R. Pratap et al. / Tetrahedron 63 (2007) 10309–10319
10317
hexane) 0.43; mp 190–192 ꢀC; IR (KBr): 3405, 3389, 2924,
2854, 2364, 2341, 2192, 1591, 1527, 1496, 1428, 1385,
1352, 1282, 1242, 1216, 1157, 1088, 1014, 928, 846, 807,
126.66, 127.19, 143.01, 152.97, 160.21, 160.31; MS m/z
285 (M++1); HRMS (EI, 70 eV): calcd for C15H16N4S
284.10957 (M+), found for m/z 284.10957.
1
764 cmꢁ1; H NMR (300 MHz, CDCl3): d 1.66–1.78 (m,
6H, CH2), 3.49 (t, J¼4.9 Hz, 4H, CH2NCH2), 5.16 (br s,
2H, NH2), 6.50 (s, 1H, ArH), 7.39 (d, J¼8.9 Hz, 2H,
ArH), 7.82 (d, J¼8.9 Hz, 2H, ArH); 13C NMR (75 MHz,
CDCl3): 22.89, 24.56, 49.71, 97.99, 116.91, 127.14,
127.48, 134.40, 136.15, 157.26, 160.26, 160.42; MS m/z
313 (M++1); HRMS (EI, 70 eV): calcd for C17H17ClN4
312.11417 (M+), found for m/z 312.11411.
4.4.7. 20-Amino-60-benzo[1,3]dioxol-5-yl-3,4,5,6-tetra-
hydro-2H-[1,40]bipyridinyl-30-carbonitrile (10g). White
powder; yield: 245 mg (76%); Rf (6% ethyl acetate in hex-
ane) 0.35; mp 170–172 ꢀC; IR (KBr): 3383, 2933, 2853,
2364, 2341, 2195, 1587, 1501, 1424, 1387, 1352, 1247,
1157, 1102, 1038, 1005, 932, 857, 807, 766, 724 cmꢁ1; 1H
NMR (300 MHz, CDCl3): d 1.66–1.74 (m, 6H, CH2), 3.47
(t, J¼4.9 Hz, 4H, CH2NCH2), 5.09 (br s, 2H, NH2), 6.00
(s, 2H, CH2), 6.46 (s, 1H, ArH), 6.86 (d, J¼7.9 Hz, 1H,
ArH), 7.40–7.43 (m, 2H, ArH); 13C NMR (75 MHz,
CDCl3): 22.92, 24.56, 49.75, 97.63, 100.11, 106.26,
117.04, 120.15, 132.11, 146.79, 147.69, 158.02, 160.35;
MS m/z 323 (M++1); HRMS (EI, 70 eV): calcd for
C18H18N4O2 322.14297 (M+), found for m/z 322.14300.
4.4.3. 20-Amino-60-(4-bromophenyl)-3,4,5,6-tetrahydro-
2H-[1,40]bipyridinyl-30-carbonitrile (10c). White powder;
yield: 264 mg (74%); Rf (7% ethyl acetate in hexane) 0.45;
mp 198–200 ꢀC; IR (KBr): 2889, 2394, 2333, 2218, 1599,
1
1470, 1534, 1063, 1023, 861 cmꢁ1; H NMR (300 MHz,
CDCl3): d 1.67–1.75 (m, 6H, CH2), 3.49 (t, J¼4.8 Hz, 4H,
CH2NCH2), 5.14 (br s, 2H, NH2), 6.50 (s, 1H, ArH), 7.55
(d, J¼8.3 Hz, 2H, ArH), 7.75 (d, J¼8.3 Hz, 2H, ArH); 13C
NMR (75 MHz, CDCl3): 22.88, 24.56, 49.69, 76.68, 97.94,
116.86, 122.77, 127.40, 130.43, 136.62, 157.29, 160.25,
160.43; MS m/z 358 (M++2); HRMS (EI, 70 eV): calcd for
C17H17Br N4 356.06365 (M+), found for m/z 356.06345.
4.5. General procedure for the synthesis of
[2,6-diarylpyrimidin-4-yl]acetonitriles (13a–h)
A mixture of 6-aryl-4-sec-amino-2H-pyran-2-one-3-carbo-
1
nitriles
(1 mmol) and arylamidine hydrochloride
(1.5 mmol) in presence of KOH (2 mmol) in dry DMF
(8 mL) was stirred for 2–3 h. Completion of reaction was
monitored by the TLC. Thereafter, reaction mixture was
poured onto crushed ice (60 g) with vigorous stirring. The
precipitate obtained was filtered, washed with water, dried,
and purified through neutral alumina column chromato-
graphy using 40% chloroform in hexane as eluant.
4.4.4. 20-Amino-60-(p-tolyl)-3,4,5,6-tetrahydro-2H-
[1,40]bipyridinyl-30-carbonitrile (10d). White amorphous
solid; yield: 211 mg (72%); Rf (8% ethyl acetate in hexane)
0.45; mp 170–172 ꢀC; IR (KBr): 3434, 3398, 2937, 2369,
2191, 1637, 1530, 1428, 1352, 1272, 1158 cmꢁ1; 1H NMR
(300 MHz, CDCl3): d 1.67–1.77 (m, 6H, CH2), 2.38 (s,
3H, CH3), 3.48 (t, J¼5.0 Hz, 4H, CH2NCH2), 5.28 (br s,
2H, NH2), 6.51 (s, 1H, ArH), 7.23 (d, J¼8.0 Hz, 2H,
ArH), 7.77 (d, J¼8.0 Hz, 2H, ArH); 13C NMR (75 MHz,
CDCl3): 20.04, 22.91, 24.57, 49.74, 76.66, 97.90, 116.96,
126.63, 128.89, 134.67, 138.60, 158.33, 160.27, 160.34;
MS m/z 293 (M++1); HRMS (EI, 70 eV): calcd for
C18H20N4 292.16879 (M+), found for m/z 292.16824.
4.5.1. (2,6-Diphenylpyrimidin-4-yl)acetonitrile (13a).
White powder; yield: 198 mg (73%); Rf (0.5% ethyl acetate
in chloroform) 0.50; mp 110–112 ꢀC; IR (KBr): 2925, 2828,
2367, 2341, 2254, 1591, 1460, 1356, 1169, 1069, 1025, 927,
832, 746, 712 cmꢁ1; 1H NMR (200 MHz, CDCl3): d 3.97 (s,
2H, CH2), 7.41–7.54 (m, 6H, ArH), 7.74 (s, 1H, ArH), 8.21–
8.26 (m, 2H, ArH), 8.52–8.57 (m, 2H, ArH); MS m/z 272
(M++1); HRMS (EI, 70 eV): calcd for C18H13N3
271.11095 (M+), found for m/z 271.11101.
4.4.5. 20-Amino-60-(3,4-dichlorophenyl)-3,4,5,6-tetra-
hydro-2H-[1,40]bipyridinyl-30-carbonitrile (10e). White
powder; yield: 246 mg (71%); Rf (6% ethyl acetate in hex-
ane) 0.40; mp 168–170 ꢀC; IR (KBr): 3409, 3399, 2924,
2347, 2197, 1591, 1496, 1428, 1289, 1242 cmꢁ1; 1H NMR
(300 MHz, CDCl3): d 1.68–1.75 (m, 6H, CH2), 3.51 (t, J¼
4.9 Hz, 4H, CH2NCH2), 5.14 (br s, 2H, NH2), 6.48 (s, 1H,
ArH), 7.48 (d, J¼8.4 Hz, 1H, ArH), 7.72 (dd, J¼2.1 and
2.1 Hz, 1H, ArH), 7.99 (d, J¼2.0 Hz, 1H, ArH); 13C NMR
(75 MHz, CDCl3): 22.85, 24.56, 49.68, 76.70, 96.93,
116.72, 124.89, 127.76, 129.18, 131.58, 132.38, 137.63,
155.81, 160.16, 160.40; MS m/z 347 (M++1); HRMS (EI,
70 eV): calcd for C17H16Cl2N4 346.07520 (M+), found for
m/z 346.07504.
4.5.2. [6-(4-Chloro-phenyl)-2-phenylpyrimidin-4-yl]-
acetonitrile (13b). White powder; yield: 240 mg (79%); Rf
(0.5% ethyl acetate in chloroform) 0.50; mp 118–120 ꢀC;
IR (KBr): 3010, 2819, 2368, 2341, 2258, 1592, 1381,
1351, 1092, 1014, 855, 752 cmꢁ1 1H NMR (200 MHz,
;
CDCl3): d 3.98 (s, 2H, CH2), 7.46–7.52 (m, 5H, ArH),
7.71 (s, 1H, ArH), 8.19 (d, J¼8.5 Hz, 2H, ArH), 8.50–8.55
(m, 2H, ArH); MS m/z 306 (M++1); HRMS (EI, 70 eV):
calcd for C18H12ClN3 305.07197 (M+), found for m/z
305.07189.
4.5.3. [6-(4-Bromo-phenyl)-2-phenylpyrimidin-4-yl]-
acetonitrile (13c). White powder; yield: 283 mg (81%); Rf
(0.5% ethyl acetate in chloroform) 0.54; mp 124–126 ꢀC;
IR (KBr): 2926, 2819, 2371, 2340, 2257, 1592, 1487,
4.4.6. 20-Amino-60-thiophen-2-yl-3,4,5,6-tetrahydro-2H-
[1,40]bipyridinyl-30-carbonitrile (10f). White powder; yield:
197 mg (69%); Rf (8% ethyl acetate in hexane) 0.40; mp 120–
1
122 ꢀC; IR (KBr): cmꢁ1
;
1H NMR (300 MHz, CDCl3):
1383, 1175, 1072, 1009, 929, 827, 756 cmꢁ1; H NMR
d 1.67–1.77 (m, 6H, CH2), 3.46 (t, J¼5.0 Hz, 4H, CH2NCH2),
5.16 (br s, 2H, NH2), 6.50 (s, 1H, ArH), 7.08 (dd, J¼3.8 and
3.8 Hz, 1H, ArH), 7.39 (dd, J¼1.1 and 1.1 Hz, 1H, ArH), 7.55
(dd, J¼0.8 and 0.8 Hz, 1H, ArH); 13C NMR (75 MHz,
CDCl3): 22.89, 24.54, 49.70, 76.64, 97.27, 116.94, 124.50,
(200 MHz, CDCl3): d 3.97 (s, 2H, CH2), 7.46–7.51 (m,
3H, ArH), 7.66 (d, J¼8.6 Hz, 2H, ArH), 7.70 (s, 1H, ArH),
8.11 (d, J¼8.6 Hz, 2H, ArH), 8.49–8.54 (m, 2H ArH); MS
m/z 349 (M+), 351 (M++2); HRMS (EI, 70 eV): calcd for
C18H12BrN3 349.02145 (M+), found for m/z 349.02160.