CN116082204B - β-亚磺酰基烯基砜类化合物及其制备方法和应用 - Google Patents
β-亚磺酰基烯基砜类化合物及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 105
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 102
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001544 thienyl group Chemical group 0.000 claims description 8
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 6
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 6
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 6
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 6
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 6
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 6
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 6
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 6
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 3
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 3
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 3
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- -1 alkyne compound Chemical class 0.000 abstract description 38
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 134
- 238000001228 spectrum Methods 0.000 description 65
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 31
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- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 18
- XTEOJPUYZWEXFI-UHFFFAOYSA-N butyl n-[3-[4-(imidazol-1-ylmethyl)phenyl]-5-(2-methylpropyl)thiophen-2-yl]sulfonylcarbamate Chemical compound S1C(CC(C)C)=CC(C=2C=CC(CN3C=NC=C3)=CC=2)=C1S(=O)(=O)NC(=O)OCCCC XTEOJPUYZWEXFI-UHFFFAOYSA-N 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 9
- 125000005037 alkyl phenyl group Chemical group 0.000 description 8
- 125000005059 halophenyl group Chemical group 0.000 description 6
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
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- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
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- 229940125877 compound 31 Drugs 0.000 description 4
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 3
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
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- 229940126657 Compound 17 Drugs 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了β‑亚磺酰基烯基砜类化合物及其制备方法和应用,提供了一系列的β‑亚磺酰基烯基砜类化合物,丰富了β‑亚磺酰基烯基砜类化合物分子库。本发明通过炔烃类化合物和亚磺酸钠类化合物在无金属催化、无需控制无水环境下即可成功合成式I化合物(β‑亚磺酰基烯基砜类化合物),反应体系简单,底物适用范围广、原子利用率高、产率较高。
Description
技术领域
本发明涉及有机合成技术领域,特别涉及β-亚磺酰基烯基砜类化合物及其制备方法和应用。
背景技术
有机含硫化合物因在天然产物、药物化学、材料科学等领域的出彩表现备受关注。其中,乙烯基砜作为一种特殊的烯烃骨架,不仅广泛应用于生物医药领域,而且在有机合成是一种重要合成子,故它的合成引起了有机工作者的广泛关注。通常,乙烯基砜的构建方法主要有:①硫醇与烯烃的氧化偶联;②炔基砜与氢源的加氢反应或与亲核试剂的加成反应。然而,这些反应通常需要硫醇或预官能团化前驱体。近年来,通过炔烃的双功能化构建乙烯基砜的方法已经备受关注,因为其可高效地在一步反应同时引入两种不同的官能团,具有原子利用率高、产率高等优点,因此,研究人员开发了氧磺酰化、碳磺酰化、卤代磺酰化等多种方式合成乙烯基砜类化合物。但是,关于β-亚磺酰基烯基砜的合成研究近年来进展相对缓慢,因此,开发一种更绿色,使用更方便的反应合成β-亚磺酰基烯基砜类化合物仍有必要。
发明内容
本发明旨在至少解决现有技术中存在的上述技术问题之一。为此,本发明的目的在于提供β-亚磺酰基烯基砜类化合物及其制备方法和应用。
为了实现上述目的,本发明所采取的技术方案是:
根据本发明的第一个方面,提供了式I化合物或其立体异构体:
其中,R1选自取代或未取代芳基;R2为H;R3选自取代或未取代芳基、取代或未取代噻吩基;
或R1选自取代或未取代芳基;R2为甲基,R3选自取代或未取代噻吩基。
在本发明的一些实施方式中,R1中,所述芳基选自苯基、联苯基或萘基。
在本发明的一些优选的实施方式中,R1中,所述芳基的取代基选自卤素、氰基、硝基、C1~C4烷基、C1~C4烷氧基、C6~C10芳基。
在本发明的一些更优选的实施方式中,R1选自丁基、卤代苯基、氰基苯基、硝基苯基、C1~C4烷基苯基、卤代C1~C4烷基苯基、C1~C4烷氧基苯基、联苯基、萘基。
在本发明的一些更优选的实施方式中,R1选自正丁基、4-甲基苯基、4-乙基苯基、4-联苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-硝基苯基、4-三氟甲基苯基、3-甲基苯基、3-氯苯基、3-甲氧基苯基、2-甲氧基苯基、2-氟苯基、2-萘基。
在本发明的一些更优选的实施方式中,R3中,所述芳基选自苯基、联苯基或萘基。
在本发明的一些更优选的实施方式中,R3中,所述芳基的取代基选自卤素、C1~C4烷基、C1~C4烷氧基、C6~C10芳基。
在本发明的一些更优选的实施方式中,R3选自卤代苯基、C1~C4烷基苯基、卤代C1~C4烷基苯基、C1~C4烷氧基苯基、联苯基、萘基。
在本发明的一些更优选的实施方式中,R3选自苯基、4-甲氧基苯基、4-联苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-碘苯基、4-三氟甲基苯基、3-溴苯基、3-甲基苯基、2-萘基。
在本发明的一些更优选的实施方式中,式I化合物选自:
根据本发明的第二个方面,提供一种β-亚磺酰基烯基砜类化合物的制备方法,包括以下步骤:
惰性氛围下,式I-A化合物与式I-B化合物在Lewis酸催化下反应制得式I化合物,即β-亚磺酰基烯基砜类化合物;
其中,R1选自丁基、取代或未取代芳基、取代或未取代噻吩基;R2选自H、甲基;R3选自取代或未取代芳基、取代或未取代噻吩基。
本发明中,式I-A化合物(炔烃类化合物)和式I-B化合物(亚磺酸钠类化合物)在无金属催化、无需控制无水环境下即可成功合成式I化合物(β-亚磺酰基烯基砜类化合物),反应体系简单,底物适用范围广、原子利用率高、产率较高。
在本发明的一些实施方式中,R1中,所述芳基选自苯基、联苯基或萘基。
在本发明的一些优选的实施方式中,R1中,所述芳基的取代基选自卤素、氰基、硝基、C1~C4烷基、C1~C4烷氧基、C6~C10芳基。
在本发明的一些更优选的实施方式中,R1选自丁基、卤代苯基、氰基苯基、硝基苯基、C1~C4烷基苯基、卤代C1~C4烷基苯基、C1~C4烷氧基苯基、联苯基、噻吩基、萘基。
在本发明的一些更优选的实施方式中,R1选自正丁基、4-甲基苯基、4-乙基苯基、4-联苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-硝基苯基、4-三氟甲基苯基、3-甲基苯基、3-氯苯基、3-甲氧基苯基、2-甲氧基苯基、2-氟苯基、2-噻吩基、2-萘基。
在本发明的一些更优选的实施方式中,R3中,所述芳基选自苯基、联苯基或萘基。
在本发明的一些更优选的实施方式中,R3中,所述芳基的取代基选自卤素、C1~C4烷基、C1~C4烷氧基、C6~C10芳基。
在本发明的一些更优选的实施方式中,R3选自卤代苯基、C1~C4烷基苯基、卤代C1~C4烷基苯基、C1~C4烷氧基苯基、联苯基、噻吩基、萘基。
在本发明的一些更优选的实施方式中,R3选自苯基、4-甲氧基苯基、4-联苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-碘苯基、4-三氟甲基苯基、3-溴苯基、3-甲基苯基、2-噻吩基、2-萘基。
在本发明的一些更优选的实施方式中,式I化合物选自:
在本发明的一些更优选的实施方式中,所述反应的溶剂选自二氯甲烷(DCM)、乙酸乙酯(EA)、甲苯(Toluene)、氯仿的至少一种。
在本发明的一些更优选的实施方式中,所述反应的温度为30℃~50℃,时间为0.5h~2h。
在本发明的一些更优选的实施方式中,所述反应可在有水或无水环境下进行。
在本发明的一些更优选的实施方式中,所述Lewis酸包括BF3·OEt2、AlCl3的任意一种。
在本发明的一些更优选的实施方式中,所述BF3·OEt2的用量为所示式I-A化合物的2.4~4.0eq。
在本发明的一些更优选的实施方式中,所述β-亚磺酰基烯基砜类化合物的制备方法还包括对所述反应的产物进行纯化处理的步骤;优选地,所述纯化包括将产物稀释、萃取、分液、干燥、过色谱柱;优选地,所述纯化包括用乙酸乙酯将产物稀释,用饱和氯化钠萃取、分液,有机层干燥,减压旋干,粗产品过色谱柱。
根据本发明的第三个方面,提出了一种所述式I化合物或其立体异构体和/或所述的β-亚磺酰基烯基砜类化合物的制备方法在有机合成中的应用。
本发明的有益效果是:
(1)本发明提供了一系列的β-亚磺酰基烯基砜类化合物,丰富了β-亚磺酰基烯基砜类化合物分子库。
(2)本发明通过炔与芳基亚磺酸钠反应实现,其无过渡金属催化、绿色高效,不仅具有反应体系简单,底物适用范围广、产率较高、而且避免了反应前复杂的无水处理,有利于工业化生产。
附图说明
图1为本申请实施例1化合物1的X射线单晶衍射图。
图2为本申请实施例3化合物3的X射线单晶衍射图。
具体实施方式
以下通过具体的实施例对本发明的内容作进一步详细的说明。实施例和对比例中所用的原料、试剂或装置如无特殊说明,均可从常规商业途径得到,或者可以通过现有技术方法得到。除非特别说明,试验或测试方法均为本领域的常规方法。
实施例1
本实施例制备了化合物1((E)-1-Methyl-4-((2-phenyl-2-(p-tolylsulfinyl)vinyl)sulfonyl)benzene),具体过程为:
将0.30mmol(33μL)苯乙炔和1.20mmol(0.2136g)对甲苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物1,白色固体(0.1164g,98%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.33(s,3H,CH3-20),2.40(s,3H CH3-1),6.92(d,J=7.2Hz,ArH-11,15),7.08-7.13(m,4H,ArH-3,4,17,22),7.22(d,J=7.8Hz,2H,ArH-18,21),7.23-7.27(m,2H,ArH-12,14),7.32(s,1H,H-8),7.36(t,J=7.8Hz,1H,ArH-13),7.55(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-20),21.8(C-1),125.6(C-12,14),128.0(C-11,15),128.2(C-18,21),182.3(C-8),129.4(C-3,4),129.6(C-10),129.8(C-17,22),130.0(C-5,6),130.2(C-13),137.0(C-9),137.6(C-19),142.9(C-2),144.9(C-16),160.7(C-7);
ESI-HRMS,m/z:Calcd for C22H21O3S2[M+H]+:397.0927,Found:397.0920.
化合物1的X射线单晶衍射图如附图1所示。
核磁共振氢谱、核磁共振碳谱、高分辨质谱和X射线单晶衍射结果显示化合物1的结构和预期一致。
实施例2
本实施例制备了化合物2((E)-((2-Phenyl-2-phenylsulfinylvinyl)sulfonyl)benzene),具体过程为:
将0.30mmol(33μL)苯乙炔和1.20mmol(0.1970g)苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物2,白色固体(0.1027g,93%)。
化合物2相关表征数据为:
1H NMR(600MHz,CDCl3),δ,ppm:6.90(d,J=7.2Hz,2H,ArH-10,14),7.20(d,J=7.2Hz,2H,ArH-16,20),7.24-7.27(m,2H,ArH-11,13),7.31-7.33(m,2H,ArH-17,19),7.35(s,1H,H-7),7.37(t,J=7.8Hz,1H,ArH-12),7.41-7.45(m,3H,ArH-1,2,3),7.58(t,J=7.2Hz,1H,ArH-18),7.68(d,J=7.2Hz,2H,ArH-4,5);
13C NMR(150MHz,CDCl3),δ,ppm:125.5(C-17,19),128.0(C-16,20),128.1(C-7),128.3(C-4,5),129.2(C-11,13),129.3(C-10,14),129.4(C-2,3),129.5(C-9),130.4(C-12),132.2(C-18),133.9(C-1),140.3(C-8),140.5(C-15),161.3(C-6);
ESI-HRMS,m/z:Calcd for C20H17O3S2[M+H]+:369.0614,Found:369.0609.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物2的结构和预期一致。
实施例3
本实施例制备了化合物3((E)-1-Fluoro-4-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(34μL)4-氟苯乙炔、1.20mmol(0.2136g)对甲苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物3,白色固体(0.1106g,89%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.35(s,1H,CH3-20),2.42(s,1H,CH3-1),6.91-6.98(m,4H,ArH-11,12,14,15),7.11-7.15(m,4H,ArH-3,4,17,22),7.26(d,2H,J=7.2Hz,ArH-18,21),7.33(s,1H,H-8),7.58(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-20),21.8(C-1),115.6(d,J=22.5Hz,C-12,14),124.3(d,J=3.0Hz,C-10),125.6(C-18,21),128.0(C-17,22),129.9(C-3,4),130.0(C-8),130.1(C-5,6),131.5(d,J=9.0Hz,C-11,15),136.9(C-19),137.5(C-2),143.1(C-9),145.2(C-16),159.7(C-7),163.8(d,J=249.0Hz,C-13);
19F NMR(564MHz,CDCl3),δ,ppm:-109.3.
化合物3的X射线单晶衍射图如附图2所示。
核磁共振氢谱、核磁共振碳谱结果显示化合物3的结构和预期一致。
实施例4
本实施例制备了化合物4((E)-1-Methoxy-4-(2-(4-methoxyphenylsulfinyl)-2-phenylvinyl)sulfonylbenzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2328g)4-甲氧基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物4,白色固体(0.1207g,94%)。
1H NMR(600MHz,CDCl3),δ,ppm:3.77(s,1H,OCH3-20),3.83(s,1H,OCH3-1),6.80(d,J=9.0Hz,2H,ArH-11,15),6.86(d,J=9.0Hz,2H,ArH-18,21),6.89(d,J=8.4Hz,2H,ArH-3,4),7.16(d,J=9.0Hz,2H,ArH-17,22),7.21-7.25(m,2H,ArH-12,14),7.31-7.34(m,2H,CH-8,ArH-13),7.57(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:55.6(C-20),55.8(C-1),114.4(C-18,21),114.7(C-3,4),127.7(C-12,14),128.1(C-11,15),128.4(C-8),129.3(C-17,21),129.9(C-13),130.0(C-10),130.2(C-5,6),130.9(C-16),132.0(C-7),160.3(C-9),162.7(C-19),163.9(C-2).
ESI-HRMS,m/z:Calcd for C22H21O5S2[M+H]+:429.0825,Found:429.0820.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物4的结构和预期一致。
实施例5
本实施例制备了化合物5((E)-1-Methyl-4-((2-(p-tolyl)-2-(p-tolylsulfinyl)vinyl)sulfonyl)benzene),具体过程为:
将0.30mmol(38μL)4-甲基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物5,白色固体(0.1156g,94%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-13),2.35(s,3H,CH3-21),2.41(s,3H,CH3-1),6.85(d,J=7.8Hz 2H,ArH-12,15),7.07(d,J=8.4Hz,2H,ArH-19,22),7.10-7.15(m,4H,ArH-3,4,18,23),7.23(d,J=7.8Hz,2H,ArH-11,16),7.28(s,1H,H-8),7.58(d,J=7.8Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-21),21.7(C-1),21.8(C-13),125.3(C-8),125.6(C-11,16),128.1(C-18,23),129.0(C-5,6),129.1(C-10),129.3(C-12,15),129.9(C-19,22),130.0(C-3,4),137.2(C-20),137.7(C-9),140.6(C-14),142.8(C-2),144.9(C-7),160.8(C-17).
核磁共振氢谱、核磁共振碳谱结果显示化合物5的结构和预期一致。
实施例6
本实施例制备了化合物6((E)-1-Ethyl-4-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(42μL)4-乙基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物6,白色固体(0.1171g,92%)。
1H NMR(600MHz,CDCl3),δ,ppm:1.23(t,J=7.2Hz,3H,CH3-15),2.33(s,3H,CH3-21),2.40(s,3H,CH3-1),2.64(q,2H,CH2-14),6.85(d,J=8.4Hz 2H,ArH-12,16),7.07(d,J=8.4Hz,2H,ArH-11,17),7.09-7.12(m,4H,ArH-3,4,19,24),7.20(d,J=9.0Hz,2H,ArH-20,23),7.30(s,1H,H-8),7.55(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:15.4(C-15),21.6(C-21),21.8(C-1),28.8(C-14),125.4(C-8),125.5(C-11,17),127.7(C-19,24),128.1(C-12,16),129.2(C-10),129.4(C-5,6),129.8(C-20,23),129.9(C-3,4),137.2(C-22),137.7(C-9),142.7(C-2),144.8(C-7),146.8(C-18),160.9(C-13);
ESI-HRMS,m/z:Calcd for C24H25O3S2[M+H]+:425.1240,Found:425.1230.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物6的结构和预期一致。
实施例7
本实施例制备了化合物7((E)-1-Methoxy-4-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(39μL)4-甲氧基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物7,白色固体(0.1214g,95%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-21),2.41(s,3H,CH3-1),3.82(s,3H,OCH3-14),6.80(d,J=9.0Hz,2H,ArH-12,15),6.94(d,J=9.0Hz,2H,ArH-11,16),7.11-7.13(m,4H,ArH-3,4,18,23),7.24(d,J=7.8Hz,2H,ArH-19,22),7.27(s,1H,H-8),7.58(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-21),21.8(C-1),55.4(C-14),113.8(C-12,15),120.4(C-10),125.5(C-11,16),128.0(C-19,22),128.8(C-8),129.9(18,23),130.0(C-3,4),131.0(C-5,6),137.5(C-20),137.8(C-9),142.7(C-2),144.9(C-17),160.5(C-7),161.3(C-13).
核磁共振氢谱、核磁共振碳谱结果显示化合物7的结构和预期一致。
实施例8
本实施例制备了化合物8((E)-4-(1-(p-tolylsulfinyl)-2-tosylvinyl)-1,1'-biphenyl),具体过程为:
将0.30mmol(0.0534g)4-乙炔联苯、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物8,白色固体(0.1204g,85%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-28),2.40(s,3H,CH3-1),7.01(d,J=8.4Hz,2H,ArH-11,21),7.12-7.16(m,4H,ArH-3,4,23,24),7.22(d,J=7.8Hz,2H,ArH-25,26),7.36(s,1H,H-8),7.38(t,J=7.8Hz,1H,ArH-17),7.44-4.47(m,2H,ArH-16,18),7.49(d,J=8.4Hz,2H,ArH-12,20),7.58-7.60(m,4H,ArH-5,6,15,19);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-28),21.8(C-1),125.6(C-23,24),126.7(C-11,21),127.2(C-12,17,20),128.0(C-15,19),128.1(C-8),129.0(C-5,6),129.6(C-10),129.8(C-16,18,25,26),130.0(C-3,4),137.1(C-9),137.6(C-27),139.8(C-2),142.8(C-13),142.9(C-14),145.0(C-22),160.5(C-7).
核磁共振氢谱、核磁共振碳谱结果显示化合物8的结构和预期一致。
实施例9
本实施例制备了化合物9((E)-1-Chloro-4-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(0.0408g)4-氯苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化9合物9,白色固体(0.1200g,93%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-28),2.40(s,3H,CH3-1),7.01(d,J=8.4Hz,2H,ArH-11,21),7.12-7.16(m,4H,ArH-3,4,23,24),7.22(d,J=7.8Hz,2H,ArH-25,26),7.36(s,1H,H-8),7.38(t,J=7.8Hz,1H,ArH-17),7.44-4.47(m,2H,ArH-16,18),7.49(d,J=8.4Hz,2H,ArH-12,20),7.58-7.60(m,4H,ArH-5,6,15,19);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-28),21.8(C-1),125.6(C-23,24),126.7(C-11,21),127.2(C-12,17,20),128.0(C-15,19),128.1(C-8),129.0(C-5,6),129.6(C-10),129.8(C-16,18,25,26),130.0(C-3,4),137.1(C-9),137.6(C-27),139.8(C-2),142.8(C-13),142.9(C-14),145.0(C-22),160.5(C-7).
核磁共振氢谱、核磁共振碳谱结果显示化合物9的结构和预期一致。
实施例10
本实施例制备了化合物10((E)-1-Bromo-4-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(0.0543g)4-溴苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物10,白色固体(0.1294g,91%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.36(s,3H,CH3-20),2.43(s,3H,CH3-1),6.79(d,J=9.0Hz,2H,ArH-11,15),7.13-7.17(m,4H,ArH-3,4,17,22),7.26(d,J=7.8Hz,2H,ArH-18,21),7.33(s,1H,H-8),7.40(d,J=8.4Hz,2H,ArH-12,14),7.58(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.7(C-20),21.8(C-1),125.0(C-13),125.7(C-17,22),127.3(C-8),128.1(C-5,6),130.0(C-11,15),130.1(C-10),130.2(C-18,21),130.8(C-3,4),131.5(C-12,14),136.7(C-10),137.4(C-19),143.3(C-7),145.3(C-2),159.4(C-16).
核磁共振氢谱、核磁共振碳谱结果显示化合物10的结构和预期一致。
实施例11
本实施例制备了化合物11((E)-1-Methyl-4-((2-(4-nitrophenyl)-2-(p-tolylsulfinyl)vinyl)sulfonyl)benzene),具体过程为:
将0.30mmol(0.0441g)4-硝基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物11,白色固体(0.1151g,87%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.37(s,3H,CH3-20),2.45(s,3H,CH3-1),7.09(d,J=9.0Hz,1H,ArH-11,15),7.14-7.18(m,4H,ArH-3,4,17,22),7.30(d,J=7.8Hz,2H,ArH-18,21),7.37(s,1H,H-8),7.62(d,J=8.4Hz,2H,ArH-5,6),8.12(d,J=9.0Hz,2H,ArH-12,14);
13C NMR(150MHz,CDCl3),δ,ppm:21.7(C-20),21.9(C-1),123.3(C-12,14),125.8(C-17,22),128.1(C-11,15),130.2(C-5,6),130.3(C-18,21),130.4(C-3,4),131.2(C-8),135.2(C-10),136.1(C-19),137.0(C-9),143.8(C-2),145.7(C-7),148.6(C-16),158.3(C-13).
核磁共振氢谱、核磁共振碳谱结果显示化合物11的结构和预期一致。
实施例12
本实施例制备了化合物12((E)-1-Methyl-4-((2-(p-tolylsulfinyl)-2-(4-trifluoromethylphenyl)vinyl)sulfonyl)benzene),具体过程为:
将0.30mmol(49μL)4-三氟甲基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物12,白色固体(0.1225g,88%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.36(s,3H,CH3-20),2.42(s,3H,CH3-1),7.00(d,J=7.8Hz,2H,ArH-11,16),7.12-7.17(m,4H,ArH-3,4,12,15),7.25(d,J=8.4Hz,2H,ArH-19,22),7.38(s,1H,H-8),7.50(d,J=8.4Hz,2H,ArH-18,23),7.56(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.7(C-21),21.8(C-1),123.7(q,J=271.5Hz,C-13),125.1(q,J=3.0Hz,C-12,15),125.7(C-11,16),128.1(C-19,22),129.7(C-3,4),130.0(C-18,23),130.2(C-5,6),130.9(C-8),132.0(q,J=33.0Hz,C-14),132.2(C-10),136.4(C-9),137.1(C-20),143.5(C-2),145.4(C-17),159.0(C-7);
19F NMR(564MHz,CDCl3),δ,ppm:-62.9.
核磁共振氢谱、核磁共振碳谱、核磁共振氟谱结果显示化合物12的结构和预期一致。
实施例13
本实施例制备了化合物13((E)-1-Methyl-3-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(39μL)3-甲基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物13,白色固体(0.1132g,92%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.24(s,3H,CH3-13),2.34(s,3H,CH3-21),2.40(s,3H,CH3-1),6.65(s,1H,ArH-11),6.68(d,J=7.8Hz,1H,ArH-14),7.08-7.15(m,6H,ArH-3,4,15,16,18,23),7.21(d,J=7.8Hz,2H,ArH-19,22),7.30(s,1H,H-8),7.54(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.4(C-13),21.6(C-21),21.8(C-1),125.6(C-18,23),126.7(C-16),128.0(C-5,6),128.1(C-8),129.5(C-11),129.6(C-14),129.8(C-19,22),129.9(C-3,4),130.9(C-15),137.1(C-9),137.6(C-20),137.8(C-12),142.8(C-2),144.8(C-7),160.9(C-17).核磁共振氢谱、核磁共振碳谱结果显示化合物13的结构和预期一致。
实施例14
本实施例制备了化合物14((E)-1-Methoxy-3-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(38μL)3-甲氧基苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物14,白色固体(0.1150g,90%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-21),2.40(s,3H,CH3-1),3.66(s,3H,OCH3-13),6.35-6.36(m,1H,ArH-11),6.50(d,J=7.8Hz,1H,ArH-14),6.87-6.88(dd,J=2.4Hz,J=8.4Hz,1H,ArH-16),7.11-7.13(m,4H,ArH-3,4,18,23),7.14-7.17(m,1H,ArH-15),7.22(d,J=7.8Hz,2H,ArH-19,22),7.32(s,1H,H-8),7.56(d,J=7.8Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-21),21.8(C-1),55.4(C-13),114.3(C-11),116.4(C-14),121.7(C-16),125.7(C-18,23),128.1(C-5,6),129.3(C-8),129.4(C-10),129.7(C-15),129.8(C-19,22),130.0(C-3,4),137.1(C-20),137.6(C-9),142.9(C-2),144.9(C-7),159.1(C-17),160.5(C-12).
核磁共振氢谱、核磁共振碳谱结果显示化合物14的结构和预期一致。
实施例15
本实施例制备了化合物15((E)-1-Chloro-3-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(37μL)3-氯苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物15,白色固体(0.1135g,88%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.36(s,3H,CH3-21),2.42(s,3H,CH3-1),6.74-6.76(m,2H,ArH-13,15),7.12-7.19(m,5H,ArH-3,4,11,19,22),7.24(d,J=7.8Hz,2H,ArH-17,18),7.30-7.32(m,1H,ArH-14),7.35(s,1H,H-8),7.55(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.7(C-21),21.8(C-1),125.7(C-17,18),127.9(C-11),128.1(C-5,6),128.8(C-15),129.5(C-10),129.9(C-19,22),130.0(C-8),130.1(C-3,4),130.2(C-13),130.7(C-14),134.2(C-12),136.5(C-20),137.3(C-9),143.3(C-2),145.3(C-7),159.1(C-16).
核磁共振氢谱、核磁共振碳谱结果显示化合物15的结构和预期一致。
实施例16
本实施例制备了化合物16((E)-1-Methoxy-2-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(39μL)2-乙炔基苯甲醚、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物16,白色固体(0.1099g,86%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-21),2.40(s,3H,CH3-1),3.47(s,3H,OCH3-12),6.47-6.61(m,1H,ArH-13),6.68(d,J=8.4Hz,1H,ArH-16),6.77-6.82(m,1H,ArH-15),7.11-7.14(m,4H,ArH-3,4,18,23),7.19(d,J=8.4Hz,2H,ArH-19,22),7.28-7.31(m,1H,ArH-14),7.39(s,1H,H-8),7.53(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-21),21.8(C-1),55.2(C-12),110.4(C-15),117.0(C-8),120.0(C-16),125.8(C-18,23),128.2(C-5,6),129.5(C-19,22),129.6(C-3,4),129.9(C-14),131.3(C-20),131.8(C-9),137.5(C-2),142.6(C-7),144.5(C-17),156.5(C-11).
核磁共振氢谱、核磁共振碳谱结果显示化合物16的结构和预期一致。
实施例17
本实施例制备了化合物17((E)-1-Fluoro-2-(1-(p-tolylsulfinyl)-2-tosylvinyl)benzene),具体过程为:
将0.30mmol(34μL)2-氟苯乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物17,白色固体(0.0993g,80%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.35(s,3H,CH3-21),2.43(s,3H,CH3-1),6.75-6.82(m,1H,ArH-13),6.93-6.97(m,1H,ArH-12),7.03-7.07(m,1H,ArH-15),7.13-7.16(m,4H,ArH-3,4,17,18),7.28(d,J=7.8Hz,2H,ArH-19,22),7.33-7.37(m,1H,ArH-14),7.41(s,1H,H-8),7.64(d,J=7.8Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.7(C-21),21.8(C-1),115.6(d,J=21.0Hz,C-10),116.5(d,J=16.5Hz,C-12),123.8(d,J=3.0Hz,C-14),125.8(C-3,4),128.2(C-19,22),129.9(C-5,6),130.0(C-17,18),131.0(d,J=12.0Hz,C-15),131.1(C-8),132.3(d,J=7.5Hz,C-13),136.6(C-20),137.1(C-9),143.2(C-2),145.2(C-7),155.0(C-16),159.1(d,J=250.5Hz,C-11);
19F NMR(564MHz,CDCl3),δ,ppm:-110.74.
核磁共振氢谱、核磁共振碳谱结果显示化合物17的结构和预期一致。
实施例18
本实施例制备了化合物18((E)-2-(1-(p-Tolylsulfinyl)-2-tosylvinyl)naphthalene),具体过程为:
将0.30mmol(0.0456g)2-萘乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物18,白色固体(0.1084g,81%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.31(s,3H,CH3-26),2.33(s,3H,CH3-1),6.93-6.95(dd,J=8.4Hz,1.8Hz,1H,ArH-11),7.07(d,J=7.8Hz,2H,ArH-23,24),7.10-7.12(m,4H,ArH-3,4,21,22),7.40-7.43(m,2H,H-8,ArH-19),7.50-7.56(m,4H,ArH-5,6,15,16),7.67(d,J=8.4Hz,1H,ArH-12),7.73(d,J=7.8Hz,1H,ArH-14),7.81(d,J=7.8Hz,1H,ArH-17);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-26),21.7(C-1),125.6(C-21,22),125.9(C-8),126.6(C-11),126.9(C-19),127.6(C-14),127.92(C-15),127.93(C-16),128.1(C-5,6),128.5(C-17),129.0(C-12),129.7(C-23,24),129.9(C-13),130.0(C-3,4),132.3(C-18),133.7(C-25),137.0(C-10),137.5(C-9),142.9(C-2),145.0(C-7),160.6(C-20).
核磁共振氢谱、核磁共振碳谱结果显示化合物18的结构和预期一致。
实施例19
本实施例制备了化合物19((E)-2-(1-(p-Tolylsulfinyl)-2-tosylvinyl)thiophene),具体过程为:
将0.30mmol(30μL)2-噻吩乙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物19,白色固体(0.0712g,59%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.34(s,3H,CH3-18),2.42(s,3H,CH3-1),7.02-7.04(m,1H,ArH-12),7.14-7.15(m,3H,ArH-11,16,19),7.21(d,J=8.4Hz,2H,ArH-15,20),7.26(d,J=8.4Hz,2H,ArH-3,4),7.33(s,1H,H-8),7.48(d,J=4.8Hz,1H,ArH-13),7.66(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:21.6(C-18),21.8(C-1),125.5(C-15,20),127.6(C-8),127.8(C-11),128.0(C-5,6),129.6(C-12),129.9(C-16,19),130.1(C-3,4),130.7(C-13),132.2(C-17),137.4(C-9),137.9(C-10),143.0(C-2),145.1(C-7),154.0(C-14).
核磁共振氢谱、核磁共振碳谱结果显示化合物19的结构和预期一致。
实施例20
本实施例制备了化合物20((E)-1-Methyl-4-((2-(p-tolylsulfinyl)hex-1-en-1-yl)sulfonyl)benzene),具体过程为:
将0.30mmol(34μL)1-己炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物20,白色固体(0.0575g,51%)。
1H NMR(600MHz,CDCl3),δ,ppm:0.85(t,J=7.2Hz,3H,CH3-13),1.25-1.33(m,2H,CH2-12),1.49-1.57(m,2H,CH2-11),1.97-2.02(m,1H,CH2-10a),2.42(s,3H,CH3-18),2.47(s,3H,CH3-1),2.96-3.01(m,1H,CH2-10b),7.13(s,1H,H-8),7.30(d,J=8.4Hz,2H,ArH-3,4),7.37(d,J=7.8Hz,2H,ArH-16,19),7.47(d,J=7.8Hz,2H,ArH-15,20),7.82(d,J=8.4Hz,2H,ArH-5,6);
13C NMR(150MHz,CDCl3),δ,ppm:13.7(C-13),21.7(C-18),21.8(C-1),22.9(C-12),26.7(C-10),31.5(C-11),126.7(C-15,20),127.7(C-8),127.8(C-5,6),130.2(C-16,19),130.5(C-3,4),137.9(C-17),138.0(C-2),143.7(C-7),145.2(C-14),162.3(C-9).
核磁共振氢谱、核磁共振碳谱结果显示化合物20的结构和预期一致。
实施例21
本实施例制备了化合物21((E)-1-Methyl-4-((1-phenyl-1-(p-tolylsulfinyl)prop-1-en-2-yl)sulfonyl)benzene),具体过程为:
将0.30mmol(38μL)1-苯基-1-丙炔、1.20mmol(0.2136g)4-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物21,白色固体(0.1058g,86%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.37(s,3H,CH3-21),2.38(s,3H,CH3-1),2.72(s,3H,CH3-9),6.21(d,J=6.0Hz,1H,ArH-12),6.76(d,J=6.0Hz,1H,ArH-16),6.99-7.02(m,3H,ArH-13,14,15),7.10(d,J=7.8Hz,2H,ArH-18,23),7.15(d,J=8.4Hz,2H,ArH-3,4),7.24-7.28(m,4H,ArH-5,6,19,22);
13C NMR(150MHz,CDCl3),δ,ppm:15.8(C-9),21.6(C-21),21.7(C-1),124.4(C-18,23),126.6(C-14),126.8(C-12,16),128.1(C-5,6),128.9(C-13,15),129.6(C-19,22),129.8(C-3,4),131.0(C-8),136.6(C-11),137.9(C-10),142.1(C-20),144.2(C-7),144.6(C-2),153.4(C-17).
核磁共振氢谱、核磁共振碳谱结果显示化合物21的结构和预期一致。
实施例22
本实施例制备了化合物22((E)-4-(2-([1,1'-biphenyl]-4-ylsulfinyl)-2-phenylvinyl)sulfonyl-1,1'-biphenyl),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2880g)1,1'-联苯-4-亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物22,白色固体(0.1123g,72%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.97(d,J=7.2Hz,2H,ArH-16,20),7.27-7.29(m,3H,ArH-17,18,19),7.38-7.40(m,2H,ArH-22,23),7.43(s,1H,H-13),7.44-7.46(m,3H,ArH-30,31,32),7.48-7.50(m,3H,ArH-1,2,3),7.53-7.55(m,4H,ArH-4,5,24,25),7.58(d,J=6.6Hz,2H,ArH-28,29),7.62(d,J=8.4Hz,2H,ArH-8,9),7.73(d,J=8.4Hz,2H,ArH-10,11);
13C NMR(150MHz,CDCl3),δ,ppm:125.6(C-24,25),127.4(C-8,9),127.5(C-4,5),127.8(C-28,29),127.9(C-17,19),128.2(C-13),128.3(C-10,11),128.5(C-15),128.6(C-16,20),128.8(C-1),129.1(C-30,31),129.2(C-2,3),129.5(C-22,23),129.8(C-32),130.4(C-18),138.8(C-26),138.9(C-7),139.3(C-14),139.5(C-6),145.2(C-27),146.9(C-12),161.0(C-21);
ESI-HRMS,m/z:Calcd for C32H23O3S2[M-H]-:519.1094,Found:519.1093.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物22的结构和预期一致。
实施例23
本实施例制备了化合物23((E)-1-Fluoro-4-(2-(4-fluorophenylsulfinyl)-2-phenylvinyl)sulfonylbenzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2184g)4-氟苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物23,白色固体(0.0715g,59%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.90(d,J=7.2Hz,2H,ArH-10,14),7.00-7.04(m,2H,ArH-11,13),7.07-7.11(m,2H,ArH-17,19),7.19-7.21(m,2H,ArH-16,20),7.27-7.30(m,2H,ArH-2,3),7.34(s,1H,H-7),7.39(t,J=7.8Hz,1H,ArH-12),7.65-7.67(m,2H,ArH-4,5);
13C NMR(150MHz,CDCl3),δ,ppm:116.5(d,J=22.5Hz,C-17,19),116.7(d,J=22.5Hz,C-2,3),127.8(d,J=9.0Hz,C-16,20),127.9(C-7),128.5(C-11,13),129.2(C-10,14),129.7(C-12),130.6(C-9),131.0(d,J=9.0Hz,C-4,5),135.6(d,J=3.0Hz,C-15),136.3(d,J=3.0Hz,C-6),161.3(C-8),164.9(d,J=253.0Hz,C-18),166.0(d,J=255.0Hz,C-1);
19F NMR(564MHz,CDCl3),δ,ppm:-102.8,-105.9;
ESI-HRMS,m/z:Calcd for C20H15F2O3S2[M+H]+:405.0425,Found:405.0419.
核磁共振氢谱、核磁共振碳谱、核磁共振氟谱和高分辨质谱结果显示化合物23的结构和预期一致。
实施例24
本实施例制备了化合物24((E)-1-Chloro-4-(2-(4-chlorophenylsulfinyl)-2-phenylvinyl)sulfonylbenzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2376g)4-氯苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物24,白色固体(0.1190g,91%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.91(d,J=7.2Hz,2H,ArH-10,14),7.11(d,J=8.4Hz,2H,ArH-2,3),7.28-7.31(m,4H,ArH-11,13,16,20),7.32(s,1H,H-7),7.39(d,J=9.0Hz,2H,ArH-17,19),7.42(t,J=7.8Hz,1H,ArH-12),7.57(d,J=8.4Hz,2H,ArH-4,5);
13C NMR(150MHz,CDCl3),δ,ppm:126.6(C-11,13),127.7(C-7),128.5(C-10,14),129.3(C-17.19),129.4(C-2,3),129.5(C-16,20),129.6(C-4,5,12),130.7(C-9),138.5(C-18),138.6(C-1),138.7(C-8),140.1(C-15),161.4(C-6);ESI-HRMS,m/z:Calcd forC20H15Cl2O3S2[M+H]+:436.9834,Found:436.9826.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物24的结构和预期一致。
实施例25
本实施例制备了化合物25((E)-1-Bromo-4-(2-(4-bromophenylsulfinyl)-2-phenylvinyl)sulfonylbenzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2916g)4-溴苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物25,黄色固体(0.1367g,87%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.91(d,J=7.2Hz,2H,ArH-10,14),7.03(d,J=9.0Hz,2H,ArH-4,5),7.29-7.32(m,3H,H-7,ArH-11,13),7.42(t,J=7.8Hz,1H,ArH-12),7.46(d,J=8.4Hz,2H,ArH-16,20),7.49(d,J=8.4Hz,2H,ArH-17,19),7.56(d,J=9.0Hz,2H,ArH-2,3);
13C NMR(150MHz,CDCl3),δ,ppm:126.7(C-11,13),127.0(C-18),127.7(C-7),128.6(C-10,14),129.3(C-4,5),129.4(C-9),129.5(C-17,19),129.6(C-12),130.8(C-1),132.5(C-16,20),132.6(C-2,3),139.2(C-8),139.3(C-6),161.3(C-15);
ESI-HRMS,m/z:Calcd for C20H15Br2O3S2[M+H]+:526.8803,Found:526.8795.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物25的结构和预期一致。
实施例26
本实施例制备了化合物26((E)-1-Iodo-4-(2-(4-iodophenylsulfinyl)-2-phenylvinyl)sulfonylbenzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.3480g)4-碘苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物26,黄色固体(0.1450g,78%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.87(d,J=8.4Hz,2H,ArH-16,20),6.91(d,J=7.2Hz,2H,ArH-10,14),7.29-7.33(m,4H,ArH-4,5,11,13),7.34(s,1H,H-7),7.42(t,J=7.8Hz,1H,ArH-12),7.66(d,J=8.4Hz,2H,ArH-17,19),7.77(d,J=8.4Hz,2H,ArH-2,3);
13C NMR(150MHz,CDCl3),δ,ppm:99.1(C-18),102.1(C-1),126.6(11,13),127.7(C-7),128.6(C-10,14),129.3(C-17,19),129.4(C-2,3),129.5(C-12),130.8(C-9),138.4(C-16,20),138.5(C-4,5),139.9(C-8),140.1(C-15),161.3(C-6);
ESI-HRMS,m/z:Calcd for C20H15I2O3S2[M+H]+:620.8547,Found:620.8536.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物26的结构和预期一致。
实施例27
本实施例制备了化合物27((E)-1-(2-Phenyl-2-(4-trifluoromethylphenylsulfinyl)vinyl)sulfonyl-4-trifluoromethylbenz-ene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2784g)4-三氟甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物27,白色固体(0.0801g,53%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.92(d,J=7.8Hz,2H,ArH-10,14),7.26(d,J=8.4Hz,2H,ArH-16,20),7.29-7.33(m,2H,ArH-11,13),7.36(s,1H,H-7),7.44(t,J=7.8Hz,1H,ArH-12),7.58(d,J=8.4Hz,2H,ArH-17,19),7.68(d,J=8.4Hz,2H,ArH-4,5),7.78(d,J=8.4Hz,2H,ArH-2,3);
13C NMR(150MHz,CDCl3),δ,ppm:123.1(q,J=271.5Hz,C-21),123.3(q,J=271.5Hz,C-22),125.5(C-16,20),126.2(q,J=3.0Hz,C-17,19),126.3(q,J=3.0Hz,C-2,3),127.3(C-7),128.7(C-10,11,13,14),129.3(C-4,5),129.5(C-12),131.1(C-9),134.0(q,J=33.0Hz,C-18),135.0(q,J=33.0Hz,C-1),143.5(C-8),144.5(C-15),161.8(C-6);
19F NMR(564MHz,CDCl3),δ,ppm:-63.0,-63.3;
ESI-HRMS,m/z:Calcd for C22H15F6O3S2[M+H]+:505.0361,Found:505.0355.
核磁共振氢谱、核磁共振碳谱、核磁共振氟谱和高分辨质谱结果显示化合物27的结构和预期一致。
实施例28
本实施例制备了化合物28((E)-1-Bromo-3-(2-((3-bromophenyl)sulfinyl)-2-phenylvinyl)sulfonylbenzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2940g)3-溴苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物28,白色固体(0.1147g,73%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.90(d,J=7.8Hz,2H,ArH-10,14),7.04(d,J=7.8Hz,1H,ArH-20),7.18(t,J=7.8Hz,1H,ArH-12),7.26-7.27(m,1H,ArH-19),7.30-7.34(m,4H,H-7,ArH-11,13,16),7.44-7.46(m,1H,ArH-4),7.55(d,J=7.2Hz,1H,ArH-5),7.62(d,J=7.2Hz,1H,ArH-3),7.68-7.69(m,2H,ArH-2,18);
13C NMR(150MHz,CDCl3),δ,ppm:123.2(C-17),123.4(C-1),123.7(C-7),126.6(C-9),127.4(C-20),127.9(C-5),128.6(C-10,14),129.3(C-11,13),129.7(C-12),130.6(C-19),130.8(C-2),131.0(C-4),131.1(C-18),135.2(C-16),137.0(C-8),142.0(C-3),142.2(C-6),161.8(C-15);ESI-HRMS,m/z:Calcd for C20H15Br2O3S2[M+H]+:524.8658,Found:524.8650.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物28的结构和预期一致。
实施例29
本实施例制备了化合物29((E)-1-Methyl-3-(2-phenyl-2-(m-tolylsulfinyl)vinylsulfonyl)benzene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2136g)3-甲基苯亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物29,白色固体(0.0974g,82%)。
1H NMR(600MHz,CDCl3),δ,ppm:2.27(s,3H,CH3-19),2.34(s,3H,CH3-1),6.89(d,J=7.2Hz,2H,ArH-11,15),6.91(d,J=7.8Hz,1H,ArH-3),7.02(s,1H,ArH-17),7.17(t,J=7.8Hz,1H,ArH-13),7.21(d,J=7.2Hz,1H,ArH-22),7.25-7.27(m,2H,ArH-20,21),7.30-7.34(m,1H,ArH-4),7.34(s,1H,H-8),7.35-7.38(m,2H,ArH-12,14),7.43(s,1H,ArH-6),7.48(d,J=7.8Hz,1H,ArH-5);
13C NMR(150MHz,CDCl3),δ,ppm:21.3(C-19),21.4(C-1),122.7(C-22),125.1(C-5),125.5(C-10),128.1(C-12,14),128.2(C-8),128.4(C-6),128.9(C-13),129.1(C-21),129.4(C-11,15),129.6(C-20),130.2(C-4),133.0(C-17),134.6(C-3),139.5(C-9),139.6(C-18),139.9(C-7),140.3(C-2),161.1(C-16);
ESI-HRMS,m/z:Calcd for C22H19O3S2[M-H]-:395.0781,Found:395.0777.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物29的结构和预期一致。
实施例30
本实施例制备了化合物30((E)-2-(2-(Naphthalen-2-ylsulfinyl)-2-phenylvinyl)sulfonylnaphthalene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2568g)萘-2-亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物30,白色固体(0.1053g,75%)。
1H NMR(600MHz,CDCl3),δ,ppm:6.86(d,J=7.2Hz,2H,ArH-14,18),7.13-7.16(m,2H,ArH-15,17),7.24-7.27(m,1H,ArH-24),7.28(t,J=7.8Hz,1H,ArH-16),7.50-7.53(m,2H,H-11,ArH-25),7.56-7.60(m,2H,ArH-2,3),7.64-7.70(m,4H,ArH-1,4,23,26),7.80-7.82(m,2H,ArH-8,20),7.84(s,1H,ArH-28),7.88-7.90(m,2H,ArH-9,21),8.15(s,1H,ArH-6);
13C NMR(150MHz,CDCl3),δ,ppm:120.4(C-8),122.6(C-24),127.0(C-25),127.5(C-3),127.7(C-2),128.0(C-20),128.1(C-11),128.2(C-13),128.3(C-15,17),128.5(C-16),128.7(C-26),129.3(C-14,18),129.5(C-23),129.6(C-1,C-4),129.7(C-28),130.0(C-21),130.1(C-6),130.4(C-9),132.1(C-19),132.5(C-12),134.9(C-27),135.4(C-22),137.1(C-5),137.2(C-7),161.2(C-10);
ESI-HRMS,m/z:Calcd for C28H21O3S2[M+H]+:469.0926,Found:469.0920.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物30的结构和预期一致。
实施例31
本实施例制备了化合物31((E)-2-(2-Phenyl-2-(thiophen-2-ylsulfinyl)vinyl)sulfonylthiophene),具体过程为:
将0.30mmol(33μL)苯乙炔、1.20mmol(0.2064g)噻吩-2-亚磺酸钠,0.84mmol(0.22mL)BF3·OEt2,二氯甲烷4mL,在40℃下搅拌反应1h,反应结束后,用15mL乙酸乙酯稀释,再用饱和氯化钠溶液(15mL×3)萃取、分液,有机层无水硫酸钠干燥,减压旋干,粗产品硅胶柱色谱纯化分离得到化合物31,黄色固体(0.786g,69%)。
(E)-2-(2-Phenyl-2-(thiophen-2-ylsulfinyl)vinyl)sulfonylthiophene(化合物31),黄色固体,m.p.:133-134℃,收率69%;1H NMR(600MHz,CDCl3),δ,ppm:6.91-6.92(m,1H,ArH-15),7.05-7.06(m,1H,ArH-2),7.07-7.08(m,3H,ArH-8,12,14),7.29-7.31(m,2H,ArH-9,11),7.38(t,J=7.2Hz,1H,ArH-10),7.48-7.49(dd,J=3.6Hz,1.2Hz,1H,ArH-3),7.49(s,1H,H-5),7.61-7.62(dd,J=5.4Hz,1.2Hz,1H,ArH-16),7.67-7.68(dd,J=4.8Hz,1.2Hz,1H,ArH-1);
13C NMR(150MHz,CDCl3),δ,ppm:127.4(C-10),127.9(C-5),128.1(C-7),128.4(C-9,11),129.1(C-8,12),130.3(C-16),130.5(C-1),132.8(C-14),133.2(C-15),134.6(C-2),134.9(C-3),141.47(C-6),141.49(C-13),160.2(C-4);
ESI-HRMS,m/z:Calcd for C16H13O3S4[M+H]+:380.9742,Found:380.9734.
核磁共振氢谱、核磁共振碳谱和高分辨质谱结果显示化合物31的结构和预期一致。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
1.一种β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:包括以下步骤:
惰性氛围下,式I-A化合物与式I-B化合物在Lewis酸催化下反应制得式I化合物,即β-亚磺酰基烯基砜类化合物;
其中,R1选自丁基、取代或未取代芳基、取代或未取代噻吩基;R2选自H、甲基;R3选自取代或未取代芳基、取代或未取代噻吩基;
R1或R3中,所述芳基选自苯基、联苯基或萘基;
所述Lewis酸为BF3•OEt2。
2.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:R1选自正丁基、4-甲基苯基、4-乙基苯基、4-联苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-硝基苯基、4-三氟甲基苯基、3-甲基苯基、3-氯苯基、3-甲氧基苯基、2-甲氧基苯基、2-氟苯基、2-噻吩基、2-萘基。
3.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:R3选自苯基、4-甲氧基苯基、4-联苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-碘苯基、4-三氟甲基苯基、3-溴苯基、3-甲基苯基、2-噻吩基、2-萘基。
4.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:式I化合物选自:
、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、。
5.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:所述反应的溶剂选自二氯甲烷、乙酸乙酯、甲苯、氯仿的至少一种。
6.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:所述反应的温度为30℃~50℃,时间为0.5h~2h。
7.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:所述反应在有水或无水环境下进行。
8.根据权利要求1所述的β-亚磺酰基烯基砜类化合物的制备方法,其特征在于:所述BF3•OEt2的用量为所示式I-A化合物的2.4~4.0eq。
9.一种如权利要求1~8任一项所述的β-亚磺酰基烯基砜类化合物的制备方法在制备所述的β-亚磺酰基烯基砜类化合物中的应用。
Priority Applications (1)
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Trace water in a BF 3· OEt 2 system: a facile access to sulfinyl alkenylsulfones from alkynes and sodium sulfinates;Yu S W等;《Organic & Biomolecular Chemistry》;20230907;第21卷(第38期);第7776-7781页 * |
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