Page 238 - 《精细化工》2023年第2期

·460· 精细化工 FINE CHEMICALS 第 40 卷

CF 3 COOH+CDCl 3 ), δ：166.97 (d, J = 262.5 Hz), Hz, 2H), 3.942 (s, 3H), 1.468 (t, J = 6.6 Hz, 3H)；
166.63, 166.09, 156.08, 154.78 (d, J = 13.5 Hz), 13 CNMR (150 MHz, CDCl 3 ), δ ： 168.99, 163.07,
153.43, 146.80, 144.71, 142.78 (d, J = 15 Hz), 140.78, 159.62 (d, J = 244.5 Hz), 155.60, 152.13, 151.12,
118.64, 116.56, 111.69 (d, J = 27 Hz), 107.99, 106.15 149.48 (d, J = 10.5 Hz), 130.61, 122.18 (d, J = 10.5 Hz),
(d, J = 24 Hz), 104.00, 64.24, 13.93；HRMS(ESI)， 112.53 (d, J = 22.5 Hz), 109.34 (d, J = 24 Hz), 108.85,
+
m/Z：理论值 C 17 H 12 FN 3 O 3 [M+H] 326. 0935，实测值 107.73, 105.75, 101.97, 61.38, 56.00, 14.43；HRMS(ESI)，
+
326.0933。 m/Z：理论值 C 19 H 15 FN 2 O 4 [M+H] 355.1089，实测值
5-甲氧基-12H-苯并[2,3][1,4]氧杂氮杂环庚并 355.1093。
[5,6,7-de]喹啉-1-甲酸乙酯(Ⅲh)：白色固体，50 mg， 5,10-二甲氧基-12H-苯并[2,3][1,4]氧杂氮杂环
1
收率 为 75.0% ， HPLC 纯度 99.46% ； HNMR 庚并[5,6,7-de]喹啉-1-甲酸乙酯(Ⅲl)：淡黄色固体，
1
(600 MHz, CDCl 3 ), δ：11.535 (s, 1H), 9.122 (s, 1H), 44 mg，收率为 59.4%，HPLC 纯度 99.25%； HNMR
7.276~7.290 (m, 1H), 7.081~7.169 (m, 4H), 6.937~ (600 MHz, DMSO-d 6 ), δ：10.955 (s, 1H), 9.766 (s, 1H),
6.941 (m, 1H), 4.483 (q, J = 7.2 Hz, 2H), 3.959 (s, 8.894 (s, 1H), 8.582 (s, 1H), 8.321 (s, 1H), 7.165 (m,
13
3H), 1.494 (t, J = 7.2 Hz, 3H) ； CNMR (150 MHz, 1H), 6.194~6.199 (m, 1H), 4.435 (q, J = 7.2 Hz, 2H),
CDCl 3 ), δ：168.99, 163.05, 156.11, 153.64, 152.18, 3.939 (s, 3H), 3.737 (s, 3H), 1.408 (t, J = 7.2 Hz,
13
151.32, 149.00, 134.20, 125.58, 125.24, 121.79, 3H) ； CNMR (150 MHz, CDCl 3 ), δ：168.98, 163.32,
121.61, 108.68, 107.97, 105.52, 101.94, 61.27, 55.91, 157.24, 156.53, 153.29, 151.88, 151.63, 143.03,
14.46 ； HRMS(ESI) ， m/Z ：理论 值 C 19 H 16 N 2 O 4 134.70, 122.35, 111.01, 108.57, 108.09, 106.30,
+
[M+H] 337. 1183，实测值 337.1187。 105.11, 101.93, 61.38, 55.96, 14.46；HRMS(ESI)，
+
m/Z：理论值 C 20 H 18 N 2 O 5 [M+H] 367.1288，实测值
5-甲氧基-12H-苯并[2,3][1,4]硫杂氮杂环庚并
367.1289。
[5,6,7-de]喹啉-1-甲酸乙酯(Ⅲi)：淡黄固体，45 mg，
1
收率为 64.0%，HPLC 纯度 99.37%；HNMR (600 MHz, 5-甲氧基-12H-吡啶并[4',3':2,3][1,4]氧杂氮杂环
庚并[5,6,7-de]喹啉-1-甲酸乙酯(Ⅲm)：白色固体，55
DMSO-d 6 ), δ：11.565 (s, 1H), 9.051 (s, 1H), 7.611 (d,
1
J = 7.2 Hz, 1H), 7.399~7.422 (m, 1H), 7.338 (d, J = mg，收率为 81.2%，HPLC 纯度 99.42%； HNMR
3.0 Hz, 2H), 7.279 (d, J = 3.0 Hz, 1H), 7.197~7.242 (600 MHz, DMSO-d 6 ), δ：11.456 (s, 1H), 9.058 (s, 1H),
(m, 2H), 4.454 (q, J = 7.2 Hz, 2H), 3.909 (s, 3H), 8.493 (s, 1H), 8.350 (d, J = 5.4 Hz, 1H), 7.442 (d, J =
13
1.417 (t, J = 7.2 Hz, 3H) ； CNMR (150 MHz, 5.4 Hz, 1H), 7.265 (d, J = 2.4 Hz, 1H), 7.161 (d, J =
CDCl 3 ), δ：169.10, 161.96, 154.33, 154.13, 151.90, 2.4 Hz, 1H), 4.464 (q, J = 7.2 Hz, 2H), 3.962 (s, 3H),
13
145.07, 134.17, 131.88, 129.59, 128.77, 125.74, 1.427 (t, J = 7.2 Hz, 3H)； CNMR (150 MHz, CDCl 3 ),
123.49, 121.56, 116.46, 108.45, 104.12, 61.50, 55.87, δ：175.53, 158.63, 163.25, 153.84, 152.10, 151.08,
14.45 ； HRMS(ESI) ， m/Z ：理论值 C 19 H 16 N 2 O 3 S 150.34, 145.88, 142.68, 130.14, 116.44, 109.87,
+
[M+H] 353.0954，实测值 353.0959。 106.14, 105.17, 102.37, 61.81, 56.12, 14.34 ；
5-甲氧基-7,12-二氢苯并[2,3][1,4]二氮杂环庚 HRMS(ESI) ， m/Z ：理论值 C 18 H 15 N 3 O 4
+
并 [5,6,7-de]喹啉 -1-甲酸 乙酯 (Ⅲ j)： 黄色固体， [M+H] 338.1135，实测值 338.1131。
1
53 mg，收率为 79.0%，HPLC 纯度 98.78%； HNMR 5-甲氧基-12H-吡啶并[3′,4′:2,3][1,4]氧杂氮杂环
(600 MHz, CDCl 3 ), δ：11.641 (s, 1H), 9.109 (s, 1H), 庚并[5,6,7-de]喹啉-1-甲酸乙酯(Ⅲn)：白色固体，
1
6.899~6.963 (m, 4H), 6.772~6.785 (m, 1H), 62 mg，收率为 89.4%，HPLC 纯度 98.87%； HNMR
6.406~6.409 (m, 1H), 6.085 (s, 1H), 4.431 (q, J = (600 MHz, CDCl 3 ), δ：11.831 (s, 1H), 9.145 (s, 1H),
7.2 Hz, 2H), 3.878(s, 3H), 1.452 (t, J = 7.2 Hz, 3H) ； 8.508 (s, 1H), 8.273 (s, 1H), 7.182 (m, 1H),
13 CNMR (150 MHz, CDCl 3 ), δ ： 169.20, 162.68, 6.948~6.988 (m, 2H), 4.471 (q, J = 7.2 Hz, 2H), 3.946
13
153.63, 152.28, 151.58, 144.79, 135.46, 131.39, (s, 3H), 1.473 (t, J = 7.2 Hz, 3H) ； CNMR (150
124.64, 122.84, 121.62, 119.15, 105.33, 104.62, MHz, CDCl 3 ), δ：168.99, 163.10, 154.94, 153.65,
102.77, 101.68, 61.20, 55.61, 14.41；HRMS(ESI)， 151.98, 149.68, 146.62, 144.38, 143.81, 140.10,
+
m/Z：理论值 C 19 H 17 N 3 O 3 [M+H] 336.1343，实测值 115.09, 109.56, 107.02, 106.06, 102.75, 61.74, 56.02,
336.1342。 14.40 ； HRMS(ESI) ， m/Z ：理论 值 C 18 H 15 N 3 O 4
+
9-氟-5-甲氧基-12H-苯并[2,3][1,4]氧杂氮杂环 [M+H] 338.1135，实测值 338.1138。
庚并[5,6,7-de]喹啉-1-甲酸乙酯(Ⅲk)：淡黄色固体， 5-氟-7,7a,8,9,10,11,11a,12-八氢环己并[1',2':2,
1
40 mg，收率为 56.3%，HPLC 纯度 99.31%； HNMR 3][1,4] 二氮 杂环 庚 并 [5,6,7-de] 喹啉 -1- 甲酸 乙酯
(600 MHz, CDCl 3 ), δ：11.481 (s, 1H), 9.102 (s, 1H), (Ⅲo)：黄色固体，63 mg，收率为 95.7%，HPLC 纯
1
7.169~7.173 (m, 1H), 7.002~7.035 (m, 2H), 6.902~ 度 99.49%；HNMR (600 MHz, CDCl 3 ), δ：10.086 (s,
6.906 (m, 1H), 6.839~6.871 (m, 1H), 4.458 (q, J = 6.6 1H), 8.911 (s, 1H), 6.860~6.880 (m, 1H), 6.215~6.236