REACTIONS OF TRICYCLO[4.1.0.02,7]HEPTANE
1019
6-endo-Bromo-7-syn-(2-bromoethanesulfonyl)-6-
exo-methylbicyclo[3.1.1]heptane (4b). Yield 0.29 g
(8.0%), mp 95–96°C (from CH2Cl2–hexane). IR spec-
trum, ν, cm–1: 2961 m, 1450 m, 1304 s (SO2, asym.),
1288 s, 1134 v.s (SO2, sym.), 1030 m, 740 s, 686 s.
1H NMR spectrum, δ, ppm: 1.72–1.83 m (1H,
3-endo-H), 1.87–1.96 m (1H, 3-exo-H), 2.12 s (3H,
CH3), 2.10–2.27 m (2H, 2-endo-H, 4-endo-H), 2.38–
2.58 m (2H, 2-exo-H, 4-exo-H), 2.90 br.d (2H, 1-H,
5-H), 3.40 t (2H, CH2Br, J = 8.0 Hz), 3.59 t (2H,
CH2SO2, J = 7.9 Hz), 3.85 t (1H, 7-anti-H, J = 5.7 Hz).
13C NMR spectrum, δC, ppm: 12.7 (C3), 20.5 (CH2Br),
25.2 (C2, C4), 29.0 (CH3), 51.2 (C1, C5), 54.4 (C7), 57.2
(CH2SO2), 66.3 (C6). Found, %: C 33.39; H 4.51.
C10H16Br2O2S. Calculated, %: C 33.35; H 4.48.
disappeared (TLC). The solvent was removed under
reduced pressure, and the residue was analyzed by TLC
and H NMR. The main products were isolated by
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alumina column chromatography and crystallization.
7-anti-Bromo-6-endo-(2-bromoethanesulfonyl)-
bicyclo[3.1.1]heptane (3a). Yield 1.64 g (47.5%),
mp 112–113°C (from CH2Cl2–hexane). IR spectrum, ν,
cm–1: 2955 m, 1454 m, 1308 s (SO2, asym.), 1290 s,
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1137 v.s (SO2, sym.), 1025 m, 745 s, 690 s. H NMR
spectrum, δ, ppm: 1.71–1.80 m (1H, 3-endo-H), 1.84–
1.94 m (1H, 3-exo-H), 1.99–2.11 m (2H, 2-endo-H,
4-endo-H), 2.49–2.57 m (2H, 2-exo-H, 4-exo-H),
3.08 br.d (2H, 1-H, 5-H), 3.45 t (2H, CH2Br, J =
8.0 Hz), 3.65 t (2H, CH2SO2, J = 7.9 Hz), 4.10 s (1H,
7-syn-H), 4.27 t (1H, 6-exo-H, J = 5.8 Hz). 13C NMR
spectrum, δC, ppm: 13.4 (C3), 20.6 (CH2Br), 25.0 (C2,
C4), 48.7 (C1, C5), 51.2 (C7), 57.0 (CH2SO2), 57.9 (C6).
Found, %: C 31.23; H 4.06. C9H14Br2O2S. Calculat-
ed, %: C 31.24; H 4.08.
Reaction of bicycloheptanes 3a, 3b, 4a, and 4b
with triethylamine (general procedure). A solution of
0.069 mL (0.5 mmol) of triethylamine in 2 mL of
anhydrous benzene was added to a solution of
0.5 mmol of compound 3a, 3b, 4a, or 4b in 5 mL of
anhydrous benzene. The mixture was stirred for 1 h at
0°C, the precipitate of triethylamine hydrobromide was
filtered off and washed with 10 mL of benzene, the
filtrate was combined with the washings, washed with
water (2×5 mL), and dried over MgSO4. The solvent
was distilled off on a rotary evaporator, and the
7-syn-Bromo-6-endo-(2-bromoethanesulfonyl)-
bicyclo[3.1.1]heptane (4a). Yield 1.03 g (29.7%),
mp 99–100°C (from CH2Cl2–hexane). IR spectrum, ν,
cm–1: 2951 m, 1450 m, 1304 s (SO2, asym.), 1288 s,
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1134 v.s (SO2, sym.), 1030 m, 740 s, 686 s. H NMR
spectrum, δ, ppm: 1.75–1.84 m (2H, 3-H), 1.98–2.08 m
(2H, 2-endo-H, 4-endo-H), 2.35–2.44 m (2H, 2-exo-H,
4-exo-H), 3.00 br.d (2H, 1-H, 5-H), 3.39 t (2H, CH2Br,
J = 7.8 Hz), 3.40 t (1H, 7-anti-H, J = 5.7 Hz), 3.68 t
(2H, CH2SO2, J = 8.0 Hz), 4.41 t (1H, 6-exo-H, J =
5.8 Hz). 13C NMR spectrum, δC, ppm: 12.5 (C3), 20.7
(CH2Br), 21.6 (C2, C4), 45.2 (C1, C5), 48.6 (C7), 56.8
(C6), 57.2 (CH2SO2). Found, %: C 31.29; H 4.11.
C9H14Br2O2S. Calculated, %: C 31.24; H 4.08.
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crystalline residue was analyzed by H and 13C NMR
and purified by crystallization.
7-anti-Bromo-6-endo-(ethenesulfonyl)bicy-
clo[3.1.1]heptane (5a). Yield 91 mg (68.6%), mp 98–
99°C (from CH2Cl2–hexane). IR spectrum, ν, cm–1:
3091 m, 2950 m, 1648 m (C=C), 1451 m, 1311 s (SO2,
asym.), 1291 s, 1142 v.s (SO2, sym.), 1041 m, 746 s,
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695 s. H NMR spectrum, δ, ppm: 1.75–1.80 m (1H,
3-endo-H), 1.86–1.97 m (1H, 3-exo-H), 2.00–2.15 m
(2H, 2-endo-H, 4-endo-H), 2.53–2.64 m (2H, 2-exo-H,
4-exo-H), 3.16 br.d (2H, 1-H, 5-H), 4.11 s (1H,
7-syn-H, J = 5.7 Hz), 4.47 t (1H, 6-exo-H, J = 5.8 Hz),
6.57 d.d (1H, CH2=, J = 10.7, 1.8 Hz), 7.08 d.d (1H,
CH2=, J = 17.1, 1.8 Hz), 7.60 d.d (1H, SO2CH=, J =
6-exo-Bromo-7-syn-(2-bromoethanesulfonyl)-6-
endo-methylbicyclo[3.1.1]heptane (3b). Yield 2.54 g
(70.5%), mp 126–127°C (from CH2Cl2–hexane). IR
spectrum, ν, cm–1: 2963 m, 1456 m, 1308 s (SO2,
asym.), 1290 s, 1129 v.s (SO2, sym.), 1027 m, 743 s,
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13
17.1, 10.7 Hz). NMR spectrum, δC, ppm: 13.5 (C3),
681 s. H NMR spectrum, δ, ppm: 1.45–1.55 m (1H,
25.1 (C2, C4), 49.3 (C1, C5), 51.8 (C7), 58.1 (C6), 130.5
(CH2=), 137.2 (=CHSO2). Found, %: C 40.71; H 4.90.
C9H13BrO2S. Calculated, %: C 40.77; H 4.94.
3-endo-H), 1.57–1.69 m (1H, 3-exo-H), 1.92 s (3H,
CH3), 1.94–2.17 m (2H, 2-endo-H, 4-endo-H),
2.28–2.50 m (2H, 2-exo-H, 4-exo-H), 3.09 br.d (2H,
1-H, 5-H), 3.44 t (2H, CH2Br, J = 7.9 Hz), 3.61 t
(2H, CH2SO2, J = 7.9 Hz), 4.59 t (1H, 7-anti-H, J =
5.7 Hz). 13C NMR spectrum, δC, ppm: 12.3 (C3),
20.6 (CH2Br), 23.8 (C2, C4), 23.8 (CH3), 53.4 (C1, C5),
57.1 (CH2SO2), 57.8 (C7), 68.1 (C6). Found, %:
C 33.39; H 4.51. C10H16Br2O2S. Calculated, %:
C 33.35; H 4.48.
7-syn-Bromo-6-endo-(ethenesulfonyl)bicy-
clo[3.1.1]heptane (6a). Yield 86 mg (65.0%), mp 81–
82°C (from CH2Cl2–hexane). IR spectrum, ν, cm–1:
3090 m, 2949 m, 1647 m (C=C), 1448 m, 1310 s (SO2,
asym.), 1295 s, 1139 v.s (SO2, sym.), 1031 m, 745 s,
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690 s. H NMR spectrum, δ, ppm: 1.55–1.74 m (2H,
3-H), 1.78–1.98 m (2H, 2-endo-H, 4-endo-H), 2.15–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 6 2020