1,1-二氟取代-1,3-烯炔化合物的制备方法 |
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| 申请号 | CN202410134963.4 | 申请日 | 2024-01-31 | 公开(公告)号 | CN118026807A | 公开(公告)日 | 2024-05-14 |
| 申请人 | 国科大杭州高等研究院; | 发明人 | 张丰华; 王旭; 何国学; 黄蔚; | ||||
| 摘要 | 本 发明 公开了一种1,1‑二氟取代‑1,3‑烯炔化合物的制备方法，包括：在光催化剂和 碱 的存在以及蓝光照射的条件下，式(1)化合物和式(2)化合物反应生成式(3)的1,1‑二氟取代‑1,3‑烯炔化合物；其中，R1选自取代或未取代的C1～C10链状烷基，取代或未取代的C3～C10环状烷基，取代或未取代的芳基、杂芳基；式(2)化合物为 羧酸 ；所述的光催化剂选自金属铱光催化剂、金属钌光催化剂、咔唑类光催化剂。本发明的制备方法具有反应原料廉价易得、反应操作简便、反应底物适用范围广、反应容易放大、反应条件温和等优点，能够实现工业化生产和应用。#imgabs0# | ||||||
| 权利要求 | 1.一种1,1‑二氟取代‑1,3‑烯炔化合物的制备方法，其特征在于，包括：在光催化剂和碱的存在以及蓝光照射的条件下，式(1)化合物和式(2)化合物反应生成式(3)的1,1‑二氟取代‑1,3‑烯炔化合物： |
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| 说明书全文 | 1,1‑二氟取代‑1,3‑烯炔化合物的制备方法技术领域[0001] 本发明涉及有机合成技术领域，尤其涉及一种1,1‑二氟取代‑1,3‑烯炔化合物的制备方法。 背景技术[0002] 有机氟化学的研究是一个重要的领域，由于氟原子具有电负性大，原子半径小的特点，能有效的改善含氟化合物的理化性质，从而使其具有部分独特的性质。因此，含氟化合物在生物医药、农药化学、材料化学等一系列与人类生活有着密切关系的领域中发挥着重要的作用。 [0003] 1,1‑二氟取代‑1,3‑烯炔是一类非常重要的有机合成中间体，可以通过各类化学转化成多种含氟化合物。 [0004] 公开号为CN104844410A的中国专利文献公开了一种1,1‑二氟‑1,3‑烯炔化合物的合成方法，使α,α,α‑三氟甲基酮的对甲苯磺酰腙与端炔化合物在有机溶剂中进行反应，在一价铜CuX催化下，且有碱和添加剂存在时，得到1,1‑二氟‑1,3‑烯炔化合物。该方法需要使用金属催化剂。 [0005] 通过从2‑三氟甲基取代‑1,3‑烯炔出发，借助于自由基极性交叉偶联策略，可以顺利得到1,1‑二氟取代‑1,3‑烯炔。2023年，Guo课题组基于胺氧化脱质子策略，报道了一种1,1‑二氟取代‑1,3‑烯炔的合成方法(Yuan,Z.‑H.；Xin,H.；Zhang,L.；Gao,P.；Yang,X.；Duan,X.‑H.；Guo,L.‑N.；Green Chem.,2023,25,6733–6738)，公开了一种无金属、可见光驱动的甘氨酸衍生物与三氟甲基烯烃取代1,3‑炔的二氟烯基化反应，反应过程如下述方程式所示： [0006] [0008] 现有合成1,1‑二氟取代‑1,3‑烯炔的方法反应条件严苛，反应底物较窄。 发明内容[0009] 本发明提供了一种1,1‑二氟取代‑1,3‑烯炔化合物的制备方法，本发明首次实现了以简单易得的羧酸作为自由基前体，光诱导条件下实现多类1,1‑二氟取代‑1,3‑烯炔化合物的合成。 [0010] 本发明的技术方案如下： [0011] 一种1,1‑二氟取代‑1,3‑烯炔化合物的制备方法，包括：在光催化剂和碱的存在以及蓝光照射的条件下，式(1)化合物和式(2)化合物反应生成式(3)的1,1‑二氟取代‑1,3‑烯炔化合物： [0012] [0013] 其中，R1选自取代或未取代的C1～C10链状烷基，取代或未取代的C3～C10环状烷基，取代或未取代的芳基、杂芳基； [0014] 式(2)化合物为羧酸； [0015] 所述的光催化剂选自金属铱光催化剂、金属钌光催化剂、咔唑类光催化剂。 [0016] 式(2)化合物可以为一级羧酸、二级羧酸、三级羧酸、天然的氨基酸以及药物衍生的羧酸。 [0017] 优选的，R2选自取代或未取代的C1～C10链状烷基，取代或未取代的C3～C10环状烷基，取代或未取代的C3～C10杂环烷基，取代或未取代的C1～C10烷氧基，取代或未取代的芳基、杂芳基。 [0018] 优选的，R1中，取代的链状烷基上的取代基为卤素和/或酯基；取代的环状烷基上的取代基为环状烷基；取代的芳基、杂芳基上的取代基为卤素、取代或未取代的C1～C6烷氧基、取代或未取代的C1～C6烷基； [0019] R2中，取代的烷基上的取代基为卤素和/或酯基；取代的烷氧基上的取代基为卤素和/或酯基；取代的芳基、杂芳基上的取代基为卤素取代或未取代的C1～C6烷基、卤素取代或未取代的C1～C6烷氧基、卤素和/或酯基，取代的芳基、杂芳基上的取代基为卤素、取代或未取代的C1～C6烷氧基、取代或未取代的C1～C6烷基。 [0020] 芳基为苯基或萘基；杂芳基为苯并噻吩基。 [0021] 优选的，式(1)化合物选自： [0022] [0023] 式(2)化合物选自： [0024] [0025] [0026] 优选的，所述的催化剂选自： [0027] [0028] 优选的，所述的蓝光的波长为390～440nm；进一步优选为427nm或440nm。 [0029] 优选的，反应在有机溶剂中进行，所述的有机溶剂为乙腈、二甲基亚砜、乙二醇二甲醚、四氢呋喃中的至少一种。 [0031] 优选的，式(1)化合物、式(2)化合物、碱、光催化剂的摩尔比为1:0.5‑1.5:0.5‑1.5:0.01‑0.05。 [0032] 反应温度为室温；反应温度优选为25～30℃。 [0033] 本发明制备的1,1‑二氟取代‑1,3‑烯炔化合物是一类非常重要的有机合成中间体，可以通过各类化学反应转化成多种含氟化合物。 [0034] 与现有技术相比，本发明的有益效果为： [0035] (1)本发明首次实现了以简单易得的羧酸作为自由基前体，光诱导条件下实现多类1,1‑二氟取代‑1,3‑烯炔化合物的合成。 [0036] (2)本发明提供的制备方法可以适用于一级羧酸、二级羧酸、三级羧酸、天然的氨基酸以及药物衍生的羧酸，具有底物简单易得、普适性广泛的优点。 [0037] (3)本发明的制备方法具有反应原料廉价易得、反应操作简便、反应底物适用范围广、反应容易放大、反应条件温和等优点，能够实现工业化生产和应用。 具体实施方式[0038] 下面结合实施例对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。 [0039] 下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。如无特殊说明，各实施例中的光催化剂mol％用量均以化合物1为基准。 [0040] 以下实施例中，光催化剂为： [0041] [0042] 实施例1：PC2对反应的影响 [0043] [0044] 在手套箱中，将PC2(3mol％)、羧酸2、碳酸钾称入4mL样品瓶中，依次加入溶剂MeCN(2.0mL)、1,3‑烯炔1(0.1mmol)，旋紧PTFE盖子。将样品瓶拿出手套箱，放置于440nm的蓝光下，25℃反应12小时。反应结束后，旋转蒸发仪脱除溶剂后得粗产物。经短硅胶柱过滤除去催化剂，用薄层层析或者核磁共振分析反应的转化率、收率，所得实验结果：核磁收率为89％。 [0045] 实施例2：PC1对反应的影响 [0046] 与实施例1的区别仅在于用等摩尔量的PC1替代PC2，其余均相同，所得实验结果：核磁收率为25％。 [0047] 实施例3：PC3对反应的影响 [0048] 与实施例1的区别仅在于用等摩尔量的PC3替代PC2，其余均相同，所得实验结果：核磁收率为56％。 [0049] 实施例4：PC4对反应的影响 [0050] 与实施例1的区别仅在于用等摩尔量的PC4替代PC2，其余均相同，所得实验结果：核磁收率为75％。 [0051] 实施例5：427nm蓝光对反应的影响 [0052] 与实施例1的区别仅在于蓝光波长为427nm，其余均相同，所得实验结果：核磁收率为85％。 [0053] 实施例6：THF溶剂对反应的影响 [0054] 与实施例1的区别仅在于用等体积的THF替换溶剂MeCN，其余均相同，所得实验结果：核磁收率为39％。 [0055] 实施例7：DMSO溶剂对反应的影响 [0056] 与实施例1的区别仅在于用等体积的DMSO替换溶剂MeCN，其余均相同，所得实验结果：核磁收率为80。 [0057] 实施例8：DME溶剂对反应的影响 [0058] 与实施例1的区别仅在于用等体积的DME替换溶剂MeCN，其余均相同，所得实验结果：核磁收率为65％。 [0059] 实施例9：NaOH对反应的影响 [0060] 与实施例1的区别仅在于用等量的NaOH替换碱K2CO3，其余均相同，所得实验结果：核磁收率为65％。 [0061] 实施例10：KOH对反应的影响 [0062] 与实施例1的区别仅在于用等量的KOH替换碱K2CO3，其余均相同，所得实验结果：核磁收率为35％。 [0063] 实施例11：三乙胺对反应的影响 [0064] 与实施例1的区别仅在于用等量的三乙胺替换碱K2CO3，其余均相同，所得实验结果：核磁收率为20％。 [0065] 实施例12：K3PO4对反应的影响 [0066] 与实施例1的区别仅在于用等量的K3PO4替换碱K2CO3，其余均相同，所得实验结果：核磁收率为24％。 [0067] 实施例13：磷酸氢二钾对反应的影响 [0068] 与实施例1的区别仅在于用等量的磷酸氢二钾替换碱K2CO3，其余均相同，所得实验结果：核磁收率为31％。 [0069] 实施例14：二异丙基乙基胺对反应的影响 [0070] 与实施例1的区别仅在于用等量的二异丙基乙基胺替换碱K2CO3，其余均相同，所得实验结果：核磁收率为15％。 [0071] 实施例15：1,3‑烯炔和羧酸反应底物考察 [0072] [0073] 在手套箱中，将PC2(3mol％)、羧酸2、碳酸钾称入4mL样品瓶中，依次加入溶剂MeCN(2.0mL)、1,3‑烯炔1(0.1mmol)，旋紧PTFE盖子。将样品瓶拿出手套箱，放置于440nm的蓝光下，25℃反应12小时。反应结束后，旋转蒸发仪脱除溶剂后得粗产物。经短硅胶柱过滤除去催化剂，用薄层层析或者核磁共振分析反应的转化率、分离收率，所得实验结果见表1。 [0074] 表1 1,3‑烯炔和羧酸反应底物考察 [0075] [0076] [0077] [0078] [0079] [0080] 化合物3‑44的分析数据如下： [0081] 1,1‑二氟取代1,3‑烯炔3的分析数据 [0082] 1H NMR(400MHz,CDCl3)δ7.44–7.36(m,2H),7.35–7.27(m,3H),3.81–3.71(m,2H),3.66(ddd,J＝11.8,8.8,3.1Hz,2H),2.19(t,J＝2.2Hz,2H),1.66(ddd,J＝13.2,8.8, 4.1Hz,2H),1.50–1.37(m,2H),1.11(s,3H). [0083] 13C NMR(101MHz,CDCl3)δ159.73(dd,J＝296.9,294.2Hz),131.13(s),128.33(two carbons,s),122.91(s),93.40(t,J＝5.8Hz),82.74(dd,J＝8.1,4.2Hz),75.32(dd,J＝34.3,15.2Hz),63.86(s),39.36(s),37.30(s),32.59(t,J＝2.4Hz),23.85(s).[0084] 19F NMR(377MHz,CDCl3)δ‑78.22(d,J＝13.0Hz),‑82.38(d,J＝12.7Hz).[0085] 1,1‑二氟取代1,3‑烯炔4的分析数据 [0086] 1H NMR(400MHz,CDCl3)δ7.42–7.31(m,2H),7.05–6.96(m,2H),3.80–3.70(m,2H),3.65(ddd,J＝11.8,8.9,3.1Hz,2H),2.17(t,J＝2.1Hz,2H),1.65(ddd,J＝13.2,8.8, 4.1Hz,2H),1.51–1.36(m,2H),1.10(s,3H). [0087] 13C NMR(101MHz,CDCl3)δ162.50(d,J＝249.7Hz),159.75(dd,J＝296.9,294.4Hz),133.02(d,J＝8.4Hz),119.00(d,J＝3.5Hz),115.64(d,J＝22.1Hz),92.29(t,J＝5.8Hz),82.42(dd,J＝8.1,4.2Hz),75.19(dd,J＝34.6,15.2Hz),63.82(s),39.37(s), 37.27(s),32.59(t,J＝2.4Hz),23.78(s). [0088] 19F NMR(377MHz,CDCl3)δ‑78.16(d,J＝12.6Hz),‑82.18(d,J＝12.6Hz),‑110.61–‑110.74(m). [0089] 1,1‑二氟取代1,3‑烯炔5的分析数据 [0090] 1H NMR(400MHz,CDCl3)δ7.35–7.26(m,4H),3.80–3.71(m,2H),3.65(ddd,J＝11.9,8.9,3.1Hz,2H),2.17(t,J＝2.2Hz,2H),1.64(ddd,J＝13.3,8.9,4.1Hz,2H),1.49–1.36(m, 2H),1.10(s,3H). [0091] 13C NMR(101MHz,CDCl3)δ159.83(dd,J＝297.5,294.7Hz),134.41(s),132.34(s),128.71(s),121.41(s),92.29(t,J＝5.8Hz),83.76(dd,J＝8.2,4.2Hz),75.22(dd,J＝ 34.5,15.2Hz),63.84(s),39.38(s),37.30(s),32.62(t,J＝2.5Hz),23.80(s).[0092] 19F NMR(377MHz,CDCl3)δ‑77.75(d,J＝11.0Hz),‑81.76(d,J＝11.8Hz).[0093] 1,1‑二氟取代1,3‑烯炔6的分析数据 [0094] 1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.3Hz,2H),7.49(d,J＝8.2Hz,2H),3.81–3.71(m,2H),3.65(ddd,J＝11.9,9.0,3.1Hz,2H),2.19(t,J＝2.1Hz,2H),1.65(ddd,J＝13.3,9.0,4.1Hz,2H),1.48–1.37(m,2H),1.11(s,3H). [0095] 13C NMR(151MHz,CDCl3)δ160.03(dd,J＝298.3,295.4Hz),131.34(s),130.05(q,J＝32.7Hz),126.67(s),125.29(q,J＝3.4Hz),123.84(q,J＝272.2Hz),92.04(t,J＝5.6Hz),85.27(dd,J＝8.2,4.2Hz),75.09(dd,J＝34.6,15.0Hz),63.82(s),39.39(s), 37.25(s),32.64(s),23.70(s). [0096] 19F NMR(377MHz,CDCl3)δ‑62.85(s),‑76.89(d,J＝9.5Hz),‑80.79(d,J＝9.5Hz).[0097] 1,1‑二氟取代1,3‑烯炔7的分析数据 [0098] 1H NMR(400MHz,CDCl3)δ7.38–7.30(m,2H),6.88–6.80(m,2H),3.81(s,3H),3.76(ddd,J＝11.5,5.3,4.3Hz,2H),3.65(ddd,J＝11.8,8.7,3.2Hz,2H),2.17(t,J＝2.2Hz,2H),1.65(ddd,J＝13.2,8.8,4.1Hz,2H),1.48–1.39(m,2H),1.10(s,3H). [0099] 13C NMR(151MHz,CDCl3)δ159.66(s),159.56(dd,J＝296.4,294.0Hz),132.60(s),115.07(s),113.98(s),93.33(t,J＝5.6Hz),81.35(dd,J＝8.0,4.0Hz),75.43(dd,J＝ 34.1,15.3Hz),63.88(s),55.29(s),39.39(s),37.33(s),32.59(s),23.91(s).[0100] 19F NMR(377MHz,CDCl3)δ‑79.06(d,J＝14.5Hz),‑83.29(d,J＝14.9Hz).[0101] 1,1‑二氟取代1,3‑烯炔8的分析数据 [0102] 1H NMR(400MHz,CDCl3)δ7.92(s,1H),7.85–7.74(m,3H),7.53–7.41(m,3H),3.84–3.73(m,2H),3.68(ddd,J＝11.8,8.8,3.1Hz,2H),2.22(t,J＝2.1Hz,2H),1.69(ddd,J＝ 13.2,8.8,4.1Hz,2H),1.52–1.43(m,2H),1.14(s,3H). [0103] 13C NMR(151MHz,CDCl3)δ159.85(dd,J＝297.2,294.5Hz),132.93(s),132.81(s),130.95(s),128.04(s),127.89(s),127.76(s),127.73(s),126.73(s),126.62(s),120.22(s),93.83(t,J＝5.9Hz),83.10(dd,J＝7.8,4.3Hz),75.44(dd,J＝34.3,15.1Hz),63.90(s),39.45(s),37.37(s),32.67(s),23.90(s). [0104] 19F NMR(377MHz,CDCl3)δ‑78.06(d,J＝12.5Hz),‑82.19(d,J＝12.4Hz).[0105] 1,1‑二氟取代1,3‑烯炔9的分析数据 [0106] 1H NMR(400MHz,CDCl3)δ7.37(d,J＝1.4Hz,1H),7.07–6.99(m,2H),3.80–3.72(m,2H),3.65(ddd,J＝11.8,8.7,3.1Hz,2H),3.09–2.95(m,2H),2.18(t,J＝2.1Hz,2H),1.97– 1.90(m,2H),1.66(ddd,J＝13.1,8.7,4.1Hz,2H),1.49–1.39(m,2H),1.32(s,6H),1.10(s, 3H). [0107] 13C NMR(151MHz,CDCl3)δ159.60(t,J＝295.4Hz),142.04(s),133.19(s),129.06(s),128.52(s),126.51(s),118.21(s),93.83–93.64(m),81.92(dd,J＝7.7,3.8Hz),75.43(dd,J＝33.8,15.3Hz),63.88(s),39.37(s),37.32(s),37.17(s),32.90(s),32.61(s),29.91(s),23.89(s),23.16(s). [0108] 19F NMR(377MHz,CDCl3)δ‑78.69(d,J＝14.8Hz),‑82.96(d,J＝14.0Hz).[0109] 1,1‑二氟取代1,3‑烯炔10的分析数据 [0110] 1H NMR(400MHz,CDCl3)δ3.74–3.65(m,5H),3.61(ddd,J＝11.8,8.9,3.1Hz,2H),2.67–2.57(m,2H),2.52(dd,J＝11.3,4.4Hz,2H),2.02(t,J＝2.2Hz,2H),1.56(ddd,J＝ 13.3,8.8,4.2Hz,2H),1.39–1.28(m,2H),1.02(s,3H). [0111] 13C NMR(101MHz,CDCl3)δ172.11(s),160.06(dd,J＝295.3,292.5Hz),92.07(t,J＝5.7Hz),74.88(dd,J＝34.0,15.6Hz),74.54(dd,J＝8.0,3.8Hz),63.80(s),51.74(s),39.41(s),37.26(s),33.16(s),32.48(t,J＝2.5Hz),23.72(s),15.33(s). [0112] 19F NMR(377MHz,CDCl3)δ‑80.43(d,J＝17.5Hz),‑83.85(d,J＝17.5Hz).[0113] 1,1‑二氟取代1,3‑烯炔11的分析数据 [0114] 1H NMR(400MHz,CDCl3)δ3.72(dt,J＝9.6,4.5Hz,2H),3.66–3.56(m,4H),2.49(t,J＝6.8Hz,2H),2.04(t,J＝2.2Hz,2H),1.96(p,J＝6.6Hz,2H),1.58(ddd,J＝13.3,8.9,4.2Hz,2H),1.40–1.31(m,2H),1.04(s,3H). [0115] 13C NMR(101MHz,CDCl3)δ160.10(dd,J＝295.0,292.8Hz),92.17(t,J＝5.7Hz),74.93(dd,J＝30.2,19.2Hz),74.82(t,J＝4.0Hz),63.81(s),43.50(s),39.52(s),37.27(s),32.51(t,J＝2.5Hz),31.16(s),23.72(s),16.80(s). [0116] 19F NMR(377MHz,CDCl3)δ‑80.47(d,J＝17.8Hz),‑83.78(d,J＝17.7Hz).[0117] 1,1‑二氟取代1,3‑烯炔12的分析数据 [0118] 1H NMR(400MHz,CDCl3)δ5.74(s,1H),3.75–3.67(m,2H),3.66–3.57(m,2H),2.45–2.17(m,5H),2.10–1.97(m,4H),1.78–1.65(m,3H),1.65–1.50(m,7H),1.47–1.26(m,7H), 1.20(s,3H),1.05(s,3H),0.90(s,3H). [0119] 13C NMR(151MHz,CDCl3)δ199.46(s),170.98(s),159.94(t,J＝295.2Hz),123.89(s),96.56(t,J＝5.8Hz),80.01(s),79.47(dd,J＝8.1,3.8Hz),74.59(dd,J＝34.1,15.3Hz),63.75(s),53.58(s),50.08(s),46.97(s),39.42(s),38.76(s),38.56(s),37.24(s),37.17(s),36.15(s),35.69(s),33.88(s),32.69(s),32.50(s),31.52(s),23.75(s), 23.02(s),20.67(s),17.37(s),12.76(s). [0120] 19F NMR(377MHz,CDCl3)δ‑78.42(d,J＝13.8Hz),‑82.12(d,J＝13.8Hz).[0121] 1,1‑二氟取代1,3‑烯炔13的分析数据 [0122] 1H NMR(400MHz,CDCl3)δ7.00(d,J＝7.5Hz,1H),6.66(d,J＝7.5Hz,1H),6.62(s,1H),5.73(s,1H),3.92(t,J＝6.4Hz,2H),2.48–2.21(m,8H),2.17(s,3H),2.08–1.93(m, 4H),1.90–1.64(m,6H),1.63–1.49(m,2H),1.48–1.22(m,6H),1.19(s,3H),1.09–0.79(m, 12H). [0123] 13C NMR(101MHz,CDCl3)δ199.49(s),171.06(s),159.89(dd,J＝295.9,294.9Hz),156.94(s),136.43(s),130.29(s),123.89(s),123.57(s),120.78(s),112.21(s),96.26(t,J＝5.6Hz),80.04(s),79.66(dd,J＝8.2,4.0Hz),75.40(dd,J＝33.9,14.9Hz),68.63(s),53.53(s),50.03(s),46.98(s),39.16(d,J＝2.0Hz),38.75(s),38.57(s),38.15(s), 36.18(s),35.69(s),34.58(t,J＝2.4Hz),33.91(s),32.73(s),32.51(s),31.50(s),26.87(s),26.82(s),24.31(s),23.03(s),21.36(s),20.69(s),17.38(s),15.75(s),12.76(s).[0124] 19F NMR(377MHz,CDCl3)δ‑78.97(d,J＝14.5Hz),‑82.67(d,J＝14.5Hz).[0125] 1,1‑二氟取代1,3‑烯炔14的分析数据 [0126] 1H NMR(400MHz,CDCl3)δ7.74–7.66(m,2H),7.41–7.34(m,2H),7.08(d,J＝8.4Hz,2H),6.96–6.85(m,2H),6.45(t,J＝6.1Hz,1H),5.72(s,1H),3.64(dd,J＝15.0,7.1Hz,2H), 2.85(t,J＝7.1Hz,2H),2.51–2.29(m,5H),2.23(dt,J＝9.2,7.4Hz,2H),2.07–1.95(m,2H), 1.69–1.46(m,7H),1.38–1.22(m,9H),1.17(s,3H),0.96–0.70(m,6H). [0127] 13C NMR(151MHz,CDCl3)δ199.86(s),171.50(s),166.32(s),160.16(t,J＝295.3Hz),153.66(s),137.56(s),133.80(s),132.97(s),129.25(s),128.74(s),128.35(s),123.85(s),123.74(s),96.38(t,J＝5.5Hz),80.10(s),79.96(t,J＝2.6Hz),79.16(dd,J＝8.1,4.1Hz),74.87(dd,J＝33.4,16.8Hz),53.32(s),49.88(s),46.97(s),41.22(s),39.77(s),38.74(s),38.59(s),36.13(s),35.70(s),34.88(s),34.01(s),32.76(s), 32.47(s),31.36(s),26.59(s),26.12(s),23.02(s),20.64(s),17.32(s),12.76(s).[0128] 19F NMR(377MHz,CDCl3)δ‑78.35(d,J＝12.4Hz),‑82.39(d,J＝12.4Hz).[0129] 1,1‑二氟取代1,3‑烯炔15的分析数据 [0130] 1H NMR(400MHz,CDCl3)δ7.10(d,J＝8.1Hz,2H),6.93(d,J＝7.9Hz,2H),5.71(d,J＝2.4Hz,1H),2.83(t,J＝9.5Hz,1H),2.48–2.28(m,5H),2.27–2.15(m,2H),2.09–1.90(m,4H),1.77(dd,J＝16.7,9.2Hz,2H),1.70–1.34(m,8H),1.30(d,J＝10.2Hz,7H),1.16(s, 3H),0.89–0.74(m,5H). [0131] 13C NMR(151MHz,CDCl3)δ199.56(s),171.25(s),160.14(t,J＝295.4Hz),154.32(s),129.70(s),129.35(s),123.76(s),123.74(s),96.58(s),80.22(d,J＝1.6Hz),80.02(s),78.96(dd,J＝7.7,4.2Hz),74.85(dd,J＝34.0,16.1Hz),60.81(s),53.31(s),53.25(s),49.84(d,J＝2.0Hz),46.97(s),40.02(s),38.73(s),38.52(s),36.09(d,J＝1.5Hz),35.63(s),34.85(s),33.89(s),32.70(s),32.42(s),31.32(s),31.26(s),26.34(d,J＝ 2.7Hz),26.08(s),26.03(s),25.82(s),23.00(s),20.64(s),17.32(s),12.73(s).[0132] 19F NMR(377MHz,CDCl3)δ‑78.38(t,J＝11.8Hz),‑82.40(t,J＝12.5Hz).[0133] 1,1‑二氟取代1,3‑烯炔16的分析数据 [0134] 1H NMR(400MHz,CDCl3)δ7.41(dd,J＝6.6,3.0Hz,2H),7.35–7.26(m,3H),2.07(t,J＝2.2Hz,2H),1.02(s,9H). [0135] 13C NMR(151MHz,CDCl3)δ159.65(dd,J＝296.3,294.3Hz),131.17(s),128.28(s),128.20(s),123.18(s),93.13(t,J＝5.9Hz),83.08(dd,J＝8.4,4.2Hz),76.46(dd,J＝ 34.4,14.7Hz),41.06(d,J＝1.8Hz),32.40(s),29.31(s). [0136] 19F NMR(377MHz,CDCl3)δ‑79.16(d,J＝13.8Hz),‑83.24(d,J＝14.0Hz).[0137] 1,1‑二氟取代1,3‑烯炔17的分析数据 [0138] 1H NMR(400MHz,CDCl3)δ7.45–7.37(m,2H),7.34–7.25(m,3H),2.24(t,J＝2.2Hz,2H),2.11–1.99(m,2H),1.98–1.81(m,2H),1.81–1.70(m,2H),1.21(s,3H). [0139] 13C NMR(101MHz,CDCl3)δ159.53(dd,J＝296.3,293.0Hz),131.19(s),128.32(s),128.25(s),123.17(s),93.34(t,J＝5.6Hz),82.29(dd,J＝8.0,3.9Hz),76.34(d,J＝ 14.4Hz),39.20(s),39.18(s),39.15(s),33.34(s),25.72(s),15.37(s). [0140] 19F NMR(377MHz,CDCl3)δ‑79.72(d,J＝15.3Hz),‑84.32(d,J＝16.0Hz).[0141] 1,1‑二氟取代1,3‑烯炔18的分析数据 [0142] 1H NMR(400MHz,CDCl3)δ7.43–7.37(m,2H),7.33–7.26(m,3H),2.11(t,J＝2.2Hz,2H),1.55–1.39(m,8H),1.38–1.30(m,2H),0.99(s,3H). [0143] 13C NMR(101MHz,CDCl3)δ159.63(dd,J＝296.3,293.8Hz),131.16(s),128.28(s),128.16(s),123.22(s),92.95(t,J＝5.7Hz),83.23(dd,J＝8.2,4.1Hz),75.90(dd,J＝ 34.5,14.7Hz),39.09(s),37.56(s),34.75(s),26.31(s),25.01(s),22.06(s).[0144] 19F NMR(377MHz,CDCl3)δ‑78.83(d,J＝13.9Hz),‑82.81(d,J＝13.9Hz).[0145] 1,1‑二氟取代1,3‑烯炔19的分析数据 [0146] 1H NMR(400MHz,CDCl3)δ7.43–7.35(m,2H),7.32(dd,J＝4.1,2.3Hz,3H),2.41(t,J＝6.3Hz,4H),2.28(t,J＝2.1Hz,2H),1.96–1.84(m,2H),1.78(dt,J＝13.3,6.5Hz,2H),1.19(s,3H). [0147] 13C NMR(101MHz,CDCl3)δ211.84(s),159.85(dd,J＝297.4,294.5Hz),131.19(s),128.53(s),128.42(s),122.75(s),93.56(t,J＝5.8Hz),82.33(dd,J＝8.1,4.1Hz),75.52(dd,J＝34.2,15.7Hz),53.46(s),37.83(d,J＝2.0Hz),37.61(s),37.05(s),34.27(t,J＝ 2.3Hz),23.99(s). [0148] 19F NMR(377MHz,CDCl3)δ‑77.74(d,J＝12.1Hz),‑82.19(d,J＝12.1Hz).[0149] 1,1‑二氟取代1,3‑烯炔20的分析数据 [0150] 1H NMR(400MHz,CDCl3)δ7.45–7.39(m,2H),7.35–7.28(m,3H),1.98(s,3H),1.94(d,J＝1.9Hz,2H),1.72(s,1H),1.69(s,2H),1.65(s,2H),1.61(s,7H). [0151] 13C NMR(151MHz,CDCl3)δ159.55(dd,J＝296.3,294.1Hz),131.19(s),128.28(s),128.16(s),123.22(s),92.94(t,J＝5.8Hz),83.40(dd,J＝8.2,3.9Hz),75.10(dd,J＝ 34.9,14.8Hz),42.13(s),41.86(d,J＝2.4Hz),36.88(s),34.22(s),28.60(s).[0152] 19F NMR(377MHz,CDCl3)δ‑78.92(d,J＝13.9Hz),‑82.69(d,J＝13.9Hz).[0153] 1,1‑二氟取代1,3‑烯炔21的分析数据 [0154] 1H NMR(400MHz,CDCl3)δ7.44–7.35(m,2H),7.34–7.27(m,3H),2.56(s,2H),2.16–2.15(m,1H),2.07–1.79(m,12H). [0155] 13C NMR(101MHz,CDCl3)δ217.85(s),159.63(dd,J＝297.6,294.4Hz),131.16(s),128.42(s),128.33(s),122.78(s),93.55(t,J＝5.8Hz),82.50(dd,J＝8.0,4.3Hz),74.78(dd,J＝34.6,15.5Hz),46.31(s),43.12(s),40.77(s),39.97(d,J＝2.1Hz),38.55(s), 34.15(t,J＝2.4Hz),27.75(s). [0156] 19F NMR(377MHz,CDCl3)δ‑78.01(d,J＝12.4Hz),‑82.20(d,J＝12.4Hz).[0157] 1,1‑二氟取代1,3‑烯炔22的分析数据 [0158] 1H NMR(400MHz,CDCl3)δ7.44–7.38(m,2H),7.35–7.27(m,3H),3.66(s,3H),2.36(t,J＝2.0Hz,2H),2.05(s,6H). [0159] 13C NMR(151MHz,CDCl3)δ170.34(s),159.12(dd,J＝296.9,293.8Hz),131.26(s),128.43(s),128.34(s),122.77(s),93.59(t,J＝5.8Hz),81.43–81.03(m),75.94(dd,J＝ 35.0,15.6Hz),51.94(s),51.60(s),38.45(t,J＝3.1Hz),37.98(s),29.69(s).[0160] 19F NMR(377MHz,CDCl3)δ‑79.53(d,J＝15.2Hz),‑85.29(d,J＝16.1Hz).[0161] 1,1‑二氟取代1,3‑烯炔23的分析数据 [0162] 1H NMR(400MHz,CDCl3)δ7.48–7.40(m,2H),7.36–7.27(m,3H),4.74(s,1H),2.55(s,2H),1.39(s,15H). [0163] 13C NMR(151MHz,CDCl3)δ160.04(t,J＝296.2Hz),154.23(s),131.36(s),128.39(s),128.24(s),122.83(s),93.62(t,J＝5.7Hz),82.05(s),78.87(s),75.36(dd,J＝33.9,16.2Hz),52.99(t,J＝2.3Hz),37.09(s),28.34(s),27.15(s). [0164] 19F NMR(377MHz,CDCl3)δ‑77.72(d,J＝7.5Hz),‑82.42(d,J＝7.5Hz).[0165] 1,1‑二氟取代1,3‑烯炔24的分析数据 [0166] 1H NMR(400MHz,CDCl3)δ7.47–7.37(m,2H),7.35–7.27(m,3H),4.83(s,1H),3.08(d,J＝6.7Hz,2H),2.10(t,J＝1.9Hz,2H),1.45(s,9H),0.99(s,6H). [0167] 13C NMR(101MHz,CDCl3)δ159.74(dd,J＝297.4,294.4Hz),156.23(s),131.24(s),128.49(s),128.37(s),122.72(s),93.50(t,J＝5.7Hz),82.58(dd,J＝8.0,4.1Hz),79.14(s),75.51(dd,J＝34.4,15.3Hz),49.74(s),37.00(s),36.44(s),28.40(s),24.90(s).[0168] 19F NMR(377MHz,CDCl3)δ‑77.92(d,J＝12.2Hz),‑82.41(d,J＝12.2Hz).[0169] 1,1‑二氟取代1,3‑烯炔25的分析数据 [0170] 1H NMR(400MHz,CDCl3)δ7.45–7.38(m,2H),7.36–7.28(m,3H),5.88(ddt,J＝17.7,10.4,7.4Hz,1H),5.11–5.00(m,2H),2.10(s,1H),2.10–2.05(m,3H),0.99(s,6H).[0171] 13C NMR(101MHz,CDCl3)δ159.65(dd,J＝296.3,294.3Hz),135.09(s),131.16(s), 128.29(s),128.24(s),123.08(s),117.43(s),93.21(t,J＝5.7Hz),82.94(dd,J＝7.9, 4.0Hz),76.09(dd,J＝34.2,15.0Hz),46.47(s),39.06(d,J＝2.0Hz),35.03(t,J＝2.4Hz), 26.62(s). [0172] 19F NMR(377MHz,CDCl3)δ‑78.67(d,J＝13.9Hz),‑82.75(d,J＝13.4Hz).[0173] 1,1‑二氟取代1,3‑烯炔26的分析数据 [0174] 1H NMR(400MHz,CDCl3)δ7.48–7.40(m,2H),7.36–7.28(m,3H),3.98(dd,J＝10.8,3.6Hz,2H),3.40(td,J＝11.8,2.0Hz,2H),2.10(dt,J＝7.2,2.3Hz,2H),1.93–1.78(m,1H), 1.69(dd,J＝13.1,1.7Hz,2H),1.35(ddd,J＝25.0,12.0,4.4Hz,2H). [0175] 13C NMR(101MHz,CDCl3)δ159.17(dd,J＝296.6,293.4Hz),131.38(s),128.42(s),128.34(s),122.85(s),93.39(t,J＝5.8Hz),81.14(dd,J＝8.2,4.2Hz),76.76(dd,J＝ 58.3,23.3Hz),67.85(s),34.27(d,J＝1.2Hz),33.81(t,J＝2.1Hz),32.47(s).[0176] 19F NMR(377MHz,CDCl3)δ‑79.21(d,J＝16.3Hz),‑84.53(d,J＝15.6Hz).[0177] 1,1‑二氟取代1,3‑烯炔27的分析数据 [0178] 1H NMR(400MHz,CDCl3)δ7.47–7.39(m,2H),7.37–7.27(m,3H),4.11(s,2H),2.72(t,J＝12.0Hz,2H),2.14–2.02(m,2H),1.82–1.66(m,3H),1.46(s,9H),1.23–1.07(m,2H).[0179] 13C NMR(101MHz,CDCl3)δ159.11(dd,J＝296.7,293.2Hz),154.80(s),131.36(s),128.41(s),128.32(s),122.78(s),93.48–93.31(m),81.09(dd,J＝8.2,4.1Hz),79.30(s), 76.68(d,J＝34.9Hz),43.68(s),34.82(t,J＝2.0Hz),33.90(d,J＝1.1Hz),31.52(s), 28.42(s). [0180] 19F NMR(377MHz,CDCl3)δ‑79.15(d,J＝15.3Hz),‑84.44(d,J＝15.6Hz).[0181] 1,1‑二氟取代1,3‑烯炔28的分析数据 [0182] 1H NMR(400MHz,CDCl3)δ7.48–7.39(m,2H),7.36–7.28(m,3H),2.03(dt,J＝7.1,2.2Hz,2H),1.84–1.57(m,6H),1.35–1.12(m,3H),0.95(qd,J＝12.0,2.4Hz,2H).[0183] 13C NMR(151MHz,CDCl3)δ159.04(dd,J＝295.9,292.7Hz),131.39(s),128.28(s), 128.24(s),123.07(s),93.00(t,J＝5.7Hz),81.65(dd,J＝8.1,4.0Hz),77.46(d,J＝ 14.3Hz),36.33(s),34.74(s),32.68(s),26.40(s),26.10(s). [0184] 19F NMR(377MHz,CDCl3)δ‑79.91(d,J＝17.8Hz),‑85.06(d,J＝17.5Hz).[0185] 1,1‑二氟取代1,3‑烯炔29的分析数据 [0186] 1H NMR(400MHz,CDCl3)δ7.46–7.40(m,2H),7.36–7.30(m,3H),2.75–2.55(m,4H),2.16–2.01(m,4H),1.71–1.60(m,1H),1.41(ddd,J＝25.0,11.7,3.5Hz,2H). [0187] 13C NMR(151MHz,CDCl3)δ159.16(dd,J＝296.6,293.2Hz),131.39(s),128.44(s),128.34(s),122.81(s),93.44(t,J＝5.6Hz),81.08(dd,J＝7.9,4.1Hz),76.53(d,J＝ 15.2Hz),35.88(s),34.65(s),33.49(s),28.58(s). [0188] 19F NMR(377MHz,CDCl3)δ‑79.04(d,J＝15.2Hz),‑84.37(d,J＝15.5Hz).[0189] 1,1‑二氟取代1,3‑烯炔30的分析数据 [0190] 1H NMR(400MHz,CDCl3)δ7.48–7.39(m,2H),7.36–7.27(m,3H),5.68(s,2H),2.66–2.47(m,3H),2.22(dt,J＝7.4,2.2Hz,2H),2.12–2.02(m,2H). [0191] 13C NMR(151MHz,CDCl3)δ159.14(dd,J＝295.9,292.8Hz),131.38(s),129.64(s),128.30(s),122.98(s),93.31(t,J＝5.8Hz),81.35(dd,J＝8.2,4.0Hz),78.15(dd,J＝ 34.5,14.5Hz),38.35(s),35.93(t,J＝1.8Hz),33.32(d,J＝1.5Hz). [0192] 19F NMR(377MHz,CDCl3)δ‑79.84(d,J＝16.7Hz),‑84.98(d,J＝16.9Hz).[0193] 1,1‑二氟取代1,3‑烯炔31的分析数据 [0194] 1H NMR(400MHz,CDCl3)δ7.47–7.39(m,2H),7.35–7.27(m,3H),4.14(p,J＝6.8Hz,1H),3.90(dd,J＝14.2,7.7Hz,1H),3.78(td,J＝7.9,6.4Hz,1H),2.46(dddd,J＝13.9,6.6, 2.5,1.5Hz,1H),2.25(ddt,J＝14.0,6.6,2.6Hz,1H),2.15–2.02(m,1H),2.01–1.82(m,2H), 1.62(ddd,J＝15.7,12.1,7.2Hz,1H). [0195] 13C NMR(101MHz,CDCl3)δ159.40(dd,J＝296.3,293.9Hz),131.40(s),128.36(s),128.29(s),122.91(s),93.50(t,J＝5.8Hz),80.99(dd,J＝8.2,4.0Hz),76.06(dd,J＝ 34.5,16.6Hz),67.93(s),33.31(d,J＝1.4Hz),30.89(s),25.64(s). [0196] 19F NMR(377MHz,CDCl3)δ‑78.70(d,J＝14.8Hz),‑84.21(d,J＝14.6Hz).[0197] 1,1‑二氟取代1,3‑烯炔32的分析数据 [0198] 1H NMR(400MHz,CDCl3)δ7.48–7.38(m,2H),7.36–7.28(m,3H),4.76(t,J＝5.8Hz,1H),3.71(dq,J＝9.2,7.1Hz,2H),3.57(dq,J＝9.2,7.0Hz,2H),2.47(dt,J＝5.5,2.1Hz, 2H),1.23(t,J＝7.1Hz,6H). [0199] 13C NMR(151MHz,CDCl3)δ159.57(t,J＝295.5Hz),131.38(s),128.38(s),128.31(s),122.87(s),100.93(s),93.33(t,J＝5.6Hz),80.90(dd,J＝7.8,4.3Hz),74.86(dd,J＝34.6,17.6Hz),61.90(s),32.21(s),15.27(s). [0200] 19F NMR(377MHz,CDCl3)δ‑78.58(d,J＝12.5Hz),‑83.67(d,J＝12.6Hz).[0201] 1,1‑二氟取代1,3‑烯炔33的分析数据 [0202] 1H NMR(400MHz,CDCl3)δ7.50–7.42(m,2H),7.36–7.28(m,3H),2.15(dt,J＝7.2,2.3Hz,2H),1.10(s,6H),1.00(s,6H),0.43(t,J＝7.2Hz,1H). [0203] 13C NMR(101MHz,CDCl3)δ158.20(dd,J＝295.9,293.0Hz),131.41(s),128.33(s),128.24(s),123.22(s),93.08(t,J＝5.8Hz),81.75(dd,J＝8.4,4.3Hz),79.02(dd,J＝ 34.4,13.6Hz),31.94(s),23.63(s),23.37(s),21.34(s),16.97(s). [0204] 19F NMR(377MHz,CDCl3)δ‑80.63(d,J＝18.7Hz),‑85.14(d,J＝18.3Hz).[0205] 1,1‑二氟取代1,3‑烯炔34的分析数据 [0206] 1H NMR(400MHz,CDCl3)δ7.48–7.40(m,2H),7.35–7.28(m,3H),6.80(d,J＝8.0Hz,1H),6.77–6.71(m,2H),3.86(s,3H),3.85(s,3H),2.69–2.59(m,2H),2.21(ddd,J＝7.4, 4.5,2.2Hz,2H),1.97–1.86(m,2H). [0207] 13C NMR(101MHz,CDCl3)δ158.63(dd,J＝296.1,293.2Hz),148.77(s),147.16(s),134.34(s),131.35(s),128.34(s),128.29(s),122.87(s),120.17(s),111.65(s),111.16(s),93.69–93.44(m),81.00(dd,J＝8.3,4.1Hz),78.34(dd,J＝34.7,14.7Hz),55.86(s), 55.69(s),34.40(s),29.47(s),26.39(s). [0208] 19F NMR(377MHz,CDCl3)δ‑79.70(d,J＝16.8Hz),‑84.84(d,J＝16.7Hz).[0209] 1,1‑二氟取代1,3‑烯炔35的分析数据 [0210] 1H NMR(400MHz,CDCl3)δ7.83–7.75(m,2H),7.56–7.49(m,1H),7.47–7.40(m,4H),7.36–7.29(m,3H),6.81(d,J＝3.9Hz,1H),6.02(d,J＝3.9Hz,1H),4.64–4.51(m,1H),4.38(dt,J＝12.2,7.7Hz,1H),3.62–3.48(m,1H),2.90–2.75(m,1H),2.66–2.54(m,1H),2.50– 2.38(m,1H),2.38–2.23(m,1H). [0211] 13C NMR(151MHz,CDCl3)δ184.89(s),159.31(dd,J＝297.0,294.1Hz),148.14(s),139.49(s),131.45(s),131.24(s),128.88(s),128.61(s),128.39(s),128.10(s),126.68(s),125.15(s),122.61(s),101.91(s),94.35–94.16(m),80.35(dd,J＝7.9,3.8Hz),47.57(s),36.07(s),33.71(s),31.75(s). [0212] 19F NMR(377MHz,CDCl3)δ‑78.47(d,J＝13.8Hz),‑83.43(d,J＝13.8Hz).[0213] 1,1‑二氟取代1,3‑烯炔36的分析数据 [0214] 1H NMR(400MHz,CDCl3)δ7.42–7.35(m,2H),7.33–7.27(m,3H),7.15(d,J＝8.5Hz,2H),7.01(d,J＝8.5Hz,2H),2.87(dd,J＝10.6,8.5Hz,1H),2.56(s,2H),1.96(dd,J＝10.7, 7.4Hz,1H),1.84–1.76(m,1H),1.41(s,6H). [0215] 13C NMR(101MHz,CDCl3)δ163.18–156.88(m),154.48(s),131.24(s),129.55(s),129.41(s),128.33(s),128.28(s),123.62(s),122.92(s),93.50(t,J＝5.8Hz),82.27(dd,J＝7.8,4.4Hz),80.48(t,J＝2.9Hz),75.44(dd,J＝33.7,16.9Hz),60.84(s),40.05(d,J＝ 1.9Hz),34.93(s),26.27(s),25.86(s). [0216] 19F NMR(377MHz,CDCl3)δ‑77.71(d,J＝10.7Hz),‑82.01(d,J＝9.9Hz).[0217] 1,1‑二氟取代1,3‑烯炔37的分析数据 [0218] 1H NMR(400MHz,CDCl3)δ7.60(d,J＝8.5Hz,2H),7.43–7.26(m,7H),7.11(d,J＝8.4Hz,2H),6.99(d,J＝8.4Hz,2H),6.24(s,1H),3.66(q,J＝6.7Hz,2H),2.87(t,J＝6.9Hz, 2H),2.55(t,J＝1.9Hz,2H),1.40(s,6H). [0219] 13C NMR(101MHz,CDCl3)δ166.37(s),160.01(t,J＝296.1Hz),153.58(s),137.56(s),133.71(s),132.92(s),131.18(s),129.24(s),128.73(s),128.32(s),128.26(s),128.20(s),124.24(s),122.88(s),93.46(t,J＝5.8Hz),82.26(dd,J＝7.9,4.4Hz),80.31(t,J＝2.9Hz),75.43(dd,J＝33.5,16.8Hz),41.19(s),39.98(d,J＝1.5Hz),34.81(s), 26.22(s). [0220] 19F NMR(377MHz,CDCl3)δ‑77.69(d,J＝10.5Hz),‑82.00(d,J＝10.5Hz).[0221] 1,1‑二氟取代1,3‑烯炔38的分析数据 [0222] 1H NMR(400MHz,CDCl3)δ7.39(dd,J＝7.7,1.7Hz,2H),7.30–7.19(m,3H),6.99(d,J＝7.5Hz,1H),6.65(d,J＝7.4Hz,1H),6.56(s,1H),3.90(t,J＝6.6Hz,2H),2.28(s,3H),2.17(s,3H),2.12(t,J＝2.1Hz,2H),1.90–1.78(m,2H),1.54–1.45(m,2H),1.03(s,6H).[0223] 13C NMR(101MHz,CDCl3)δ159.70(dd,J＝296.5,294.0Hz),157.00(s),136.39(s), 131.12(s),130.23(s),128.27(s),128.21(s),123.53(s),123.03(s),120.57(s),111.93(s),93.14(t,J＝5.8Hz),82.88(dd,J＝8.1,4.2Hz),76.11(dd,J＝34.2,14.7Hz),68.44(s),39.02(d,J＝2.0Hz),37.94(s),34.62(t,J＝2.2Hz),26.92(s),24.39(s),21.37(s), 15.75(s). [0224] 19F NMR(377MHz,CDCl3)δ‑78.66(d,J＝13.5Hz),‑82.74(d,J＝13.4Hz).[0225] 1,1‑二氟取代1,3‑烯炔39的分析数据 [0226] 1H NMR(400MHz,CDCl3)δ7.48–7.41(m,2H),7.37–7.28(m,3H),7.17(d,J＝8.0Hz,2H),7.09(d,J＝8.0Hz,2H),3.15–3.02(m,1H),2.46(d,J＝7.1Hz,2H),2.43–2.32(m,2H), 1.86(dp,J＝13.4,6.7Hz,1H),1.34(d,J＝7.0Hz,3H),0.91(d,J＝6.6Hz,6H). [0227] 13C NMR(101MHz,CDCl3)δ159.18(dd,J＝296.3,293.1Hz),143.09(s),139.67(s),131.46(s),129.14(s),128.33(s),126.66(s),123.03(s),93.59–93.42(m),81.27(dd,J＝ 8.3,4.1Hz),77.62(dd,J＝42.8,23.3Hz),45.08(s),38.01–37.88(m),36.08(d,J＝ 1.8Hz),30.25(s),22.42(s),21.03(s). [0228] 19F NMR(377MHz,CDCl3)δ‑79.71(d,J＝15.9Hz),‑84.80(d,J＝16.0Hz).[0229] 1,1‑二氟取代1,3‑烯炔40的分析数据 [0230] 1H NMR(400MHz,CDCl3)δ7.50–7.38(m,2H),7.36–7.26(m,5H),7.23(dd,J＝11.3,5.7Hz,3H),4.65(d,J＝7.3Hz,1H),4.23–3.98(m,1H),2.89(d,J＝6.4Hz,2H),2.46–2.22(m,2H),1.38(s,9H). [0231] 13C NMR(101MHz,CDCl3)δ159.46(dd,J＝297.0,294.6Hz),155.17(s),137.81(s),131.47(s),129.39(s),128.55(s),128.50(s),128.35(s),126.54(s),122.70(s),94.30– 94.08(m),81.14–80.78(m),79.34(s),75.79(dd,J＝34.6,15.9Hz),50.88(s),40.15(s), 31.34(s),28.33(s). [0232] 19F NMR(377MHz,CDCl3)δ‑77.79(d,J＝12.4Hz),‑83.20(d,J＝12.3Hz).[0233] 1,1‑二氟取代1,3‑烯炔41的分析数据 [0234] 1H NMR(400MHz,CDCl3)δ7.48–7.39(m,2H),7.31(s,3H),4.17–3.92(m,1H),3.47–3.27(m,2H),2.73–2.46(m,1H),2.37–2.11(m,1H),2.05–1.75(m,4H),1.47(s,9H).[0235] 13C NMR(101MHz,CDCl3)δ159.52(dd,J＝296.8,293.7Hz),154.39(s),131.43(s), 128.43(s),128.33(s),122.83(s),93.42(dd,J＝10.1,5.6Hz),81.29–80.90(m),79.48(s),76.23(dd,J＝33.5,16.7Hz),56.10(s),46.22(s),31.83(s),30.09(s),28.52(s), 22.83(s). [0236] 19F NMR(377MHz,CDCl3)δ‑78.60(d,J＝13.4Hz),‑84.29(d,J＝14.0Hz).[0237] 1,1‑二氟取代1,3‑烯炔42的分析数据 [0238] 1H NMR(400MHz,CDCl3)δ7.49–7.40(m,2H),7.35–7.27(m,3H),4.73–4.54(m,1H),4.07–3.84(m,1H),2.34(d,J＝4.8Hz,2H),1.43(s,9H),1.22(d,J＝6.7Hz,3H).[0239] 13C NMR(101MHz,CDCl3)δ159.55(dd,J＝297.1,294.3Hz),155.08(s),131.45(s), 128.49(s),128.30(s),122.74(s),94.05–93.75(m),81.10(dd,J＝7.9,3.7Hz),79.25(s), 75.56(dd,J＝35.1,15.5Hz),45.57(s),33.90(s),28.37(s),20.06(s). [0240] 19F NMR(377MHz,CDCl3)δ‑78.19(d,J＝12.9Hz),‑83.81(d,J＝12.7Hz).[0241] 1,1‑二氟取代1,3‑烯炔43的分析数据 [0242] 1H NMR(400MHz,CDCl3)δ7.51–7.40(m,2H),7.36–7.28(m,3H),4.57(d,J＝8.6Hz,0.75H),4.22(brs,0.19H),3.95(d,J＝5.7Hz,0.82H),3.86(brs,0.18H),2.46–2.15(m, 2H),1.80–1.62(m,1H),1.42(s,9H),1.39–1.30(m,2H),0.93(d,J＝6.6Hz,6H).[0243] 13C NMR(101MHz,CDCl3)δ159.47(dd,J＝296.7,294.1Hz),155.22(s),131.36(s), 128.39(s),128.25(s),122.75(s),93.83(t,J＝6.0Hz),81.41–81.09(m),79.07(s),75.47(dd,J＝35.0,14.7Hz),47.79(s),43.17(s),32.61(s),28.31(s),24.82(s),22.98(s), 22.16(s). [0244] 19F NMR(377MHz,CDCl3)δ‑78.12(d,J＝13.5Hz),‑83.78(d,J＝13.5Hz).[0245] 1,1‑二氟取代1,3‑烯炔44的分析数据 [0246] 1H NMR(400MHz,CDCl3)δ7.46(dd,J＝6.6,2.9Hz,2H),7.37–7.28(m,3H),4.71(d,J＝8.8Hz,1H),4.03–3.84(m,1H),2.65–2.49(m,2H),2.47–2.28(m,2H),2.10(s,3H),1.95–1.73(m,2H),1.42(s,9H). [0247] 13C NMR(101MHz,CDCl3)δ159.52(dd,J＝297.4,294.5Hz),155.29(s),131.45(s),128.56(s),128.33(s),122.62(s),94.14(dd,J＝8.8,4.6Hz),81.02–80.78(m),79.43(s), 75.40(dd,J＝33.2,17.2Hz),49.21(s),33.71(s),32.28(s),30.75(s),28.34(s),15.60(s). [0248] 19F NMR(377MHz,CDCl3)δ‑77.73(d,J＝12.7Hz),‑83.43(d,J＝12.6Hz).[0249] 以上所述的实施例对本发明的技术方案和有益效果进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充和等同替换等，均应包含在本发明的保护范围之内。 |
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