EXPERIMENTAL
The course of reactions and purity of products were monitored by TLC on Silufol UV-254 and Sorbfil plates (detector
EtOH–H SO –anisaldehyde, 90:5:5). Preparative chromatography used KSKG silica gel (fr. 0.10–0.16, Ekofarm). Solvents
2
4
were purified and dried by the usual methods [11]. (+)-Camphene was purchased from Acros Organics.
13
PMR and C NMR spectra were recorded with HMDS internal standard on Bruker Avance 400 (operating frequency
1
13
1
400 and 100 MHz for H and C) and Varian Unity-300 (operating frequency 300 MHz for H) spectrometers. Chemical
shifts were measured relative to residual nuclei in the deuterated solvent.
GC-MS used a DFS Thermo Electron Corp. (USA) instrument with electron-impact ionization. The ionizing-electron
energy was 70 eV; ion-source temperature, 280°C. We used an Agilent DB-5MS capillary column (30 m ꢂ 0.254 mm) and He
carrier gas at flow rate 1 mL/min. Mass spectral data were processed using the Xcalibur program. Samples were diluted
–6
before injection into the instrument in chromatography-grade benzene to a concentration of ~10 mol/ꢃL. The sample
volume was 1 ꢃL.
General Method for Synthesizing Sulfenyl Chlorides from Disulfides [2]. Disulfide (1 mmol) in CH Cl (5 mL)
2
2
was treated with a solution of sulfuryl chloride (1 mmol) in CH Cl (5 mL) at 25–30°C and stirred for 2–5 min. The solvent
2
2
was evaporated. The sulfenyl chlorides were used in the reactions with (+)-camphene.
General Method for Reacting (+)-Camphene with Sulfenyl Chlorides. Freshly prepared sulfenyl chloride
(2 mmol) in CH Cl (4 mL) at room temperature was stirred, treated with the terpene (1, 2 mmol) dissolved in CH Cl (4 mL,
2
2
2
2
reagent ratio 1:1), and stirred in a flask on a magnetic stirrer. The course of the reaction was monitored by TLC. When the
reaction was finished (5–10 d), the solvent was evaporated (water aspirator). The reaction products were isolated by column
chromatography over silica gel (n-hexane–CH Cl , 60:40) and were yellowish odorless oils. Product yields (%): 40 (2),
2
2
70 (3), 87 (5).
1
2-{[(Z)-(3,3-Dimethylbicyclo[2.2.1]hept-2-ylidene)methyl]thio}-4,6-dimethylpyrimidine (2a). H NMR spectrum
(400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.23, 1.27 (each 3H, s, H-8, 9), 1.91, 2.85 (each 1H, br.s, H-1, 4), 1.17–1.82 (6H, m, H-5, 6,
3
13
7), 2.42 (6H, s, 2ÑÍ -Ar), 6.68 (1H, s, H-10), 6.75 (1H, s, Ar-H). C NMR spectrum (100 MHz, CDCl , ꢄ, ppm): 23.5
3
3
(C-8), 23.7, 23.8 (2ÑÍ -Ar), 23.9 (C-9), 24.5 (C-5), 28.9 (C-6), 37.1 (C-7), 42.5 (C-3), 49.0 (C-4), 50.0 (C-1), 104.4 (C-2),
3
115.8 (C-10), 156.2 (C-13), 167.0 (C-12, 14), 169.5 (C-11).
1
2-{[(E)-(3,3-Dimethylbicyclo[2.2.1]hept-2-ylidene)methyl]thio}-4,6-dimethylpyrimidine (2b). H NMR spectrum
(400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.23, 1.25 (each 3H, s, H-8, 9), 1.95, 3.05 (each 1H, br.s, H-1, 4), 1.17–1.82 (6H, m, H-5, 6,
3
13
7), 2.42 (6H, s, 2ÑÍ -Ar), 6.34 (1H, s, H-10), 6.75 (1H, s, Ar-H). C NMR spectrum (100 MHz, CDCl , ꢄ, ppm): 23.5
3
3
(C-8), 23.7, 23.8 (2ÑÍ -Ar), 23.9 (C-9), 24.5 (C-5), 28.9 (C-6), 37.1 (C-7), 43.9 (C-3), 48.2 (C-4), 50.0 (C-1), 104.4 (C-2),
3
115.8 (C-10), 156.2 (C-13), 167.0 (C-12, 14), 169.5 (C-11).
1
2-{[(E)-(3,3-Dimethylbicyclo[2.2.1]hept-2-en-2-yl)methyl]thio}-1,3-benzothiazole (3a). H NMR spectrum
(400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.14, 1.26 (each 3H, s, H-8, 9), 2.08, 3.36 (each 1H, br.s, H-1, 4), 1.17–1.77 (6H, m, H-5, 6,
3
13
7), 6.03 (1H, s, H-10), 7.32, 7.44, 7.79, 7.91 (each 1H, s, Ar-H). C NMR spectrum (100 MHz, CDCl , ꢄ, ppm): 23.4 (C-8),
3
23.6, 23.7 (2ÑÍ -Ar), 25.5 (C-9), 27.7 (C-5), 28.6 (C-6), 37.3 (C-7), 44.1 (C-3), 44.2 (C-4), 48.3 (C-1), 102.4 (C-2), 162.1
3
+
(C-10), 120.8, 121.6, 123.9, 126.0, 135.1, 154.2, 172.7 (7Ñ-Ar). Mass spectrum, m/z (I , %): 301 [M ] (48), 286 (18), 268
rel
(15), 258 (26), 232 (80), 218 (30), 205 (48), 167 (37), 135 (42), 119 (28), 107 (63), 91 (100), 77 (56), 67 (47), 65 (30), 53
(27).
1
2-{[(Z)-(3,3-Dimethylbicyclo[2.2.1]hept-2-en-2-yl)methyl]thio}-1,3-benzothiazole (3b). H NMR spectrum
(400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.14, 1.26 (each 3H, s, H-8, 9), 1.96, 3.04 (each 1H, br.s, H-1, 4), 1.17–1.77 (6H, m, H-5, 6,
3
13
7), 6.32 (1H, s, H-10), 7.32, 7.44, 7.79, 7.91 (each 1H, s, Ar-H). C NMR spectrum (100 MHz, CDCl , ꢄ, ppm): 23.6 (C-8),
3
25.6 (C-9), 27.7 (C-5), 28.6 (C-6), 37.0 (C-7), 44.1 (C-3), 50.0 (C-4), 53.5 (C-1), 102.8 (C-2), 162.1 (C-10), 120.9, 121.6,
+
124.0, 126.0, 135.1, 154.2, 172.7 (7Ñ-Ar). Mass spectrum, m/z (I , %): 301 [M ] (48), 286 (18), 268 (15), 258 (26), 232 (80),
rel
218 (30), 205 (48), 167 (37), 135 (42), 119 (28), 107 (63), 91 (100), 77 (56), 67 (47), 65 (30), 53 (27).
8ꢅ-(Methoxycarbonyl)-3,3-dimethylspiro[bicyclo[2.2.1]heptane-2,3ꢅ-[1,3]thiazolo[3,2-a]pyridin[4]ium] Chloride
1
(5). H NMR spectrum (400 MHz, ÑDCl , ꢄ, ppm, J/Hz): 1.20, 1.28 (each 3H, s, H-8, 9), 1.17–1.85 (6H, m, H-5, 6, 7), 3.26
3
13
(2H, br.s, H-1, 4), 3.88–4.07 (2Í, m, SCH ), 3.98 (3Í, s, OCH ), 8.21, 8.73, 9.79 (each 1H, s, Ar-H). C NMR spectrum
2
3
(100 MHz, CDCl , ꢄ, ppm): 22.7 (C-8), 24.4 (C-9), 26.3 (C-5), 26.3 (C-6), 37.5 (C-7), 35.9 (C-2), 44.4 (C-3), 48.5 (C-4), 49.6
3
(C-1), 50.2 (C-10), 54.0 (ÎCÍ ), 90.8 (CÎ), 124.4, 145.2, 147.6, 162.8, 163.1 (5Ñ-Ar). Mass spectrum, m/z (I , %): 304
3
rel
673