CH2Cl2 (2×20 ml). The organic layer was separated, washed with water, dried with Na2SO4, and filtered. The
filtrate was evaporated in vacuo at a bath temperature not above 35ºC to give compound 9 (1 g, 88%) as a
1
2
3
19
colorless oil. H NMR spectrum (CDCl3), δ, ppm (J, Hz): 6.15 (1H, tt, JHF = 52.1, JHF = 5.3, HCF2). F NMR
spectrum (СDCl3), δ, ppm (J, Hz): -112.57 (2F, m, CF2); –131.04 (2F, m, CF2); -137.68, -137.96 (2F, dm,
JFH = 52.1, HCF2). Found, %: C 20.82; H 0.38; Cl 24.64. C5HCl2F6N3. Calculated, %: C 20.85; H 0.35; Cl 24.62.
4-Hexafluoropropyl(trifluoromethyl)-1,2,3-triazoles 10a,b (General Method). Sodium amalgam
(3%, 125 g) was added with stirring to a solution containing the corresponding triazole 1a,b (0.3 mol) and
sodium hydrophosphate (17 g, 0.12 mol) in absolute methanol (150 ml) under an argon atmosphere and stirred
for 72 h at 30ºC. The methanol solution was decanted and the mercury washed with methanol (2×70 ml). The
combined methanol solutions were evaporated in vacuo and the residue was dissolved in water (200 ml). The
aqueous solution was acidified with conc. HCl to pH 2-2.5, the oil produced was extracted with ether
(4×100 ml), and the ether solution was dried over Na2SO4, filtered, and evaporated in vacuo. Compound 10a was
purified by distillation and 10b by crystallization from CHCl3.
4-(1,1,2,2,3,3-Hexafluoropropyl)-2H-[1,2,3]triazole (10a). Yield 56%; mp 26ºC, bp 65-67ºC
1
(0.04 mm Hg). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 11.60 (1Н, br. s, NH); 8.08 (1Н, s, N=CH–); 6.19
2
3
(1H, tt, JHF = 52.1, JHF = 5.6, HCF2). 19F NMR spectrum (СDCl3), δ, ppm (J, Hz): –111.22 (2F, m, CF2);
-131.84 (2F, m, CF2); -137.78, -138.04 (2F, dm, JFH = 52.1, HCF2). Found, %: C 27.43; H 1.35; N 19.19.
C5H3F6N3. Calculated, %: C 27.41; H 1.38; N 19.18.
1
4-Trifluoromethyl-2H-[1,2,3]triazole (10b). Yield 60%; mp 78-79ºC (CHCl3). H NMR spectrum
(acetone-d6), δ, ppm (J, Hz): 14.80 (1H, br. s, NH); 8.45 (1H, s, CH). 19F NMR spectrum (MeOH), δ, ppm:
-57.88 (3F, s, CF3). Found, %: C 26.31; H 1.45; N 30.69. C3H2F3N3. Calculated, %: C 26.29; H 1.47; N 30.66.
1(2)-Chloro-4-(1,1,2,2,3,3-hexafluoropropyl)-2H-[1,2,3]triazoles (11a). An aqueous solution of
NaOCl (8%, 10 g, 10.74 mmol) was added dropwise with vigorous stirring at 15ºC to a solution of compound
10a (1.5 g, 6.85 mmol) in acetic acid (60%, 6 ml), stirred for 5 h, water (4 ml) added, and extracted with CH2Cl2
(2×7 ml). The organic layer was washed with water (10 ml), dried over Na2SO4, solvent evaporated in vacuo at
30-35ºC, and the residue was distilled in vacuo collecting the fraction with bp 50-55ºC (0.3 mm Hg). Compound
1
11a (0.9 g, 52%) was obtained as a colorless liquid as a mixture of isomers in the molar ratio 3:1. H NMR
spectrum (CDCl3), δ, ppm (J, Hz) (mixture of isomers): 8.09 (1Н, s, N=CH–); 7.96* (1Н, s, N=CH–); 6.23 (1H,
2
3
2
3
tt, JHF = 52.1, JHF = 5.4, HCF2); 6.14* (1H, tt, JHF = 52.1, JHF = 5.4, HCF2,). 19F NMR spectrum (СDCl3),
δ, ppm (J, Hz) (mixture of isomers): -111.66 (2F, m, CF2); -111.88* (2F, m, CF2); -131.87 (2F, m, CF2);
2
2
-131.45* (2F, m, CF2); -137.60*, -137.89* (2F, dm, JFH = 52.1, HCF2); -137.76, -138.0 (2F, dm, JFH = 52.1,
HCF2). Mass spectrum, m/z (Irel, %): 218.0 [M+Н–Cl]+ (100), 199.0 [M+Н–Cl–F]+ (10). Found, %: C 23.65;
H 0.84; Сl 14.00. C5H2ClF6N3. Calculated, %: C 23.69; H 0.80; Cl 3.98.
2-(2-Chloro-1-ethoxyethyl)-5-(1,1,2,2,3,3-hexafluororopyl)-4-(p-tolylsulfonyl)-2H-[1,2,3]triazole
(12). Ethyl vinyl ether (0.24 g, 3.33 mmol) in CHCl3 (1 ml) was added dropwise with stirring at 0ºC to a solution
of the N-chlorotriazole 3a (0.7 g, 1.72 mmol) in CHCl3 (10 ml). The reaction mixture was stirred for 2 h at room
temperature and the solvent was removed in vacuo. The residue was extracted with refluxing hexane (2×15 ml),
the hexane solution cooled, and the precipitated crystals of compound 12 were filtered off. Yield 0.61 g (74%);
mp 72-74ºC (hexane)). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.36 (2H, d, 3JHH = 8.0, C6H4); 7.90 (2H, d,
2
3
3JHH = 8.0, С6Н4); 6.26 (1H, tt, JHF = 52.0, JHF = 5.6, HCF2,); δX 5.80 (1H, dd, JAX = 7.8, JBX = 5.5, N–CH); δA
3
3
4.03 and δB 3.93 AB (2H, JAB = 12.0, JHAHX = 7.8, JHBHX = 5.3, CHACHBCl,); δA 3.64 and δB 3.47 ABX3 (2H,
J
AX = JBX = 7.0, OCHACHB); 2.45 (3H, s, ArCH3); δX 1.15 (3H, t, JAX = JBX = 7.0, CHACHBCH3). 19F NMR
spectrum (СDCl3), δ, ppm (J, Hz): -108.56 (2F, m, CF2); -131.66 (2F, m, CF2); -137.93, -138.16 (2F, dm,
2JFH = 52.0, HCF2). Found, %: C 40.06; H 3.39; Сl 7.37. C16H16ClF6N3O3S. Calculated, %: C 40.05; H 3.36;
Сl 7.39.
_______
* Isomer formed in larger amount.
1145