Multicomponent Strategy for the Preparation of Pyrrolo[1,2-a]pyrimidine Derivatives
7.495 (m, 5H, ArH), 6.31 (s, 1H, CH), 4.24 (q, J=7.2
Hz, 2H, OCH2), 3.43 (q, J=7.2 Hz, 2H, OCH2), 2.94 (d,
J=4.4 Hz, 3H, NCH3), 1.23 (t, J=7.2 Hz, 3H, CH3),
1.01 (t, J=7.2 Hz, 3H, CH3); 13C NMR (100 MHz,
DMSO-d6) δ: 162.1, 160.1, 156.7, 149.2, 145.8, 132.7,
130.8, 129.1, 128.0, 120.4, 116.7, 115.5, 105.7, 76.1,
61.8, 61.6, 27.7, 14.3, 13.8; IR (KBr) ν: 3197, 2212,
1721, 1416, 1385, 1217, 1185, 1135 cm‒1. HRMS (ESI)
calcd for C21H20N4NaO4 [(M+Na)+] 415.1382, found
415.1387.
2984, 1715, 1569, 1492, 1329, 1296, 891, 696 cm‒1.
HRMS (ESI) calcd for C26H21N4O4 [(MH)] 453.1563,
found 453.1582.
Dimethyl 2-amino-8-cyano-4-cyclopropylpyrrolo-
[1,2-a]pyrimidine-6,7-dicarboxylate (4i)
Yellow
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solid, yield 72%, m.p. 250-252 ℃; H NMR (400
MHz, DMSO-d6) δ: 7.44 (s, 2H, NH2), 6.30 (s, 1H, CH),
3.87 (s, 3H, OCH3), 3.83 (s, 3H, OCH3), 2.02-1.95 (m,
1H, CH), 0.98-0.93 (m, 2H, CH2), 0.77-0.73 (m, 2H,
CH2); 13C NMR (100 MHz, DMSO-d6) δ: 162.9, 162.6,
158.2, 149.0, 148.6, 118.9, 117.1, 115.6, 102.4, 75.0,
53.7, 52.8, 13.3, 7.4; IR (KBr) ν: 3152, 2949, 1719,
1536, 1449, 1342, 1252, 874, 785, 685 cm1. HRMS
(ESI) calcd for C15H14N4NaO4 [(M+Na)+] 337.0913,
found 337.0907.
Dimethyl 8-cyano-4-methyl-2-(methylamino)pyr-
rolo[1,2-a]pyrimidine-6,7-dicarboxylate (5e) White
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solid, yield 11%, m.p. 196-198 ℃; H NMR (400
MHz, DMSO-d6) δ: 7.99-7.96 (s, 1H, NH), 6.32 (s, 1H,
CH), 3.87 (s, 3H, OCH3), 3.83 (s, 3H, OCH3), 2.88 (d,
J=4.8 Hz, 3H, NCH3), 2.37 (s, 3H, CH3); 13C NMR
(100 MHz, DMSO-d6) δ: 162.8, 162.6, 156.6, 148.8,
143.9, 119.2, 116.6, 115.6, 104.4, 75.4, 53.8, 52.8, 27.4,
18.8; IR (KBr) ν: 3121, 2216, 1734, 1643, 1480, 1384,
1184, 1092, 846 cm1. HRMS (ESI) calcd for
C14H14N4NaO4 [(M+Na)+] 325.0907, found 325.0905.
Diethyl 8-cyano-4-methyl-2-(methylamino)pyrro-
Dimethyl 8-cyano-4-cycloprpopyl-2-(phenyl-
amino)pyrrolo[1,2-a]pyrimidine-6,7-dicarboxylate
1
(5i) Yellow solid, yield 13%, m.p. 194-195 ℃; H
NMR (400 MHz, DMSO-d6) δ: 10.01 (s, 1H, NH), 7.85
(d, J=7.6 Hz, 2H, ArH), 7.38 (t, J=7.6 Hz, 2H, ArH),
7.08 (t, J=7.6 Hz, 1H, ArH), 6.56 (s, 1H, CH), 3.90 (s,
3H, OCH3), 3.86 (s, 3H, OCH3), 2.06-2.02 (m, 1H,
CH), 1.02-1.00 (m, 2H, CH2), 0.82-0.80 (m, 2H,
CH2); 13C NMR (100 MHz, DMSO-d6) δ: 162.8, 162.4,
153.7, 148.8, 147.2, 139.8, 129.4, 123.6, 119.8, 118.9,
117.9, 115.2, 103.9, 77.2, 53.9, 53.0, 13.4, 7.6; IR (KBr)
ν: 3343, 2946, 1720, 1623, 1571, 1450, 1384, 1234,
1020, 922, 692 cm1. HRMS (ESI) calcd for
C21H18N4NaO4 [(M+Na)+] 413.1226, found 413.1217.
Diethyl 2-amino-8-cyano-4-cyclopropylpyrrolo-
[1,2-a]pyrimidine-6,7-dicarboxylate (4j) White solid,
lo[1,2-a]pyrimidine-6,7-dicarboxylate (5f)
White
solid, yield 9%, m.p. 138-140 ℃; 1H NMR (400 MHz,
DMSO-d6) δ: 7.97-7.93 (m, 1H, NH), 6.31 (s, 1H, CH),
4.35-4.26 (m, 4H, 2×CH2), 2.88 (d, J=4.8 Hz, 3H,
NCH3), 2.39 (s, 3H, CH3), 1.32-1.26 (m, 6H, 2×CH3);
13C NMR (100 MHz, DMSO-d6) δ: 162.3, 162.0, 156.4,
148.7, 143.9, 119.3, 116.8, 115.6, 104.4, 75.6, 62.9,
61.6, 27.5, 18.9, 14.3, 14.0; IR (KBr) ν: 3411, 2215,
1704, 1584, 1440, 1385, 1225, 1159, 1088, 858, 688
cm1. HRMS (ESI) calcd for C16H18N4NaO4 [(M+Na)+]
353.1226, found 353.1219.
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yield 69%, m.p. 180-182 ℃; H NMR (400 MHz,
DMSO-d6) δ: 7.43 (s, 2H, NH2), 6.29 (s, 1H, CH),
4.33-4.26 (m, 4H, 2×CH2), 2.04-1.98 (m, 1H, CH),
1.31-1.26 (m, 6H, 2×CH3), 0.97-0.94 (m, 2H, CH2),
0.78 - 0.74 (m, 2H, CH2); 13C NMR (100 MHz,
DMSO-d6) δ: 162.3, 162.1, 158.1, 149.0, 148.6, 119.2,
117.1, 115.6, 102.3, 75.1, 62.8, 61.6, 14.4, 14.1, 13.3,
7.6; IR (KBr) ν: 2988, 2214, 1718, 1656, 1528, 1458,
1302, 1219, 1151, 1094, 1028, 680 cm1. HRMS (ESI)
calcd for C17H18N4NaO4 [(M+Na)+] 365.1226, found
365.1227.
Dimethyl 8-cyano-4-phenyl-2-(phenylamino)pyr-
rolo[1,2-a]pyrimidine-6,7-dicarboxylate
(5g)
1
Yellow solid, yield 14%, m.p. 233-235 ℃; H NMR
(400 MHz, DMSO-d6) δ: 10.19 (s, 1H, NH), 7.89 (d,
J=8.0 Hz, 2H, ArH), 7.59-7.56 (m, 5H, ArH), 7.41 (t,
J=8.0 Hz, 2H, ArH), 7.12 (t, J=7.2 Hz, 1H, ArH),
6.59 (s, 1H, CH), 3.81 (s, 3H, OCH3), 3.16 (s, 3H,
OCH3); 13C NMR (100 MHz, DMSO-d6) δ: 162.3,
160.4, 153.6, 147.9, 146.7, 139.6, 132.4, 131.0, 129.4,
129.2, 128.0, 127.1, 123.8, 120.0, 117.3, 115.1, 106.5,
77.5, 52.9, 52.6; IR (KBr) ν: 3467, 2221, 1731, 1560,
1537, 1426, 1256, 993, 672 cm1. HRMS (ESI) calcd
for C24H17N4O4 [(MH)] 425.1250, found 425.1250.
Diethyl 8-cyano-4-phenyl-2-(phenylamino)pyrro-
lo[1,2-a]pyrimidine-6,7-dicarboxylate (5h) Yellow
Diethyl 8-cyano-4-cyclopropyl-2-(phenylamino)-
pyrrolo[1,2-a]pyrimidine-6,7-dicarboxylate
(5j)
1
Yellow solid, yield 12%, m.p. 192-194 ℃; H NMR
(400 MHz, DMSO-d6) δ: 9.99 (s, 1H, NH), 7.85 (d, J=
8.0 Hz, 2H, ArH), 7.37 (t, J=7.6 Hz, 2H, ArH), 7.07 (t,
J=7.6 Hz, 1H, ArH), 6.55 (s, 1H, CH), 4.37-4.28 (m,
4H, 2×CH2), 2.10-2.03 (m, 1H, CH), 1.33-1.28 (m,
6H, 2×CH3), 1.03-1.00 (m, 2H, CH2), 0.84-0.82 (m,
2H, CH2); 13C NMR (100 MHz, DMSO-d6) δ: 162.3,
161.9, 153.6, 148.9, 147.1, 139.8, 129.4, 123.5, 119.8,
119.2, 117.9, 115.2, 103.8, 77.4, 63.0, 61.7, 14.4, 14.1,
13.4, 7.7; IR (KBr) ν: 3347, 2982, 2213, 1714, 1622,
1572, 1410, 1383, 1096, 1032, 763, 693 cm1. HRMS
(ESI) calcd for C23H22N4NaO4 [(M+Na)+ 441.1539,
found 441.1527.
1
solid, yield 12%, m.p. 190-192 ℃; H NMR (400
MHz, DMSO-d6) δ: 10.18 (s, 1H, NH), 7.89 (d, J=8.0
Hz, 2H, ArH), 7.57-7.54 (m, 5H, ArH), 7.41 (t, J=7.6
Hz, 2H, ArH), 7.11 (t, J=7.2 Hz, 1H, ArH), 6.58 (s, 1H,
CH), 4.27 (q, J=7.2 Hz, 2H, OCH2), 3.47 (q, J=7.2 Hz,
2H, OCH2), 1.25 (t, J=7.2 Hz, 3H, CH3), 1.03 (t, J=
7.2 Hz, 3H, CH3); 13C NMR (100 MHz, DMSO-d6) δ:
161.9, 160.0, 153.6, 147.9, 146.7, 139.7, 132.6, 131.0,
129.4, 129.2, 128.1, 123.8, 120.8, 120.1, 117.4, 115.1,
106.6, 77.7, 62.0, 61.7, 14.3, 13.8; IR (KBr) ν: 3357,
Dimethyl 8-cyano-4-cyclopropyl-2-(methylami-
Chin. J. Chem. 2016, XX, 1—7
© 2016 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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