Page 229 - 《精细化工》2023年第2期

第 2 期 陈学华，等: 水介质中离子液体催化合成四氢喹唑啉衍生物 ·451·

149.20, 143.47, 132.04, 127.98, 126.93, 125.99, 3H), 1.48 (d, J = 10.4 Hz, 1H), 1.35 (d, J = 12.8 Hz,
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120.46, 117.82, 116.41, 111.44, 76.52, 57.09, 47.01, 1H)。 CNMR (126 MHz, CDCl 3 )，δ：147.73, 142.68,
31.77, 22.24。 129.72, 129.52, 127.73, 126.55, 117.93, 117.87,
4-(4-腈基苯基)-1,2,3,3a,4,5-六氢吡咯并[1,2-a] 115.49, 109.97, 75.74, 47.11, 46.53, 33.15, 26.37,
喹唑啉（Ⅲaj）：白色固体，熔点 115.8~117.6 ℃（文 26.13, 24.81, 20.56。
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[5]
献值 116.3~117.2 ℃ ），产率 30%。 HNMR (500 6-(4-氟苯基)-5,6,6a,7,8,9,10,11-八氢氮杂[1,2-a]
MHz, CDCl 3 )，δ：7.52 (d, J = 8.8 Hz, 2H), 7.20 (t, J = 喹唑啉（Ⅲbg）：白色固体，熔点 87.4~89.0 ℃，产
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7.3 Hz, 1H), 7.02 (dd, J = 16.9、8.1 Hz, 3H), 6.77 (t, 率 51%。HNMR (500 MHz, CDCl 3 ) ，δ：7.17 (d, J =
J = 7.4 Hz, 1H), 6.64 (d, J = 8.0 Hz, 1H), 4.58 (t, J = 8.9 Hz, 2H), 7.09 (t, J = 7.7 Hz, 1H), 6.99 (d, J = 7.3
6.9 Hz, 1H), 4.46 (d, J = 14.6 Hz, 1H), 4.29 (d, J = Hz, 1H), 6.86 (d, J = 8.5 Hz, 2H), 6.65~6.57 (m, 2H),
14.8 Hz, 1H), 3.48~3.39 (m, 1H), 3.34 (s, 1H), 2.37 (s, 4.79 (dd, J = 9.9、4.2 Hz, 1H), 4.56 (d, J = 16.2 Hz,
1H), 2.00 (dd, J = 22.5、14.9 Hz, 2H), 1.83~1.72 (m, 1H), 4.32 (d, J = 16.1 Hz, 1H), 3.86 (d, J = 12.2 Hz,
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1H)。 CNMR (126 MHz, CDCl 3 ) ，δ：152.87, 144.30, 1H), 3.18~3.24 (m, 1H), 2.19~2.08 (m, 1H), 1.88 (dd,
133.14, 128.26, 125.70, 122.18, 120.09, 119.73, 118.10, J = 22.1、8.1 Hz, 2H), 1.72~1.60 (m, 3H), 1.49 (d, J =
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112.25, 103.32, 75.03, 52.63, 46.17, 31.29, 21.53。 10.1 Hz, 1H), 1.39~1.30 (m, 1H)。 CNMR (126 MHz,
CDCl 3 )，δ：157.37(d, J C—F =239.4 Hz), 146.78, 142.66,
4-[4-(1,1- 联苯 基 )]-1,2,3,3a,4,5- 六氢吡咯并
127.87, 126.51, 119.84(d, J C—F = 7.56 Hz), 117.52,
[1,2-a]喹唑啉（Ⅲak）：白色固体，熔点 104.4~105.7 ℃， 115.59(d, J C—F =22.68 Hz), 115.50, 109.98, 76.32,
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产率 25%。 HNMR (500 MHz, CDCl 3 )，δ：7.55 (dd,
47.12, 47.02, 33.83, 26.30, 26.11, 24.75；HRMS (ESI),
J = 15.7、8.0 Hz, 4H), 7.43 (t, J = 7.7 Hz, 2H), 7.32 (t, m/Z：[M+H] 理论值 297.1762；实测值 297.1761。
+
J = 7.4 Hz, 1H), 7.24 (d, J = 7.0 Hz, 2H), 7.15 (t, J = 6-(4-氯苯基)-5,6,6a,7,8,9,10,11-八氢氮杂[1,2-a]
7.7 Hz, 1H), 6.99 (d, J = 7.3 Hz, 1H), 6.67 (t, J = 7.3
Hz, 1H), 6.55 (d, J = 8.0 Hz, 1H), 4.68 (dd, J = 8.1、 喹唑啉（Ⅲbh）：白色固体，熔点 93.9~94.6 ℃（文
[5]
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5.4 Hz, 1H), 4.43 (d, J = 14.9 Hz, 1H), 4.17 (d, J = 献值 95.1~95.6 ℃ ），产率 60%。HNMR (500 MHz,
15.0 Hz, 1H), 3.50~3.35 (m, 2H), 2.18~2.11 (m, 1H), CDCl 3 )，δ：7.16 (d, J = 9.0 Hz, 2H), 7.09 (t, J = 7.5 Hz,
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2.03~1.88 (m, 2H), 1.79 (t, J = 8.4 Hz, 1H)。 CNMR 1H), 6.98 (d, J = 7.3 Hz, 1H), 6.85 (d, J = 8.9 Hz, 2H),
(126 MHz, CDCl 3 )，δ：149.46, 143.50, 140.72, 137.55, 6.65~6.56 (m, 2H), 4.79 (dd, J = 9.9、4.1 Hz, 1H), 4.55
128.83, 127.94, 127.68, 127.13, 126.97, 126.04, (d, J = 16.2 Hz, 1H), 4.31 (d, J = 16.2 Hz, 1H),
125.28, 120.73, 116.36, 111.47, 76.75, 57.26, 47.13, 3.83~3.88 (m, 1H), 3.17~3.23 (m, 1H), 2.18~2.09 (m,
+
32.01, 22.32。HRMS (ESI), m/Z：[M+H] 理论值 1H), 1.83~1.93 (m, 2H), 1.71~1.59 (m, 3H), 1.46~1.52
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(m, 1H), 1.39~1.30 (m, 1H)。 CNMR (126 MHz,
327.1856；实测值 327.1855。
CDCl 3 ) ，δ：148.51, 142.50, 129.06, 127.93, 126.56,
6-苯基-5,6,6a,7,8,9,10,11-八氢氮杂[1,2-a]喹唑 124.78, 118.76, 117.45, 115.79, 110.17, 75.23, 47.13,
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啉（Ⅲba）：黏稠液体，产率 56%。HNMR (500 MHz,
46.50, 33.18, 26.38, 26.02, 24.74。
CDCl 3 )，δ：7.25~7.21 (m, 2H), 7.08 (t, J = 7.5 Hz, 1H), 6-(4-溴苯基)-5,6,6a,7,8,9,10,11-八氢氮杂[1,2-a]
7.00 (d, J = 7.3 Hz, 1H), 6.95 (d, J = 8.0 Hz, 2H), 6.83
(t, J = 7.7 Hz, 1H), 6.64~6.57 (m, 2H), 4.87 (dd, J = 喹唑啉（Ⅲbi）：白色固体，熔点 104.8~106.2 ℃（文
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10.0、4.2 Hz, 1H), 4.57 (d, J = 16.1 Hz, 1H), 4.38 (d, 献值 105.3~107.6 ℃ ），产率 52%。HNMR (500 MHz,
J = 16.2 Hz, 1H), 3.87 (ddd, J = 14.9、6.2、3.2 Hz, 1H), CDCl 3 )，δ：7.33~7.27 (m, 2H), 7.09 (t, J = 7.4 Hz, 1H),
3.20~3.26 (m, 1H), 2.19~2.10 (m, 1H), 1.96~1.83 (m, 6.98 (d, J = 7.4 Hz, 1H), 6.83~6.78 (m, 2H),
2H), 1.73~1.60 (m, 3H), 1.53~1.45 (m, 1H), 1.41~1.32 6.65~6.56 (m, 2H), 4.80 (dd, J = 10.0、4.2 Hz, 1H),
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(m, 1H)。 CNMR (126 MHz, CDCl 3 )，δ：149.78, 4.55 (d, J = 16.2 Hz, 1H), 4.31 (d, J = 16.2 Hz, 1H),
142.65, 129.20, 127.78, 126.56, 119.96, 117.85, 3.90~3.83 (m, 1H), 3.17~3.24 (m, 1H), 2.10~2.17 (m,
117.41, 115.61, 110.09, 75.11, 47.14, 46.34, 32.96, 1H), 1.81~1.94 (m, 2H), 1.61~1.70 (m, 3H), 1.53~1.43
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26.45, 26.06, 24.79。 (m, 1H), 1.34 (ddd, J = 13.6、9.6、4.5 Hz, 1H)。 CNMR
6-(4-甲苯基)-5,6,6a,7,8,9,10,11-八氢氮杂[1,2-a] (126 MHz, CDCl 3 )，δ：148.86, 142.47, 131.97, 127.94,
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喹唑啉（Ⅲbd）：黏稠液体，产率 40%。 HNMR 126.56, 119.08, 117.42, 115.82, 112.09, 110.20, 75.06,
47.15, 46.39, 33.07, 26.40, 26.01, 24.73。
(500 MHz, CDCl 3)，δ：7.03 (td, J = 22.4、20.4、7.5 Hz,
6-(4- 腈基苯 基 )-5,6,6a,7,8,9,10,11- 八 氢氮杂
4H), 6.87 (d, J = 7.9 Hz, 2H), 6.60 (dd, J = 19.8、
[1,2-a]喹唑啉（Ⅲbj）：白色固体，熔点 121.7~122.5 ℃
7.7 Hz, 2H), 4.81 (dd, J = 10.1、4.0 Hz, 1H), 4.57 (d, [5] 1
J = 16.2 Hz, 1H), 4.32 (d, J = 16.2 Hz, 1H), 3.86 (d, （文献值 142.7~143.2 ℃ ），产率 61%。 HNMR
J = 15.0 Hz, 1H), 3.28~3.16 (m, 1H), 2.24 (s, 3H), (500 MHz, CDCl 3 ) ，δ：7.50 (d, J = 8.9 Hz, 2H), 7.13
2.10~2.16 (m, 1H), 1.97~1.82 (m, 2H), 1.71~1.60 (m, (t, J = 7.7 Hz, 1H), 7.03 (d, J = 7.4 Hz, 1H), 6.87 (d,