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一種可見光誘導(dǎo)高效合成β?酮類磺酰化合物的方法與流程

文檔序號：12775921閱讀：808來源：國知局

本發(fā)明屬于合成化學(xué)領(lǐng)域，具體涉及一種可見光誘導(dǎo)的烯醇磺酸酯類化合物的自由基重排反應(yīng)，該反應(yīng)可以實(shí)現(xiàn)在溫和條件下以烯醇磺酸酯類化合物為原料高效地合成β-酮類磺?；衔铩?/p>



背景技術(shù)：

β-酮類磺?；衔镒鳛橐活愔匾挠袡C(jī)化合物，其在生物醫(yī)藥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?；衔锏暮铣傻拇硇院铣煞桨赣型榛亢吐人?，酯或N-苯并三唑的?；?；芳香亞磺酸酯和α-鹵代、對甲基苯磺酰酮的烷基化；用化學(xué)計(jì)量的氧化劑氧化β-羥基磺酸化合物 (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，這些方法都有一定的局限性，原料需要預(yù)官能團(tuán)化，反應(yīng)條件相對復(fù)雜嚴(yán)苛（高溫，昂貴的催化劑等），有副產(chǎn)物（原子經(jīng)濟(jì)性不高）以及受限的底物范圍（脂肪族的化合物），故限制了其在大量反應(yīng)或者工業(yè)生產(chǎn)中的應(yīng)用。因而發(fā)展一種原料廉價(jià)易得、步驟簡單、操作方便，條件溫和，底物適用范圍廣而且效率高的合成β-酮類化合物的方法是重點(diǎn)和難點(diǎn)。本發(fā)明人發(fā)展了一種簡便實(shí)用的β-酮類磺?；衔锖铣煞椒ǎ涸诳梢姽庹T導(dǎo)下以烯醇磺酸酯為原料，催化重排制得β-酮類磺?；衔?。



技術(shù)實(shí)現(xiàn)要素：

本發(fā)明目的是要提供一種高效地合成β-酮類磺酰化合物的方法。

該方法是以烯醇磺酸酯為原料，在可見光激發(fā)下，以無金屬有機(jī)化合物作為光催化劑，反應(yīng)1-12小時(shí)制得β-酮類磺酰化合物。

本發(fā)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-酮類磺?；衔锏姆肿油ㄊ绞牵?。式中： R1、R2任意選自H、C1-C16的烷基、C3-C16的環(huán)烷基；C4-C10的含N、O或S的雜環(huán)基或者雜芳基、芳基、R取代的芳基；所述的芳基是苯基或萘基；R3為C1-C4的烷基、各種取代的芳基。

本發(fā)明的β-酮類磺酰化合物均是在有機(jī)溶劑存在和室溫下，以烯醇磺酸酯為原料，在可見光激發(fā)下，以有機(jī)化合物作為光催化劑，反應(yīng)1-12小時(shí)制得β-酮類磺酰化合物。

可用下式表示：

所述的烯醇磺酸酯類化合物的結(jié)構(gòu)式為：， R1、R2任意選自H、C1-C16的烷基、C3-C16的環(huán)烷基；C4-C10的含N、O或S的雜環(huán)基或雜芳基、芳基、R取代的芳基；所述的芳基是苯基或萘基；R3為C1-C4的烷基、各種取代的芳基。

所述的可見光光源：白光LED，藍(lán)光LED，綠光LED，節(jié)能燈或太陽光；

所述的無金屬有機(jī)光催化劑為：曙紅Y，曙紅B，亞甲藍(lán)，酸性紅94，熒光素，9-芴酮，苯乙酮或二苯甲酮；

上述的烯醇磺酸酯、有機(jī)化合物光催化劑的摩爾比為1 : 0.005-0.5；

反應(yīng)溫度推薦為室溫。

本發(fā)明中所提到的烷基、烴氧基、酰基等，除非另外說明，均推薦碳數(shù)為1～18的基團(tuán)，進(jìn)一步推薦碳數(shù)為1～10的，尤其推薦碳數(shù)為1～5的。本發(fā)明中所提到的環(huán)烷基，除非另外說明，均指碳數(shù)為3～18的基團(tuán)，進(jìn)一步推薦碳數(shù)為3～10的，尤其推薦碳數(shù)為3～7的。本發(fā)明中所提到的芳基，除非另外說明，均指苯基、C5～C10的含N、O或S的雜環(huán)基，推薦為苯基。本發(fā)明中提到的雜芳基，推薦C5～C10的含N、O和S的雜環(huán)基。

本發(fā)明方法中，所述有機(jī)溶劑可以是極性或非極性溶劑。如叔丁醇、丙酮、乙腈、苯、四氯化碳、石油醚、四氫呋喃、二甲基亞砜、二甲基甲酰胺、乙醚、二氯甲烷、三氯甲烷、甲苯、二甲苯、環(huán)己烷、正己烷、正庚烷或二氧六環(huán)等。

采用本發(fā)明方法所得產(chǎn)物可以經(jīng)過重結(jié)晶，薄層層析，柱層析等方法加以分離。如用重結(jié)晶的方法，推薦溶劑為極性溶劑與非極性溶劑的混合溶劑。推薦溶劑可為二氯甲烷―正己烷、異丙醇―石油醚、乙酸乙酯―石油醚、乙酸乙酯―正己烷或異丙醇―乙酸乙酯―石油醚等混合溶劑。用薄層層析和柱層析方法，所用的展開劑為極性溶劑與非極性溶劑的混合溶劑。推薦溶劑可為異丙醇―石油醚、乙酸乙酯―石油醚、乙酸乙酯―正己烷或異丙醇―乙酸乙酯―石油醚等混合溶劑，其體積比可以分別是：極性溶劑：非極性溶劑＝ 1 : 0.1-500。例如：乙酸乙酯：石油醚＝ 1 : 0.1-50，異丙醇：石油醚＝1 : 0.1-500。

本發(fā)明提供了一種高效的以烯醇磺酸酯為原料，在有機(jī)溶劑存在下，有機(jī)化合物作為催化劑，高效率一步合成β-酮類磺?；衔锘衔锏姆椒?。與現(xiàn)有方法相比，該方法可適用于多種不同類型的烯醇磺酸酯類化合物，反應(yīng)條件溫和，原料廉價(jià)易得，操作簡便，反應(yīng)的產(chǎn)率也較好,很好地體現(xiàn)了原子經(jīng)濟(jì)性。

具體實(shí)施方式

通過下述實(shí)施例將有助于理解本發(fā)明，但并不限制本發(fā)明的內(nèi)容。

在氬氣保護(hù)下，向一干燥反應(yīng)管中依次加入曙紅B (0.008 mmol)或者9-芴酮(0.04 mmol)，向體系中加入4 mL 二甲亞砜，再加入烯醇磺酸酯 (0.8 mmol)，最后將反應(yīng)管放入繞有白光LED燈帶的器皿中，反應(yīng)約1-12 h結(jié)束，停止攪拌，用乙醚和水萃取，旋蒸除去溶劑，柱層析，淋洗劑：乙酸乙酯和石油醚，收集組分，得相應(yīng)產(chǎn)物A。（注：9-芴酮推薦更適用脂肪族的底物拓展，環(huán)狀脂肪族底物在降低體系濃度為0.01 mol/L時(shí)反應(yīng)效果好。）

A1

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1670, 1485, 1260, 1146, 1083, 994, 726, 510.

A19

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1685, 1369, 1278, 1147, 990, 713, 657, 546.

A21

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 512, 731, 812, 1016, 1149, 1321, 1566, 1696.

A22

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax(cm-1) = 511, 728, 810, 987, 1148, 1320, 1492, 1703.

A23

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax(cm-1) = 1650, 1458, 1383, 1251, 1086, 681, 656, 485.

A25

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax(cm-1) = 1674, 1579, 1272, 1082, 990, 735, 683, 587.

A28

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1671, 1358, 1264, 1151, 1084, 951, 719, 680.

A29

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1670, 1443, 1280, 1134, 987, 804, 727, 586.

A30

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1678, 1450, 1149, 1083, 1002, 826, 728, 518.

A31

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1672, 1446, 1204, 1122, 960, 745, 685, 575.

A35

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1674, 1447, 1263, 987, 886, 727, 698, 545.

A36

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 1739, 1676, 1448, 1270, 987, 887, 728, 687, 508.

A37

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 2980, 2836, 1764, 1288, 968, 800, 732, 569.

A42

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 550, 654, 810, 932, 1040, 1174, 1363, 1681.

A47

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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): νmax (cm-1) = 546, 658, 709, 936, 1068, 1170, 1363, 1644.

A48

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 無色油狀物, 產(chǎn)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

石油醚與乙酸乙酯 (10:1) 淋洗; 淡黃色油狀物, 產(chǎn)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。

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