一种可见光诱导高效合成β‑酮类磺酰化合物的方法与流程

本发明属于合成化学领域，具体涉及一种可见光诱导的烯醇磺酸酯类化合物的自由基重排反应，该反应可以实现在温和条件下以烯醇磺酸酯类化合物为原料高效地合成β-酮类磺酰化合物。

背景技术：

β-酮类磺酰化合物作为一类重要的有机化合物，其在生物医药和合成研究中具有十分重要的作用(a) Alghamdi H. A.; Maghrabi A. I., Bioorg. Chem., 2013, 46, 17; (b)Yang H.; Carter R. G.; Zakharov L. N., J. Am. Chem. Soc., 2008, 130, 9238; (c) Morisaki Y.; Kawada M.; Otera J.; J. Am. Chem. Soc. 1984, 106, 3670-3672. 目前，β-酮磺酰化合物的合成的代表性合成方案有烷基砜和氯酸，酯或N-苯并三唑的酰基化；芳香亚磺酸酯和α-卤代、对甲基苯磺酰酮的烷基化；用化学计量的氧化剂氧化β-羟基磺酸化合物 (d) Katritzky A. R.; Abdel-Fattah A. A.; Wang M. Y., J. Org. Chem., 2003, 68, 1443; (e) Xie Y.-Y.; Chen Z.-C., Synth. Commun.,2001, 31, 3145; (f) Trost B. M.; Curran D. P., Tetrahedron Lett.,1981, 22,1287; (g) Singh A. K.; Chawla R.; Yadav L. S., Tetrahedron Lett., 2014, 55, 4742-4746. 但是，这些方法都有一定的局限性，原料需要预官能团化，反应条件相对复杂严苛（高温，昂贵的催化剂等），有副产物（原子经济性不高）以及受限的底物范围（脂肪族的化合物），故限制了其在大量反应或者工业生产中的应用。因而发展一种原料廉价易得、步骤简单、操作方便，条件温和，底物适用范围广而且效率高的合成β-酮类化合物的方法是重点和难点。本发明人发展了一种简便实用的β-酮类磺酰化合物合成方法：在可见光诱导下以烯醇磺酸酯为原料，催化重排制得β-酮类磺酰化合物。

技术实现要素：

本发明目的是要提供一种高效地合成β-酮类磺酰化合物的方法。

该方法是以烯醇磺酸酯为原料，在可见光激发下，以无金属有机化合物作为光催化剂，反应1-12小时制得β-酮类磺酰化合物。

本发明的方法所使用的起始原料烯醇磺酸酯的分子通式是：，所合成的β-酮类磺酰化合物的分子通式是：。式中： R¹、R²任意选自H、C₁-C₁₆的烷基、C₃-C₁₆的环烷基；C₄-C₁₀的含N、O或S的杂环基或者杂芳基、芳基、R取代的芳基；所述的芳基是苯基或萘基；R³为C₁-C₄的烷基、各种取代的芳基。

本发明的β-酮类磺酰化合物均是在有机溶剂存在和室温下，以烯醇磺酸酯为原料，在可见光激发下，以有机化合物作为光催化剂，反应1-12小时制得β-酮类磺酰化合物。

可用下式表示：

所述的烯醇磺酸酯类化合物的结构式为：， R¹、R²任意选自H、C₁-C₁₆的烷基、C₃-C₁₆的环烷基；C₄-C₁₀的含N、O或S的杂环基或杂芳基、芳基、R取代的芳基；所述的芳基是苯基或萘基；R³为C₁-C₄的烷基、各种取代的芳基。

所述的可见光光源：白光LED，蓝光LED，绿光LED，节能灯或太阳光；

所述的无金属有机光催化剂为：曙红Y，曙红B，亚甲蓝，酸性红94，荧光素，9-芴酮，苯乙酮或二苯甲酮；

上述的烯醇磺酸酯、有机化合物光催化剂的摩尔比为1 : 0.005-0.5；

反应温度推荐为室温。

本发明中所提到的烷基、烃氧基、酰基等，除非另外说明，均推荐碳数为1～18的基团，进一步推荐碳数为1～10的，尤其推荐碳数为1～5的。本发明中所提到的环烷基，除非另外说明，均指碳数为3～18的基团，进一步推荐碳数为3～10的，尤其推荐碳数为3～7的。本发明中所提到的芳基，除非另外说明，均指苯基、C₅～C₁₀的含N、O或S的杂环基，推荐为苯基。本发明中提到的杂芳基，推荐C₅～C₁₀的含N、O和S的杂环基。

本发明方法中，所述有机溶剂可以是极性或非极性溶剂。如叔丁醇、丙酮、乙腈、苯、四氯化碳、石油醚、四氢呋喃、二甲基亚砜、二甲基甲酰胺、乙醚、二氯甲烷、三氯甲烷、甲苯、二甲苯、环己烷、正己烷、正庚烷或二氧六环等。

采用本发明方法所得产物可以经过重结晶，薄层层析，柱层析等方法加以分离。如用重结晶的方法，推荐溶剂为极性溶剂与非极性溶剂的混合溶剂。推荐溶剂可为二氯甲烷―正己烷、异丙醇―石油醚、乙酸乙酯―石油醚、乙酸乙酯―正己烷或异丙醇―乙酸乙酯―石油醚等混合溶剂。用薄层层析和柱层析方法，所用的展开剂为极性溶剂与非极性溶剂的混合溶剂。推荐溶剂可为异丙醇―石油醚、乙酸乙酯―石油醚、乙酸乙酯―正己烷或异丙醇―乙酸乙酯―石油醚等混合溶剂，其体积比可以分别是：极性溶剂：非极性溶剂＝ 1 : 0.1-500。例如：乙酸乙酯：石油醚＝ 1 : 0.1-50，异丙醇：石油醚＝1 : 0.1-500。

本发明提供了一种高效的以烯醇磺酸酯为原料，在有机溶剂存在下，有机化合物作为催化剂，高效率一步合成β-酮类磺酰化合物化合物的方法。与现有方法相比，该方法可适用于多种不同类型的烯醇磺酸酯类化合物，反应条件温和，原料廉价易得，操作简便，反应的产率也较好,很好地体现了原子经济性。

具体实施方式

通过下述实施例将有助于理解本发明，但并不限制本发明的内容。

在氩气保护下，向一干燥反应管中依次加入曙红B (0.008 mmol)或者9-芴酮(0.04 mmol)，向体系中加入4 mL 二甲亚砜，再加入烯醇磺酸酯 (0.8 mmol)，最后将反应管放入绕有白光LED灯带的器皿中，反应约1-12 h结束，停止搅拌，用乙醚和水萃取，旋蒸除去溶剂，柱层析，淋洗剂：乙酸乙酯和石油醚，收集组分，得相应产物A。（注：9-芴酮推荐更适用脂肪族的底物拓展，环状脂肪族底物在降低体系浓度为0.01 mol/L时反应效果好。）

A1

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 99%；；¹H NMR (400 MHz, CDCl₃) δ 7.91 (d, J = 7.6 Hz, 2H), 7.75(d, J = 8.0Hz,2H), 7.57 (t, J = 7.2 Hz, 1H), 7.43 (t, J = 6.8 Hz, 2H), 7.29 (d, J = 7.6 Hz, 2H), 4.73(s, 2H), 2.39 (s, 3H) ;¹³C NMR (101 MHz, CDCl₃) δ 188.3, 145.3, 136.0, 135.8, 134.3, 129.8, 129.3, 128.8, 128.6, 63.5, 21.7.

A2

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 94%；¹H NMR (400 MHz, CDCl₃) δ 8.05 (d, J = 8.4 Hz, 2H), 7.73 (t, J = 9.0 Hz, 4H), 7.32 (d, J = 8.4 Hz, 2H), 4.77 (s, 2H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.6, 145.7, 138.4, 135.6, 135.2 (q, J = 32.8 Hz), 129.9, 129.7, 128.5, 125.8 (q, J = 3.7 Hz), 123.4 (q, J = 271.3 Hz), 63.8, 21.6; ¹⁹F NMR (376 MHz, CDCl₃) δ -63.31.

A3

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 98%；¹H NMR (400 MHz, CDCl₃) δ 7.99 (brs, 2H), 7.75 (d, J = 8.00 Hz, 2H), 7.33 (d, J = 7.6 Hz, 2H), 7.14 (t, J = 8.2 Hz, 2H), 4.70 (s, 2H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 186.6, 167.7, 165.2, 145.5, 135.7, 132.3, 132.2, 129.9, 128.5, 116.2, 116.0, 63.7, 21.7; ¹⁹F NMR (376 MHz, None) δ -103.62.

A4

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 86%；¹H NMR (400 MHz, CDCl₃) δ 7.87 (d, J = 8.0 Hz, 2H), 7.73 (d, J = 7.8 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 7.8 Hz, 2H), 4.71 (s, 2H), 2.42 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.2, 145.5, 140.9, 135.7, 134.1, 130.8, 129.9, 129.1, 128.5, 63.6, 21.7.

A5

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 82%；¹H NMR (400 MHz, CDCl₃) δ 7.79 (d, J = 8.8 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.4Hz, 2H), 7.32 (d, J = 8.14Hz, 2H), 4.70 (s, 2H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.4, 145.5, 135.7, 134.5, 132.2, 130.8, 129.9, 128.5, 63.6, 21.7.

A6

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 92%；¹H NMR (400 MHz, CDCl₃) δ 7.84 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 8.0 Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 4.67 (s, 2H), 2.44 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.6, 145.6, 138.2, 135.6, 135.0, 130.6, 129.9, 128.6, 103.0, 63.6, 21.7.

A7

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 95%；¹H NMR (400 MHz, CDCl₃) δ 8.08 (d, J = 8.4 Hz, 2H), 7.77 (dd, J = 21.3, 8.1 Hz, 4H), 7.36 (d, J = 8.0 Hz, 2H), 4.74 (s, 2H), 2.46 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ187.2, 145.9, 138.5, 135.4, 132.6, 130.0, 129.8, 128.5, 117.6, 117.4, 63.9, 21.8.

A8

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 87%；¹H NMR (400 MHz, CDCl₃) δ 8.12 (d, J = 8.0 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.75 (s, 2H), 3.96 (s, 3H), 2.44 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.9, 165.9, 145.6, 138.8, 135.6, 134.8, 129.9, 129.3, 128.6, 63.8, 52.6, 21.7; HRMS (ESI) exact mass calculated for C₁₇H₁₆O₅S [M+ Na]⁺: 355.0611, found: 355.0601; IR (neat): νmax (cm^-1) = 1716, 1677, 1261, 1085, 996, 728, 594, 522.

A9

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 91%；¹H NMR (400 MHz, CDCl₃) δ 8.48 (d, J = 8.0 Hz, 2H), 8.03 (d, J = 7.9 Hz, 2H), 8.06 (d, J = 7.9 Hz, 2H), 7.54 (d, J = 8.0 Hz, 2H), 4.67 (s, 2H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 189.0, 152.3, 142.8, 139.4, 135.9, 130.0, 129.7, 128.2, 123.8, 69.6, 21.3.

A10

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 99%；¹H NMR (400 MHz, CDCl₃) δ 7.79 (dd, J = 30.9, 7.6 Hz, 4H), 7.28 (dd, J = 23.2, 8.0 Hz, 4H), 4.69 (s, 2H), 2.41 (d, J = 6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 187.7, 145.5, 145.3, 135.9, 133.4, 129.8, 129.5, 129.5, 128.6, 63.5, 21.8, 21.7.

A11

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 95%；¹H NMR (400 MHz, CDCl₃) δ 7.91 (d, J = 8.0 Hz, 2H), 7.72 (d, J = 7.9 Hz, 2H), 7.08 (d, J = 7.9 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 4.66 (s, 2H), 3.81 (s, 3H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 189.0, 165.0, 139.4, 135.9, 130.0, 129.8, 128.2, 123.8, 114.2, 69.5, 55.8, 21.3.

A12

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 93%；¹H NMR (400 MHz, CDCl₃) δ 7.82 (d, J = 4.8 Hz, 2H), 7.74 (d, J = 8.0 Hz, 2H), 7.59-7.51 (m, 1H), 7.40 (t, J = 7.9 Hz, 1H), 7.32 (d, J = 8.0 Hz, 2H), 4.71 (s, 2H), 2.42 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.2, 145.6, 137.2, 135.7, 135.1, 134.1, 130.2, 129.9, 129.1, 128.5, 127.6, 63.6, 21.7.

A13

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 94%；¹H NMR (400 MHz, CDCl₃) δ 7.97 (s, 1H), 7.87 (d, J = 7.6 Hz, 1H), 7.79-7.63 (m, 3H), 7.42-7.22 (m, 3H), 4.70 (s, 2H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.1, 145.6, 137.4, 137.0, 135.7, 132.0, 130.4, 129.9, 128.6, 128.0, 123.1, 63.6, 21.7.

A14

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 99%；¹H NMR (400 MHz, CDCl₃) δ 7.76 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 7.6 Hz, 1H), 7.44 -7.27 (m, 4H), 7.14 (d, J = 8.1, 1H), 4.72 (s, 2H), 3.81 (s, 3H), 2.42 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 188.0, 159.9, 145.3, 137.1, 135.9, 129.8, 128.6, 122.2, 121.0, 113.0, 63.6, 55.5, 21.7.

A15

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 83%；¹H NMR (400 MHz, CDCl₃) δ 7.75 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 7.6 Hz, 1H), 7.41 (t, J = 7.2 Hz, 1H), 7.37-7.27 (m, 4H), 4.81 (s, 2H), 2.42 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 190.2, 145.4, 137.2, 136.0, 133.1, 131.5, 130.7, 130.6, 129.9, 128.5, 127.2, 66.4, 21.7.

A16

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 90%；¹H NMR (400 MHz, CDCl₃) δ 7.76 (d, J = 7.6 Hz, 3H), 7.55 (d, J = 5.6 Hz, 1H), 7.30 (d, J = 7.6 Hz, 2H), 7.22 (t, J = 7.3 Hz, 1H), 7.14-7.03 (m, 1H), 4.78 (s, 2H), 2.41 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 186.1, 163.1 (d, J = 248.8 Hz), 145.3, 136.1 (t, J = 7.9 Hz), 131.1, 129.8, 128.5, 124.8 (d, J = 3.3 Hz), 124.5 (d, J = 11.0 Hz), 116.9 (d, J = 23.5 Hz), 67.1 (d, J = 8.7 Hz), 21.7; ¹⁹F NMR (376 MHz, None) δ -109.04.

A17

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 97%；¹H NMR (400 MHz, CDCl₃) δ 7.74 (t, J = 8.5 Hz, 3H), 7.42 (t, J = 7.3 Hz, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.26 (t, J = 7.5 Hz, 2H), 4.68 (s, 2H), 2.44 (brs, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 190.6, 145.2, 140.0, 136.1, 135.8, 132.7, 132.3, 130.4, 129.8, 128.5, 125.9, 65.6, 21.7, 21.5.

A18

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 95%；¹H NMR (400 MHz, DMSO) δ 7.39 (dd, J = 6.7, 2.2 Hz, 1H), 7.14 (ddd, J = 8.7, 4.8, 2.3 Hz, 1H), 6.89 (d, J = 8.3 Hz, 2H), 6.67 (d, J = 17.3 Hz, 1H), 6.57 (d, J = 7.9 Hz, 2H), 4.46 (s, 2H), 1.55 (s, 3H); ¹³C NMR (101 MHz, DMSO) δ 187.5, 163.4 (d, J= 252.3 Hz), 145.2, 136.8, 135.4 (d, J = 1.9 Hz), 134.2 (d, J = 3.3 Hz), 131.4 (d, J = 9.1 Hz), 130.1, 128.6, 117.8 (d, J = 23.0 Hz), 109.3 (d, J = 21.6 Hz), 63.0, 21.6; HRMS (ESI) exact mass calculated for C₁₅H₁₂BrFO₃S [M+ Na]⁺: 392.9567, found: 392.9557; IR (neat): ν_max (cm^-1) = 1670, 1485, 1260, 1146, 1083, 994, 726, 510.

A19

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 97%；¹H NMR (400 MHz, CDCl₃) δ 7.75 (d, J = 8.0 Hz, 2H), 7.67 (s, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.25-7.17 (m, 1H), 4.68 (s, 2H), 2.43 (s, 3H), 2.31 (s, 3H), 2.29 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 187.9, 145.2, 144.3, 137.3, 135.9, 133.8, 130.3, 130.1, 129.8, 128.6, 127.2, 63.5, 29.7, 21.7, 20.2, 19.7.

A20

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 86%；¹H NMR (400 MHz, CDCl₃) δ 7.73 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.3 Hz, 1H), 7.32 (dd, J = 18.5, 10.9 Hz, 4H), 4.80 (s, 2H), 2.42 (s, 3H); ¹³C NMR (101 MHz, CDCl3) δ 189.0, 145.5, 138.9, 135.8, 135.3, 132.7, 131.8, 130.6, 129.9, 128.5, 127.6, 66.3, 21.7; HRMS (ESI) exact mass calculated for C₁₅H₁₂Cl₂O₃S [M+ Na]⁺: 364.9776, found: 364.9769; IR (neat): ν_max (cm^-1) = 1685, 1369, 1278, 1147, 990, 713, 657, 546.

A21

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 72%；¹H NMR (400 MHz, CDCl₃) δ 7.71 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 1H), 7.36 (d, J = 8.4 Hz, 1H), 7.32 (d, J = 8.0 Hz, 2H), 4.78 (s, 2H), 2.44 (s, 3H).¹³C NMR (101 MHz, CDCl₃) δ 189.0, 145.7, 137.9, 137.6, 135.6, 133.1, 131.3, 129.9, 128.9, 128.4, 128.2, 66.5, 21.7; HRMS (ESI) exact mass calculated for C₁₅H₁₁Cl₃NaO₃S [M+Na]⁺: 398.9387, found: 398.9380; IR (neat): ν_max (cm^-1) = 512, 731, 812, 1016, 1149, 1321, 1566, 1696.

A22

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 41%；¹H NMR (400 MHz, CDCl₃) δ 7.73 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 4.61 (s, 2H), 2.47 (s, 3H).¹³C NMR (101 MHz, CDCl₃) δ 181.7 (q, J = 1.8 Hz), 146.1, 145.2, 143.7, 142.6, 138.9, 136.4, 135.2, 130.1, 128.3, 113.5, 68.5 (t, J = 2.9 Hz), 21.7 (CH₃); ¹⁹F NMR (376 MHz, None) δ -139.72 (dq, J = 6.0 Hz, 21.2 Hz, 2F), -146.92 (tt, J = 5.2 Hz, 22.4 Hz, F) , -159.36 (m, 2F); HRMS (ESI) exact mass calculated for C₁₅H₉F₅NaO₃S [M+Na]⁺: 387.0085, found: 387.0073; IR (neat): ν_max(cm^-1) = 511, 728, 810, 987, 1148, 1320, 1492, 1703.

A23

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 94%；¹H NMR (400 MHz, CDCl₃) δ 8.42 (s, 1H), 7.99-7.89 (m, 2H), 7.85 (d, J = 8.8 Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.65-7.52 (m, 2H), 7.28 (d, J = 8.0 Hz, 2H), 4.84 (s, 2H), 2.38 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 188.1, 145.4, 136.0, 135.8, 133.1, 132.3, 132.2, 130.0, 129.9, 129.3, 128.8, 128.6, 127.8, 127.1, 124.0, 63.8, 21.7.

A24

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 92%；¹H NMR (400 MHz, CDCl₃) δ 8.83 (d, J = 5.6 Hz, 2H), 7.80-7.67 (m, 4H), 7.35 (d, J = 8.0 Hz, 2H), 4.73 (s, 2H), 2.45 (s, 3H); ¹³C NMR (101 MHz, CDCl3) δ 188.1, 151.0, 145.8, 141.5, 135.5, 130.0, 128.5, 121.8, 63.7, 21.7; HRMS (ESI) exact mass calculated for C₁₄H₁₃NO₃S [M+ Na]⁺: 298.0508, found: 298.0500; IR (neat): ν_max(cm^-1) = 1650, 1458, 1383, 1251, 1086, 681, 656, 485.

A25

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 51%；¹H NMR (400 MHz, CDCl₃) δ 9.72 (s, 1H), 7.73 (d, J = 7.8 Hz, 2H), 7.56-7.44 (m, 5H), 7.36 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H), 1.88 (s, 3H); ¹³C NMR (101 MHz, CDCl3) δ 200.6, 139.4, 135.9, 135.8, 130.0, 128.2, 129.6, 129.2, 127.6, 96.2, 21.3, 10.6.

A26

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 46%；¹H NMR (400 MHz, CDCl₃) δ 9.70 (s, 1H), 7.76 (d, J = 8.0 Hz, 2H), 7.64-7.43 (m, 10H), 7.38 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H); ¹³C NMR (101 MHz, CDCl3) δ 199.5, 143.0, 139.3, 135.7, 130.0, 128.2, 129.6, 129.2, 126.2, 102.9, 21.5.

A27

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 84%；¹H NMR (400 MHz, CDCl₃) δ 7.96-7.86 (m, 4H), 7.68-7.57 (m, 2H), 7.53 (t, J = 7.7 Hz, 2H), 7.46 (t, J = 7.7 Hz, 2H), 4.75 (s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 188.0, 138.8, 135.7, 134.4, 134.3, 129.3, 129.2, 128.9, 128.6, 63.4; HRMS (ESI) exact mass calculated for C₁₄H₁₂O₃S [M+ Na]⁺: 283.0399, found: 283.0393; IR (neat): ν_max(cm^-1) = 1674, 1579, 1272, 1082, 990, 735, 683, 587.

A28

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 88%；¹H NMR (400 MHz, CDCl₃) δ 7.92 (d, J = 7.6 Hz, 2H), 7.83 (d, J = 8.4Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.55-7.40 (m, 4H), 4.76 (s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 188.0, 141.1, 137.2, 135.6, 134.5, 130.2, 129.5, 129.2, 129.0, 63.3; HRMS (ESI) exact mass calculated for C₁₄H₁₁ClO₃S [M+ Na]⁺: 317.0010, found: 317.0002; IR (neat): ν_max (cm^-1) = 1671, 1358, 1264, 1151, 1084, 951, 719, 680.

A29

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 97%；¹H NMR (400 MHz, CDCl₃) δ 7.94 (d, J = 7.6 Hz, 2H), 7.74 (d, J = 8.0 Hz, 1H), 7.59 (t, J = 7.4 Hz, 1H), 7.45 (t, J = 7.7 Hz, 2H), 7.15-7.05 (m, 2H), 4.73 (s, 2H), 2.66 (s, 3H), 2.36 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 188.2, 145.2, 138.2, 135.9, 134.3, 134.1, 133.5, 130.7, 129.4, 128.8, 127.3, 63.0, 21.4, 20.4; HRMS (ESI) exact mass calculated for C₁₆H₁₆O₃S [M+ Na]⁺: 311.0712, found: 311.0706; IR (neat): ν_max (cm^-1) = 1670, 1443, 1280, 1134, 987, 804, 727, 586.

A30

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 83%；¹H NMR (400 MHz, CDCl₃) δ 7.85 (d, J = 8.8 Hz, 2H), 7.80 (t, J = 8.5 Hz, 1H), 7.62-7.55 (m, 1H), 7.50 (d, J = 8.8 Hz, 2H), 7.25 (t, J = 8.0 Hz, 1H), 7.12 (dd, J = 11.6, 8.4 Hz, 1H), 4.81 (s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 185.8 (d, J = 3.1 Hz), 163.20 (d, J = 253.8 Hz), 141.0, 137.6, 136.4 (d, J = 9.5 Hz), 131.1 (d, J = 1.5 Hz), 130.2, 129.5, 125.0 (d, J = 3.4 Hz), 124.4 (d, J = 11.0 Hz), 117.0 (d, J = 23.6 Hz), 67.0 (d, J = 8.9 Hz); ¹⁹F NMR (376 MHz, CDCl₃) δ -108.85; HRMS (ESI) exact mass calculated for C₁₄H₁₀FClO₃NaS [M+Na]⁺: 334.9915, found: 334.9904; IR (neat): ν_max (cm^-1) = 1678, 1450, 1149, 1083, 1002, 826, 728, 518.

A31

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 86%；¹H NMR (400 MHz, CDCl₃) δ 8.47 (d, J = 7.8 Hz, 2H), 8.04 (d, J = 8.0 Hz, 2H), 8.01 (d, J = 7.6 Hz, 2H), 7.54-7.68 (m, 3H), 4.73 (s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 189.0, 152.6, 145.1, 136.7, 133.1, 128.6, 128.2, 129.2, 124.7, 64.8.

A32

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 81%；¹H NMR (400 MHz, CDCl₃) δ7.68 (t, J = 7.3 Hz, 1H), 7.65-7.52 (m, 4H), 7.50 (d, J = 7.9 Hz, 2H), 6.69 (d, J = 8.0 Hz, 2H), 6.04 (s, 2H), 4.74 (s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 189.3, 153.4, 136.7, 133.1, 129.0, 129.1, 128.8, 128.6, 113.0, 65.2.

A33

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 88%；¹H NMR (400 MHz, CDCl₃) δ 8.34-8.13 (m, 3H), 7.92 (d, J = 7.6 Hz, 2H), 7.88-7.69 (m, 4H), 7.64 (t, J = 7.3 Hz, 1H), 7.55-7.40 (m, 4H), 4.69 (s, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 189.1, 134.9, 136.7, 135.9, 134.7, 133.2, 130.2, 128.8, 128.6, 127.2, 124.3, 126.2, 126.1, 64.6.

A34

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 93%；¹H NMR (400 MHz, CDCl₃) δ 7.99 (d, J = 7.6 Hz, 2H), 7.65 (t, J = 7.3 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H), 4.63 (s, 2H), 3.14 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 189.3, 135.7, 134.7, 129.2, 129.0, 61.2, 41.9; HRMS (ESI) exact mass calculated for C₉H₁₀O₃S [M+ Na]⁺: 221.0243, found: 221.0238; IR (neat): ν_max (cm^-1) = 1672, 1446, 1204, 1122, 960, 745, 685, 575.

A35

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 85%；¹H NMR (400 MHz, CDCl₃) δ 8.05-7.96 (m, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.8 Hz, 2H), 4.58 (s, 2H), 3.28 (q, J = 7.5 Hz, 2H), 1.44 (t, J = 7.5 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 189.3, 135.8, 134.6, 129.3, 129.0, 58.7, 48.3, 6.6; HRMS (ESI) exact mass calculated for C₁₀H₁₂O₃S [M+ Na]⁺: 235.0399, found: 235.0394; IR (neat): ν_max (cm^-1) = 1674, 1447, 1263, 987, 886, 727, 698, 545.

A36

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 87%；¹H NMR (400 MHz, CDCl₃) δ 8.00 (d, J = 8 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.7 Hz, 2H), 5.12 (d, J = 15.2 Hz, 1H), 4.81 (d, J = 15.2 Hz, 1H), 3.97 (d, J = 15.2 Hz, 1H), 3.05 (d, J = 15.2 Hz, 1H), 2.45-2.23 (m, 2H), 2.13 (t, J = 4.4 Hz, 1H), 2.10-1.88 (m, 3H), 1.53-1.39 (m, 1H), 1.04 (s, 3H), 0.93 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 215.6, 189.6, 136.0, 134.3, 129.0, 128.9, 62.5, 59.5, 52.6, 48.9, 42.7 (J = 3.00 Hz), 27.2, 26.0, 19.9, 19.6; HRMS (ESI) exact mass calculated for C₁₈H₂₂O₄S [M+ H]⁺:, found: ; IR (neat): ν_max (cm^-1) = 1739, 1676, 1448, 1270, 987, 887, 728, 687, 508.

A37

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 94%；¹H NMR (400 MHz, CDCl₃) δ 7.77 (d, J = 8Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 4.24 (s,2H), 2.97-2.81 (m,1H), 2.44 (s, 3H), 1.09(d, J =7.2Hz, 6H ); ¹³C NMR (101 MHz, CDCl₃) δ 202.1, 145.3, 136.0, 129.9, 128.4, 64.7, 41.9, 21.7, 17.5.

A38

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 97%；¹H NMR (400 MHz, CDCl₃) δ 7.82 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 4.32 (s,2H), 2.44 (s, 3H), 1.11 (s, 9H); ¹³C NMR (101 MHz, CDCl₃) δ 203.4, 145.0, 136.6, 129.7, 128.7, 60.8, 45.3, 25.6, 21.7.

A39

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 77%；¹H NMR (400 MHz, CDCl₃) δ 7.77 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 4.14 (s, 2H), 2.71 (t, J = 7.2 Hz, 2H), 2.47 (s, 3H), 1.60-1.49 (m, 2H), 1.37-1.25 (m, 2H), 0.91 (t, J = 7.6 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 198.5, 145.4, 135.8, 130.0, 128.3, 67.0, 44.1, 25.2, 22.0, 21.7, 13.8; HRMS (ESI) exact mass calculated for C₁₃H₁₈O₃NaS⁺ [M+Na]⁺: 277.0869, found: 277.0861; IR (neat): νmax (cm-1) = 2946, 2840, 1722, 1290, 972, 798, 736, 548.

A40

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 35%；¹H NMR (400 MHz, CDCl₃) δ 7.75 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 4.12 (s, 2H), 2.69 (t, J = 6.8 Hz, 2H), 2.45 (s, 3H), 1.25 (brs, 16H), 0.88 (t, J = 6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 198.5, 145.4, 135.8, 130.0, 128.3, 67.0, 44.4, 31.9, 29.5, 29.4, 29.3, 29.3, 28.8, 23.1, 22.7, 21.7, 14.1; HRMS (ESI) exact mass calculated for C₁₃H₁₈O₃NaS⁺ [M+Na]⁺: 277.0869, found: 277.0861; IR (neat): νmax (cm-1) = 2946, 2840, 1718, 1276, 957, 804, 728, 566.

A41

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 66%； ¹H NMR (400 MHz, CDCl₃) δ 7.65 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.17 (q, J = 7.0 Hz, 1H), 2.99-2.84 (m, 1H), 2.68-2.54 (m, 1H), 2.43 (s, 3H), 1.37 (d, J = 6.8 Hz, 3H), 1.04 (t, J = 7.2 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 203.01, 145.41, 133.26, 129.74, 129.29, 69.79, 37.21, 21.65, 12.02, 7.47; HRMS (ESI) exact mass calculated for C₁₉H₃₀O₃NaS⁺ [M+Na]⁺: 361.1808, found: 361.1798; IR (neat): ν_max (cm^-1) = 2980, 2836, 1764, 1288, 968, 800, 732, 569.

A42

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 93%；¹H NMR (400 MHz, CDCl₃) δ 7.81 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 4.28 (s, 2H), 2.45 (s, 3H), 2.05 (s, 3H), 1.79-1.69 (m, 9H), 1.69-1.60 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 203.0, 145.0, 136.7, 129.7, 129.4, 128.7, 60.4, 47.5, 37.4, 36.2, 27.6, 21.7.

A43

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 80%；¹H NMR (400 MHz, CDCl₃) δ 7.75 (d, J = 8.0 Hz, 2H), 7.36(d, J=8.0 Hz，2H), 3.74 (t, J = 7.9 Hz, 1H), 2.69-2.54 (m, 1H), 2.46 (s, 3H), 2.44-2.23 (m, 3H), 2.23-2.10 (m, 1H), 1.97-1.82 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 207.4, 145.2, 135.1, 129.8, 129.0, 69.5, 38.8, 25.1, 21.7, 20.0.

A44

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 28%；¹H NMR (400 MHz, CDCl₃) δ 7.76 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 3.83 (t, J = 4.0 Hz, 1H), 2.83-2.71 (m, 1H), 2.54-2.46 (m, 1H), 2.43 (s, 3H), 2.42-2.36 (m, 1H), 2.28-2.13 (m, 2H), 2.03-1.93 (m, 1H), 1.87-1.68 (m, 2H).¹³C NMR (101 MHz, CDCl₃) δ 202.3, 145.1, 135.2, 129.7, 128.9, 72.8, 41.6, 27.5, 26.5, 21.9, 21.7.

A45

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 88%；¹H NMR (400 MHz, CDCl₃) δ 7.69 (d, J = 7.6 Hz, 2H), 7.33 (d, J = 7.8 Hz, 2H), 3.88 (dd, J = 11.9, 5.2 Hz, 1H), 2.79 (t, J = 11.9 Hz, 1H), 2.51-2.36 (m, 5H), 2.05 (t, J = 12.4 Hz, 2H), 2.00-1.84 (m, 2H), 1.47-1.27 (m, 2H), 1.26-1.08 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 204.6, 145.2, 129.8, 128.9, 76.2, 42.5, 29.8, 26.4, 26.1, 24.2, 21.7.

A46

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 48%；¹H NMR (400 MHz, CDCl₃) δ 7.70 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 7.9 Hz, 2H), 4.03-3.90 (m, 1H), 2.80-2.66 (m, 1H), 2.44(s, 3H), 2.40-2.29 (m, 2H), 2.28-2.15 (m, 1H), 1.92-1.83(m, 1H), 1.82-1.71 (m, 2H), 1.71-1.63 (m, 1H), 1.51-1.42 (m, 2H), 1.41-1.29 (m, 1H), 1.23-1.09 (m, 1H).¹³C NMR (101 MHz, CDCl₃) δ 208.2, 145.2, 134.5, 129.7, 129.2, 75.2, 41.5, 26.8, 26.4, 25.5, 25.4, 24.4, 21.7. HRMS (ESI) exact mass calculated for C₁₅H₂₀NaO₃S [M+Na]⁺: 303.1025, found: 303.1012; IR (neat): ν_max (cm^-1) = 550, 654, 810, 932, 1040, 1174, 1363, 1681.

A47

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 33%；¹H NMR (400 MHz, CDCl₃) δ 7.76 (d, J = 8.0Hz, 1H), 7.37 (d, J = 8.0 Hz, 1H), 4.78 (dd, J = 12.8 , 2.4 Hz, 1H), 4.27-4.19 (m, 1H), 4.06 (dd, J = 12.8, 4.8 Hz, 1H), 3.85-3.76 (m, 2H), 3.10-2.98 (m, 1H), 2.53-2.47 (m, 1H), 2.46 (s, 3H).¹³C NMR (101 MHz, CDCl₃) δ 197.7, 145.6, 135.1, 130.0, 128.9, 72.9, 67.8, 66.7, 42.0, 21.7; HRMS (ESI) exact mass calculated for C₁₂H₁₄NaO₄S [M+Na]⁺: 277.0505, found: 277.0499; IR (neat): ν_max (cm^-1) = 546, 658, 709, 936, 1068, 1170, 1363, 1644.

A48

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 92%；¹H NMR (400 MHz, CDCl₃) δ 7.99 (d, J = 7.3 Hz, 1H), 7.81 (d, J = 8.2 Hz, 2H), 7.52 (t, J = 7.2 Hz, 1H), 7.42-7.24 (m, 4H), 4.11 (t, J = 5.7 Hz, 1H), 3.56-3.46 (m, 1H), 2.99 (dt, J = 16.9, 5.3 Hz, 1H), 2.86 (ddd, J = 16.8, 10.8, 5.9 Hz, 1H), 2.65 (qd, J = 10.0, 5.1 Hz, 1H), 2.46 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 188.8, 145.1, 143.6, 136.0, 134.5, 131.8, 129.7, 129.1, 129.0, 127.9, 127.0, 69.7, 26.6, 23.7, 21.7.

A49

石油醚与乙酸乙酯 (10:1) 淋洗; 无色油状物, 产率: 91%；¹H NMR (400 MHz, CDCl₃) δ 7.96 (d, J = 7.8 Hz, 1H), 7.81 (d, J = 8.0 Hz, 2H), 7.50 (t, J = 7.2 Hz, 1H), 7.46-7.28 (m, 4H), 4.54 (t, J = 5.8 Hz, 1H), 3.37-3.26 (m, 1H), 3.24-3.13 (m, 1H), 2.45 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 190.6, 145.0, 143.5, 136.3, 134.2, 131.2, 129.7, 129.1, 128.6, 128.2, 126.7, 71.3, 26.6, 23.9, 21.6.

A50

石油醚与乙酸乙酯 (10:1) 淋洗; 淡黄色油状物, 产率: 95%；¹H NMR (400 MHz, CDCl₃) δ 7.96 (d, J = 7.6 Hz, 2H), 7.65 (d, J = 7.6 Hz, 2H), 7.62-7.53 (m, 1H), 7.45 (t, J = 6.9 Hz, 2H), 7.28 (d, J = 7.2 Hz, 2H), 5.17 (d, J = 6.4 Hz, 1H), 2.40 (s, 3H), 1.55 (d, J = 6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 192.6, 145.4, 136.3, 134.0, 133.2, 129.8, 129.6, 129.2, 128.7, 65.0, 21.7, 13.2。