Page 166 - 《精细化工》2020年第9期

·1880· 精细化工 FINE CHEMICALS 第 37 卷

2.12 (d, J = 10.9 Hz, 6H), 1.99 (d, J = 18.7 Hz, 1H), 1.48 1-(2,6-二异丙基)苯基-3-(7,7-二甲基-2-氧代双环
(m, 1H), 1.38 (s, 3H), 1.21 (m, 1H), 1.02 (s, 3H)； [2.2.1]庚-1-基)甲基-咪唑-3- 四氟硼酸盐（Ⅳc），棕
13
CNMR (100 MHz, CDCl 3), δ: 217.8, 141.5, 138.5, 色固体，收率 84%，熔点：239~240 ℃。 HNMR
1
134.3, 134.2, 130.5, 130.1, 120.0, 125.9, 122.5, 60.5, (400 MHz, CDCl 3 ), δ: 10.05 (t, J = 1.6 Hz, 1H), 8.51
48.6, 47.7, 44.1, 43.3, 26.9, 25.9, 21.2, 20.87, 20.2, (t, J = 1.7 Hz, 1H), 7.60 (t, J = 7.9 Hz, 1H), 7.36 (m,
19
17.8； FNMR (376 MHz, CDCl 3 ), δ: –151.1, –151.2； 2H), 7.19 (t, J = 1.8 Hz, 1H), 5.24 (d, J = 14.2 Hz, 1H),
+
HRMS (ESI-TOF), m/Z: [C 22 H 29 N 2 O] 理论值 4.72 (d, J = 14.2 Hz, 1H), 2.57~2.40 (m, 2H),
337.2280，测试值 337.2274。 2.40~2.30 (m, 1H), 2.30~2.15 (m, 3H), 2.00 (d, J =
3-(7,7- 二甲基 -2- 氧 代双环 [2.2.1] 庚 -1- 基 ) 甲 18.7 Hz, 1H), 1.49 (m, 1H), 1.34 (s, 3H), 1.27 (dd, J =
14.8, 6.8 Hz, 6H), 1.20 (dd, J = 6.9、5.3 Hz, 7H), 1.02
基-1-(2,4,6-三甲基)苯基-咪唑-3- 双三氟甲磺酰亚
13
(s, 3H)； CNMR (100 MHz, CDCl 3 ), δ: 218.1, 145.5,
胺盐（Ⅲd），黄色固体，收率 85%，熔点：90~92 ℃。
1 HNMR (400 MHz, CDCl 3 ), δ: 9.43 (t, J = 1.6 Hz, 1H), 145.3, 138.6, 132.1, 130.0, 126.1, 124.9, 124.7, 123.4,
8.13 (t, J = 1.7 Hz, 1H), 7.15 (t, J = 1.8 Hz, 1H), 7.07 60.6, 48.7, 47.8, 44.1, 43.4, 28.8, 26.9, 25.7, 24.7,
19
(s, 2H), 4.79 (d, J = 14.5 Hz, 1H), 4.62 (d, J = 14.4 Hz, 24.2, 24.1, 20.9, 20.2； FNMR (376 MHz, CDCl 3 ), δ:
1H), 2.57~2.46 (m, 1H), 2.40 (s, 3H), 2.31~2.15 (m, –151.0, –151.1；HRMS (ESI-TOF), m/Z: [C 25 H 35 N 2 O] +
3H), 2.08 (d, J = 9.4 Hz, 6H), 1.99 (d, J = 18.8 Hz, 理论值 379.2749，测试值 379.2749。
1H), 1.49 (t, J = 9.9 Hz, 1H), 1.30 (s, 3H), 1.26~1.16 1-(2,6-二异丙基)苯基-3-(7,7-二甲基-2-氧代双
13
(m, 1H), 1.01 (s, 3H)； CNMR (100 MHz, CDCl 3), δ: 环[2.2.1]庚-1-基)甲基-咪唑-3- 双三氟甲磺酰亚胺
217.8, 141.6, 138.2, 130.5, 130.0, 125.7, 122.9, 60.3,
48.4, 48.0, 44.0, 43.3, 26.9, 25.9, 21.2, 20.1, 19.8, 17.5； 盐（Ⅳd），棕色固体，收率 83%，熔点：76~78 ℃。
1 HNMR (400 MHz, CDCl 3 ), δ: 10.13 (s, 1H), 8.51 (s,
19
FNMR (376 MHz, CDCl 3 ), δ: –79.0；HRMS (ESI-TOF), 1H), 7.59 (t, J = 7.8 Hz, 1H), 7.38~7.31 (m, 2H), 7.16
+
m/Z: [C 22H 29N 2O] 理论值 337.2280，测试值 337.2282。 (s, 1H), 5.30 (d, J = 14.2 Hz, 1H), 4.71 (d, J = 14.2 Hz,
1-(2,6-二异丙基)苯基-3-(7,7-二甲基-2-氧代双 1H), 2.61~2.41 (m, 2H), 2.34 (m, 1H), 2.31~2.16 (m,
3H), 2.00 (d, J = 18.8 Hz, 1H), 1.57~1.47 (m, 1H),
环[2.2.1]庚-1-基)甲基-咪唑-3- 碘盐（Ⅳa），棕色 1.41 (s, 3H), 1.28 (d, J = 6.8 Hz, 3H), 1.27 (d, J =
1
固体，收率 80%，熔点： 238~239 ℃。 HNMR 6.8 Hz, 3H), 1.18 (m, 7H), 1.00 (s, 3H)； CNMR
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(400 MHz, CDCl 3 ), δ: 9.17 (s, 1H), 8.14 (s, 1H), 7.59 (100 MHz, CDCl 3 ), δ: 217.8, 145.5, 145.3, 138.4,
(t, J = 7.8 Hz, 1H), 7.35 (dd, J = 7.8、1.8 Hz, 2H), 7.22 132.2, 129.9, 125.7, 124.8, 124.8, 124.0, 60.3, 48.3,
(t, J = 1.8 Hz, 1H), 4.73~4.58 (m, 2H), 2.55~2.44 (m, 48.2, 44.0, 43.3, 28.8, 26.9, 25.8, 24.2, 20.0, 19.6；
1H), 2.27 (m, 5H), 1.98 (d, J = 18.8 Hz, 1H), 1.50 (t, 19
J = 9.3 Hz, 1H), 1.27 (s, 3H), 1.26~1.13 (m, 13H), FNMR (376 MHz, CDCl 3 ), δ: –78.9；HRMS (ESI-TOF),
+
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1.00 (s, 3H)； CNMR (100 MHz, CDCl 3 ), δ: 218.2, m/Z: [C 25H 35N 2O] 理论值 379.2749，测试值 379.2751。
145.5, 145.3, 138.7, 132.1, 130.0, 126.1, 124.9, 124.7, 1-(4-氯苯基)-3-(7,7-二甲基-2-氧代双环[2.2.1]
123.3, 60.7, 48.7, 47.8, 44.1, 43.4, 28.8, 26.9, 25.7, 庚-1-基)甲基-咪唑-3- 碘盐（Ⅴa）， 棕色固体，收
24.7, 24.6, 24.2, 24.1, 21.0, 20.2；HRMS (ESI-TOF), 率 82%，熔点：104~105 ℃。 HNMR (400 MHz,
1
+
m/Z: [C 25H 35N 2O] 理论值 379.2749，测试值 379.2751。 CDCl 3 ), δ: 11.07 (s, 1H), 8.06 (t, J = 1.7 Hz, 1H),
1-(2,6-二异丙基)苯基-3-(7,7-二甲基-2-氧代双环 7.82~7.72 (m, 4H), 7.64 (t, J = 1.8 Hz, 1H), 4.96 (d,
J = 14.2 Hz, 1H), 4.57 (d, J = 14.2 Hz, 1H), 2.53~2.46
[2.2.1]庚-1-基)甲基-咪唑-3- 六氟磷酸盐（Ⅳb），黄 (m, 1H), 2.44~2.36 (m, 1H), 2.24 (t, J = 4.5 Hz, 1H),
1
色固体，收率 83%，熔点：222~224 ℃。HNMR (400 2.18 (m, 1H), 1.97 (d, J = 18.8 Hz, 1H), 1.45 (m, 1H),
MHz, CDCl 3), δ: 9.91 (s, 1H), 8.44 (d, J = 1.8 Hz, 1H), 1.36 (s, 3H), 1.24 (m, 1H), 1.00 (s, 3H)； CNMR
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7.59 (t, J = 7.8 Hz, 1H), 7.34 (dd, J = 7.8、4.7 Hz, 2H), (100 MHz, CDCl 3 ), δ: 217.5, 136.5, 133.8, 133.3,
7.13 (d, J = 1.8 Hz, 1H), 5.18 (d, J = 14.3 Hz, 1H), 126.0, 124.5, 123.8, 120.2, 60.5, 48.6, 47.9, 44.1, 43.2,
4.67 (d, J = 14.3 Hz, 1H), 2.51 (dt, J = 18.7、4.0 Hz, 26.8, 25.8, 20.5, 20.2 ； HRMS (ESI-TOF), m/Z:
1H), 2.46~2.37 (m, 1H), 2.33 (q, J = 7.1 Hz, 1H), [C 19 H 22 N 2 OCl] 理论值 329.1421，测试值 329.1423。
+
2.29~2.14 (m, 3H), 1.99 (d, J = 18.8 Hz, 1H),
1.54~1.44 (m, 1H), 1.40 (s, 3H), 1.26 (dd, J = 15.0、 1-(4-氯苯基)-3-(7,7-二甲基-2-氧代双环[2.2.1]
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6.8 Hz, 6H), 1.23~1.13 (m, 7H), 1.01 (s, 3H)； CNMR 庚-1-基)甲基-咪唑-3- 六氟磷酸盐（Ⅴb），棕色固
1
(100 MHz, CDCl 3 ), δ: 218.0, 145.5, 145.3, 138.5, 体，收率 80%，熔点：140~141 ℃。HNMR (400 MHz,
132.1, 130.0, 126.0, 124.9, 124.7, 123.6, 60.5, 48.6, CDCl 3 ), δ: 10.86 (s, 1H), 8.06~8.03 (m, 1H), 7.75 (s,
47.9, 44.1, 43.3, 28.8, 28.8, 26.9, 25.7, 24.6, 24.5, 4H), 7.62 (t, J = 1.9 Hz, 1H), 4.89 (d, J = 14.2 Hz, 1H),
19
24.2, 24.1, 20.7 20.2； FNMR (376 MHz, CDCl 3 ), δ: 4.56 (d, J = 14.2 Hz, 1H), 2.49 (m, 1H), 2.41~2.33 (m,
1H), 2.33 (t, J = 4.5 Hz, 1H), 2.21~2.13 (m, 1H), 1.96
+
–71.2, –73.0；HRMS (ESI-TOF), m/Z: [C 25 H 35 N 2 O] (d, J = 18.8 Hz, 1H), 1.45 (m, 1H), 1.33 (s, 3H), 1.24
理论值 379.2749，测试值 379.2746。 (m, 1H), 0.99 (s, 3H)； CNMR (100 MHz, CDCl 3 ), δ:
13