Mao et al.
FULL PAPER
calcd for C17H16N2O4: C 65.38, H 5.16, N 8.97; found C
65.84, H 5.48, N 9.08.
+
-1
cm ; MS m/z: 355.22 (M ). Anal. calcd for C22H18N4O:
C 74.56, H 5.12, N 15.81; found C 74.61, H 4.81, N
15.48.
4f: Yellow powder (74% yield), m.p. 285—287 ℃;
1H NMR (DMSO-d6, 400 MHz) δ: 3.89 (s, 3H, OCH3),
4.77 (s, 2H, OCH2), 7.06 (d, J=8.0 Hz, 1H, Ar-H), 7.75
(d, J=8.0 Hz, 1H, Ar-H), 7.80 (s, 1H, Ar-H), 8.11 (d,
J=5.6 Hz, 1H, Ar-H), 8.43—8.48 (m, 2H, Ar-H), 13.48
(s, 2H, NH and COOH); 13C NMR (DMSO-d6, 100
MHz) δ: 56.2, 65.4, 110.9, 113. 5, 118.2, 120.3, 122.4,
142.9, 149.5, 150.0, 170.3; IR (KBr) ν: 3434, 2913,
2623, 16-31, 1601, 1501, 1486, 134+6, 1259, 1154, 1028,
731 cm 1; MS m/z: 342.48 (M ). Anal. calcd for
C16H13N3O6: C 55.98, H 3.82, N 12.24; found C 55.69,
H 3.61, N 12.46.
5d: Offwhite powder (89% yield), m.p. 199—201
℃; 1H NMR (DMSO-d6, 400 MHz) δ: 2.39 (s, 6H, CH3),
5.35 (s, 2H, OCH2), 6.96—7.00 (m, 2H, Ar-H), 7.23 (d,
J=8.4 Hz, 2H, Ar-H), 7.31 (s, 2H, Ar-H), 7.40—7.43
(m, 2H, Ar-H), 8.07 (d, J=8.4 Hz, 2H, Ar-H), 12.56 (s,
2H, NH); 13C NMR (DMSO-d6, 100 MHz) δ: 21.6, 64.4,
115.5, 115.7, 123.7, 123.9, 128.4, 131.4, 138.9, 149.8,
151.3, 159.6; IR (KBr) ν: 3435,-2913, 1613, 1581, 146+6,
1
1445, 1279, 1054, 834, 741 cm ; MS m/z: 369.32 (M ).
Anal. calcd for C23H20N4O: C 74.98, H 5.47, N 15.21;
found C 74.60, H 5.40, N 15.69.
5e: Offwhite powder (82% yield), m.p. 166—168
℃; 1H NMR (DMSO-d6, 400 MHz) δ: 2.39 (s, 3H, CH3),
5.51 (s, 2H, CH2), 6.97 (s, 1H, Ar-H), 7.20—7.44 (m,
4H, Ar-H), 7.74—7.82 (m, 1H, Ar-H), 8.08—8.18 (m,
3H, Ar-H), 8.48 (s, 1H, Ar-H), 12.63 (s, 2H, NH); 13C
NMR (DMSO-d6, 100 MHz) δ: 21.7, 64.2, 115.6, 118.3,
123.8, 124.0, 128.4, 131.5, 139.4, 143.1, 151.2, 155.3,
155.4, 159.4; IR (KBr) ν: 3423,-2922, 1632, 1511, 148+9,
Preparation of target molecules 5 via direct heating
with oil bath
To the mixture of 4 (0.25 mmol) and 3 (0.30 mmol)
was added the catalyst (10 mL), PPA/HCl with
V(PPA)/V(HCl)=1/1, or H3PO4. After stirring for 8 h at
150 ℃, the cooled solution was poured into ice water
(40 mL), and neutralized with ammonia in water-ice
bath to pH 8—9. Then, the mixture was filtered, and the
crude product was recrystallized with ethanol affording
target molecules 5a—5j.
1
1441, 1268, 1054, 801, 736 cm ; MS m/z: 400.34 (M ).
Anal. calcd for C22H17N5O3: C 66.16, H 4.29, N 17.53;
found C 66.26, H 4.39, N 17.40.
5a: Offwhite powder (88% yield), m.p.>300 ℃;
1H NMR (DMSO-d6, 400 MHz) δ: 5.39 (s, 2H, OCH2),
7.14—7.24 (m, 6H, Ar-H), 7.44—7.47 (m, 2H, Ar-H),
7.60 (d, J=5.6 Hz, 2H, Ar-H), 8.07—8.12 (m, 2H,
Ar-H), 12.71 (s, 2H, NH); 13C NMR (DMSO-d6, 100
MHz) δ: 64.4, 111.9, 115.7, 121.9, 121.9, 122.0, 123.8,
128.5, 135.4, 150.2, 151.6, 159.7; IR (KBr) ν: 3442,
5f: Yellowish powder (80% yield), m.p. 232—234
1
℃; H NMR (DMSO-d6, 400 MHz) δ: 5.41 (s, 2H,
OCH2), 7.16—7.19 (m, 2H, Ar-H), 7.28 (d, J=8.4 Hz,
2H, Ar-H), 7.54—7.61 (m, 2H, Ar-H), 7.72 (d, J=8.8
Hz, 1H, Ar-H), 8.08 (d, J=8.8 Hz, 1H, Ar-H), 8.19 (d,
J=8.4 Hz, 2H, Ar-H), 8.42 (s, 1H, Ar-H), 12.67 (s, 2H,
NH); 13C NMR (DMSO-d6, 100 MHz) δ: 64.4, 115.8,
118.1, 122.4, 122.7, 122.8, 129.2, 142.8, 150.9, 156.3,
160.4, 160.5; IR (KBr) ν: 3115,-2927, 1610, 1577, 143+5,
-1
1606, 1497+, 1469, 1450, 1234, 1049, 739 cm ; MS m/z:
341.47 (M ). Anal. calcd for C21H16N4O: C 74.10, H
4.74, N 16.46; found C 74.00, H 4.99, N 16.06.
1
1414, 1252, 1085, 832, 734 cm ; MS m/z: 386.30 (M ).
5b: Yellowish powder (88% yield), m.p. 188—190
℃; 1H NMR (DMSO-d6, 400 MHz) δ: 2.38 (s, 3H, CH3),
5.36 (s, 2H, OCH2), 6.99 (d, J=8.4 Hz, 1H, Ar-H),
7.13—7.16 (m, 2H, Ar-H), 7.24 (d, J=8.8 Hz, 2H,
Ar-H), 7.32 (s, 1H, Ar-H), 7.42 (d, J=8.4 Hz, 1H,
Ar-H), 7.52—7.54 (m, 2H, Ar-H), 8.10 (d, J=8.8 Hz,
2H, Ar-H), 12.69 (s, 2H, NH); 13C NMR (DMSO-d6,
100 MHz) δ: 21.7, 64.4, 115.7, 122.3, 123.7, 123.9,
128.5, 131.6, 149.8, 151.6, 159.7; IR (KBr) ν: 3405,
2950, 1606, 1505, 1469,+1458, 1262, 1046, 836, 753
Anal. calcd for C21H15N5O3: C 65.45, H 3.92, N 18.17;
found C 65.86, H 3.81, N 17.94.
5g: White powder (77% yield), m.p. 281—283 ℃;
1H NMR (DMSO-d6, 400 MHz) δ: 3.91 (s, 3H, OCH3),
5.41 (s, 2H, OCH2), 7.15—7.22 (m, 4H, Ar-H), 7.28 (d,
J=8.4 Hz, 1H, Ar-H), 7.54—7.62 (m, 5H, Ar-H), 7.72
(d, J=8.4 Hz, 1H, Ar-H), 12.76 (s, 2H, NH); 13C NMR
(DMSO-d6, 100 MHz) δ: 56.1, 65.3, 110.5, 114.8, 118.3,
122.2, 124.0, 124.5, 138.9, 147.6, 148.2, 149.6, 150.1,
150.7, 151.8; IR (KBr) ν: 31-21, 2895, 1620, 1513, 1447,
-1
+
1
cm ; MS m/z: 355.17 (M ). Anal. calcd for C22H18N4O:
1395, 1287, 1100, 735 cm ; MS m/z: 371.25 (M ).
Anal. calcd for C22H18N4O2: C 71.34, H 4.90, N 15.13;
found C 71.27, H 4.85, N 15.02.
C 74.56, H 5.12, N 15.81; found C 74.26, H 5.49, N
15.34.
5c: Offwhite powder (84% yield), m.p. 284—286
℃; 1H NMR (DMSO-d6, 400 MHz) δ: 2.38 (s, 3H, CH3),
5.38 (s, 2H, OCH2), 6.95 (d, J=8.4 Hz, 1H, Ar-H),
7.15—7.18 (m, 2H, Ar-H), 7.22 (d, J=8.8 Hz, 2H,
Ar-H), 7.29 (s, 1H, Ar-H), 7.39—7.42 (m, 1H, Ar-H),
7.53—7.55 (m, 2H, Ar-H), 8.06 (d, J=8.8 Hz, 2H,
Ar-H), 12.60 (s, 2H, NH); 13C NMR (DMSO-d6, 100
MHz) δ: 21.6, 64.3, 115.5, 122.4, 123.6, 124.0, 128.2,
128.3, 131.4, 150.2, 151.3, 159.5; IR (KBr) ν: 3427,
2971, 1602, 1588, 1439, 1414, 1252, 1190, 836, 739
5h: Offwhite powder (83% yield), m.p. 263—265
℃; 1H NMR (DMSO-d6, 400 MHz) δ: 2.40 (s, 3H, CH3),
3.90 (s, 3H, CH3), 5.42 (s, 2H, OCH2), 7.00 (d, J=8.4
Hz, 1H, Ar-H), 7.18—7.22 (m, 2H, Ar-H), 7.30 (d, J=
8.4 Hz, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.53—7.60 (m,
2H, Ar-H), 7.68 (d, J=8.4 Hz, 1H, Ar-H), 7.78 (s, 1H,
Ar-H), 13.44 (s, 2H, NH); 13C NMR (DMSO-d6, 100
MHz) δ: 21.7, 56.5, 64.7, 114.7, 114.9, 118.4, 122.4,
123.9, 124.2, 133.6, 147.5, 148.3, 150.2, 151.6, 151.7;
IR (KBr) ν: 3170, 2922, 1627, 1585, 1443, 1373, 1281,
820
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 818— 824