CYCLOCONDENSATION OF UNSYMMETRICAL PERFLUOROALKYL-SUBSTITUTED
493
665, 790 (C=S); 1020–1320 (C–F); 1540, 1600, 1680,
4-Methyl-6-[1,2,2,2-tetrafluoro-1-(heptafluoro-
propoxy)ethyl]pyrimidin-2-ol (IIIc). Yield 60%,
colorless crystals, mp 178–180°C (from acetone),
Rf 0.93 (CHCl3−EtOH, 4:1). UV spectrum, λmax, nm
(logε): 218 (3.30), 270 (3.18). IR spectrum, ν, cm–1:
1100–1380 (C–F, C–O); 1540, 1620, 1660, 1700
(C=C, C=N, C=O, δNH); 2650, 2850, 3200 (C–H),
1690 (C=C, C=N, δNH); 2350, 2500 (S–H); 2900,
1
3100, 3250, 3380 (C–H). H NMR spectrum, δ, ppm:
2.80 t (3H, CH3), 7.05 br.s (1H, 5-H), 8.45 br.s (1H,
NH). Found, %: F 55.62; S 7.20. C11H5F13N2S. Cal-
culated, %: F 55.60; S 7.12.
Compounds IVb–IVf were synthesized in a similar
way.
1
3450 (O–H). H NMR spectrum, δ, ppm: 1.55 t (3H,
CH3), 7.47 d.d (1H, 5-H, JHF = 10 Hz), 8.95 br.s (1H,
NH). Found, %: F 53.07. C10H5F11N2O2. Calculated,
%: F 53.02.
4-Methyl-6-perfluorooctylpyrimidine-2-thiol
(IVb). Yield 51%, amorphous substance, Rf 0.67
(CHCl3−EtOH, 1:1). UV spectrum: λmax 212 nm, sh.
IR spectrum (KBr), ν, cm–1: 635, 805 (C=S); 970–1390
(C–F); 1430, 1450, 1590, 1770 (C=C, C=N, δNH);
2310 (S–H); 2760, 2980 (C–H). Found, %: F 59.35;
S 5.88. C13H5F17N2S. Calculated, %: F 59.34; S 5.89.
4-Methyl-6-[perfluoro(1,4-dimethyl-2,5-dioxa-
octyl)]pyrimidin-2-ol (IIId). Yield 72%, amorphous
substance, Rf 0.92 (CHCl3−EtOH, 3:2). UV spectrum,
λmax, nm (logε): 202 (2.72), 217 (3.02). IR spectrum
(KBr), ν, cm–1: 950–1350 (C–F, C–O); 1520, 1580,
1680, 1770 (C=C, C=N, C=O, δNH); 2520, 2850,
4-Methyl-6-[1,2,2,2-tetrafluoro-1-(heptafluoro-
propoxy)ethyl]pyrimidine-2-thiol (IVc). Yield 39%,
colorless crystals, mp 94–96°C (from EtOH), Rf 0.67
(CHCl3−EtOH, 1:1). UV spectrum: λmax 235 nm
(logε 4.29). IR spectrum (KBr), ν, cm–1: 666, 769
(C=S); 990–1380 (C–F, C–O); 1540, 1610, 1640, 1660,
1770 (C=C, C=N, δNH); 2400 (S–H); 3130, 3200,
1
3200 (C–H); 3400 (OH). H NMR spectrum, δ, ppm:
1.25 t (3H, CH3), 7.25 d.d (1H, 5-H, JHF = 11 Hz),
9.20 br.s (1H, NH). Found, %: F 57.71. C13H5F17N2O3.
Calculated, %: F 57.66.
4-Methyl-6-[perfluoro(1,4,7-trimethyl-2,5,8-tri-
oxaundecyl)]pyrimidin-2-ol (IIIf). Yield 97%, oily
substance, Rf 0.91 (CHCl3−EtOH, 4:1). UV spectrum:
λmax 210 nm (logε 3.95). IR spectrum (film), ν, cm–1:
950–1340 (C–F, C–O); 1450, 1560, 1680, 1780 (C=C,
C=N, C=O, δNH); 2500, 2880, 3150 (C–H); 3340
(O–H). Found, %: F 60.28. C16H5F23N2O4. Calculated,
%: F 60.17.
1
3350 (C–H). H NMR spectrum, δ, ppm: 2.68 t (3H,
CH3), 7.15 br.s (1H, 5-H), 8.88 br.s (1H, NH). Found,
%: F 50.98; S 7.84. C10H5F11N2SO. Calculated, %:
F 50.94; S 7.82.
4-Methyl-6-[perfluoro(1,4-dimethyl-2,5-dioxa-
octyl)]pyrimidine-2-thiol (IVd). Yield 45%, amor-
phous substance, Rf 0.92 (CHCl3−EtOH, 1:1). UV
spectrum: λmax 206 nm (logε 3.80). IR spectrum (KBr),
ν, cm–1: 709, 744 (C=S); 1107–1330 (C–F, C–O);
1526, 1558, 1640, 1668, 1777 (C=C, C=N, δNH);
2490 (S–H); 2993, 3170, 3340 (C–H). Found, %:
F 56.12; S 5.59. C13H5F17N2SO2. Calculated, %:
F 56.05; S 5.57.
4-Methyl-6-[perfluoro(1,4,7,10,13,16,19,22,25,28-
decamethyl-2,5,8,11,14,17,20,23,26,29-decaoxadotri-
acontyl)]pyrimidin-2-ol (IIIf). Yield 95%, oily
substance, Rf 0.81 (CHCl3−EtOH, 4:1). UV spectrum,
λmax, nm (logε): 202 (3.13), 217 (3.31). IR spectrum
(film), ν, cm–1: 930–1370 (C–F, C–O); 1440, 1690,
1770 (C=C, C=N, C=O, δNH); 2310, 2910, 2970
(C–H); 3300 (O–H).
4-Methyl-6-[perfluoro(1,4,7-trimethyl-2,5,8-tri-
oxaundecyl)]pyrimidine-2-thiol (IVe). Yield 57%,
oily substance, Rf 0.79 (CHCl3−EtOH, 1:1). UV spec-
trum, λmax, nm (logε): 202 (2.74), 217 (3.01). IR spec-
trum (film), ν, cm–1: 610, 715 (C=S); 995–1330 (C–F,
C–O); 1540, 1660, 1770 (C=C, C=N, δNH); 2500
(S–H); 3200, 3300 (C–H). 1H NMR spectrum, δ, ppm:
2.25 t (3H, CH3), 7.10 br.s (1H, 5-H), 8,80 br.s (1H,
NH). Found, %: F 58.92; S 4.34. C16H5F23N2SO3. Cal-
culated, %: F 58.87; S 4.32.
4-Methyl-6-perfluorohexylpyrimidine-2-thiol
(IVa). Compound Ia, 28.28 g (0.07 mol), was added to
a solution of 6.08 g (0.08 mol) of thiourea and 2 ml of
concentrated hydrochloric acid in propan-2-ol, and the
mixture was heated for 3–5 h at 70°C. The mixture
was then neutralized with a 5% solution of sodium
carbonate, the organic phase was separated and dried
over sodium sulfate, the solvent was distilled off, and
the residue was recrystallized from acetone. Yield
33.0 g (60%), light red crystals, mp 114–116°C (from
acetone), Rf 0.59 (CHCl3−EtOH, 1:1). UV spectrum:
λmax 235 nm (logε 3.92). IR spectrum (KBr), ν, cm–1:
4-Methyl-6-[perfluoro(1,4,7,10,13,16,19,22,25,29-
decamethyl-2,5,8,11,14,17,20,23,26,29-decaoxado-
triacontyl)]pyrimidine-2-thiol (IVf). Yield 70%, oily
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008