10.1002/ejoc.201901364
European Journal of Organic Chemistry
FULL PAPER
2-(Benzylthio)pyrimidine (10a)[41]
5H); 13C NMR (75 MHz, CDCl3) δ (ppm): 173.0, 157.0, 116.1, 37.7, 37.5,
32.6, 26.2, 26.0; ESI-MS: m/z 209.12 [M+H]+.
Yield 92% (186 mg); yellow solid; IR (KBr) ν 3415, 2924, 2853, 2361,
1566, 1546, 1382, 1185, 773, 630 cm-1; 1H NMR (300 MHz, CDCl3) δ
(ppm): 8.52 (d, J = 4.8 Hz, 2H), 7.43 (d, J = 7.3 Hz, 2H), 7.33−7.24 (m,
3H), 6.96 (t, J = 4.8 Hz, 1H), 4.42 (s, 2H); 13C NMR (75 MHz, CDCl3) δ
(ppm): 172.1, 157.2, 137.4, 129.0, 128.4, 127.2, 116.5, 35.2;ESI-MS:
m/z 203.05 [M+H]+.
2-(Allylthio)pyrimidine (10j)[42]
Yield 93% (142 mg); yellow oil; IR (KBr) ν 3434, 3082, 3032, 2925, 1960,
1565, 1547, 1382, 1203, 1186, 920, 773, 630 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm): 8.52 (d, J = 4.8 Hz, 2H), 6.97 (t, J = 4.9 Hz, 1H),
6.04−5.93 (m, 1H), 5.33 (dd, J1 = 17.0 Hz, J2 = 1.4 Hz, 1H), 5.14 (d, J =
10 Hz, 1H), 3.83 (d, J = 6.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ (ppm):
172.0, 157.2, 133.3, 117.8, 116.5, 33.7; ESI-MS: m/z 153.16 [M+H]+.
2-(Pent-4-en-1-ylthio)pyrimidine (10k)[42]
2-(dodecylthio)pyrimidine (10b)[42]
Yield 93% (261 mg); yellow oil; IR (KBr) ν 3749, 3648, 3445, 3031, 2924,
2853, 1566, 1546, 1464, 1383, 1205, 774, 630 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm): 8.49 (d, J = 4.8 Hz, 2H), 6.93 (t, J = 4.8 Hz, 1H), 3.14 (t,
J = 7.3 Hz, 2H), 1.78−1.68 (m, 2H), 1.47−1.40 (m, 2H), 1.26 (s, 16H),
0.90−0.85 (m, 3H); 13C NMR (75 MHz, CDCl3) δ (ppm): 172.7, 156.9,
116.0, 31.7, 30.7, 29.5, 29.45, 29.42, 29.3, 29.2, 29.0, 28.9, 28.7, 22.5,
13.9; ESI-MS: m/z 281.13 [M+H]+.
Yield 96% (173 mg); yellow oil; IR (KBr) ν 3437, 3077, 2927, 2853, 1641,
1438, 1251, 1193, 990, 849, 770, 630 cm-1; 1H NMR (300 MHz, CDCl3) δ
(ppm): 8.51 (d, J = 4.9 Hz, 2H), 6.96 (t, J = 4.9 Hz, 1H), 5.90−5.77 (m,
1H), 5.11−5.09 (m, 2H), 3.16 (t, J = 7.2 Hz, 2H), 2.23 (dd, J1 = 14.8 Hz, J2
= 7.0 Hz, 2H), 1.90−1.64 (m, 2H); 13C NMR (75 MHz, CDCl3) δ (ppm):
172.6, 157.2, 137.7, 116.3, 115.3, 32.8, 30.2, 28.2; ESI-MS: m/z 181.06
[M+H]+.
2-(Dodecylthio)pyrimidine (10d)[43]
Yield 95% (213 mg); yellow oil; IR (KBr) ν 3852, 3749, 3648, 3444, 3031,
2956, 2926, 2855, 1566, 1383, 1205, 774, 630 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm):8.50 (d, J = 4.8 Hz, 2H), 6.93 (t, J = 4.8 Hz, 1H), 3.14 (t,
J = 7.4 Hz, 2H), 1.78−1.68 (m, 2H), 1.48-1.43 (m, 2H), 1.29−1.28 (m, 8H),
0.90−0.86 (m, 3H); 13C NMR (75 MHz, CDCl3) δ (ppm):172.8, 157.1,
116.2, 31.8, 30.8, 29.1, 29.0, 28.9, 22.6, 14.0; ESI-MS: m/z 225.10
[M+H]+.
2-((3,3,3-Trifluoropropyl)thio)pyrimidine (10m)
Yield 90% (187 mg); yellow oil; IR (KBr) ν 3446, 3039, 2939, 1567, 1550,
1384, 1261, 1243, 1138, 1098, 956, 774, 642 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm): 8.54 (d, J = 4.9 Hz, 2H), 7.01 (t, J = 4.8 Hz, 1H),
3.32−3.27 (m, 2H), 2.65−2.56 (m, 2H); 13C NMR (75 MHz, CDCl3) δ
(ppm): 171.1, 157.4, 126.1 (q, J = 275.6Hz), 116.8, 34.2 (q, J = 28.4 Hz),
23.0 (q, J = 3.5 Hz); 19F NMR (376 MHz, CDCl3) δ (ppm):-66.43; HRMS
(ESI): m/z calcd for C7H8F3N2S: 209.0355, found: 209.0358 [M+H]+.
2-((3,3,4,4,5,5,6,6,6-Nonafluorohexyl)thio)pyrimidine (10n)
Yield 89% (319 mg); yellow oil; IR (KBr) ν 3443, 3039, 2943, 2354, 1567,
1551, 1415, 1385, 1352, 1223, 1133, 1011, 879, 749, 693 cm-1; 1H NMR
(300 MHz, CDCl3) δ (ppm): 8.55 (d, J = 4.9 Hz, 2H), 7.02 (t, J = 4.9 Hz,
1H), 3.38−3.32 (m, 2H), 2.70−2.53 (m, 2H). 13C NMR (75 MHz, CDCl3) δ
(ppm):171.1, 157.5, 116.9, 31.6 (t, J = 21.8Hz), 21.9 (t, J = 4.7 Hz); 19F
NMR (376 MHz, CDCl3) δ (ppm): -81.02−-81.09, -114.65−-114.67, -
124.37−-124.41, -125.99−-126.07; HRMS (ESI): m/z calcd for
C10H8F9N2S: 359.0259, found: 359.0255 [M+H]+
2-(Hexadecylthio)pyrimidine (10e)[42]
Yield 91% (306 mg); yellow solid; IR (KBr) ν 3854, 3439, 2952, 2918,
2848, 2362, 1565, 1378, 1190, 801, 773, 751, 630 cm-1; 1H NMR (300
MHz, CDCl3) δ (ppm): 8.50 (d, J = 4.8 Hz, 2H), 6.94 (t, J = 4.8 Hz, 1H),
3.14 (t, J = 7.4 Hz, 2H), 1.73−1.64 (m, 2H), 1.37−1.25 (m, 26H),
0.90−0.86 (m, 3H); 13C NMR (75 MHz, CDCl3) δ (ppm): 172.9, 157.1,
116.2, 31.9, 30.9, 29.7, 29.65, 29.59, 29.5, 29.3, 29.2, 29.1, 28.9, 22.7,
14.1; ESI-MS: m/z 337.12 [M+H]+.
2-((Cyclopropylmethyl)thio)pyrimidine (10f)[42]
Yield 97% (161 mg); yellow oil; IR (KBr) ν 3396, 3079, 3004, 2923, 2852,
1565, 1547, 1382, 1190, 1018, 773, 630 cm-1; 1H NMR (300 MHz, CDCl3)
δ (ppm): 8.50 (t, J = 4.9 Hz, 2H), 6.95 (t, J = 4.9 Hz, 1H), 3.10 (t, J = 7.1
Hz, 2H), 1.65 (s, 1H), 0.64−0.58 (m, 2H), 0.36−0.31 (m, 2H); 13C NMR
(75 MHz, CDCl3) δ (ppm): 172.9, 157.1, 116.3, 36.7, 10.4, 5.7; ESI-MS:
m/z 167.09 [M+H]+.
2-((3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)thio)pyrimidine (10o)
Yield 85% (390 mg); yellow oil; IR (KBr) ν 3447, 3039, 3943, 1567, 1551,
1416, 1238, 1144, 983, 775, 737, 649, 564 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm): 8.55 (d, J = 4.9 Hz, 2H), 7.02 (t, J = 4.8 Hz, 1H),
3.38−3.33 (m, 2H), 2.71−2.53 (m, 2H); 13C NMR (75 MHz, CDCl3) δ
(ppm):171.1, 157.5, 116.9, 31.7 (t, J = 21.8 Hz), 21.9 (t, J = 4.6 Hz); 19F
NMR (376 MHz, CDCl3) δ (ppm): -80.80−-80.85, -114.35−-114.47, -
121.91, -122.89, -123.44, -126.12−-126.21; HRMS (ESI): m/z calcd for
C12H8F13N2S: 459.0195, found: 459.0198 [M+H]+
2-((Cyclobutylmethyl)thio)pyrimidine (10g)[42]
Yield 96% (173 mg); yellow oil; IR (KBr) ν 3438, 3030, 2972, 2864, 2131,
1957, 1565, 1382, 1189, 980, 773, 630 cm-1; H NMR (300 MHz, CDCl3)
1
δ (ppm): 8.50 (d, J = 4.8 Hz, 2H), 6.95 (t, J = 4.8 Hz, 1H), 3.24 (d, J = 7.5
Hz, 2H), 2.70−2.64 (m, 1H), 2.16−2.13 (m, 2H), 1.87−1.75 (m, 4H); 13C
NMR (75 MHz, CDCl3) δ (ppm): 172.8, 157.1, 116.3, 37.1, 34.6, 27.7,
18.0; ESI-MS: m/z 181.02 [M+H]+.
2-((3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl)thio)-
pyrimidine (10p)
2-(Cyclopentylthio)pyrimidine (10h)[42]
Yield 83% (390 mg); yellow oil; IR (KBr) ν 3441, 3923, 2852, 1565, 1549,
1383, 1205, 1147, 1115, 1035, 773, 652, 559 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm): 8.55 (d, J = 4.9 Hz, 2H), 7.02 (t, J = 4.9 Hz, 1H),
3.38−3.32 (m, 2H), 2.71−2.53 (m, 2H); 13C NMR (75 MHz, CDCl3) δ
(ppm):171.1, 157.5, 116.9, 31.7 (t, J = 21.8 Hz), 21.9 (t, J = 4.4 Hz); 19F
NMR (376 MHz, CDCl3) δ (ppm): -80.75 (t, J = 9.8 Hz), -114.38 (t, J =
13.0 Hz), -121.66, -121.89, -122.69, -123.35, -126.05−-126.11; HRMS
(ESI): m/z calcd for C14H8F17N2S: 559.0131, found: 559.0136 [M+H]+
General synthetic procedure for aminopyrimidines 12 (Table 4).
Yield 93% (167 mg); yellow oil; IR (KBr) ν 3438, 3111, 2959, 2867, 2131,
1957, 1565, 1382, 1189, 980, 773, 630 cm-1; H NMR (300 MHz, CDCl3)
1
δ (ppm): 8.42 (d, J = 4.8 Hz, 2H), 6.86 (t, J = 4.9 Hz, 1H), 3.98−3.89 (m,
1H), 2.14−2.12 (m, 2H), 1.77−1.58 (m, 6H); 13C NMR (75 MHz, CDCl3) δ
(ppm): 173.4, 157.0, 116.1, 43.5, 33.1, 24.8; ESI-MS: m/z 1181.18
[M+H]+.
2-((Cyclohexylmethyl)thio)pyrimidine (10i)[42]
Yield 92% (192 mg); yellow oil; IR (KBr) ν 3437, 3029, 2929, 2246, 1957,
1730, 1564, 1382, 1207, 1070, 773, 699, 630 cm-1; 1H NMR (300 MHz,
CDCl3) δ (ppm): 8.50 (d, J = 4.8 Hz, 2H), 6.94 (t, J = 4.9 Hz, 1H), 3.07 (d,
J = 6.8 Hz, 2H), 1.94−1.89 (m, 2H), 1.75−1.59 (m, 4H), 1.27−1.00 (m,
A mixture of cyanopyrimidines (1, 1.0 mmol), amines (11, 2.0 mmol)
and cesium carbonate (326 mg, 1.0 mmol) in DMSO (3 mL) was
heated at 80 oC for 6–10 h. After completion of the reaction, the
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