CN111170914A - 硒/硫化磺酰芳胺类化合物及其硒/硫化方法 - Google Patents

硒/硫化磺酰芳胺类化合物及其硒/硫化方法 Download PDF

Info

Publication number
CN111170914A
CN111170914A CN201811332588.5A CN201811332588A CN111170914A CN 111170914 A CN111170914 A CN 111170914A CN 201811332588 A CN201811332588 A CN 201811332588A CN 111170914 A CN111170914 A CN 111170914A
Authority
CN
China
Prior art keywords
selenium
sulfonyl
compound
arylamine
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811332588.5A
Other languages
English (en)
Other versions
CN111170914B (zh
Inventor
辜玲慧
马文博
方新月
翁正云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu University
Original Assignee
Chengdu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu University filed Critical Chengdu University
Priority to CN201811332588.5A priority Critical patent/CN111170914B/zh
Publication of CN111170914A publication Critical patent/CN111170914A/zh
Application granted granted Critical
Publication of CN111170914B publication Critical patent/CN111170914B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/37—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
    • C07D317/66—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
    • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Communicable Diseases (AREA)
  • Oncology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明提供硒/硫化磺酰芳胺类化合物及其硒/硫化方法，以磺酰胺为导向基团，通过弱配位作用构建过渡金属钯催化邻位C(sp2)—H选择性硒/硫化反应，合成一系列硒/硫化磺酰芳胺类衍生物。

Description

硒/硫化磺酰芳胺类化合物及其硒/硫化方法
技术领域
本发明属于化学合成领域，特别涉及导向基团辅助的过渡金属催化C(sp2)—H硒(硫)化反应。
背景技术
近年来，有机硒(硫)类化合物被广泛地应用于有机合成，功能性材料，荧光探针等领域。另外，该类化合物表现出抗肿瘤，抗氧化，抗炎，抗菌，抗病毒等生物活性，因此在药物开发领域也具有重要意义。
利用传统合成方法，有机硒(硫)类化合物主要通过芳基卤化物、芳胺或者芳基硼酸化物与硒(硫)醚(醇)反生偶联反应得到。该方法存在底物局限，步骤繁琐，底物需要预官能团化等不足。
过渡金属催化C(sp2)—H直接硒(硫)化已经成为合成有机硒(硫)类化合物的有效策略。Ackermann,Nishihara,Kambe,Jana,Baidya,Zhang等课题组已经对导向基团辅助的过渡金属催化C(sp2)—H直接硒(硫)化反应做出了相关报道，但是他们构建的方法多以8-氨基喹啉，吡啶，嘧啶，肟，氮氧化合物等强配位作用基团作为导向基团。以磺胺为导向基团辅助的硒(硫)化反应未见文献报道。
通过弱配位导向基团辅助的硒(硫)化反应报道较少。Ackermannn报道了通过酰胺氧弱配位辅助的铜催化C—H硒(硫)化反应。随后，Baidya首次构建了钌催化的芳基羧酸衍生物邻位C—H硒(硫)化反应方法。这些方法能以高化学和位点选择性合成有机硒(硫)化合物，但是仍存在反应体系复杂，反应时间长，后处理繁琐等不足。开发操作简捷，底物适用范围广，官能团耐受性好，化学和位点选择性高的有机硒(硫)类化合物合成方法具有重要意义。
发明内容
本发明提的目的在于提供硒/硫化磺酰芳胺类化合物及其硒/硫化方法。
本发明文字中，“/”表示“或”的关系。
本发明以磺酰胺为导向基团，提供钯催化的磺酰芳胺类化合物邻位C(sp2)—H硒/硫化反应方法即得到的硒/硫化磺酰芳胺类化合物，通过弱配位作用构建过渡金属钯催化邻位C(sp2)—H选择性硒/硫化反应方法，合成一系列硒/硫化磺酰芳胺类衍生物。所述硒/硫化磺酰芳胺类化合物具有以下结构通式：
Figure BDA0001860415420000021
式中，X为Se(硒)或S(硫)；
R1为H，-CH3，-Cl，-F，-Br，-CF3，-Et，-OCH3，1,3二氧五环，1,4二氧六环，苯环，溴苯中的一种，R1为对位和/或间位取代)；
当为1,3二氧五环或1,4二氧六环时，连接方式为与苯环并环连接；当为苯环或溴苯时候，连接方式为呈萘环连接。此时结构通式依次为：
Figure BDA0001860415420000022
R2为-CH3、-Et、环丙基、-Ph(苯基)，-Bn(苄基)，
Figure BDA0001860415420000023
Figure BDA0001860415420000024
中的一种；
R3为-Ph(苯基)，
Figure BDA0001860415420000025
中的一种，其中R4为-Cl，-F，-Br，-CF3，烷基，烷氧基中的一种。
本发明提供的上述化合物的制备方法，包括以下步骤：
将磺酰芳胺类底物、二芳基二硒/硫醚混合按照摩尔比1:2混合，加入钯催化剂和氧化剂、溶剂，在氩气保护下于100～125℃反应10～15h，反应结束后进行纯化，得到硒/硫化磺酰芳胺类化合物。
进一步地，所述钯催化剂为Pd(TFA)2或Pd(OAc)2；优选为Pd(TFA)2。
进一步地，所述氧化剂为Ag2O、Ag2CO3、AgOAc、AgCF3CO2、AgNO3、Cu(OAc)2、Cu(CF3CO2)2、m-CPBA、K2O8S2、tBuOOH、PhI(OAc)2、Cu(OAc)2，优选为Cu(OAc)2。
进一步地，所述纯化方法为将反应所得反应液加水和乙酸乙酯萃取至少三次，然后合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析，得到。优选地，硅胶柱层析的流动相选用石油醚/乙酸乙酯体积比为(5-30)：1。
进一步地，所述溶剂优选为甲苯。
进一步地，所述催化剂的加入量为磺酰芳胺类底物的摩尔量的8-12％的摩尔量，优选为10％的摩尔量；所述氧化剂的加入量为磺酰芳胺类底物的1.5-2.5倍摩尔量，优选为2倍摩尔量。
进一步地，所述反应温度优选为110-125℃，进一步优选为125℃。
进一步地，所述溶剂的用量根据溶解反应物料和提供反应环境所需来确定，优选为每0.25mmol/3mL。
进一步地，所述磺酰芳胺类底物包括以下结构通式中的化合物中的一种：
Figure BDA0001860415420000031
式中，R1为H，-CH3，-Cl，-F，-Br，-CF3，-Et，-OCH3中的一种；R1为对位和/或间位取代；
R2为-CH3、-Et、环丙基、-Ph(苯基)，-Bn(苄基)，
Figure BDA0001860415420000032
Figure BDA0001860415420000033
中的一种；
所述二芳基二硒/硫醚的为以下结构通式的化合物：
R3XXR3
式中，X为Se(硒)或S(硫)；
R3为-Ph(苯基)，
Figure BDA0001860415420000034
中的一种，其中R4为-Cl，-F，-Br，-CF3，烷基，烷氧基中的一种。
本发明所述方法中，反应方程式如下：
Figure BDA0001860415420000041
式中，X为Se(硒)或S(硫)；
R1为H，-CH3，-Cl，-F，-Br，-CF3，-Et，-OCH3，1,3二氧五环，1,4二氧六环，苯环，溴苯中的一种，R1为对位和/或间位取代；当为1,3二氧五环或1,4二氧六环时，连接方式为与苯环并环连接；当为苯环或溴苯时候，连接方式为呈萘环连接。即所述化合物1可以是取代的苯环或萘环。
R2为-CH3、-Et、环丙基、-Ph(苯基)，-Bn(苄基)，
Figure BDA0001860415420000042
Figure BDA0001860415420000043
中的一种；
R3为-Ph(苯基)，
Figure BDA0001860415420000044
中的一种，其中R4为-Cl，-F，-Br，-CF3，烷基，烷氧基中的一种。
本发明提供的上述硒/硫化磺酰芳胺类化合物在制备抗菌药物中的应用。
磺胺类化合物是一类常用的抗菌药物，有机硒(硫)类化合物也具有抗炎作用。本发明利用过渡金属钯催化碳氢官能化的方法，对磺胺类化合物进行硒醚或者硫醚修饰，可得到抗菌活性更强，耐药性低的活性分子，可作为药物活性组分应用于制备抗菌药物中。
与现有技术相比，本发明具有以下有益效果：
1.本发明提供了一种操作简单，制备条件易得的磺胺药物的后阶段修饰方法。磺酰芳胺类底物结构简单易制备，衍生范围广，丰富了此类化合物的结构多样性，解决了传统反应条件苛刻，操作复杂，底物局限，步骤繁琐，底物的官能团不耐受等不足。
2.本发明提供的钯催化的磺酰芳胺类化合物邻位C(sp2)—H硒/硫化反应方法，具有优异的化学和位置选择性，在广泛的底物上提供了新的各种硒/硫化磺酰芳胺类衍生物。
3.本发明方法可应用于磺胺类药物的结构修饰，通过硒醚或者硫醚修饰可增强磺胺类的抗菌作用，得到抗菌活性更强，耐药性低的活性分子为新药开发奠定基础。
附图说明
图1-图19分为对图中对应化学结构式的化合物的氢谱图和碳谱图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。以下所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
实施例1
将0.25 mmol磺酰芳胺类底物1和2倍摩尔量的二芳基二硒醚2混合，加入磺酰芳胺类底物摩尔量的10％的摩尔量的催化剂Pd(TFA)2和2倍磺酰芳胺类底物摩尔量的氧化剂Cu(OAc)2到反应管中，在氩气保护下加入干燥甲苯3 mL，125℃反应12h得混合液体，反应结束后添加水和乙酸乙酯萃取三次，合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析(流动相：石油醚/乙酸乙酯＝30/1—5/1)分离纯化得到硒化磺酰芳胺类化合物3。
Figure BDA0001860415420000051
R1为H，-CH3，-Cl，-F，-Br，-CF3，-Et，-OCH3，1,3二氧五环，1,4二氧六环，苯环，溴苯中的一种，R1为对位和/或间位取代；
当为1,3二氧五环或1,4二氧六环时，连接方式为与苯环并环连接；当为苯环或溴苯时候，连接方式为呈萘环连接。此时结构通式依次为：
Figure BDA0001860415420000061
R2为-CH3、-Et、环丙基、-Ph(苯基)，-Bn(苄基)，
Figure BDA0001860415420000062
Figure BDA0001860415420000063
中的一种；
R3为-Ph(苯基)，
Figure BDA0001860415420000064
中的一种，其中R4为-Cl，-F，-Br，-CF3的一种。
所用反应物均为现有化合物，可于市场购买或根据现有技术合成。
按照以上方法，根据所需要合成的硒化磺酰芳胺类化合物的具体结构式，选择相应的磺酰芳胺类底物进行反应，如制备化合物3aa，结构式如下：
Figure BDA0001860415420000065
化合物3aa的制备:在反应管中加入N-苯基甲磺酰胺(1a)(42.7mg,0.25mmol)，1,2-二苯基二硒醚(2a)(156.0mg,0.5mmol)，Pd(TFA)2(8.3mg,0.025mmol),Cu(OAc)2(91mg,0.5mmol)，在氩气保护下加入干燥甲苯(3mL)，125℃反应12h得混合液体，反应结束后添加水和乙酸乙酯萃取三次，合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析(石油醚/乙酸乙酯＝30/1—5/1)分离纯化得到3aa(66mg,81％)。
同理，选择相应的反应底物可得到以下结构式的硒化磺酰芳胺类化合物，以及对应收率如下：
Figure BDA0001860415420000071
实施例2
加入磺酰芳胺类底物摩尔量的10％的摩尔量的催化剂Pd(TFA)2和2倍磺酰芳胺类底物摩尔量的氧化剂Cu(OAc)2到反应管中，在氩气保护下加入干燥甲苯3mL，125℃反应12h得混合液体，反应结束后添加水和乙酸乙酯萃取三次，合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析(流动相：石油醚/乙酸乙酯＝30/1—5/1)分离纯化得到硫化磺酰芳胺类化合物5。
Figure BDA0001860415420000081
R1为-CH3，-Cl，-CF3，-Et，-OCH3，1,3二氧五环；
R2为-CH3；
R3为-Ph(苯基)，
Figure BDA0001860415420000082
中的一种，其中R4为-Cl，甲基，甲氧基中的一种。
所用反应物均为现有化合物，可于市场购买或根据现有技术合成。
按照以上方法，根据所需要合成的硒化磺酰芳胺类化合物的具体结构式，选择相应的磺酰芳胺类底物进行反应，如制备化合物5a，结构式如下：
Figure BDA0001860415420000083
化合物5a的制备:在反应管中加入N-(对甲基苯基)甲磺酰胺(1b)(46.2mg,0.25mmol)，1,2-二对甲苯基二硫醚(4a)(123.0mg,0.5mmol)，Pd(TFA)2(8.3mg,0.025mmol),Cu(OAc)2(91mg,0.5mmol)，在氩气保护下加入干燥甲苯(3mL)，125℃反应12h得混合液体，反应结束后添加水和乙酸乙酯萃取三次，合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析(石油醚/乙酸乙酯＝30/1—5/1)分离纯化得到5a(72mg，94％)。
同理，选择相应的反应底物可得到以下结构式的硫化磺酰芳胺类化合物，以及对应收率如下：
Figure BDA0001860415420000091
产品表征
对实施例1和实施例2制备的化合物产品进行表征，表征数据如下：
Figure BDA0001860415420000092
N-(2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.77(dd,J＝7.6,1.4Hz,1H),7.72(dd,J＝8.2,1.1Hz,1H),7.46–7.43(m,1H),7.41(s,1H),7.31–7.27(m,2H),7.27–7.22(m,3H),7.15–7.13(m,1H),2.61(s,3H).13C NMR(150MHz)δ＝139.1,138.5,131.5,131.0,130.5,129.9,127.6,125.5,120.5,119.6,39.1.HR-MS(ESI)m/z calcd for:C13H12NO2S80Se-[M-H-]325.9769,found 325.9759.
Figure BDA0001860415420000093
N-(2-(phenylselanyl)phenyl)ethanesulfonamide：1H NMR(600 MHz)δ＝7.75–7.72(m,2H),7.45–7.39(m,2H),7.29–7.22(m,5H),7.12–7.09(m,1H),2.92(q,J＝7.4 Hz,2H),1.17(t,J＝7.4 Hz,3H).13C NMR(150 MHz)δ＝139.4,138.6,131.4,130.6,130.4,129.8,127.5,125.0,119.3,118.7,46.3,8.1.HR-MS(ESI)m/z calcd for:C14H14NO2S80Se-[M-H-]339.9915,found 339.9916.
Figure BDA0001860415420000101
N-(2-(phenylselanyl)phenyl)propane-2-sulfonamide：1H NMR(600 MHz)δ＝7.76(dd,J＝8.3,1.1 Hz,1H),7.72(dd,J＝7.8,1.6 Hz,1H),7.44–7.37(m,2H),7.25–7.21(m,5H),7.08–7.06(m,1H),3.21(hept,J＝6.9Hz,1H),1.25(d,J＝6.9 Hz,6H).13C NMR(150MHz)δ＝139.8,138.7,131.4,130.4,130.3,129.8,127.4,124.6,118.5,118.1,53.2,16.5.HR-MS(ESI)m/z calcd for:C15H16NO2S80Se-[M-H-]354.0081,found 354.0072.
Figure BDA0001860415420000102
N-(2-(phenylselanyl)phenyl)cyclopropanesulfonamide：1H NMR(600 MHz)δ＝7.82–7.66(m,2H),7.47–7.34(m,2H),7.32–7.17(m,5H),7.17–7.07(m,1H),2.17–2.09(m,1H),1.10–1.00(m,2H),0.79–0.67(m,2H).13C NMR(150 MHz)δ＝139.3,138.3,131.2,130.6,129.7,127.4,125.4,120.6,120.5,30.1,5.7.HR-MS(ESI)m/z calcd for:C15H14FNO2S80Se-[M-H-]351.9915,found 351.9916.
Figure BDA0001860415420000103
1-phenyl-N-(2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.72(dd,J＝7.7,1.3 Hz,1H),7.69(d,J＝8.2 Hz,1H),7.46(s,1H),7.43–7.38(m,1H),7.33(t,J＝7.3 Hz,1H),7.28(t,J＝7.5 Hz,2H),7.23–7.18(m,5H),7.12(d,J＝7.4Hz,2H),7.09(t,J＝7.6 Hz,1H),4.14(s,2H).13C NMR(150 MHz)δ＝139.5,138.7,131.5,130.8,130.6,130.5,129.7,129.1,129.0,128.1,127.4,124.9,119.4,118.1,57.8.HR-MS(ESI)m/z calcd for:C19H16NO2S80Se-[M-H-]402.0084,found402.0072.
Figure BDA0001860415420000111
N-(2-(phenylselanyl)phenyl)thiophene-2-sulfonamide：1H NMR(600 MHz)δ＝7.82–7.77(m,1H),7.74(s,1H),7.61(dd,J＝7.6,1.3 Hz,1H),7.48–7.46(m,1H),7.43–7.39(m,1H),7.36(dd,J＝3.6,1.1 Hz,1H),7.21–7.14(m,3H),7.10–7.06(m,3H),6.92(dd,J＝4.9,3.9 Hz,1H).13C NMR(150 MHz)δ＝139.2,138.6,138.3,132.9,132.7,131.1,130.6,130.3,129.7,127.4,127.2,125.8,120.9,120.5.HR-MS(ESI)m/z calcd for:C16H12NO2S2 80Se-[M-H-]393.9488,found 393.9480.
Figure BDA0001860415420000112
4-methoxy-N-(2-(phenylselanyl)phenyl)benzenesulfonamide：1H NMR(600MHz)δ＝7.72(dd,J＝8.2,0.9 Hz,1H),7.67(s,1H),7.58(dd,J＝7.6,1.3 Hz,1H),7.57–7.54(m,2H),7.38–7.34(m,1H),7.22–7.18(m,1H),7.17–7.14(m,2H),7.06–7.00(m,3H),6.78–6.74(m,2H),3.81(s,3H).13C NMR(150 MHz)δ＝163.2,139.1,138.4,131.1,130.8,130.3,130.1,129.6,129.5,127.0,125.2,120.0,119.7,114.2,55.6.HR-MS(ESI)m/z calcd for:C19H16NO3S80Se-[M-H-]418.0034,found 418.0022.
Figure BDA0001860415420000113
4-methyl-N-(2-(phenylselanyl)phenyl)benzenesulfonamide：1H NMR(600MHz)δ＝7.73–7.68(m,2H),7.57(dd,J＝7.7,1.4 Hz,1H),7.53–7.50(m,2H),7.37–7.33(m,1H),7.20(dd,J＝8.3,6.3 Hz,1H),7.16–7.12(m,2H),7.10(d,J＝8.1 Hz,2H),7.06–7.04(m,2H),7.03–7.00(m,1H),2.34(s,3H).13C NMR(150 MHz)δ＝144.0,139.0,138.4,135.8,131.1,130.7,130.2,129.7,129.6,127.4,127.0,125.2,120.0,119.7,21.7.HR-MS(ESI)m/z calcd for:C19H16NO2S80Se-[M-H-]402.0083,found 402.0072.
Figure BDA0001860415420000121
N-(4-methyl-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.63–7.58(m,2H),7.30–7.28(m,2H),7.27–7.21(m,5H),2.59(s,3H),2.34(s,3H).13C NMR(150 MHz)δ＝138.7,136.5,135.6,132.1,130.9,130.6,129.8,127.5,120.6,120.1,38.9,20.7.HR-MS(ESI)m/z calcd for:C14H14NO2S80Se-[M-H-]339.9924,found339.9916.
Figure BDA0001860415420000122
N-(4-ethyl-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.63(d,J＝8.3 Hz,1H),7.60(d,J＝2.0 Hz,1H),7.30–7.20(m,7H),2.64(q,J＝7.6Hz,2H),2.60(s,3H),1.24(t,J＝7.6 Hz,3H).13C NMR(150 MHz)δ＝141.9,137.6,136.7,130.9,130.8,130.6,129.8,127.5,120.7,120.2,39.0,28.1,15.5.HR-MS(ESI)m/z calcdfor:C15H16NO2S80Se-[M-H-]354.0080,found 354.0072.
Figure BDA0001860415420000123
N-(4-methoxy-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.62(d,J＝8.9 Hz,1H),7.37–7.33(m,2H),7.30–7.27(m,3H),7.21(d,J＝3.1Hz,1H),6.95(dd,J＝8.9,3.0 Hz,1H),6.91(s,1H),3.79(s,3H),2.63(s,3H).13C NMR(150MHz)δ＝157.4,134.5,131.6,131.3,129.9,127.9,124.0,123.6,122.2,116.2,55.8,39.0.HR-MS(ESI)m/z calcd for:C14H14NO3S80Se-[M-H-]355.9873,found 355.9865.
Figure BDA0001860415420000124
N-(2-(phenylselanyl)-4-(trifluoromethyl)phenyl)methanesulfonamide：1HNMR(600 MHz)δ＝8.05(d,J＝1.6 Hz,1H),7.82(d,J＝8.5 Hz,1H),7.68(dd,J＝8.5,1.8Hz,1H),7.61(s,1H),7.34–7.27(m,5H),2.65(s,3H).13C NMR(150 MHz)δ＝142.2,135.2(q,J＝3.1 Hz),131.4,130.1,129.4,128.5(q,J＝2.9 Hz),128.2,126.9(q,J＝33.4 Hz),123.4(q,J＝272.6 Hz),120.4,118.2,39.6.HR-MS(ESI)m/z calcd for:C14H11F3NO2S80Se-[M-H-]393.9644,found 393.9633.
Figure BDA0001860415420000131
N-(4-chloro-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.72(d,J＝2.4 Hz,1H),7.65(d,J＝8.8 Hz,1H),7.39(dd,J＝8.8,2.5 Hz,1H),7.37–7.32(m,2H),7.31–7.26(m,4H),2.61(s,3H).13C NMR(150 MHz)δ＝137.4,137.1,131.7,131.2,130.4,130.1,129.5,128.2,122.6,121.0,39.3.HR-MS(ESI)m/z calcd for:C13H11ClNO2S80Se-[M-H-]359.9378,found 359.9370.
Figure BDA0001860415420000132
N-(5-fluoro-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.81–7.76(m,1H),7.53(s,1H),7.51–7.49(m,1H),7.26–7.23(m,5H),6.88–6.84(m,1H),2.62(s,3H).13C NMR(150 MHz)δ＝164.6(d,J＝250.6 Hz),141.0(d,J＝11.5 Hz),140.2(d,J＝9.1 Hz),130.6,130.5,129.9,127.7,114.4,112.2(d,J＝21.6Hz),106.6(d,J＝27.5 Hz),39.3.HR-MS(ESI)m/z calcd for:C13H11FNO2S80Se-[M-H-]343.9672,found343.9665.
Figure BDA0001860415420000133
N-(5-chloro-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.74(d,J＝2.1 Hz,1H),7.71(d,J＝8.2 Hz,1H),7.43(s,1H),7.30–7.27(m,2H),7.27–7.25(m,3H),7.12(dd,J＝8.3,2.1 Hz,1H),2.63(s,3H).13C NMR(150 MHz)δ＝140.2,139.2,137.6,131.0,130.0,127.9,125.4,119.2,118.3,39.4.HR-MS(ESI)m/z calcd for:C13H11ClNO2S80Se-[M-H-]369.9378,found 369.9370.
Figure BDA0001860415420000141
N-(4,5-dimethoxy-2-(phenylselanyl)phenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.35(s,1H),7.24–7.21(m,6H),7.14(s,1H),3.93(s,3H),3.89(s,3H),2.56(s,3H).13C NMR(150 MHz)δ＝151.4,146.7,133.3,131.4,130.0,129.8,127.3,120.3,110.6,105.1,56.4,56.3,38.8.HR-MS(ESI)m/z calcd for:C15H16NO4S80Se-[M-H-]385.9983,found 385.9971.
Figure BDA0001860415420000142
N-(6-(phenylselanyl)benzo[d][1,3]dioxol-5-yl)methanesulfonamide：1HNMR(600 MHz)δ＝7.31(s,1H),7.29–7.27(m,2H),7.26–7.21(m,4H),7.20(s,1H),6.04(s,2H),2.59(s,3H).13C NMR(150 MHz)δ＝150.3,145.4,134.0,131.1,130.4,129.8,127.5,116.9,112.0,102.9,102.2,39.0.HR-MS(ESI)m/z calcd for:C14H12NO4S80Se-[M-H-]369.9663,found 369.9658.
Figure BDA0001860415420000143
N-(7-(phenylselanyl)-2,3-dihydrobenzo[b][1,4]dioxin-6-yl)methanesulfonamide：1H NMR(600 MHz)δ＝7.30(s,1H),7.28(s,1H),7.28–7.20(m,6H),4.31–4.29(m,2H),4.28–4.24(m,2H),2.58(s,3H).13C NMR(150 MHz)δ＝146.0,141.2,133.0,131.0,130.5,129.8,127.4,126.5,112.0,110.0,64.6,64.3,38.8.HR-MS(ESI)m/zcalcd for:C15H14NO4S80Se-[M-H-]383.9824,found 383.9814.
Figure BDA0001860415420000144
N-(1-(phenylselanyl)naphthalen-2-yl)methanesulfonamide：1H NMR(600MHz)δ＝8.51(d,J＝8.5 Hz,1H),8.08(s,1H),8.00–7.90(m,2H),7.85(d,J＝8.1 Hz,1H),7.59–7.55(m,1H),7.48(t,J＝7.6 Hz,1H),7.15–7.12(m,5H),2.65(s,3H).13C NMR(150MHz)δ＝139.1,136.1,132.5,131.4,130.9,129.8,129.7,128.7,128.6,128.5,127.2,125.8,118.3,117.0,39.7.HR-MS(ESI)m/z calcd for:C17H14NO2S80Se-[M-H-]375.9924,found 375.9916.
Figure BDA0001860415420000151
N-(6-bromo-1-(phenylselanyl)naphthalen-2-yl)methanesulfonamide：1H NMR(600 MHz)δ＝8.39(d,J＝9.1 Hz,1H),8.07(s,1H),8.03–8.00(m,2H),7.88(d,J＝9.0 Hz,1H),7.63(dd,J＝9.2,2.0 Hz,1H),7.19–7.14(m,3H),7.14–7.10(m,2H),2.68(s,3H).13CNMR(150 MHz)δ＝139.3,134.7,132.3,131.8,131.4,130.5,129.9,129.7,127.4,119.9,119.2,117.0,39.9.HR-MS(ESI)m/z calcd for:C17H13BrNO4S80Se-[M-H-]453.9034,found453.9021.
Figure BDA0001860415420000152
N-(2-((4-fluorophenyl)selanyl)-4-methylphenyl)methanesulfonamide：1HNMR(600 MHz)δ＝7.58(d,J＝8.3 Hz,1H),7.52(d,J＝1.6 Hz,1H),7.32–7.28(m,2H),7.25–7.20(m,2H),6.99–6.96(m,2H),2.71(s,3H),2.33(s,3H).13C NMR(150 MHz)δ＝162.5(d,J＝247.9 Hz),138.1,136.1,135.8,133.2(d,J＝8.1 Hz),132.0,124.8,121.2,120.3,117.1(d,J＝21.8 Hz),39.2,20.7.HR-MS(ESI)m/z calcd for:C14H13FNO2S80Se-[M-H-]357.9831,found 357.9822.
Figure BDA0001860415420000153
N-(2-((4-chlorophenyl)selanyl)-4-methylphenyl)methanesulfonamide：1HNMR(600 MHz)δ＝7.60(d,J＝8.3 Hz,1H),7.54(s,1H),7.28-7.24(m,1H),7.24–7.18(m,5H),2.73(s,3H),2.34(s,3H).13C NMR(150 MHz)δ＝138.6,136.4,135.8,133.8,132.3,132.0,129.9,128.7,120.2,120.1,39.3,20.7.HR-MS(ESI)m/z calcd for:C14H13ClNO2S80Se-[M-H-]373.9534,found 373.9526.
Figure BDA0001860415420000161
N-(2-((4-bromophenyl)selanyl)-4-methylphenyl)methanesulfonamide：1HNMR(600 MHz)δ＝7.60(d,J＝8.1 Hz,1H),7.54(s,1H),7.36(d,J＝8.3 Hz,2H),7.32–7.18(m,2H),7.13(d,J＝6.8 Hz,2H),2.73(s,3H),2.34(s,3H).13C NMR(150MHz)δ＝138.6,136.4,135.8,132.8,132.7,132.4,132.2,129.5,121.7,120.1,39.3,20.7.HR-MS(ESI)m/zcalcd for:C14H13BrNO2S80Se-[M-H-]417.9032,found 417.9021.
Figure BDA0001860415420000162
N-(4-methyl-2-((4-(trifluoromethyl)phenyl)selanyl)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.65(d,J＝8.3 Hz,1H),7.58(d,J＝1.6 Hz,1H),7.48(d,J＝8.3 Hz,2H),7.32–7.28(m,3H),7.24(s,1H),2.79(s,3H),2.35(s,3H).13CNMR(150 MHz)δ＝139.2,136.9,136.1,135.9,132.9,129.7,129.4(q,J＝32.7 Hz),126.4(q,J＝3.0 Hz),123.9(q,J＝272.0 Hz),119.9,118.5,39.5,20.6.HR-MS(ESI)m/z calcdfor:C15H13F3NO2S80Se-[M-H-]407.9799,found 407.9790.
Figure BDA0001860415420000163
N-(2-((3-chlorophenyl)selanyl)-4-methylphenyl)methanesulfonamide：1HNMR(600 MHz)δ＝7.64(d,J＝8.3 Hz,1H),7.57(d,J＝1.7 Hz,1H),7.28(dd,J＝8.3,1.7Hz,1H),7.23–7.16(m,4H),7.14–7.12(m,1H),2.74(s,3H),2.35(s,3H).13C NMR(150 MHz)δ＝139.0,136.6,135.8,135.6,132.6,132.4,130.7,129.8,128.2,127.6,119.9,119.2,39.3,20.7.HR-MS(ESI)m/z calcd for:C14H13ClNO2S80Se-[M-H-]373.9534,found373.9526.
Figure BDA0001860415420000171
N-(4-methyl-2-(p-tolylthio)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.59(d,J＝8.3 Hz,1H),7.40(d,J＝1.6 Hz,1H),7.23–7.20(m,2H),7.10–7.04(m,4H),2.67(s,3H),2.33(s,3H),2.30(s,3H).13C NMR(150 MHz)δ＝137.2,136.9,136.1,135.5,131.7,131.5,130.4,128.9,123.6,120.6,39.0,21.1,20.7.HR-MS(ESI)m/z calcd for:C15H16NO2S2 -[M-H-]306.0639,found 306.0628.
Figure BDA0001860415420000172
N-(4-methoxy-2-(p-tolylthio)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.59(d,J＝8.9 Hz,1H),7.15–7.10(m,4H),7.00(d,J＝2.8 Hz,1H),6.91(dd,J＝8.9,2.8 Hz,1H),6.86(s,1H),3.77(s,3H),2.71(s,3H),2.32(s,3H).13C NMR(150 MHz)δ＝157.5,137.9,130.6,130.5,130.4,130.0,127.7,124.2,119.9,115.6,55.7,39.1,21.1.HR-MS(ESI)m/z calcd for:C15H16NO3S2 -[M-H-]322.0587,found 322.0577.
Figure BDA0001860415420000173
N-(2-(p-tolylthio)-4-(trifluoromethyl)phenyl)methanesulfonamide：1HNMR(600 MHz)δ＝7.84(d,J＝1.7 Hz,1H),7.79(d,J＝8.6 Hz,1H),7.63(dd,J＝8.7,1.7Hz,1H),7.56(s,1H),7.15–7.06(m,4H),2.74(s,3H),2.30(s,3H).13C NMR(150 MHz)δ＝141.6,138.2,133.3(q,J＝3.0 Hz),130.7,129.9,129.6,127.9(q,J＝3.3 Hz),127.0(q,J＝33.3 Hz),124.0,123.5(q,J＝272.3 Hz),118.8,39.8,21.1.HR-MS(ESI)m/z calcdfor:C15H13F3NO2S2 -[M-H-]360.0358,found 360.0345.
Figure BDA0001860415420000181
N-(4-chloro-2-(p-tolylthio)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.62(d,J＝8.7 Hz,1H),7.49(d,J＝2.4 Hz,1H),7.34(dd,J＝8.8,2.4 Hz,1H),7.21(s,1H),7.14–7.10(m,4H),2.72(s,3H),2.32(s,3H).13C NMR(150 MHz)δ＝138.3,136.6,134.8,132.6,130.7,130.5,130.1,129.9,126.6,121.8,39.5,21.2.HR-MS(ESI)m/z calcdfor:C14H13ClNO2S2 -[M-H-]326.0093,found 326.0082.
Figure BDA0001860415420000182
N-(5-chloro-2-(p-tolylthio)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.73(d,J＝2.1 Hz,1H),7.53(d,J＝8.3 Hz,1H),7.42(s,1H),7.14(dd,J＝8.3,2.1Hz,1H),7.10(d,J＝8.2 Hz,2H),7.07–7.04(m,2H),2.72(s,3H),2.30(s,3H).13C NMR(150MHz)δ＝139.7,137.7,137.5,137.1,130.9,130.5,129.0,125.3,121.5,119.5,39.5,21.1.HR-MS(ESI)m/z calcd for:C14H13ClNO2S2 -[M-H-]326.0093,found 326.0082.
Figure BDA0001860415420000183
N-(6-(p-tolylthio)benzo[d][1,3]dioxol-5-yl)methanesulfonamide：1H NMR(600MHz)δ＝7.28(s,1H),7.24(s,1H),7.08(d,J＝8.2 Hz,2H),7.05(s,1H),7.04(d,J＝8.2 Hz,2H),6.03(s,2H),2.66(s,3H),2.30(s,3H).13C NMR(150 MHz)δ＝150.1,145.3,137.1,134.0,132.2,130.3,128.2,115.5,115.2,103.1,102.2,39.0,21.1.HR-MS(ESI)m/zcalcd for:C15H14NO4S2 -[M-H-]336.0380,found 336.0370.
Figure BDA0001860415420000191
N-(4-methyl-2-(phenylthio)phenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.62(d,J＝8.3 Hz,1H),7.45(d,J＝1.6 Hz,1H),7.27(d,J＝7.6 Hz,2H),7.26–7.25(m,2H),7.21–7.18(m,1H),7.13(t,J＝1.6 Hz,1H),7.11(d,J＝0.9 Hz,1H),2.67(s,3H),2.34(s,3H).13C NMR(150 MHz)δ＝137.5,136.6,135.5,132.1,129.6,128.1,126.9,122.3,120.4,39.1,20.7.HR-MS(ESI)m/z calcd for:C14H14NO2S2 -[M-H-]292.0482,found292.0471.
Figure BDA0001860415420000192
N-(2-((4-methoxyphenyl)thio)-4-methylphenyl)methanesulfonamide：1H NMR(600 MHz)δ＝7.55(d,J＝8.3 Hz,1H),7.32(d,J＝1.3 Hz,1H),7.21–7.15(m,4H),6.86–6.82(m,2H),3.78(s,3H),2.70(s,3H),2.31(s,3H).13C NMR(150 MHz)δ＝159.5,135.7,135.6,135.3,131.8,131.1,125.4,125.0,121.0,115.3,55.5,39.1,20.8.HR-MS(ESI)m/zcalcd for:C15H16NO3S2 -[M-H-]322.0587,found 322.0577.
Figure BDA0001860415420000193
N-(2-((4-chlorophenyl)thio)-4-methylphenyl)methanesulfonamide：1H NMR(600MHz)δ＝7.61(d,J＝8.3 Hz,1H),7.41(d,J＝1.7 Hz,1H),7.29–7.27(m,1H),7.25–7.21(m,3H),7.05–7.02(m,2H),2.79(s,3H),2.34(s,3H).13C NMR(150 MHz)δ＝137.4,136.5,135.7,134.0,132.9,132.4,129.7,129.1,121.7,120.3,39.4,20.7.HR-MS(ESI)m/zcalcd for:C14H13ClNO2S2 -[M-H-]326.0094,found 326.0082.
经检测该产品的苯环上对位或者间位含有吸电子基团或供电子基团例如：F,Cl,CF3,Me,Et,OMe等，硒化反应进行的较为顺利，得到产物产率在45-90％之间；磺酰基部分不同取代的底物能以52-88％收率的到相应硒化产物；不同取代的磺酰芳胺底物与芳基硫醚反应，以44-95％收率得到硫化产物。
得到的硒化的F,Cl,Br等产物可以发生偶联反应，进行更复杂的化合物的制备；给电子基团例如甲基，甲氧基和乙氧基等取代的磺酰芳胺硫化产率较高，最高达到95％。
产物结构均经过核磁共振氢谱，碳谱和高分辨确认得到上述方法制备的硒化产物可以达到25个，硫化产物为9个。

Claims (10)

1.硒/硫化磺酰芳胺类化合物，其特征在于，所述硒/硫化磺酰芳胺类化合物具有以下结构通式：
Figure FDA0001860415410000011
式中，X为Se或S；
R1为H，-CH3，-Cl，-F，-Br，-CF3，-Et，-OCH3，1,3二氧五环，1,4二氧六环，苯环，溴苯中的一种；R1为对位和/或间位取代；
R2为-CH3、-Et、环丙基、-Ph，-Bn，
Figure FDA0001860415410000012
中的一种；
R3为-Ph，
Figure FDA0001860415410000013
中的一种，其中R4为-Cl，-F，-Br，-CF3，烷基，烷氧基中的一种。
2.根据权利要求1所述硒/硫化磺酰芳胺类化合物，其特征在于当R1为1,3二氧五环或1,4二氧六环时，连接方式为与苯环并环连接；当为苯环或溴苯时，连接方式为呈萘环连接，结构通式依次为:
Figure FDA0001860415410000014
3.权利要求1-2中任一权利要求所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，包括以下步骤：
将磺酰芳胺类底物、二芳基二硒/硫醚混合按照摩尔比1:2混合，加入钯催化剂和氧化剂、溶剂，在氩气保护下于100～125℃反应10～15h，反应结束后进行纯化，得到硒/硫化磺酰芳胺类化合物。
4.根据权利要求4所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，所述钯催化剂为Pd(TFA)2或Pd(OAc)2；催化剂的加入量为磺酰芳胺类底物的摩尔量的8-12％的摩尔量。
5.根据权利要求4所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，所述氧化剂为Ag2O、Ag2CO3、AgOAc、AgCF3CO2、AgNO3、Cu(OAc)2、Cu(CF3CO2)2、m-CPBA、K2O8S2、tBuOOH、PhI(OAc)2、Cu(OAc)2；氧化剂的加入量为磺酰芳胺类底物的1.5-2.5倍摩尔量，进一步为2倍摩尔量。
6.根据权利要求4所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，所述反应温度为110-125℃，进一步为125℃。
7.根据权利要求4所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，所述磺酰芳胺类底物包括以下结构通式中的化合物中的一种：
Figure FDA0001860415410000021
式中，R1为H，-CH3，-Cl，-F，-Br，-CF3，-Et，-OCH3中的一种；R1为对位和/或间位取代；
R2为-CH3、-Et、环丙基、-Ph(苯基)，-Bn(苄基)，
Figure FDA0001860415410000022
Figure FDA0001860415410000023
中的一种；
所述二芳基二硒/硫醚的为以下结构通式的化合物：
R3XXR3
式中，X为Se(硒)或S(硫)；
R3为-Ph，
Figure FDA0001860415410000024
中的一种，其中R4为-Cl，-F，-Br，-CF3，烷基，烷氧基中的一种。
8.根据权利要求4所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，所述纯化方法为将反应所得反应液加水和乙酸乙酯萃取至少三次，然后合并有机层，无水Na2SO4干燥有机层，过滤，浓缩，硅胶柱层析，得到；进一步地，硅胶柱层析的流动相选用石油醚：乙酸乙酯体积比为(5-30)：1。
9.根据权利要求4所述硒/硫化磺酰芳胺类化合物的制备方法，其特征在于，所述溶剂为甲苯。
10.权利要求1-3中任一权利要求所述硒/硫化磺酰芳胺类化合物的在制备抗菌药物中的应用。
CN201811332588.5A 2018-11-09 2018-11-09 硒/硫化磺酰芳胺类化合物及其硒/硫化方法 Active CN111170914B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811332588.5A CN111170914B (zh) 2018-11-09 2018-11-09 硒/硫化磺酰芳胺类化合物及其硒/硫化方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811332588.5A CN111170914B (zh) 2018-11-09 2018-11-09 硒/硫化磺酰芳胺类化合物及其硒/硫化方法

Publications (2)

Publication Number Publication Date
CN111170914A true CN111170914A (zh) 2020-05-19
CN111170914B CN111170914B (zh) 2021-12-21

Family

ID=70623989

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811332588.5A Active CN111170914B (zh) 2018-11-09 2018-11-09 硒/硫化磺酰芳胺类化合物及其硒/硫化方法

Country Status (1)

Country Link
CN (1) CN111170914B (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954518A (en) * 1987-10-08 1990-09-04 Toyama Chemical Company, Ltd. 4H-1-benzopyran-4-one derivative or its salt, process for producing the same and pharmaceutical composition comprising the same as active ingredient
EP1072587A1 (en) * 1998-03-30 2001-01-31 Hiroyoshi Hidaka Sulfonamide derivatives and drugs containing the same as the active ingredient
CN110878038A (zh) * 2018-09-05 2020-03-13 信越化学工业株式会社 锍化合物、正型抗蚀剂组合物和抗蚀剂图案形成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4954518A (en) * 1987-10-08 1990-09-04 Toyama Chemical Company, Ltd. 4H-1-benzopyran-4-one derivative or its salt, process for producing the same and pharmaceutical composition comprising the same as active ingredient
EP1072587A1 (en) * 1998-03-30 2001-01-31 Hiroyoshi Hidaka Sulfonamide derivatives and drugs containing the same as the active ingredient
CN110878038A (zh) * 2018-09-05 2020-03-13 信越化学工业株式会社 锍化合物、正型抗蚀剂组合物和抗蚀剂图案形成方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CH. SUBRAMANYAM 等: "Synthesis and bioactivity evaluation of some novel sulfonamide derivatives", 《PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS》 *
NITYA G. KUNDU等: "Depropargylation under palladium-copper catalysis: synthesis of diaryl sulfides", 《TETRAHEDRON》 *
WENBO MA 等: "Ruthenium(II)-Catalyzed C-H Chalcogenation of Anilides", 《ADV.SYNTH.CATAL.》 *

Also Published As

Publication number Publication date
CN111170914B (zh) 2021-12-21

Similar Documents

Publication Publication Date Title
CN103880728B (zh) 一种制备二吲哚甲烷类化合物的方法
CN109096162B (zh) 一种钪催化硫醇对邻亚甲基苯醌的亲核加成反应方法
CN112442008B (zh) 一种温度调控单质硫与活泼内炔制备1,4-二噻烯和噻吩类化合物的方法及其转化反应
CN113943252A (zh) 吡唑烷基磺酰氟化合物及其制备方法
CN111170914B (zh) 硒/硫化磺酰芳胺类化合物及其硒/硫化方法
CN106380440B (zh) 一种茚酮并吡咯类衍生物及其合成方法和应用
Kido et al. Stereoselective synthesis of contiguously substituted butyrolactones based on the cyclic allylsulfonium ylide rearrangement
CN101328143B (zh) 含氟亚砜亚胺类化合物、合成方法及其应用
CN102351621B (zh) 一种n-砜基脒的制备方法
CN115572248B (zh) 一种制备β-氨基砜类化合物的方法
CN115197108B (zh) 一种γ-酮砜类化合物的制备方法
CN109456237B (zh) 炔基砜的合成方法
CN105820174A (zh) 一种多取代噻吩并吲哚衍生物的制备方法
CN106146447A (zh) 一种制备4‑氨基亚胺香豆素衍生物的方法
CN105367464A (zh) 一种高效选择性合成2-羟基苯硫醚类化合物的方法
CN110229085A (zh) 醇促进亚胺与炔烃还原偶联反应构建烯丙胺衍生物
CN102775367B (zh) 一种3，4，5-三取代噁唑-2-酮的合成方法
CN114163313A (zh) 一种钌催化芳基重氮盐与肉桂酸偶联选择性合成ez-二苯乙烯的方法
CN107382819A (zh) 一种3‑硫代吲哚类化合物的制备方法
CN110590621B (zh) 一种铜催化端炔合成1,2-双(芳基磺酰基)乙烯衍生物的方法
CN110642689B (zh) 一种3,6-二溴-2-甲基苯甲醛及其化学合成方法
CN104447521B (zh) 一种制备高选择性单氟烯烃的试剂
CN102531995A (zh) 一种3，3'-二取代-3-羟基双吲哚酮衍生物及其制备方法和应用
CN106187825A (zh) 一种n,n‑二酰胺基取代腙衍生物及合成方法
Zhou Microwave-Assisted, Metal-and Solvent-Free Synthesis of Diaryl Thioethers from Aryl Halides and Carbon Disulfide in the Presence of [DBUH]+[OAc]−

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant