SYNTHESIS OF 7-SULFONYL-SUBSTITUTED NORPINAN-6-ONES AND -THIONES
1701
1150 v.s (SO2, sym.), 1088 m, 764 m, 725 s, 691 m,
606 s, 559 m.
This study was performed in part in the framework
of the base part of state contract no. 2014/134 (project
no. 2312).
7-exo-(Benzenesulfonyl)bicyclo[3.1.1]heptane-6-
thione (5). 1,8-Diazabicylo[5.4.0]undec-7-ene, 300 mg
(2 mmol), was added dropwise to a solution of 340 mg
(0.9 mmol) of compound 3a in 5 mL of anhydrous
methylene chloride. The mixture was stirred for 48 h at
25°C, the solvent was removed, and the residue was
purified by dry-column flash chromatography (ethyl
acetate–hexane, 1:3). Yield 123 mg (51%), light
orange crystals, mp 142–143°C (from hexane–
t-BuOMe). IR spectrum, ν, cm–1: 1446 m, 1362 m,
1303 s (SO2, asym.), 1273 m, 1242 m, 1165 m,
1146 v.s (SO2, sym.), 1088 m (C=C), 752 m, 721 m,
REFERENCES
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Spectrometric Identification of Organic Compounds,
New York: Wiley, 2005, 7th ed.
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1
687 m, 594 m, 586 m, 548 m. H NMR spectrum, δ,
Razin, V.V., Russ. J. Org. Chem., 1999, vol. 35, p. 1769.
ppm: 1.58–1.80 m (2H, 3-H), 2.89–2.55 m (4H, 2-H,
4-H), 3.52 s (2H, 1-H, 5-H), 3.75 s (1H, 7-endo-H),
7.55 t (2H, Harom, J = 7.8 Hz), 7.58 t (1H, Harom, J =
7.3 Hz), 7.90 d (2H, Harom, J = 8.1 Hz). 13C NMR spec-
trum, δC, ppm: 15.5 (C3), 38.8 (C2, C4), 63.5 (C7), 64.1
(C1, C5), 129.0 (2C, Carom), 129.6 (2C, Carom), 134.5
(Carom), 137.6 w (Carom), 261.6 (C=S). Found, %:
C 52.71; H 5.49; S 24.24. C13H14O2S2. Calculated, %:
C 58.62; H 5.30; S 24.07.
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Razin, V.V., Russ. J. Org. Chem., 2010, vol. 46, p. 624.
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vol. 30, p. 1351.
7-exo-(Benzenesulfonyl)bicyclo[3.1.1]heptan-6-
one (6). Thioketone 5, 100 mg (0.38 mmol), was
dissolved in 5 mL of dioxane, 5 mL of 5 M aqueous
sodium hydroxide and 90 mg of benzyl(triethyl)am-
monium chloride were added, and the mixture was
stirred for 3 h at 50°C. The mixture was then cooled to
0°C, neutralized with 4 mL of dilute (1:1) aqueous
HCl, and extracted with CH2Cl2 (3×15 mL). The com-
bined extracts were dried over MgSO4 and evaporated
under reduced pressure, and the residue was subjected
to dry-column flash chromatography (ethyl acetate–
hexane, 1:2). Yield 55 mg (58%), colorless crystals,
mp 128–129°C (from hexane–CHCl3). IR spectrum, ν,
cm–1: 2970 w, 2947 w, 1797 v.s. (C=O), 1450 w,
1308 s (SO2, asym.), 1265 w, 1146 v.s (SO2, sym.),
1090 m, 1030 w, 918 w, 756 w, 717 w, 694 m, 594 m,
10. Vasin, V.A., Romanova, E.V., Kostryukov, S.G., and
Razin, V.V., Russ. J. Org. Chem., 1999, vol. 35, p. 1161.
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dunarodnogo simpoziuma “Khimiya alifaticheskikh
diazosoedinenii: dostizheniya i perspektivy,” posvya-
shchennogo 100-letiyu so dnya rozhdeniya professora
I.A. D’yakonova (Proc. Vth Int. Symp. “Chemistry of
Aliphatic Diazo Compounds: Advances and Prospects,”
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1
552 m. H NMR spectrum, δ, ppm: 1.58–1.74 m (2H,
3-H), 2.33–2.47 m (4H, 2-H, 4-H), 3.40 br.s (2H, 1-H,
5-H), 3.36 s (1H, 7-endo-H), 7.60 t.t (2H, Harom, J =
1.3, 7.3 Hz), 7.77 t.t (1H, Harom, J = 1.7, 7.3 Hz),
13
7.93 d.t (2H, Harom, J = 1.7, 7.3 Hz). C NMR spec-
trum, δC, ppm: 16.1 (C3), 34.3 (C2, C4), 58.8 (C1, C5),
61.3 (C7), 128.7 (2C, Carom), 129.7 (2C, Carom), 134.4
(Carom), 137.5 (Carom), 207.0 (C=O). Found, %:
C 62.42; H 5.69; S 12.77. C13H14O3S. Calculated, %:
C 62.38; H 5.64; S 12.81.
18. Vasin, V.A., Korovin, D.Yu., and Somov, N.V., Vestn.
Nizhegorod. Gos. Univ., 2013, vol. 3, no. 1, p. 102.
19. Vasin, V.A., Masterova, Yu.Yu., Razin, V.V., and
Somov, N.V., Can. J. Chem., 2013, vol. 91, p. 465.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 12 2015