79; H, 10.14.
4
.2.4. 3-Trichlorogermyltricyclo[4.2.1.02,5]nona-3,7-diene
(15). To
4.3.4. 3-Trimethylgermyltricyclo[4.2.1.02,5]nona-3,7-diene (18). The
desired product was obtained as a colorless liquid. Yield 60%. H
1
achieve better conversion of the acetylene into the desired product
.5-fold excess of Q was used. The desired product was obtained as
4
NMR:
d
¼6.58 (s, 1H, CH]CGe(CH
3 3
) ), 6.10e6.03 (m, 2H, CH]CH),
1
2
a moisture-sensitive colorless liquid. Yield 78%. H NMR:
H, CH]CGeCl ), 5.70e5.60 (m, 2H, CH]CH), 2.31 (br s, 1H), 2.27
br s, 1H), 2.11 (br s, 1H), 2.04 (br s, 1H), 1.82e1.70 (m, 1H, C(9)H ),
¼157.6 (C(4)), 145.3 (C(3)),
d
¼6.65 (s,
2.45e2.39 (m, 1H), 2.36e2.29 (m, 3H), 1.43 (d, J¼7.7 Hz, 1H, CH
2
),
2
13
1
(
0
3
1.21 (d, J¼7.7 Hz, 1H, CH
), 0.19 (s, 9H, Ge(CH ) ); C NMR:
2 3 3
2
d
¼156.7 (C(3)), 147.7 (C(4)), 135.5, 135.3 (C(7), C(8)), 47.6, 46.9 (C(1),
1
3
.97e0.89 (m, 1H, C(9)H
2
); C NMR:
d
C(6)), 39.4 (C(9)), 38.5, 38.2 (C(2), C(5)), ꢂ2.2 (Ge(CH
3 3
) ); IR:
135.6, 135.1 (C(7), C(8)), 49.7, 48.2, 37.9, 37.7 (C(1), C(2), C(5), C(6)),
n
¼3125, 3058, 3012, 1603, 1563, 1549, 1319, 1288, 1238, 1225, 1200,
þ
3
9.0 (C(9)).
825, 751, 700, 600, 571, 493, 473; m/z (EI): 236, M (1%), 119,
Ge(CH (100%). Elemental analysis calculated for C12 18Ge: C,
61.36; H, 7.72. Found: C, 61.09; H, 7.60.
3
)
3
H
4
.3. Methylation of products 9, 13e15
General procedure. To a solution of CH
3
MgI prepared from Mg
4.3.5. 5-Trichlorogermyl-6-chloronorbornene-2 (19). Freshly dis-
tilled GeCl (1.20 g, 5.59 mmol) and Q (0.98 g, 10.7 mmol) were
(
12.4 g, 0.51 mol) and methyl iodide (71.1 g, 0.50 mol) in diethyl
ether (200 mL), 3-(trichlorosilyl)tricyclononadiene-7 (13) (20.5 g,
1.5 mmol) in diethyl ether (20 mL) was added dropwise during 1 h
4
mixed in an ampoule under an argon atmosphere. Thereafter the
ꢀ
8
ampoule was sealed and heated at 95 C for 12 h. Then the ampoule
as the mixture gently refluxed. The reaction mixture was then
refluxed for an additional 8 h, cooled to room temperature and
allowed to stand overnight. The diethyl ether was evaporated and
the residue was extracted with absolute hexane (5ꢁ80 mL). The
combined extracts were concentrated under reduced pressure
was opened and the volatile fractions were removed under reduced
pressure (2 mmHg). Compound 19 (0.43 g) was isolated as a mois-
1
ture-sensitive colorless transparent liquid. Yield 25%. H NMR:
d
¼5.74e5.72 (m, 1H, CH]CH), 5.55e5.52 (m, 1H, CH]CH), 3.51 (d,
3
J¼6.5 Hz, 1H, CHCl) 2.71 (br s, 1H), 2.56 (br s, 1H), 2.01 (d,
2
2
2
(
15 mmHg) until a viscous oil was formed. The products were pu-
rified by flash chromatography (eluentdhexane). During methyl-
ation of products and 15 with methylmagnesium iodide
compound 19 probably underwent -elimination resulting in NBD,
J¼6.5 Hz, 1H), 1.62 (d, J¼9.5 Hz, 1H, CH
2
), 1.13 (d, J¼9.5 Hz, 1H,
13
CH
2
); C NMR: 140.2, 135.2 (C(2), C(3)), 57.1, 55.2, 51.8, 43.9 (C(1),
þ
9
C(4), C(5), C(6)), 44.8 (C(7)); m/z (EI): 306, M (0.5%), 179, GeCl
3
b
(2%), 66, C
5 6
H (100%).
which was easily removed from the desired products under re-
duced pressure. The formation of NBD was confirmed by GCeMS.
4.3.6. 3-Trimethylsilyl-4-(p-methylphenyl)sulfonyltricyclo[4.2.1.02,5
]
nona-3,7-diene (20). 1-Trimethylsilyl-2-(p-methylphenyl)sulfony-
lacetylene (2.86 g, 11.3 mmol) was mixed with Q (1.56 g, 17.0 mmol)
and sealed in an ampoule under an atmosphere of argon. Then the
4
.3.1. 3-Trimethylgermyltricyclo[4.2.1.02,5]nonene-7 (12). The de-
sired product was obtained as a colorless liquid. Yield 75%. The
monomer corresponds to a mixture of syn- and anti-isomers (ratio
of the isomers is 35:65). H NMR:
2
ꢀ
ampoule was stored for 240 h at 25 C. After that the mixture was
1
d
¼5.95e5.86 (m, 2H, CH]CH),
dried under reduced pressure (2 mmHg) to remove norbornadiene
and Q. The solid residue was purified by flash chromatography
(eluentdhexane/ethylacetate 19:1) and recrystallized from etha-
nol. The desired product was obtained as a white powder (0.82 g,
.69 (br s, 0.35H, C(1)H, C(6)H), 2.61e2.52 (m, 1.65H, C(1)H, C(6)H),
.18e2.10 (m, 1.35H), 1.91e1.70 (m, 2.65H), 1.52e1.46 (m, 0.65H),
2
1.32e1.24 (m, 1.7H), 1.12e1.10 (m, 0.65H), 0.12, 0.10 (s, 9H,
1
3
ꢀ
Ge(CH
4
3
)
3
); C NMR:
d
¼135.7, 134.9, 134.7, 134.6 (C(7), C(8)), 45.6,
2.48 mmol). Yield 21%. Melting point 83e85 C. Monocrystal of 20
1
4.7, 44.6, 44.3 (C(1), C(6)), 40.8, 40.0 (C(9)), 40.3, 39.2, 37.3, 35.7
was obtained from hexane/ethylacetate mixture (9:1). H NMR: