YAGUPOL’SKII et al.
908
1
1-Methyl-3-(1,1,2,2-tetrafluoroethyl)-1H-imid-
(chloroform–acetone, 3:2). H NMR spectrum (CDCl3),
δ, ppm: 3.61 s (3H, NCH3), 7.14–7.32 m (10H, Harom).
19F NMR spectrum (CDCl3), δF, ppm: –63.68 s (2F,
CF2Br), –84.75 s (2F, NCF2). Found, %: C 46.61;
H 2.83; S 13.00. C19H13BrF4N2S2. Calculated, %:
C 46.64; H 2.68; S 13.09.
azolium-2-carbodithioate (Vb). Yield 0.93 g (72%),
mp 114–116°C, Rf 0.4 (chloroform–acetone, 4:1).
1H NMR spectrum (CDCl32), δ, ppm: 3.82 s (3H,
3
NCH3), 6.99 t.t (1H, CF2H, JHF = 55, JHF = 5 Hz),
19
7.10 s (1H 5-H), 7.17 s (1H, 4-H). F NMR spectrum
(CDCl3), δ, ppm: –91.52 d (2F, NCF2), –135.73 d (2F,
CF2H, JFH = 55 Hz). Found, %: C 32.85; H 2.43;
N 10.62; S 24.73. C7H6F4N2S2. Calculated, %:
C 32.56; H 2.34; N 10.85; S 24.81.
5,5,6,6-Tetrafluoro-1-methyl-2,3-diphenyl-
8-thioxo-5,6-dihydro-8H-imidazo[2,1-c][1,4]thiazin-
1-ium bromide (VI). Yield 0.48 g (20%), mp 199–
200°C, Rf 0.2 (acetone). 1H NMR spectrum (CDCl3), δ,
ppm: 3.60 s (3H, NCH3), 7.42–7.47 m (10H, Harom).
19F NMR spectrum, δF, ppm: –65.97 (2F, CF2S, AB
system), –84.85 (2F, NCF2, AB system). Found, %:
C 46.72; H 2.36; S 12.62. C19H13BrF4N2S2. Calculated,
%: C 46.62; H 2.66; S 13.09.
2
3-(2-Bromotetrafluoroethyl)-1-methyl-1H-imid-
azolium-2-carbodithioate (Vc). Yield 1.0 g (59%),
mp 162–165°C (decomp.), Rf 0.5 (chloroform–acetone,
1
4:1). H NMR spectrum (CDCl3), δ, ppm: 3.96 s (3H,
19
NCH3), 7.12 s (1H, 5-H), 7.16 s (1H, 4-H). F NMR
spectrum (CDCl3), δ, ppm: –65.89 s (2F, CF2Br),
–91.82 s (2F, NCF2). Found, %: C 24.91; H 1.28;
S 18.78. C7H5BrF4N2S2. Calculated, %: C 24.94;
H 1.49; S 19.02.
3-(2,2-Dichlorotrifluoroethyl)-1-methyl-4,5-
diphenyl-1H-imidazolium-2-carbodithioate (Vh).
Yield 1.42 g (62%), mp 193–195°C (decomp.), Rf 0.6
1
(chloroform–acetone, 3:2). H NMR spectrum (CDCl3),
3-(2,2-Dichlorotrifluoroethyl)-1-methyl-1H-imid-
azolium-2-carbodithioate (Vd). Yield 1.28 g (83%),
mp 158–159°C, Rf 0.5 (chloroform–acetone, 4:1).
1H NMR spectrum (CDCl3), δ, ppm: 3.68 s (3H,
δ, ppm: 3.54 s (3H, NCH3), 7.34–8.51 m (10H, Harom).
19F NMR spectrum (CDCl3), δF, ppm: –68.52 s (1F,
CFCl2), –82.74 s (2F, NCF2). Found, %: C 48.97;
H 3.07; S 14.00. C19H13Cl2F3N2S2. Calculated, %:
C 49.46; H 2.82; S 13.90.
19
NCH3), 7.19 s (1H, 5-H), 7.26 s (1H, 4-H). F NMR
spectrum (CDCl3), δF, ppm: –70.72 s (1F, CFCl2),
–90.38 s (2F, NCF2). Found, %: C 27.50; H 1.53;
Cl 22.95; S 21.13. C7H5Cl2F3N2S2. Calculated, %:
C 27.20; H 1.63; Cl 22.94; S 20.74.
3-Difluoromethyl-1-methyl-1H-benzimidazoli-
um-2-carbodithioate (Vi). Yield 0.41 g (30%),
mp 198–200°C (decomp.), Rf 0.6 (chloroform–acetone,
1
1:1). H NMR spectrum (CDCl3), δ, ppm: 3.92 s (3H,
3-Difluoromethyl-1-methyl-4,5-diphenyl-1H-
imidazolium-2-carbodithioate (Ve). Yield 1.02 g
(57%), mp 194–195°C (decomp.), Rf 0.6 (chloroform–
NCH3), 7.71–8.05 m (4H, Harom), 8.18 t (1H, CF2H,
19
2JHF = 60 Hz). F NMR spectrum (CDCl3), δF, ppm:
2
1
–100.06 d (CF2H, JFH = 60 Hz). Found, %: C 46.97;
acetone, 3:2). H NMR spectrum (CDCl3), δ, ppm:
H 3.07; S 24.70. C10H8F2N2S2. Calculated, %: C 46.50;
H 3.12; S 24.83.
3.66 s (3H, NCH3), 7.21–7.53 m (10H, Harom), 7.61 t
2
(1H, CF2H, JHF = 60 Hz). 19F NMR spectrum
2
(CDCl3): δF –94.61 ppm, d (CF2H, JFH = 60 Hz).
3-(2,2-Dichlorotrifluoroethyl)-1-methyl-1H-
benzimidazolium-2-carbodithioate (Vj). Yield 0.57 g
(32%), mp 172–174°C (decomp.), Rf 0.6 (chloroform–
Found, %: C 59.83; H 3.65; S 17.75. C18H14F2N2S2.
Calculated, %: C 60.00; H 3.89; S 17.79.
1
acetone, 1:1). H NMR spectrum (CDCl3), δ, ppm:
1-Methyl-3-(1,1,2,2-tetrafluoroethyl)-4,5-diphen-
yl-1H-imidazolium-2-carbodithioate (Vf). Yield
1.10 g (54%), mp 175–177°C (decomp.), Rf 0.6 (chloro-
19
3.95 s (3H, CH3), 7.77–8.06 m (4H, Harom). F NMR
spectrum (CDCl3), δF, ppm: –68.42 s (1F, CFCl2),
–87.38 s (2F, NCF2). Found, %: C 36.57; H 1.64;
S 17.77. C11H7Cl2F3N2S2. Calculated, %: C 36.77;
H 1.95; S 17.85.
1
form–acetone, 3:2). H NMR spectrum (CDCl3), δ,
ppm: 3.65 s (3H, NCH3), 7.48–7.69 m (10H, Harom),
2
3
19
7.97 t.t (1H, CF2H, JHF = 55, JHF = 5 Hz). F NMR
spectrum (CDCl3), δF, ppm: –91.52 s (2F, NCF2),
3-Methyl-2-[(methylsulfanyl)carbonothioyl]-
1-polyfluoroalkyl-1H-imidazol-3-ium iodides VІІa–
VIIj (general procedure). A mixture of 1 mmol of
compound Va–Vj, 0.21 g (1.5 mmol) of methyl iodide,
and 2 ml of anhydrous acetonitrile was heated for
20 min under reflux. The mixture was cooled to room
temperature, diluted with 5 ml of diethyl ether, and left
2
–135.73 d (2F, CF2H, JFH = 55 Hz). Found, %:
C 56.06; H 3.52; S 15.63. C19H14F4N2S2. Calculated,
%: C 55.61; H 3.44; S 15.62.
3-(2-Bromotetrafluoroethyl)-1-methyl-4,5-
diphenyl-1H-imidazolium-2-carbodithioate (Vg).
Yield 0.86 g (36%), mp 177–179°C (decomp.), Rf 0.5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010