CN114059090B - 一种苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的制备方法 - Google Patents
一种苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的制备方法 Download PDFInfo
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- -1 [1,4,3] oxathiazine-1, 1-dioxide derivative Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 125000005605 benzo group Chemical group 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 27
- 238000004440 column chromatography Methods 0.000 claims description 25
- 239000004744 fabric Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000008331 benzenesulfonamides Chemical class 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000007351 Smiles rearrangement reaction Methods 0.000 abstract description 2
- 150000005130 benzoxazines Chemical class 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 69
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 49
- 238000012512 characterization method Methods 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- 229910001873 dinitrogen Inorganic materials 0.000 description 20
- 238000000746 purification Methods 0.000 description 16
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 3
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- ZBGWAJQUDSCDPB-UHFFFAOYSA-N n-(benzenesulfonyl)benzamide Chemical class C=1C=CC=CC=1C(=O)NS(=O)(=O)C1=CC=CC=C1 ZBGWAJQUDSCDPB-UHFFFAOYSA-N 0.000 description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- UJVBZCCNLAAMOV-UHFFFAOYSA-N 2h-1,2-benzothiazine Chemical class C1=CC=C2C=CNSC2=C1 UJVBZCCNLAAMOV-UHFFFAOYSA-N 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- FQNOIHIJXCMLAV-UHFFFAOYSA-N N-benzylsulfonylbenzamide Chemical compound C(C1=CC=CC=C1)S(=O)(=O)NC(C1=CC=CC=C1)=O FQNOIHIJXCMLAV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RZEKVGVHFLEQIL-UHFFFAOYSA-N celecoxib Chemical class C1=CC(C)=CC=C1C1=CC(C(F)(F)F)=NN1C1=CC=C(S(N)(=O)=O)C=C1 RZEKVGVHFLEQIL-UHFFFAOYSA-N 0.000 description 1
- 229960000590 celecoxib Drugs 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DVIAHMIQFPOLSM-UHFFFAOYSA-N n-(2-methylphenyl)sulfonylbenzamide Chemical compound CC1=CC=CC=C1S(=O)(=O)NC(=O)C1=CC=CC=C1 DVIAHMIQFPOLSM-UHFFFAOYSA-N 0.000 description 1
- HWCIZGBBBWYGPR-UHFFFAOYSA-N n-(4-bromophenyl)sulfonylbenzamide Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)NC(=O)C1=CC=CC=C1 HWCIZGBBBWYGPR-UHFFFAOYSA-N 0.000 description 1
- GHRGMZSLIAQQEZ-UHFFFAOYSA-N n-(4-fluorophenyl)sulfonylbenzamide Chemical compound C1=CC(F)=CC=C1S(=O)(=O)NC(=O)C1=CC=CC=C1 GHRGMZSLIAQQEZ-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
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Abstract
本发明公开了一种苯并[e][1,4,3]恶噻嗪‑1,1‑二氧化物衍生物的制备方法,属于有机合成技术领域。本发明使用较为简单的原料通过电化学促进的smiles重排反应首次直接合成苯并恶噻嗪类衍生物,且无需使用贵重金属催化剂,无需添加氧化剂,反应原料易得,收率高,反应条件温和,反应时间短,底物范围广,后处理简便且绿色。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的制备方法。
背景技术
苯并恶噻嗪类衍生物是一类用途广泛的有机合成中间体,在天然产物、医药生产、有机合成中具有重要的应用价值。因此,研究多取代苯并恶噻嗪类衍生物的高效新颖的合成方法具有重要的应用价值,受到相关领域科研工作者的关注。
目前关于苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的合成方法普遍存在合成底物普适性差、反应选择位点少、需要多步反应、产率低、多步反应温度均在120-180℃之间等问题,因此亟需开发更加高效,绿色环保的合成方法。
发明内容
本发明的目的在于克服现有技术缺陷,提供一种苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的制备方法,无需使用贵重金属催化剂,无需添加氧化剂,反应原料易得,收率高,反应条件温和,反应时间短,底物范围广,后处理简便且绿色。
为实现上述目的,本发明采用如下技术方案:
一种苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的结构式为
制备方法包括如下步骤:
(1)将苯磺酰胺衍生物、苯甲酸化合物和有机溶剂在室温下搅拌过夜,通过重结晶可得N-(苯磺酰基)苯甲酰胺类化合物。
(2)将步骤(1)所得的物料加入到DCE(1,2-二氯乙烷)和HFIP(六氟异丙醇)的混合溶剂中,再加入电解质和添加剂,通过恒电流的条件,在氮气保护下置于室温下搅拌1-5h,待反应结束,通过柱层析纯化,得到所述苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物;
上述N-(苯磺酰基)苯甲酰胺类化合物的结构式为,其中,R1为H、卤素、烷基,R2为H,烷基,R3为H、卤素、烷基等,R4为H、卤素、烷基或烷氧基,R5为H、卤素、烷基,烷氧基,氰基,R6为H、卤素、烷基,烷氧基,三氟甲基,氰基,酯基等。
优选地,其反应溶剂DCE/HFIP的比例范围在1-10之间。
优选地,每摩尔所述N-(苯磺酰基)苯甲酰胺衍生物对应0.5~1L有机溶剂。
优选地,所用电极为碳布,碳毡,碳棒,Pt片,Ni片,Fe片中的两种。
优选地,所述电流范围在5-20mA之间。
优选地,所用为nBu4NOAc、Me4NOAc、nBu4NBF4、Et4NBF4、nBu4NPF6中的一种。
优选地,所用添加剂为CH3COOH或H2O。
本发明的有益效果在于:使用较为简单的原料通过电化学促进的smiles重排反应首次直接合成苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物,且无需使用贵重金属催化剂,无需添加氧化剂,反应原料易得,收率高,反应条件温和,反应时间短,底物范围广,后处理简便且绿色。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-(苯磺酰基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到58.3mg目标产物,收率为75%。该化合物的表征如下:IR:1625(m),1450(w),1321(s),1376(s),1180(s),808(w),692(w),585(m);1HNMR(500MHz,Chloroform-d)δ8.25(dt,J=8.6,1.6Hz,2H),7.80(dd,J=7.9,1.6Hz,1H),7.72–7.66(m,2H),7.56–7.50(m,3H),7.44(dd,J=8.5,0.9Hz,1H).13C NMR(126MHz,Chloroform-d)δ158.0,149.3,134.8,134.4,129.5,129.1,128.6,127.9,124.7,122.9,118.1;HRMS(ESI)calculated for C13H10NO3S[M+H+]:260.0376;found:260.0372。
实施例2
7-甲基-3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到59.0mg目标产物,收率为72%。该化合物的表征如下:IR:1616(m),1325(s),1295(m),1173(m),820(w),692(m),584(m),554(w);1HNMR(500MHz,Chloroform-d)δ8.23(d,J=8.3Hz,2H),7.75(s,1H),7.65(t,J=7.4Hz,1H),7.56–7.50(m,2H),7.47(d,J=8.6Hz,1H),7.31(d,J=8.6Hz,1H),2.44(s,3H).13C NMR(126MHz,Chloroform-d)δ158.0,147.2,138.4,135.3,134.6,129.4,129.0,128.7,124.0,122.3,117.8,21.2;HRMS(ESI)calculated for C14H12NO3S[M+H+]:274.0532;found:274.0524。
实施例3
7-氟-3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-((4-氟苯基)磺酰基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到35.8mg目标产物,收率为41%。该化合物的表征如下:IR:1614(m),1573(w),1325(s),1301(w),1171(s),807(w),778(w),787(m),582(w);1H NMR(500MHz,Chloroform-d)δ8.3(dt,J=8.6,1.5Hz,2H),7.7–7.6(m,2H),7.6–7.5(m,2H),7.5(dd,J=9.2,4.1Hz,1H),7.4(m,1H).13C NMR(126MHz,Chloroform-d)δ160.1(d,J=252.6H),158.1,145.5(d,J=3.0Hz),135.0,129.6,129.2,128.4,123.7(d,J=7.7Hz),122.3(d,J=24.4Hz),120.4(d,J=8.0Hz),111.1(d,J=26.0Hz);19F NMR(471MHz,Chloroform-d)δ-109.2;HRMS(ESI)calculated for C13H9FNO3S[M+H+]:278.0282;found:278.0279。
实施例4
7-溴-3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-((4-溴苯基)磺酰基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到47.7mg目标产物,收率为47%。该化合物的表征如下:IR:1608(m),1566(w),1326(s),1289(s),1216(m),1186(m),1169(s),834(w),809(w),693(m),573(w);1H NMR(500MHz,Chloroform-d)δ8.2(d,J=7.4Hz,2H),8.1(d,J=2.3Hz,1H),7.8(dd,J=8.9,2.3Hz,1H),7.7(t,J=7.5Hz,1H),7.6(t,J=7.9Hz,2H),7.3(d,J=8.9Hz,1H);13C NMR(126MHz,Chloroform-d)δ157.9,148.2,137.5,135.1,129.6,129.2,128.3,127.4,124.1,120.4,119.9;HRMS(ESI)calculated forC13H9BrNO3S[M+H+]:337.9481;found:337.9475。
实施例5
5-甲基-3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备
在室温条件下,将N-(邻甲苯磺酰基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到61.5mg目标产物,收率为75%。该化合物的表征如下:IR:1616(m),1468(w),1321(s),1291(s),1204(m),1170(m),795(w),691(w),576(w),561(w);1H NMR(500MHz,Chloroform-d)δ8.26(d,J=7.4Hz,2H),7.82(d,J=7.9Hz,1H),7.68(t,J=7.4Hz,1H),7.57–7.53(m,3H),7.40(t,J=7.7Hz,1H),2.57(s,3H);13C NMR(126MHz,Chloroform-d)δ157.9,147.6,135.4,134.7,129.4,129.1,129.0,127.8,127.2,122.6,122.1,16.2;HRMS(ESI)calculated for C14H12NO3S[M+H+]:274.0532;found:274.0527。
实施例6
5-氯-3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-((2-氯苯基)磺酰基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到51.0mg目标产物,收率为58%。该化合物的表征如下:IR:1623(m),1456(w),1291(m),1178(s),1221(m),1157(m),831(w),695(w),618(w),549(w).1H NMR(500MHz,Chloroform-d)δ8.34(dd,J=8.3,1.0Hz,2H),7.91(dd,J=7.9,1.4Hz,1H),7.76(dd,J=8.0,1.4Hz,1H),7.71(t,J=7.4Hz,1H),7.57(t,J=7.9Hz,2H),7.47(t,J=8.0Hz,1H).13C NMR(126MHz,Chloroform-d)δ157.7,145.4,135.2,134.7,129.9,129.2,128.3,127.8,124.3,123.4,123.0;HRMS(ESI)calculated forC13H9ClNO3S[M+H+]:293.9986;found:293.9982。
实施例7
6-甲基-3-苯基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-(间甲苯磺酰基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到63.1mg目标产物,收率为77%(rr=5:1)。该化合物的表征如下:IR:1626(m),1571(w),1321(s),1297(s),1186(m),1148(w),810(w),689(m),551(w);1H NMR(500MHz,Chloroform-d)δ8.24(d,J=7.6Hz,2H,diastereoisomer),7.85(d,J=8.1Hz,1H,major diastereoisomer),7.77(d,J=1.5Hz1H,minor,diastereoisomer),7.67(t,J=7.0Hz,1H,diastereoisomer),7.54(t,J=7.7Hz,2H,diastereoisomer),7.31(d,J=8.1Hz,1H,diastereoisomer),7.26(s,1H,minordiastereoisomer),7.24(s,1H,major diastereoisomer),2.49(s,3H,majordiastereoisomer),2.45(s,3H,minor diastereoisomer);13C NMR(126MHz,Chloroform-d)δ158.0,149.2,145.9,138.4,135.3,134.7,133.5,129.5,129.0,128.9,128.8,124.3,124.1,120.0,118.0,117.8,77.2,21.9,21.2.HRMS(ESI)calculated for C14H12NO3S[M+H+]:274.0532;found:274.0528。
实施例8
7-甲基-3-(对甲苯基)苯并[e][1,4,3]恶二嗪-1,1-二氧化物的制备:
在室温条件下,将4-甲基-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到56.9mg目标产物,收率为66%。该化合物的表征如下:IR:1609(m),1488(w),1323(s),1293(s),1276(m),1218(w),823(w),727(m),582(m),550(w);1H NMR(500MHz,Chloroform-d)δ8.11(d,J=8.3Hz,2H),7.75(s,1H),7.46(dd,J=8.6,2.1Hz,1H),7.32–7.29(t,J=8.8Hz,3H),2.44(s,3H),2.44(s,3H);13C NMR(126MHz,Chloroform-d)δ158.2,147.3,145.9,138.2,135.2,129.8,129.5,125.9,124.0,122.3,117.8,22.0,21.1;HRMS(ESI)calculated for C15H14NO3S[M+H+]:288.0689;found:288.0685。
实施例9
3-(4-氟苯基)-7-甲基苯并[e][1,4,3]恶二嗪-1,1-二氧化物的制备:
在室温条件下,将4-氟-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到76.0mg目标产物,收率为87%。该化合物的表征如下:IR:1620(m),1597(w),1508(w),1325(s),1172(s),1156(w),850(w),821(w),550(w);1H NMR(500MHz,Chloroform-d)δ8.27(dd,J=8.7,5.3Hz,2H),7.76(s,1H),7.48(dd,J=8.6,1.9Hz,1H),7.31(d,J=8.6Hz,1H),7.21(t,J=8.5Hz,2H),2.45(s,3H).13C NMR(126MHz,Chloroform-d)δ166.8(d,J=257.7),157.0,147.1,138.5,135.3,132.1(d,J=9.8),124.9(d,J=3.3),124.1,122.3,117.7,116.5(d,J=22.4),21.2;19FNMR(471MHz,Chloroform-d)δ-102.0;HRMS(ESI)calculated for C14H11FNO3S[M+H+]:292.0438;found:292.0434。
实施例10
3-(4-氯苯基)-7-甲基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将4-氯-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到73.7mg目标产物,收率为80%。该化合物的表征如下:IR:1621(m),1596(w),1490(w),1326(s),1297(s),1169(s),821(w),729(w),712(w),583(w);1H NMR(500MHz,Chloroform-d)δ8.17(dt,J=8.7,2.5Hz2H),7.76(s,1H),7.51(dt,J=8.7,2.4Hz,2H),7.48(dd,J=8.7,1.8,1H),7.30(d,J=8.6,1H),2.45(s,3H);13C NMR(126MHz,Chloroform-d)δ157.1,147.1,141.4,138.6,135.3,130.7,129.5,127.2,124.1,122.3,117.8,21.2;HRMS(ESI)calculated for C14H11ClNO3S[M+H+]:308.0143;found:308.0138。
实施例11
7-甲基-3-(4-(三氟甲基)苯基)苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将N-甲苯磺酰基-4-(三氟甲基)苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到57.3mg目标产物,收率为56%。该化合物的表征如下:IR:1626(m),1325(w),1295(w),1170(s),1124(m),1064(s),1017(w),852(w),821(w),678(w),583(w);1H NMR(500MHz,Chloroform-d)δ8.36(d,J=8.3Hz,2H),7.81-7.77(m,3H),7.51(d,J=8.6Hz,1H),7.35-7.34(m,1H),2.47(s,3H);13CNMR(126MHz,)δ156.5,147.0,138.9,135.8(q,J=33.3Hz),135.5,132.2,129.8,126.0(q,J=4.1Hz),124.1,123.4(q,J=273.1Hz),122.3,117.9,21.2;19F NMR(471MHz,CHLOROFORM-D)δ-63.2;HRMS(ESI)calculated for C15H11F3NO3S[M+H+]:342.0406;found:342.0404。
实施例12
4-(7-甲基-1,1-二氧化苯并[e][1,4,3]恶噻嗪-3-基)苄腈的制备:
在室温条件下,将4-氰基-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到67.0mg目标产物,收率为75%。该化合物的表征如下:IR:2227(m),1624(m),1489(w),1332(s),1289(m),1117(w),842(w),675(w),582(w);1H NMR(500MHz,Chloroform-d)δ8.36(d,J=8.6Hz,2H),7.85(d,J=8.6Hz,2H),7.78(s,1H),7.52(d,J=10.4Hz,1H),7.34(d,J=8.6Hz,1H),2.48(s,3H);13CNMR(126MHz,Chloroform-d)δ156.0,146.9,139.1,135.6,132.8,132.7,129.8,124.2,122.3,117.9,117.8,117.6,21.3;HRMS(ESI)calculated for C15H11N2O3S[M+H+]:299.0485;found:299.0483。
实施例13
4-(7-甲基-1,1-二氧化苯并[e][1,4,3]草硫嗪-3-基)苯甲酸甲酯的制备:
在室温条件下,将4-(对甲苯甲氨基甲酰基)苯甲酸甲酯0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到42.7mg目标产物,收率为43%。该化合物的表征如下:IR:2923(w),1721(s),1619(w),1318(s),1290(m),1279(w),1167(w),816(w),583(w);1H NMR(500MHz,Chloroform-d)δ8.31(dt,J=8.6,1.7Hz,,2H),8.19(t,J=1.9Hz,1H),8.18(t,J=1.7Hz,1H),7.77(s,1H),7.51(dd,J=8.7,2.0Hz,1H),7.34(d,J=8.6Hz,1H),3.97(s,3H),2.47(s,3H);13C NMR(126MHz,Chloroform-d)δ166.0,157.0,147.1,138.8,135.4,135.3,132.6,130.1,129.4,124.2,122.3,117.9,52.8,21.2;HRMS(ESI)calculated for C16H14NO5S[M+H+]:332.0587;found:332.0584。
实施例14
7-甲基-3-(4-(4,4,5,5-四甲基-1,3,2-二氧杂硼硼烷-2基)苯基)苯并[e][1,4,3]恶二嗪1,1-二氧化物的制备:
在室温条件下,将4-(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到37.1mg目标产物,收率为31%。该化合物的表征如下:IR:2925(w),1615(m),1489(w),1359(m),1324(s),1295(m),1275(w),1169(s),1143(w),1121(w),856(w),815(w),689(m),582(m),557(w);1H NMR(500MHz,Chloroform-d)δ8.22(d,J=8.4Hz,2H),7.95(d,J=8.3Hz,2H),7.77(s,1H),7.49(dd,J=8.6,1.8Hz,1H),7.34(d,J=8.6Hz,1H),2.46(s,3H),1.37(s,12H);13C NMR(126MHz,Chloroform-d)δ158.0,147.3,138.5,135.3,135.2,130.9,130.9,128.4,124.1,122.4,117.9,84.6,25.0,21.2.HRMS(ESI)calculated forC20H23BNO5S[M+H+]:400.1385;found:400.1385。
实施例15
7-甲基-3-(间甲苯基)苯并[e][1,4,3]恶二嗪-1,1-二氧化物的制备:
在室温条件下,将3-甲基-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到73.2mg目标产物,收率为85%。该化合物的表征如下:IR:2924(w),1616(s),1489(w),1323(s),1295(m),1277(w),1171(s),818(m),583(w),557(w);1H NMR(500MHz,Chloroform-d)δ=8.07(s,1H),8.04(d,J=7.8,1H),7.77(s,1H),7.49-7.47(m,2H),7.42(t,J=7.7,1H),7.32(d,J=8.6,1H),2.46(s,3H),2.45(s,3H);13C NMR(126MHz,Chloroform-d)δ158.2,147.3,139.0,138.4,135.5,135.2,130.0,128.9,128.7,126.6,124.1,122.4,117.8,21.5,21.2;HRMS(ESI)calculatedfor C15H14NO3S[M+H+]:288.0689;found:288.0690。
实施例16
3-(3-氟苯基)-7-甲基苯并[e][1,4,3]恶二嗪-1,1-二氧化物的制备:
在室温条件下,将3-氟-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到69.9mg目标产物,收率为80%。该化合物的表征如下:IR:1618(m),1585(w),1491(w),1450(w),1325(s),1299(s),1274(m),1226(m),1173(w),1160(w),951(w),721(w),580(w),563(w);1H NMR(500MHz,Chloroform-d)δ8.06-8.04(m,1H),7.93-7.91(m,1H),7.92(s,1H),7.55-7.49(m,2H),7.39-7.32(m,1H),7.33(d,J=8.6Hz,1H),2.46(s,3H);13C NMR(126MHz,Chloroform-d)δ162.8(d,J=248.4Hz),156.7(d,J=3.6Hz),147.1,138.7,135.4,130.9(d,J=8.2Hz),130.8(d,J=8.0Hz),125.2(d,J=3.4Hz),124.1,122.3,121.8(d,J=21.3Hz),117.8,116.3(d,J=24.4Hz),21.2;19F NMR(471MHz,Chloroform-d)δ-110.8;HRMS(ESI)calculated for C14H11FNO3S[M+H+]:292.0438;found:292.0439。
实施例17
3-(3-甲氧基苯基)-7-甲基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将3-甲氧基-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到42.7mg目标产物,收率为47%。该化合物的表征如下:IR:1607(m),1578(w),1490(w),1324(s),1297(s),1274(m),1278(m),1172(s),1110(w),1142(w),816(w),721(w),584(w);1H NMR(500MHz,)δ7.83(ddd,J=7.8,1.6,0.9Hz,1H),7.77(s,1H),7.74(dd,J=2.5,1.7Hz,1H),7.48(dd,J=8.9,2.3Hz,1H),7.43(t,J=8.0Hz,1H),7.32(d,J=8.6Hz,1H),7.20(ddd,J=8.3,2.6,0.9Hz,1H),3.90(s,3H),2.46(s,3H);13C NMR(126MHz,Chloroform-d)δ160.0,157.9,147.2,138.4,135.3,130.0,124.,122.3,121.8,121.4,117.8,113.7,55.8,21.2;HRMS(ESI)calculated for C14H14NO4S[M+H+]:304.0638;found:306.0639。
实施例18
3-(7-甲基-1,1-二氧化苯并[e][1,4,3]恶噻嗪-3-基)苄腈的制备:
在室温条件下,将3-氰基-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到45.6mg目标产物,收率为51%。该化合物的表征如下:IR:2233(m),1622(m),1490(w),1327(s),1278(m),1221(w),1172(s),816(w),718(w),583(w),543(w);1H NMR(500MHz,Chloroform-d)δ8.52(s,1H),8.49(d,J=8.1Hz,1H),7.95(d,J=7.7Hz,1H),7.78(s,1H),7.71(t,J=7.9Hz,1H),7.53(dd,J=8.6,1.6Hz,1H),7.36(d,J=8.6Hz,1H),2.48(s,3H).13C NMR(126MHz,Chloroform-d)δ155.7,146.9,139.1,137.4,135.6,133.4,132.7,130.3,130.2,124.2,122.3,117.8,117.5,113.8,21.3;HRMS(ESI)calculated for C15H11N2O3S[M+H+]:299.0485;found:299.0486。
实施例19
3-(2-氯苯基)-7-甲基苯并[e][1,4,3]恶噻嗪-1,1-二氧化物的制备:
在室温条件下,将2-氯-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到68.4mg目标产物,收率为74%。该化合物的表征如下:IR:1622(m),1488(m),1434(w),1325(s),1302(m),1276(m),1173(s),821(m),770(w),582(m);1H NMR(500MHz,Chloroform-d)δ7.98(m,1H),7.78(m,1H),7.53(m,2H),7.49(dd,J=8.6,2.0Hz,1H),7.42(m,1H),7.29(d,J=8.6Hz,1H),2.47(s,3H);13C NMR(126MHz,Chloroform-d)δ158.3,147.3,138.8,135.4,134.2,134.1,132.6,128.8,127.2,124.0,122.3,118.0,21.2;HRMS(ESI)calculated for C14H11ClNO3S[M+H+]:308.0143;found:308.0142。
实施例20
3-(2-甲氧基苯基)-7-甲基苯并[e][1,4,3]恶二嗪-1,1-二氧化物的制备:
在室温条件下,将2-甲氧基-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到41.9mg目标产物,收率为46%。该化合物的表征如下:IR:1607(m),1489(w),1321(s),1277(m),1228(w),1171(s),820(w),725(w),585(w);1H NMR(500MHz,Chloroform-d)δ7.95(dd,J=7.8,1.8Hz,1H),7.77(s,1H),7.57(m,1H),7.45(dd,J=8.6,2.1Hz,1H),7.24(d,J=8.6Hz,1H),7.06(td,J=7.6,1.0Hz,1H),7.03(d,J=8.4Hz,1H),3.94(s,3H),2.45(s,3H).13C NMR(126MHz,Chloroform-d)δ159.8,159.3,147.7,138.2,135.3,135.1,132.5,124.0,122.3,120.7,118.6,118.0,112.4,56.2,21.2;HRMS(ESI)calculated for C15H14NO4S[M+H+]:304.0638;found:304.0636。
实施例21
3-(3,4-二氯苯基)-7-甲基苯并[e][1,4,3]恶二嗪-1,1-二氧化物的制备:
在室温条件下,将3,4-二氯-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到77.0mg目标产物,收率为75%。该化合物的表征如下:IR:1619(m),1326(s),1169(s),1300(w),826(w),721(w),584(m),483(w);1H NMR(500MHz,Chloroform-d)δ8.31(d,J=2.1Hz,1H),8.07(dd,J=8.5,2.1Hz,1H),7.76(s,1H),7.62(d,J=8.5Hz,1H),7.50(dd,J=8.6,1.7Hz,1H),7.33(d,J=8.6Hz,1H),2.47(s,3H).13C NMR(126MHz,Chloroform-d)δ156.0,147.0,139.5,138.9,135.5,133.9,131.2,131.1,128.6,128.3,124.2,122.3,117.8,21.2;HRMS(ESI)calculated for C14H10Cl2NO3[M+H+]:341.9753;found:341.9753。
实施例22
3-苯基-7-(5-(对甲苯基)-3-(三氟甲基)-1H-吡唑-1-基)苯并[e][1,4,3]恶噻嗪-1,1-二氧化物(塞来昔布衍生物)的制备:
在室温条件下,将N-((4-(5-(对甲苯基)-3-(三氟甲基)-1H-吡唑-1-基)苯基)磺酰基)苯甲酰胺0.1mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.05mmol的醋酸和溶剂(MeCN/HFIP=7:3mL),充入氮气反应2h。待反应结束通过柱层析纯化得到20.3mg目标产物,收率为42%。该化合物的表征如下:IR:1610(w),1471(w),1323(m),1264(s),1238(w),1163(s),1131(s),1101(w),1064(m),793(m),812(w),737(w),698(m),578(m);1H NMR(500MHz,Chloroform-d)δ8.24-8.22(m,2H),7.97(d,J=2.5,1H),7.69(t,J=7.4,1H),7.62(dd,J=9.0,2.6,2H),7.55(t,J=7.9,1H),7.42(d,J=9.0,1H),7.20(d,J=8.1,2H),7.13(d,J=8.1,2H),6.75(s,1H),2.38(s,3H);13C NMR(126MHz,Chloroform-d)δ157.8,148.1,145.3,144.3(q,J=38.6),140.2,138.1,135.1,130.6,130.0,129.6,129.2,128.8,128.2,125.4,123.2,122.1(q,J=265.6),121.0,119.1,106.4((q,J=2.3),21.5;19F NMR(471MHz,Chloroform-d)δ-62.3;HRMS(ESI)calculated forC24H17F3N3O3S[M+H+]:484.0937;found:484.0949。
实施例23
4-(7-甲基-1,1-二氧化苯并[e][1,4,3]恶噻嗪-3-基)-N,N-二丙基苯磺酰胺的制备:
在室温条件下,将3,4-二氯-N-甲苯磺酰基苯甲酰胺0.3mmol,添加至装有碳布作为阳极,Pt片作为阴极的25mL的三口瓶中,随后再加入0.15mmol的醋酸和溶剂(DCE/HFIP=7:3mL),充入氮气反应1-5h。待反应结束通过柱层析纯化得到77.0mg目标产物,收率为75%。该化合物的表征如下:IR:2970(w),2875(w),2227(m),1620(m),1568(w),1326(s),1167(m),998(w),823(w),735(m),600(m),585(w);1H NMR(500MHz,Chloroform-d)δ8.36(m,2H),7.95(dd,J=8.8,0.8Hz,2H),7.77(s,1H),7.51(dd,J=8.8,1.8Hz,1H),7.34(d,J=8.6Hz,1H),3.13(t,J=7.5Hz,4H),2.47(s,3H),1.54(h,J=7.2Hz,4H),0.86(t,J=7.4Hz,6H);13C NMR(126MHz,Chloroform-d)δ156.4,147.0,145.8,138.9,135.5,132.1,130.0,127.5,124.1,122.2,117.8,49.9,21.9,21.2,11.3.HRMS(ESI)calculated forC20H25N2O5S2[M+H+]:437.1199;found:437.1202。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (4)
1.一种苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物的制备方法,其特征在于:包括以下步骤:
(1)将苯磺酰胺衍生物、苯甲酸和有机溶剂在室温下搅拌过夜,通过重结晶得到N-(苯磺酰基)苯甲酰胺类化合物,其结构式为
其中,R1为H、卤素或烷基,R2为H或烷基,R3为H、卤素或烷基,R4为H、卤素、烷基或烷氧基,R5为H、卤素、烷基、烷氧基或氰基,R6为H、卤素、烷基、烷氧基、三氟甲基或氰基;
(2)将N-(苯磺酰基)苯甲酰胺类化合物加入到1,2-二氯乙烷和六氟异丙醇的混合溶剂中,再加入电解质和添加剂,在恒电流条件下氮气保护中室温搅拌1-5h,待反应结束,通过柱层析纯化,得到所述的苯并[e][1,4,3]恶噻嗪-1,1-二氧化物衍生物,结构式为其中,R1为H、卤素或烷基,R2为H或烷基,R3为H、卤素或烷基,R4为H、卤素、烷基或烷氧基,R5为H、卤素、烷基、烷氧基或氰基,R6为H、卤素、烷基、烷氧基、三氟甲基或氰基;
所述的电解质为nBu4NOAc、Me4NOAc、nBu4NBF4、Et4NBF4、nBu4NPF6中的任一种;所述的添加剂为CH3COOH或H2O。
2.根据权利要求1所述的方法,其特征在于:步骤(1)中每摩尔苯磺酰胺衍生物对应0.5~20L有机溶剂。
3.根据权利要求1所述的方法,其特征在于:步骤(2)中所用电极为碳布、碳毡、碳棒、Pt片、Ni片、Fe片中的任意两种,控制电流范围为5-20mA。
4.根据权利要求1所述的方法,其特征在于:步骤(2)中1,2-二氯乙烷和六氟异丙醇的质量比为1-10。
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