PAPER
Mono N-Alkylation of Amines
631
13C NMR (22.5 MHz, CDCl3): d = 20.17 [C(CH3)3], 28.05
[C(CH3)3], 48.31 (CH2), 55.42 (OCH3), 65.43 (CH), 127.43 (CH),
128.05 (CH), 128.70 (CH), 138.46 (C), 173.91 (C=O).
1H NMR (90 MHz, CDCl3): d = 2.9 (2 d, J = 4.51 Hz, 2 H, CH2),
3.5–4.4 (m, 6 H, CH2, CHN, OCH3), 4.7 (br, 1 H, OH), 6.7–7.5 (m,
7 H, Ar + thiophene).
13C NMR (22.5 MHz, CDCl3): d = 38.52 (CH2N), 46.52 (CH2),
51.98 (OCH3), 61.59 (CHN), 115.85 (CH), 125.23 (CH), 125.94
(CH), 127.08 (CH), 128.66 (CH), 130.78 (C), 143.05 (C), 155.48
(C), 175.40 (C=O).
7c
Brown oil.
IR (KBr): 3310, 2910, 2345, 1726, 1443, 1197, 1165 cm–1.
1H NMR (90 MHz, CDCl3): d = 3.75 (s, 3 H, OCH3), 3.9 (s, 2 H,
7i
Oil.
CH2) 4.4 (s, 1 H, CH), 6.8–7.6 (m, 8 H, C6H5 + thiophene).
13C NMR (22.5 MHz, CDCl3): d = 45.48 (CH2), 52.00 (OCH3),
63.55 (CH), 124.75 (CH), 125.38 (CH), 126.64 (CH), 127.68 (CH),
128.25 (CH), 128.0 (CH), 138.00 (C), 143.34 (C), 173.47 (C=O).
IR (KBr): 3400, 2990, 1721, 1567, 1510, 1423, 1343, 1209, 842
cm–1.
1H NMR (90 MHz, CDCl3): d = 3.7 (s, 3 H, OCH3), 3.75 (s, 2 H,
CH2N), 3.8– 4.2 (m, 3 H, CH2, CHN), 5.5 (br, 1 H, OH), 6.75 (d,
J = 13 Hz, 2 H, ArOH), 7.0 (d, J = 13 Hz, ArOH), 7.4 (d, J = 14 Hz,
2 H, ArNO2), 8.1 (d, J = 14 Hz, 2 H, ArNO2).
13C NMR (22.5 MHz, CDCl3): d = 38.20 (CH2), 50.75 (CH2N),
51.78 (OCH3), 61.80 (CHN), 115.50 (CH), 123.65 (CH), 128.20
(CH), 128.94 (CH), 130.43 (C), 147.00 (C), 147.20 (C), 155.30 (C),
175.20 (C=O).
7d
Oil.
IR (KBr): 3305, 3175, 2835, 1726, 1438, 1199, 1165, 1021, 693
cm–1.
1H NMR (90 MHz, CDCl3): d = 3.75 (s, 3 H, OCH3), 3.95 (s, 2 H,
CH2) 4.45 (s, 1 H, CH), 6.8–7.6 (m, 9 H, C6H5 + pyridine).
13C NMR (22.5 MHz, CDCl3): d = 45.76 (CH2), 48.66 (OCH3),
63.84 (CHN), 125.17 (CH), 125.80 (CH), 127.02 (CH), 128.06
(CH), 128.62 (CH), 129.17 (CH), 138.17 (C), 143.52 (C), 173.82
(C=O).
7j
Oil.
IR (KBr): 3330, 1720, 1120, 670 cm–1.
7e
Oil.
1H NMR (90 MHz, CDCl3): d = 0.9 (s, 9 H, t-C4H9), 1.8 (m, 2 H,
CH2), 2.1 (s, 3 H, SCH3), 2.4 (s, 2 H, CH2N), 2.7 (t, J = 7 Hz, SCH2),
2.4 (dd, J = 7, 8 Hz, 1 H, CH), 3.7 (s, 3 H, OCH3).
13C NMR (22.5 MHz, CDCl3): d = 14.57 (CH2), 26.90 (CH3), 29.90
(CH3S), 31.00 (C), 32.30 (CH2S), 46.70 (CH2N), 59.70 (CHN),
60.60 (OCH3), 175.80 (C=O).
IR (KBr): 3300, 3025, 2845, 1727, 1480, 1446, 1197, 1165, 1123,
1085, 1008, 692 cm–1.
1H NMR (90 MHz, CDCl3): d = 2.5 (s, 1 H, NH), 3.7 (s, 2 H, CH2),
3.75 (s, 3 H, OCH3), 4.4 (s, 1 H, CH), 7.2–7.6 (m, 9 H, C6H5 + Ar).
13C NMR (22.5 MHz, CDCl3): d = 50.30 (CH2), 52.00 (OCH3),
64.03 (CHN), 127.67 (CH), 128.36 (CH), 128.62 (CH), 128.82
(CH), 129.80 (CH), 132.98 (C), 138.11 (C), 173.60 (C=O).
7k
Oil.
IR (KBr): 3350, 2915, 1720, 1440, 1130, 670 cm–1.
7f
1H NMR (90 MHz, CDCl3): d = 1.8 (m, 2 H, CH2), 2.1 (s, 3 H,
SCH3), 2.6 (dd, J = 13 Hz, CH2), 3.4 (m, 1 H, CH), 3.7 (s, 2 H, CH2),
3.75 (s, 3 H, OCH3), 7.2–7.5 (m, 4 H, Ar).
13C NMR: d = 14.80 (CH2), 30.00 (SCH3), 32.55 (CH2S), 48.25
(CHN), 51.51 (CH2), 59.05 (OCH3), 128.42 (CH), 129.56 (CH),
132.70 (C), 138.37 (C), 175.67 (C=O).
Yellow oil.
IR (KBr): 3335, 3060, 2945, 2445, 1727, 1592, 1509, 1444, 1342,
1200, 1160, 1006, 848, 732 cm–1.
1H NMR (90 MHz, CDCl3): d = 2.7 (br, 1 H, NH), 3.75 (s, 3 H,
OCH3), 3.85 (s, 2 H, CH2), 4.4 (s, 1 H, CH), 7.3–8.3 (m, 9 H, C6H5
+ Ar).
13C NMR (22.5 MHz, CDCl3): d = 50.51 (CH), 52.37 (OCH3),
64.53 (CHN), 123.95 (CH), 127.92 (CH), 128.78 (CH), 129.21
(CH), 133.95 (C), 147.75 (C), 173.66 (C=O).
7l
Oil.
IR (KBr): 3310, 2910, 1723, 1427, 1194, 1163, 1030, 981, 695
cm–1.
7g
Oil.
1H NMR (90 MHz, CDCl3): d = 2 (m, 2 H, CH2), 2.1 (s, 3 H, SCH3),
2.7 (t, J = 5 Hz, 2 H, SCH2), 3.5 (m, 1 H, CHN), 3.75 (s, 3 H,
OCH3), 4 (s, 2 H, CH2N), 6.8–7.5 (m, 3 H, thiophene).
13C NMR (22.5 MHz, CDCl3): d = 14.50 (CH2), 30.20 (CH3S),
32.55 (SCH2), 46.50 (CH2N), 51.60 (OCH3), 58.80 (CHN), 124.60
(CH), 125.05 (CH), 126.63 (CH), 143.90 (C), 175.60 (C=O).
IR (KBr): 3370, 2920, 1723, 1602, 1503, 1457, 1434, 1361, 1212,
1164, 1123, 1101, 819 cm–1.
1H NMR (90 MHz, CDCl3): d = 0.9 (s, 9 H, t-C4H9), 2.9 (s, 2 H,
CH2N), 3.4– 4.0 (m, 6 H, CH2, CHN, OCH3), 4.5 (br, 1 H, OH), 6.7
(d, J = 9 Hz, 2 H, C6H5), 7.1 (d, J = 9 Hz, 2 H, C6H5).
13C NMR (22.5 MHz, CDCl3): d = 27.18 [C(CH3)3], 31.11
[C(CH3)3], 38.00 (CH2N), 51.00 (OCH3), 60.00 (CH2), 64.00
(CHN), 115.54 (CH), 128.50 (CH), 130.00 (C), 155.32 (C), 175.85
(C=O).
9a
Oil.
IR (KBr): 3335, 3090, 2920, 1590, 1457, 1400, 1387, 1007, 620
cm–1.
1H NMR (90 MHz, CDCl3): d = 1.1 (s, 9 H), 3.47 (s, 2 H), 3.6–3.8
(br s, 2 H).
7h
Yellow oil.
13C NMR (22.5 MHz, CDCl3): d = 28.2 (CH3), 33.7 (C), 68.2 (CH2).
IR (KBr): 3315, 3085, 2920, 1722, 1603, 1504, 1433, 1361, 1259,
1215, 1170, 1103, 1009, 824, 698 cm–1.
Synthesis 2005, No. 4, 627–633 © Thieme Stuttgart · New York