CN110283157B - 一种四取代噻吩及其制备方法 - Google Patents
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- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000007858 starting material Substances 0.000 claims abstract description 6
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明的主要目的在于提供了一种四取代噻吩类衍生物的制备方法。该方法由含硫内鎓盐和活化的联烯作为起始原料，在二氧六环中于85度加热条件下反应。待反应物完全消失，将反应物浓缩旋干、柱色谱分离得到目标分子多取代噻吩。该反应不需要无水无氧条件，需要其它催化剂和金属试剂，操作简单，适合大量制备。
Description
技术领域
本涉及化学合成技术领域，具体为一种四取代噻吩及其制备方法。
背景技术
噻吩作为一种含硫五元杂环广泛存在于生物活性分子、药物以及功能材料中，而且在合成化学和材料化学中噻吩常作为合成子或者基本结构单元使用。目前对于噻吩的合成，已有很多报道，例如经典的噻吩合成方法Gewald反应和Paal-Knorr反应。然而，对于这些已知的方法，很多会用到金属催化剂，有着恶臭的含硫起始材料以及苛刻的反应条件等，因而发展操作简单，原料无异味，不需要金属催化的噻吩合成方法一直是有机化学的研究热点之一。
发明内容
本申请主要提供一种操作简单、绿色环保、不需要催化剂和金属试剂、适合大规模制备多取代噻吩的方法。该方法实现了含硫内鎓盐和活化的联烯作为起始原料，在二氧六环中只需要加热的条件下制备四取代噻吩。
制备方法：将通式原料含硫内鎓盐A和活化的联烯B在二氧六环中混合，在85度加热。待反应物B完全消失，将反应物浓缩旋干、柱色谱分离得到目标分子多取代噻吩。
其中
EWG1选自：CO2Me,CO2Et,COPh
EWG2选自：CO2Me,CO2Et,COPh
R1选自：OMe,OEt,OBn,OPh,Ph
R2和R3选自：H,Me；H,(CH2)7CH3；H,CH2OH；Me,Me；(CH2)5；H,H
进一步地，上述方法中，反应温度为85℃。
进一步地，上述方法中，反应物A与反应物B的优选摩尔比为1.5:1。
进一步地，上述方法中，优选溶剂为二氧六环，浓度优选0.1M。
本发明的有益效果为：起始原料易得、操作简单、不需要催化剂和金属试剂、只需要热源即可、适合大规模制备多取代噻吩的方法。
附图说明
图1为实施例产物Ⅰ-1的氢谱；
图2位实施例产物Ⅰ-1的碳谱；
具体实施方式
本发明以下结合具体实施例进行解说。在以下所有实施例中，核磁谱检测通过Varian 300,Bruker 400,JEOL 400and Varian 600MHz仪器在CDCl3、(CD3)2CO中获得。δ值为内标相对值(CDCl3定标δ7.26 1H NMR和77.00 13C NMR)。高分辨质谱(HRMS)通过4Gquadrupole time-of-flight(QTof)质谱仪器得到。
实施例1
实施例1的反应式，具体使用的原料化合物A-1和B-1以及产物Ⅰ-1结构如下：
具体实验步骤是：将127mg(0.45mmol，1.5当量)的化合物A-1和56mg(0.3mmol,1.0当量)的化合物B-1溶于3mL的二氧六环中于85℃反应。反应监测B-1完全消失，反应结束，将反应混合物在水泵减压下旋转蒸发除去溶剂。残留物以200-300目硅胶柱层析得到Ⅰ-1所示化合物，其产物经过核磁(氢谱、碳谱)、高分辨质谱鉴定。
制备本发明的其它化合物(化合物Ⅰ-2至化合物Ⅰ-12)的实施例所用的方法与实施例1相同，反应条件如下：化合物A(0.45mmol，1.5当量)和化合物B(0.3mmol，1.0当量)溶于3mL的二氧六环中与85℃反应，反应监测B完全消失，反应结束，将反应混合物在水泵减压下旋转蒸发除去溶剂。残留物以200-300目硅胶柱层析得到目标化合物，其产物经过核磁(氢谱、碳谱)、高分辨质谱鉴定。
所得各产物结构以及数据表征如下：
产物Ⅰ-1为棕色油，产率为85％。1H NMR(400MHz,CDCl3)δ7.51–7.28(m,5H),5.25(s,2H),3.84(s,3H),3.62(s,3H),3.21(q,J＝7.2Hz,2H),1.32(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ165.4,163.4,161.3,160.6,140.9,134.9,128.7,128.5,128.4,126.1,126.0,67.2,52.5,23.8,15.1,(1C missing)；ESI-HRMSm/z Calcd.for C18H18O6S+H+363.0897,found 363.0898.
产物Ⅰ-2为无色油，产率为89％。1H NMR(400MHz,CDCl3)δ7.42-7.31(m,5H),5.26(s,2H),4.30(q,J＝7.2Hz,2H),4.07(q,J＝7.2Hz,2H),3.20(q,J＝7.2Hz,2H),1.38-1.28(m,6H),1.20(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ165.0,163.2,161.4,160.2,140.7,135.0,128.6,128.5,128.4,126.6,125.9,67.0,61.7,61.6,23.8,15.1,14.0,13.7；ESI-HRMS m/z Calcd.for C20H22O6S+H+391.1210,found 391.1212.
产物Ⅰ-3为黄色油，产率为36％。1H NMR(400MHz,CDCl3)δ7.70(dd,J＝1.2,8.0Hz,2H),7.66(dd,J＝1.2,8.0Hz,2H),7.53–7.44(m,2H),7.40–7.27(m,4H),7.27–7.17(m,3H),7.01(dd,J＝1.2,8.0Hz,2H),5.02(s,2H),3.28(q,J＝7.2Hz,2H),1.38(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ192.7,186.4,163.4,161.8,148.1,137.7,137.2,134.6,134.4,132.8,132.7,129.0,128.6,128.3(3C),128.2,128.1,67.0,23.8,15.3,(1C missing)；ESI-HRMS m/z Calcd.for C28H22O4S+Na+477.1131,found 477.1132.
产物Ⅰ-4为黄色油，产率为34％。1H NMR(400MHz,CDCl3)δ7.83–7.75(m,2H),7.58(t,J＝7.4Hz,1H),7.47(t,J＝7.7Hz,2H),7.40–7.32(m,5H),5.27(s,2H),3.39(s,3H),3.20(q,J＝7.6Hz,2H),1.34(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3)δ186.9,165.1,162.0(2C),139.6,137.7,135.6,135.0,132.8,128.9,128.7,128.6,128.5,128.4,127.2,67.3,52.3,23.6,15.4；ESI-HRMS m/z Calcd.forC23H20O5S+Na+431.0924,found 431.0922.
产物Ⅰ-5为棕色油，产率为85％。1H NMR(400MHz,CDCl3)δ7.43–7.31(m,5H),5.25(s,2H),3.84(s,3H),3.63(s,3H),3.14(t,J＝8.0Hz,2H),1.71–1.62(m,2H),1.34–1.22(m,12H),0.89(t,J＝7.2Hz,3H)；13C NMR(75MHz,CDCl3)δ165.5,161.8,161.4,160.6,140.8,134.9,128.8,128.5(2C),126.2(2C),67.2,52.6,52.5,31.8,31.1,30.2,29.4,29.2,22.6,14.0,(2C missing)；ESI-HRMS m/z Calcd.for C25H32O6S+H+461.1992,found 461.1991.
产物Ⅰ-6为黄色油，产率为89％。1H NMR(400MHz,CDCl3)δ3.96(s,3H),3.86(s,3H),3.84(s,3H),3.16(t,J＝7.6Hz,2H),1.73–1.65(m,2H),1.41–1.26(m,12H),0.88(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)δ165.7,162.1,161.4,160.7,140.9,126.5,126.2,52.9,52.6,52.0,31.8,31.0,30.1,29.4,29.2,22.6,14.0,(2C missing)；ESI-HRMS m/zCalcd.for C19H28O6S+H+385.1679,found 385.1682.
产物Ⅰ-7为棕红色油，产率为73％。1H NMR(300MHz,CDCl3)δ4.30(q,J＝8.4Hz,2H),3.95(s,3H),3.91(t,J＝6.2Hz,2H),3.87(s,3H),3.42(t,J＝6.0Hz,2H),2.47(s,1H),1.34(t,J＝7.2Hz,3H)；13C NMR(75MHz,CDCl3)δ165.6,161.8,160.6,156.4,140.4,127.4,127.2,62.3,61.4,52.8,52.6,33.0,13.9；ESI-HRMS m/zCalcd.for C13H16O7S+H+317.0690,found 317.0688.
产物Ⅰ-8为无色油，产率为72％。1H NMR(400MHz,CDCl3)δ7.45–7.30(m,5H),5.25(s,2H),4.17–4.02(m,1H),3.84(s,3H),3.59(s,3H),1.33(d,J＝6.8Hz,6H)；13C NMR(100MHz,CDCl3)δ169.7,165.5,161.3,160.7,140.7,134.9,128.8,128.6,128.5,126.0,125.5,67.3,52.5(2C),29.7,24.5；ESI-HRMS m/z Calcd.forC19H20O6S+Na+399.0873,found399.0870.
产物Ⅰ-9为黄色油，产率为49％。1H NMR(400MHz,CDCl3)δ3.96(s,3H),3.86(s,3H),3.84(s,3H),3.74–3.61(m,1H),2.05(d,J＝11.2Hz,2H),1.89–1.73(m,3H),1.51–1.32(m,4H),1.30–1.23(m,1H)；13C NMR(100MHz,CDCl3)δ168.3,165.9,162.1,160.8,140.6,126.2,125.6,52.9,52.6,52.1,39.4,35.3,26.4,25.7；ESI-HRMS m/z Calcd.for C16H20O6S+H+341.1053,found 341.1050.
产物Ⅰ-10为黄色油，产率为74％。1H NMR(400MHz,CDCl3)δ7.46–7.31(m,5H),5.26(s,2H),3.84(s,3H),3.63(s,3H),2.74(s,3H).13C NMR(100MHz,CDCl3)δ165.5,161.5,160.6,155.7,140.8,135.0,128.7,128.6,128.5,126.8,126.1,67.2,52.6(2C),16.4；ESI-HRMS m/z Calcd.for C17H16O6S+H+349.0746；found:349.0740.
产物Ⅰ-11为黄色油，产率为67％。1H NMR(400MHz,CDCl3)δ7.41(t,J＝7.6Hz,2H),7.30–7.24(m,1H),7.17(d,J＝7.6Hz,2H),3.92(s,3H),3.89(s,3H),2.82(s,3H).13C NMR(100MHz,CDCl3):δ165.5,160.6,160.1,156.7,150.1,141.0,129.5,126.4,126.2,121.5,53.1,52.7,16.5,(1C missing)；ESI-HRMS m/z Calcd.forC16H14O6S+H+335.0589；found:335.4584.
产物Ⅰ-12为棕红色油，产率为31％。1H NMR(400MHz,CDCl3)δ7.75(d,J＝8.0Hz,2H),7.60(t,J＝7.6Hz,1H),7.47(t,J＝7.8Hz,2H),3.88(s,3H),3.55(s,3H),2.43(s,3H).13C NMR(100MHz,CDCl3):δ191.4,164.0,160.7,148.7,138.7,137.7,137.4,133.4,129.2,128.9,128.6,52.7,52.5,15.0；ESI-HRMS m/z Calcd.forC16H14O5S+H+271.0276,found271.0271。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (4)
1.一种四取代噻吩类衍生物的制备方法，其特征在于，制备方法如下所示：
式中：EWG1选自：CO2Me, CO2Et, COPh
EWG2选自：CO2Me, CO2Et, COPh
R1选自：OMe, OEt, OBn, OPh, Ph
R2和R3选自：H, Me; H, (CH2)7CH3; H, CH2OH; Me, Me; (CH2)5; H, H；
目标化合物Ⅰ的制备方法：将通式原料含硫内鎓盐A和活化的联烯B在二氧六环中混合，在85度加热，待反应物B完全消失，将反应物浓缩旋干、柱色谱分离得到目标分子四取代噻吩Ⅰ。
2.根据权利要求1所述的四取代噻吩类衍生物的制备方法，其特征在于：只使用通式A和联烯B所示化合物作为起始反应原料，85℃条件下反应，无需其它催化剂和金属试剂即可得到四取代噻吩Ⅰ。
3.根据权利要求1所述的四取代噻吩类衍生物的制备方法，其特征在于原料最佳摩尔比为A:B = 1.5:1。
4.根据权利要求1所述的四取代噻吩类衍生物的制备方法，其特征在于 该反应不需要无水无氧条件即可得到目标化合物Ⅰ。
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2019
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Non-Patent Citations (4)
| Title |
|---|
| A One-Pot Assembly of Fully Substituted Alkyl 5‑Aminothiophene-2-carboxylates from Allenes, Isothiocyanates, and Alkyl 2‑Bromoacetates;Nina A. Nedolya,et al.;《J. Org. Chem.》;20170621;7519-7528 * |
| Domino Synthesis of Tetrasubstituted Thiophenes from 1,3-Enynes with Mercaptoacetaldehyde;Ganesan Bharathiraja, et al.;《J. Org. Chem.》;20160229;2670-2674 * |
| Synthesis of Thieno-Fused Five- and Six-Membered Nitrogen and Oxygen Heterocycles via Intramolecular Heteroannulation of 4,5-Substituted 3‑Amino or 3‑Hydroxy 2‑Functionalized Thiophenes;Anand Acharya, et al.;《J. Org. Chem.》;20170707;7920-7938 * |
| Three-Component Diastereoselective Synthesis of Stable 1,4-Diionic Organosulfurs;Leila Moafi, et al.;《SYNTHESIS》;20110704;1399–1402 * |
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