Page 224 - 《精细化工》2022年第1期

·214· 精细化工 FINE CHEMICALS 第 39 卷

7.88~7.77 (m, 6H), 7.60~7.53 (m, 3H), 7.48~7.45 (m, 1 HNMR (CDCl 3 , 400 MHz), δ: 8.23 (d, J = 8.1 Hz,
13
6H), 7.09~7.00 (m, 2H); CNMR (CDCl 3 , 100 MHz), 2H), 7.84 (dd, J = 12.6、7.4 Hz, 6H), 7.59~7.53 (m,
δ: 175.35 (d, J C—P = 7.6 Hz), 164.83 (d, J C—F = 3H), 7.48~7.38 (m, 6H), 7.20 (d, J = 7.9 Hz, 2H), 2.39
247.8 Hz), 135.03 (d, J C—P= 23.3 Hz), 133.27 (d, J C—P = (s, 3H); CNMR (CDCl 3 , 100 MHz), δ: 176.39 (d,
13
9.9 Hz), 132.40 (d, J C—P = 2.8 Hz), 131.89 (dd, J C—F = J C—P = 7.9 Hz), 140.81, 135.98 (d, J C—P = 20.4 Hz),
8.7 Hz, J C—P = 2.5 Hz), 128.83 (d, J C—P = 12.3 Hz), 133.18 (d, J C—P = 9.8 Hz), 132.18 (d, J C—P = 2.8 Hz),
128.40 (d, J C—P = 96.7 Hz), 114.50 (d, J C—F = 129.61 (d, J C—P = 2.3 Hz), 129.02, 128.81 (d, J C—P =
21.3 Hz)。 42.3 Hz), 128.53 (d, J C—P = 98.8 Hz), 21.54。
N-(三苯基膦)-4-氯苯甲酰亚胺（Ⅲc）：白色固体， N-(三苯基膦)-4-叔丁基苯甲酰亚胺（Ⅲh）：白
1
收率 78%，熔点 163~165 ℃（文献值 152~154 ℃ [23] ）。 色固体，收率 64%，熔点 172~173 ℃。 HNMR
1
HNMR (CDCl 3 , 400 MHz), δ: 8.27 (d, J = 8.5 Hz, (CDCl 3 , 400 MHz), δ: 8.28 (d, J = 8.2 Hz, 2H), 7.85
2H), 7.87~7.77 (m, 6H), 7.59~7.53 (m, 3H), 7.51~7.44 (dd, J = 12.3、6.9 Hz, 6H), 7.60~7.53 (m, 3H),
13
(m, 6H), 7.38~7.32 (d, J = 8.4 Hz, 2H); CNMR 7.51~7.40 (m, 8H), 1.34 (s, 9H); CNMR (CDCl 3 ,
13
(CDCl 3 , 100 MHz), δ: 175.27 (d, J C—P = 7.7 Hz), 100 MHz), δ: 176.33 (d, J C—P = 7.8 Hz), 159.93,
137.28 (d, J C—P = 20.9 Hz), 136.84, 133.22 (d, J C—P = 136.05 (d, J C—P = 20.4 Hz), 133.22 (d, J C—P = 9.8 Hz),
9.9 Hz), 132.41 (d, J C—P = 2.8 Hz), 131.09 (d, J C—P = 132.19 (d, J C—P = 2.8 Hz), 129.41 (d, J C—P = 2.3 Hz),
2.4 Hz), 128.81 (d, J C—P = 12.2 Hz), 127.87, 127.76。 128.67 (d, J C—P = 12.1 Hz), 128.62 (d, J C—P = 98.8
N-(三苯基膦)-4-溴苯甲酰亚胺（Ⅲd）：白色固体， Hz), 124.64, 34.87, 31.38; HRMS (ESI), m/Z：[M+H] +
收率 86%，熔点 156~158 ℃（文献值 145~146 ℃ [22] ）。 理论值 438.1987，实测值 438.1988。
1 HNMR (CDCl 3 , 400 MHz), δ: 8.23 (d, J = 8.5 Hz, N-(三苯基膦)-2-噻吩甲酰亚胺（Ⅲi）：白色固
1H), 7.86~7.81 (m, 6H), 7.58~7.54 (m, 4H), 7.51~7.46 1
13
(m, 7H); CNMR (CDCl 3 , 100 MHz), δ: 175.31 (d, 体，收率 73%，熔点 169~170 ℃。 HNMR (CDCl 3 ,
J C—P = 7.7 Hz), 137.70 (d, J C—P = 20.9 Hz), 133.19 (d, 400 MHz), δ: 7.82 (dd, J = 12.4、7.2 Hz, 6H),
J C—P = 9.9 Hz), 132.40 (d, J C—P = 2.8 Hz), 131.33 (d, 7.59~7.53 (m, 3H), 7.48~7.44 (m, 7H), 7.12 (d, J = 3.3
13
J C—P = 2.4 Hz), 130.83, 128.79 (d, J C—P = 12.3 Hz), Hz, 1H), 6.42 (dd, J = 3.2、1.6 Hz, 1H); CNMR
128.68 (d, J C—P = 99.2 Hz), 125.47。 (CDCl 3 , 100 MHz), δ: 167.94 (d, J C—P = 6.8 Hz),
N-(三苯基膦)-3-氟苯甲酰亚胺（Ⅲe）：白色固 152.85 (d, J C—P = 26.1 Hz), 143.95, 133.15 (d, J C—P =
1
体，收率 62%，熔点 142~144 ℃。 HNMR (CDCl 3 , 10.0 Hz), 132.32 (d, J C—P = 2.8 Hz), 128.68 (d, J C—P =
400 MHz), δ: 8.10 (d, J = 7.7 Hz, 1H), 8.04 (d, J = 12.4 Hz), 127.91 (d, J C—P = 99.3 Hz), 114.20, 111.26;
+
10.1 Hz, 1H), 7.88~7.79 (d, J = 12.6 Hz, 6H), HRMS (ESI), m/Z：[M+H] 理论值 388.0925，实测值
7.61~7.54 (m, 3H), 7.52~7.48 (m, 6H), 7.41~7.34 (m, 388.0925。
13
1H), 7.18~7.12 (m, 1H); CNMR (CDCl 3 , 100 MHz), N-(三苯基膦)-2-萘甲酰亚胺（Ⅲj）：白色固体，
δ: 175.00 (dd, J C—P = 7.5 Hz, J C—F = 3.0 Hz), 162.68 收率 89%，熔点 168~170 ℃（文献值 187~189 ℃ [24] ）。
(d, J C—F = 244.0 Hz), 141.36 (dd, J C—P = 20.5 Hz, 1
J C—P = 7.0 Hz), 133.25 (d, J C—P = 10.0 Hz), 132.45 (d, HNMR (CDCl 3 , 400 MHz), δ: 9.07 (d, J = 8.4 Hz,
J C—P = 3.0 Hz), 129.14 (d, J C—F = 7.0 Hz), 128.84 (d, 1H), 8.38 (d, J = 7.1 Hz, 1H), 7.88 (dd, J = 12.8、7.7
J C—P = 13.0 Hz), 128.20 (d, J C—P = 99.0 Hz), 125.18 (dd, Hz, 7H), 7.81 (d, J = 8.0 Hz, 1H), 7.60~7.52 (m, 3H),
13
J C—P = J C—F = 3.0、2.5 Hz), 117.55 (d, J C—F = 21.0 Hz), 7.52~7.39 (m, 10H); CNMR (CDCl 3 , 101 MHz), δ:
116.44 (dd, J C—F = 22.0 Hz, J C—P = 2.0 Hz); HRMS 179.14 (d, J C—P = 8.3 Hz), 137.23 (d, J C—P = 20.4 Hz),
+
(ESI), m/Z：[M+H] 理论值 400.1267，实测值 400.1264。 134.11, 133.34 (d, J C—P = 9.9 Hz), 132.37 (d, J C—P = 2.8
Hz), 131.65 (d, J C—P = 1.4 Hz), 130.52, 128.88, 128.76,
N-(三苯基膦)-4-三氟甲基苯甲酰亚胺（Ⅲf）：
1
白色固体，收率 98%，熔点 142~144 ℃。 HNMR 128.14, 127.93, 127.29, 126.29, 125.42, 124.87。
(CDCl 3 , 400 MHz), δ: 8.43 (d, J = 8.0 Hz, 2H), 7.83 N-[三(4-甲基苯基)膦]苯甲酰亚胺（Ⅲk）：白色
1
(dd, J = 12.0、6.8 Hz, 6H), 7.65 (d, J = 8.1 Hz, 2H), 固体，收率 75%，熔点 182~184 ℃。HNMR (CDCl 3 ,
7.60~7.54 (m, 3H), 7.52~7.45 (m, 6H); 13 CNMR 400 MHz), δ: 8.28 (d, J = 6.8 Hz, 2H), 7.64 (dd, J =
(CDCl 3 , 100 MHz), δ: 174.86 (d, J C—P = 7.6 Hz), 12.4、7.6 Hz, 6H), 7.34~7.28 (m, 3H), 7.27 (d, J = 8.2
142.05 (d, J C—P = 20.3 Hz), 133.22 (d, J C—P = 9.9 Hz), Hz, 6H), 2.40 (s, 9H); CNMR (CDCl 3 , 100 MHz), δ:
13
132.52 (d, J C—P = 2.8 Hz), 132.22 (q, J C—F = 31.7 Hz), 176.25 (d, J C—P = 8.0 Hz), 142.66 (d, J C—P = 3.0 Hz),
129.88 (d, J C—P = 2.4 Hz), 128.87 (d, J C—P = 12.3 Hz), 138.98 (d, J C—P = 20.4 Hz), 133.20 (d, J C—P = 10.2
128.04 (d, J C—P = 99.2 Hz), 124.73 (q, J C—F = 3.8 Hz), Hz), 130.54, 129.58 (d, J C—P = 2.5 Hz), 129.43 (d,
124.40 (q, J C—F = 270.7 Hz); HRMS (ESI), m/Z： J C—P = 12.7 Hz), 127.63, 125.52 (d, J C—P = 101.3 Hz),
+
[M+H] 理论值 450.1235，实测值 450.1230。 21.67 (d, J C—P = 1.4 Hz); HRMS (ESI), m/Z：[M+H] +
N-(三苯基膦)-4-甲基苯甲酰亚胺（Ⅲg）：白色固体， 理论值 424.1830，实测值 424.1825。
[24]
收率 77%，熔点 160~162 ℃（文献值 159~160 ℃ ）。 N-(4-甲基苯基二苯基膦)苯甲酰亚胺（Ⅲl）：白