MIHAILOV et al.
1634
angles in HNCX (X = O, S, Se) grow in the series NCO
(172.7°) < NCS (173.8°) < NCSe (175.0°) [12].
C6H6]+ (0.5), 222 [M – PhCN]+ = [Ph2C3(=S)]+ (5.4),
221 [M – C6H6 – CN]+ (9.8), 214 [M – Ph – H2S]+ (1.1),
213 [M – C6H6 – H2S]+ (1.5), 190 [Ph2C3]+ (3.0), 178
[Ph2C2]+ (5.6), 115 [PhC3H2]+ (6.0), 113 [PhC3]+ (7.7),
103 [PhC2H2]+ (31.2), 101 [PhC2]+ (2.1), 89 [C7H5]+
(10.9), 77 [Ph]+ (14.2), 76 [C6H4]+ (18.9), 59 [HNCS]+
(4.6), 32 [S]+ (4.2), 27 [HCN]+ (9.3). Found, %: C 81.00;
H 4.77; N 4.22; S 9.68. C22H15NS. Calculated, %: C 81.20;
H 4.65; N 4.30; S 9.85.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
Specord 75IR from mulls in mineral oil in a thin film.
1H NMR spectra of compounds under investigation were
registered on a spectrometer Bruker-AM at operating
frequency 300 ΜHz at concentration of compounds
0.05 mol l–1. 13C and 13C APT spectra were obtained
on a spectrometer Bruker-AM at operating frequency
75.47 MHz at concentration of compounds 0.5 mol l–1.
Mass spectra were measured on HP 5995 A instrument
with a direct admission of the sample into the ion source,
ionizing energy 70 eV, 60°C.
Compound (V). mp 128–130°C. IR spectrum, cm–1:
2190–1990 (NCS), 1840 (C1–C3 skeletal), 1620, 1610
(C=C), 1410, 1300, 1180, 1020, 860. 1H NMR spectrum
(CDCl3, 5°C), δ, ppm: 3.64 s (3H, OMε), 6.82–7.30 br.m
(8H), 7.38–7.53 br.m (6H arom). 13C NMR spectrum
(CDCl3, 5°C), δ, ppm: 45.60, 47.75 (C3), 55.00, 55.32
(OMe), 117.51, 118.42, 119.27 (C1,2), 128.67, 128.91
(NCS), 127.81, 128.90, 136.23, 140.30, 144.30, 158.90,
161.16 (Ciarom), 115.16–132.50 (Carom). Mass spectrum,
m/z (Irel, %): 355 [Ph2(CH3OC6H4)C3NCS]+ = [M]+
(28.4), 340 [M–CH3]+ (4.7), 329 [M–CN]+ (0.4), 328
[M–HCN]+ (0.5), 324 [M–OCH3]+ (3.9), 323 [M–S]+
(13.0), 314 [M–CH3–CN]+ (0.9), 313 [M–CH3– HCN]+
(1.0), 311 [M–SC]+ (0.8), 310 [M–HCS]+ (0.9), 309
[M–H2CS]+ (1.6), 308 [M–CH3S]+ (5.3), 307 [M–
CH3SH]+ (1.5), 297 [M–NCS]+ (100), 296 [M–HNCS]+
(1.0), 292 [M–CH3O–S]+ (2.5), 291 [M–CH3O–HS]+
(2.4), 290 [M–CH3O–H2S]+ (3.1), 283 [M–NCS –CH2]+
(2.7), 282 [M–NCS–CH3]+ (7.8), 281 [M–HNCS–
CH3]+ (7.3), 280 [M–NCS–CH4]+ (6.7), 278 [M–C6H5]+
(6.5), 277 [M–C6H6]+ (4.4), 266 [M–NCS–CH3O]+
(9.7), 265 [M–NCS–CH3OH]+ (21.3), 264 [M–HNCS–
CH3OH]+ (4.8), 252 [M–C6H5CN]+ (44.3), 248 [M–
CH3OC6H4]+ (1.3), 246 [M–C6H5–S]+ (6.3), 237 [M–
C6H5–CH3CN]+ (8.5), 221 [M–CH3OC6H5–HCN]+
(5.3), 219 [M–C6H5–HNCS]+ (1.8), 214 [M–
CH3OC6H5–H2S]+ (4.8), 213 [M–CH3OC6H6–H2S]+
(4.2), 209 [M–H3OC6H5≡CC6H5]+ (6.5), 190 [Ph2C3]+
(4.6), 178 [Ph2C2]+ (7.8), 165 [CH3OC6H4NCS]+ (28.9),
151 [HOC6H4NCS]+ (11.5), 135 [C6H5NCS]+ (14.1), 115
[PhC3H2]+ (9.2), 113 [PhC3]+ (17.4), 108 [CH3OC6H5]+
(4.3), 107 [CH3OC6H4]+ (3.1), 77 [Ph]+ (25.4), 76
[C6H4]+ (12.2), 59 [HNCS]+ (11.1), 32 [S]+ (11.3), 27
[HCN]+ (8.4), 15 [CH3]+ (24.2). Found, %: C 77.67; H
4.90; N 4.01; S 8.95. C23H17NOS. Calculated, %: C 77.72;
H 4.82; N 3.94; S 9.02.
3-Iso(thio,seleno)cyanato-1,2,3-triarylcyclo-
propenes (III–VII). To a solution of 4 mmol of KOCN
(or KSCN, KSeCN) in 20 ml of CH3CN was added at
24°C while vigorous stirring 4 mmol of powdered 1,2,3-
triarylcyclopropenylium bromide I or II [6]. The mixture
was stirred at this temperature for 30 min and then it
was boiled for 15 min. The solvent was removed at
reduced pressure, the solid residue was washed with
water (10 × 2 ml), and dried in a vacuum-desiccator.
Reaction products were twice crystallized from
acetonitrile. Colorless crystals. Yields of compounds: 41
(III), 87 (IV), 85 (V), 62 (VI), 65% (VII).
Compound (III). mp 54–55°C. IR spectrum, cm–1:
2250 (NCO), 1805 (C1–C3 skeletal), 1600 (C=C).
1H NMR spectrum (CDCl3, 5°C), δ, ppm: 6.90–7.26 m
(9H), 7.49–7.51 m (6H). 13C NMR spectrum (CDCl3,
5°C), δ, ppm: 46.67 (C3), 115.83 (C1,2), 125.37 (NCO)
126.02, 141.31 (Ciarom), 125.29, 126.62, 127.72, 128.77,
129.93, 130.20 (Carom). Found, %: C 85.36; H 4.93;
N 4.46. C22H15NO. Calculated, %: C 85.43; H 4.85;
N 4.57.
Compound (IV). mp 141–142°C. IR spectrum,
cm–1: 2190–1980 (NCS), 1840 (C1–C3 skeletal), 1610
(C=C), 1500, 1460, 1320, 1170, 1080, 1040, 970, 920.
1H NMR spectrum (CDCl3, 5°C), δ, ppm: 6.95–7.16 m
(9H), 7.39–7.44 m (6H). 13C NMR spectrum (CDCl3,
5°C): 46.55 (C3), 114.10 (C1,2), 130.28 (NCS), 124.91,
139.32 (Ciarom), 125.00, 127.12, 128.81, 129.14, 129.90,
129.94 (Carom). Mass spectrum, m/z (Irel, %): 325
[Ph3C3NCS]+ = [M]+ (21.9), 299 [M – CN]+ (0.4), 298
[M – HCN]+ (0.4), 293 [M – S]+ (0.8), 292 [M – HS]+
(1.1), 291 [M –– H2S]+ (1.9), 267 [M – NCS]+ (100),
266 [M – HNCS]+ (10.2), 248 [M – Ph]+ (2.3), 247 [M –
Compound (VI).mp 131–133°C (decomp.). IR
spectrum, cm–1: 1970 (NCSe), 1810 (C1–C3 skeletal),
1610 (C=C). 1H NMR spectrum (CDCl3, 5°C), δ, ppm:
7.16–7.65 br.m (15H). 13C NMR spectrum (CDCl3,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006