CN115594602B - 一种可见光诱导的合成芳香胺的方法 - Google Patents

一种可见光诱导的合成芳香胺的方法 Download PDF

Info

Publication number
CN115594602B
CN115594602B CN202110778130.8A CN202110778130A CN115594602B CN 115594602 B CN115594602 B CN 115594602B CN 202110778130 A CN202110778130 A CN 202110778130A CN 115594602 B CN115594602 B CN 115594602B
Authority
CN
China
Prior art keywords
nmr
diboron
reaction
under
isopropanol
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.)
Active
Application number
CN202110778130.8A
Other languages
English (en)
Other versions
CN115594602A (zh
Inventor
燕红
王斌
芦昌盛
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.)
Nanjing University
Original Assignee
Nanjing 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 Nanjing University filed Critical Nanjing University
Priority to CN202110778130.8A priority Critical patent/CN115594602B/zh
Publication of CN115594602A publication Critical patent/CN115594602A/zh
Application granted granted Critical
Publication of CN115594602B publication Critical patent/CN115594602B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans 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 carbon atoms of the hetero ring
    • C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D307/85—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种芳香胺的合成方法，在光诱导条件下，使用异丙醇和联硼试剂串联还原硝基芳香化合物得到芳香胺。本发明方法反应条件温和，简单高效，成本低廉，且对环境友好，几乎对所有官能团具备兼容性，可以用来合成多官能化的药物分子，易于工业产量化。

Description

一种可见光诱导的合成芳香胺的方法
技术领域
本发明属于化学合成领域，具体涉及一种可见光诱导的合成芳香胺的方法。
背景技术
芳香胺类化合物是极其重要的合成中间体，涉及到农业、染料、高分子材料、含氮活性药物分子等领域中。胺类化合物的合成最直接的方法是将硝基还原成一级胺。在传统的合成方法中，在酸性条件下，需要使用条件过量的Zn、Fe等金属催化剂，反应后会形成金属泥，造成浪费和分离困难。目前的合成方法，主要使用均相催化还原法和非均相催化还原法。非均相催化还原反应需要添加纳米金属催化剂，并且需要H2，肼类、硅烷等试剂做为还原剂，反应条件往往需要几个大气压或者几十个大气压压力或80到300摄氏度的温度以及需要添加几倍当量的NaOH，LiOtBu，KOtBu等强碱或者盐酸类强酸等严格的条件。但是，金属纳米催化剂的合成往往需要一定的技术成本，而且合成步骤繁多，使用的耗材种类较多。其次，氢气的使用存在安全隐患，而肼类化合物具有较高的毒性。均相催化还原反应使用联硼试剂作为还原剂，但是需要使用有机强碱KOtBu类或有机催化剂吡啶类等试剂，并且需要100℃左右的温度，仍然不能达到反应体系温和的要求。此外，合成多官能团的芳香胺化合物时，很多官能团，例如烯基，炔基，醛基，酰氯等官能团对酸碱敏感或者对高温敏感，无法对硝基进行还原的同时保持这些官能团的兼容性。现有技术下，开发不添加催化剂、酸碱试剂，室温条件下具有很好的官能团兼容性的温和反应体系仍然是一大挑战。
发明内容
本发明针对现有技术不足，提供了一种芳香胺的合成方法，在光诱导催化条件下，使用异丙醇和联硼试剂串联还原硝基芳香化合物，得到芳香胺。
本发明具体技术方案如下：
一种芳香胺的合成方法，在光诱导条件下，硝基芳香化合物经还原剂还原而成，所述还原剂为异丙醇和联硼试剂。
本发明所述的硝基芳香化合物为被一个或多个硝基，以及被一个或多个H、F、Cl、Br、I、NH2、-CN、-COOH、-CHO、C1-C10烷基、C2-C10烯基、C3-C10炔基、C1-C10烷氧基、C1-C10卤代烷基、C2-C10烷硫基、C3-C10酯基、C4-C10酰烷基、C5-C10酰胺基、C6-C10酰氯基、C7-C10硼酸基、硼酸酯基中的一种或几种取代的芳香烃或者芳杂环。
所述芳香烃选自苯、联苯、萘，所述芳杂环选自呋喃、吡咯、噻吩、噻唑、咪唑、噁唑、吡喃、吡啶、嘧啶、吲哚、嘌呤、喹啉、异喹啉、哒嗪、苯并噻吩，苯并噻唑，苯并呋喃，苯并吡喃或1,2-苯并吡喃酮。。
优选的，所述光诱导条件为395-500nm波长光照，更优选波长为400nm。
本发明所述联硼试剂选自双(新戊基乙二醇)二硼、联硼酸频那醇酯、双联邻苯二酚硼酸酯、四羟基二硼中的一种或几种。优选为双(新戊基乙二醇)二硼和/或四羟基二硼。
本发明所述方法使用的反应溶剂选自二氯甲烷、二氯乙烷、乙腈、甲醇、乙醇、环己醇、二甲基亚砜、N,N-二甲基甲酰胺的一种或几种。优选为异丙醇。
本发明优选的反应条件为氮气保护下，0-50℃条件下反应1-48小时。更优选氮气保护，30℃条件下反应6-24h。
本发明所述方法反应机理路线如下：
芳基硝化物与异丙醇瞬态结合在可见光激发下，通过单电子还原为N,N-二羟基苯胺中间体，该中间体脱水得到亚硝基芳基化合物；亚硝基类化合物在联硼试剂作用下发生双硼化，不稳定的双硼化中间体脱去硼醚，形成芳基羟胺；羟胺化合物再次在联硼试剂作用下形成硼化中间体，又一次通过重排脱去硼醚化合物，形成最终目标产物芳香胺。
具体的一个示例为：
(1)添加1倍当量硝基芳香化合物，加入2到3倍当量联硼试剂，15倍当量的有机醇(优选异丙醇)试剂，在有机溶剂(优选异丙醇)中溶解；
(2)在30℃条件下，氮气氛围中，用400nm波长蓝光照射6-24小时，得到芳香胺。
进一步的，可在反应结束后，对产物进行分离纯化，如重结晶、柱层析等。
本发明优点：本发明克服了现有技术的缺陷，在提供了一种简单高效，成本低廉，环境友好条件下制备芳香胺化合物的方法。所述反应在室温常压即可完成，几乎对所有官能团具备兼容性，可以用来合成多官能化的药物分子，且易于工业产量化。
具体实施方式
以下通过实施例说明本发明的具体步骤，但不受实施例限制。在本发明中所使用的术语，除非另有说明，一般具有本领域普通技术人员通常理解的含义。
下面结合具体实例并参照数据进一步详细描述本发明。应理解，这些实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
在以下实施例中，未详细描述的各种过程和方法是本领域中公知的常规方法。
实施例1对氨基苯乙酮的制备
本实施例以对氨基苯乙酮为例，考察还原剂、溶剂、光照对反应收率的影响取一反应管，添加0.2mmol对硝基苯乙酮，0.4mmol四羟基二硼试剂，1mmol醇还原剂，0.5mL溶剂，在氮气氛围中，光照下，30℃条件下反应6h，反应结束后，旋干，用二氯甲烷/石油醚＝1/1比例的洗脱剂，硅胶柱层析分离，计算产率。
1H NMR(400MHz,Chloroform-d)δ7.79(d,J＝8.7Hz,2H),6.63(d,J＝8.7Hz,2H),4.18(br s,2H),2.49(s,3H)；13C NMR(100MHz,CDCl3)δ196.69,151.36,130.89,127.79,113.78,26.17。
(1)联硼试剂选择四羟基二硼试剂，光照波长为400nm，不同醇还原剂和溶剂的考察结果如表1所示。
表1
序号 醇还原剂 溶剂 收率
1 甲醇 二氯甲烷 11％
2 乙醇 二氯甲烷 27％
3 二苯甲醇 二氯甲烷 13％
4 环己醇 二氯甲烷 36％
5 异丙醇 二氯甲烷 82％
6 异丙醇 乙醇 80％
7 异丙醇 环己醇 87％
8 异丙醇 二甲基亚砜 89％
9 异丙醇 N,N-二甲基甲酰胺 90％
10 异丙醇 异丙醇 92％
结果表明，以异丙醇作为还原剂，以二氯甲烷、乙醇、环己醇、二甲基亚砜、N,N-二甲基甲酰胺、异丙醇为溶剂，具有较好的收率。特别是异丙醇作为还原剂和溶剂时，收率最高，达92％。
(2)光照波长为400nm，以异丙醇为还原剂和溶剂，考察不同的联硼试剂选择对收率的影响，结果如表2所示。
表2
序号 醇还原剂 联硼试剂 收率
11 异丙醇 双(新戊基乙二醇)二硼 91％
12 异丙醇 联硼酸频那醇酯 88％
13 异丙醇 双联邻苯二酚硼酸酯 65％
14 异丙醇 四羟基二硼 92％
结果显示，联硼试剂为双(新戊基乙二醇)二硼或四羟基二硼收率可达90％以上。
(3)光照波长为400nm，以四羟基二硼和异丙醇为还原剂，考察不同波长光照对收率的影响，结果如表3所示。
表3
序号 波长(nm) 收率
15 400 92％
16 420 84％
17 465 77％
18 500 38％
结果显示，400nm波长下，具有90％以上的收率。
根据上述研究结果，最终确定反应条件为：异丙醇和四羟基二硼为还原剂，在氮气氛围中，400nm光照下，30℃条件下反应，制备不同的芳香胺。
实施例2考察本发明所述方法对不同反应底物的适应性
1.的合成
取一反应管，添加0.2mmol 2-Br硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率95％。
1H NMR(500MHz,Chloroform-d)δ7.41(d,J＝8.0Hz,1H),7.10(t,J＝7.6Hz,1H),6.76(d,J＝8.0Hz,1H),6.62(t,J＝7.6Hz,1H),4.07(br s,2H)；13C NMR(125MHz,CDCl3)δ144.18,132.71,128.46,119.54,115.88,109.46；HRMS(m/z):calcd.for C6H7BrN[M+H+],171.9756；found,171.9755。
2.的合成
取一反应管，添加0.2mmol 2-甲氧基硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应20h，反应结束后，旋干，柱层析分离，得到分离产率82％。
1H NMR(400MHz,Chloroform-d)δ6.82-6.79(m,2H),6.76-6.70(m,2H),3.86(s,3H),3.78(brs,2H)；13C NMR(100MHz,CDCl3)δ147.45,136.26,121.20,118.62,115.16,110.56,55.56；HRMS(m/z):calcd.for C7H9NO[M+H+],124.0757；found,124.0756。
3.的合成
取一反应管，添加0.2mmol 2-羧基硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率89％。
1H NMR(400MHz,CDCl3)δ7.93(dd,J＝8.3,1.6Hz,1H),7.36–7.27(m,1H),6.73–6.63(m,2H),6.03(s,2H)；13C NMR(100MHz,CDCl3)δ173.64,151.25,135.25,132.27,116.94,116.61,109.69；HRMS(m/z):calcd.for C7H7NO2[M+],136.0393；found,136.0388。
4.的合成
取一反应管，添加0.2mmol 1-氟-2-4-二硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率95％。
1H NMR(400MHz,Chloroform-d)δ7.65(dd,J＝7.6,2.7Hz 1H),7.61-7.57(m,1H),7.08-7.06(m,1H),4.07(br s,2H)；19F NMR(375MHz,CDCl3)δ-125.31；13C NMR(100MHz,Chloroform-d)δ154.80(d,J＝8.7Hz),144.83,135.64(d,J＝14.6Hz),115.64(d,J＝21.4Hz),114.22(d,J＝8.2Hz),111.57(d,J＝5.9Hz)；HRMS(m/z):calcd.for C6H5FN2O2[M+H+],157.0408；found,157.0408。
5.的合成
取一反应管，添加0.2mmol对溴硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率87％。
1H NMR(400MHz,Chloroform-d)δ7.23(d,J＝8.2Hz,2H),6.56(d,J＝8.2Hz,2H),3.66(br s,2H)；13C NMR(100MHz,CDCl3)δ145.54,132.16,116.85,110.3；HRMS(m/z):calcd.for C6H7BrN[M+H+],171.9756；found,171.9755。
6.的合成
取一反应管，添加0.2mmol对碘硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率82％。
1H NMR(400MHz,Chloroform-d)δ7.40(d,J＝8.7Hz,2H),6.47(d,J＝8.7Hz,2H),3.67(brs,2H)；13C NMR(100MHz,CDCl3)δ146.18,138.05,117.42,79.52；HRMS m/z calcdfor C6H6IN[M+H+]:219.9618,Found:219.9619。
7.的合成
取一反应管，添加0.2mmol 2-硝基苯甲酸甲酯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率88％。
1H NMR(400MHz,CDCl3)δ7.85(d,J＝8.0Hz,1H),7.31–7.22(m,1H),6.72–6.59(m,2H),5.71(br s,2H),3.87(s,3H)；13C NMR(100MHz,CDCl3)δ171.51,150.57,134.24,131.37,116.82,116.44,110.92,51.66；HRMS(m/z):calcd.for C8H9NO2[M+H+],152.0706；found,152.0706。
8.的合成
取一反应管，添加0.2mmol 2-硝基苯硼酸频哪醇酯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率95％。
1H NMR(400MHz,CDCl3)δ7.61(dd,J＝7.4,1.6Hz,1H),7.22(ddd,J＝8.2,7.4,1.6Hz,1H),6.67(td,J＝7.4,0.9Hz,1H),6.60(d,J＝8.2Hz,1H),4.73(br s,2H),1.34(s,12H)；13CNMR(100MHz,CDCl3)δ153.75,136.91,136.54,132.87,117.01,114.89,83.64,25.06；HRMS(m/z):calcd.for C12H18BNO2[M+H+],220.1503；found,220.1502。
9.的合成
取一反应管，添加0.2mmol硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应24h，反应结束后，旋干，柱层析分离，得到分离产率78％。
1H NMR(400MHz,Chloroform-d)δ7.21(t,J＝7.4Hz,2H),6.81(t,J＝7.4Hz,1H),6.72(d,J＝7.4Hz,2H),3.66(s,2H)；13C NMR(100MHz,CDCl3)δ146.45,129.33,118.56,115.15；HRMS(m/z):calcd.for C6H7N[M+],93.0578；found,93.0577。
10.的合成
取一反应管，添加0.2mmol对三氟甲基硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应24h，反应结束后，旋干，柱层析分离，得到分离产率85％。
1H NMR(400MHz,Chloroform-d)δ7.39(d,J＝8.5Hz,2H),6.69(d,J＝8.5Hz,2H),3.94(br s,2H)；19F NMR(375MHz,CDCl3)δ-61.25；13C NMR(100MHz,CDCl3)δ149.40,126.69(q,J＝3Hz),124.85(q,J＝268Hz),120.15(q,J＝32Hz),114.18；HRMS(m/z):calcd.forC7H7F3N[M+H+],162.0525；found,162.0521。
11.的合成
取一反应管，添加0.2mmol对硝基苯甲醛，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应24h，反应结束后，旋干，柱层析分离，得到分离产率87％。
1H NMR(400MHz,Chloroform-d)δ9.75(s,1H),7.69(d,J＝8.4Hz,2H),6.69(d,J＝8.4Hz,2H),4.27(br s,2H)；13C NMR(100MHz,CDCl3)δ190.58,152.50,132.49,127.74,114.21；HRMS(m/z):calcd.for C7H7NO[M+],120.0444；found,120.0439。
12.的合成
取一反应管，添加0.2mmol对硝基苯甲腈，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率94％。
1H NMR(400MHz,Chloroform-d)δ7.39(d,J＝8.7Hz,2H),6.64(d,J＝8.7Hz,2H),4.21(br s,2H)；13C NMR(100MHz,CDCl3)δ150.59,133.87,120.29,114.51,100.08；HRMS(m/z):calcd.for C7H7N2[M+H+],119.0604；found,119.0601。
13.的合成
取一反应管，添加0.2mmol 3-氯-硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率77％。
1H NMR(500MHz,Chloroform-d)δ7.06(t,J＝8.0Hz,1H),6.72(d,J＝7.9Hz,1H),6.67-6.66(m,1H),6.54(dd,J＝8.0Hz,1.5Hz,1H),3.70(br s,2H)；13C NMR(125MHz,CDCl3)δ147.71,134.97,130.43,118.61,115.07,113.32；HRMS(m/z):calcd.for C6H7ClN[M+H+],128.0262；found,128.0263。
14.的合成
取一反应管，添加0.2mmol对硝基苯乙烯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应24h，反应结束后，旋干，柱层析分离，得到分离产率74％。
1H NMR(400MHz,Chloroform-d)δ7.24(d,J＝8.4Hz,2H),δ6.67-6.60(m,3H),5.57(dd,J＝17.6,0.8Hz,1H),5.06(dd,J＝10.9,0.8Hz,1H),3.69(br s,2H)；13C NMR(100MHz,CDCl3)δ146.29,136.62,128.36,127.41,115.06,110.06；HRMS(m/z):calcd.for C8H10N[M+H+],120.0808；found,120.0809。
15.的合成
取一反应管，添加0.2mmol 3-硝基苯乙炔，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应24h，反应结束后，旋干，柱层析分离，得到分离产率81％。
1H NMR(400MHz,CDCl3)δ7.10(t,J＝7.8Hz,1H),6.91-6.89(m,1H),6.82–6.81(m,1H),6.68-6.66(m,1H),3.67(br s,2H),3.01(s,1H)；13C NMR(100MHz,CDCl3)δ146.37,129.41,122.92,122.65,118.45,115.92,84.03,76.62；HRMS(m/z):calcd.for C8H7N[M+H+],118.0651；found,118.0653。
16.的合成
取一反应管，添加0.2mmol 2,6-二甲基硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率90％。
1H NMR(400MHz,Chloroform-d)δ6.97(d,J＝7.5Hz,2H),6.67(t,J＝7.5Hz,1H),3.58(s,2H),2.21(s,6H)；13C NMR(100MHz,CDCl3)δ142.82,128.35,121.80,118.10,17.74；HRMS(m/z):calcd.for C8H11N[M+H+],122.0964；found,122.0965。
17.的合成
取一反应管，添加0.2mmol 4-氯-2-三氟甲基-硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率92％。
1H NMR(400MHz,CDCl3)δ7.40(d,J＝2.4Hz,1H),7.24(dd,J＝8.7,2.4Hz,1H),6.68(d,J＝8.7Hz,1H),4.17(br s,2H)；19F NMR(375MHz,CDCl3)δ-63.24.13C NMR(100MHz,CDCl3)δ143.21(q,J＝1.4Hz),132.93,126.50(q,J＝5.5Hz),124.25(q,J＝273.7Hz),122.50,118.58,114.93(q,J＝30.6Hz)；HRMS(m/z):calcd.for C7H5ClF3N[M+H+],196.0135；found,196.0132。
18.的合成
取一反应管，添加0.2mmol 3,4,5-三氯硝基苯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应6h，反应结束后，旋干，柱层析分离，得到分离产率95％。
1H NMR(400MHz,Chloroform-d)δ6.69(s,2H),3.77(br s,2H)；13C NMR(100MHz,CDCl3)δ145.77,134.38,119.99,115.17；HRMS(m/z):calcd.for C6H4Cl3N[M+H+],195.9482；found,195.9481。
19.的合成
取一反应管，添加0.2mmol氟他胺，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率77％。
1H NMR(400MHz,Acetone-d6)δ8.38(s,1H),7.98(d,J＝2.2Hz,1H),7.71(dd,J＝8.7,2.2Hz,1H),7.07(d,J＝8.7Hz,1H),2.77(hept,J＝6.8Hz,1H),2.47(s,2H),1.42(d,J＝6.8Hz,6H)；19F NMR(376MHz,Acetone-d6)δ114.15.13C NMR(100MHz,CDCl3)δ175.40,141.35(q,J＝2.0Hz),128.73,125.91,124.50(q,J＝271.0Hz),119.07(q,J＝5.5Hz),117.85,113.84(q,J＝30Hz),36.59,19.75；HRMS(m/z):calcd.for C11H13F3N2O[M+H+],247.1037；found,247.1053。
20.的合成
取一反应管，添加0.2mmol 2-硝基-5-溴吡啶，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率87％。
1H NMR(400MHz,Chloroform-d)δ8.10(d,J＝1.9Hz,1H),7.49(dd,J＝8.7,1.9Hz,1H),6.41(d,J＝8.7Hz,1H),4.47(br s,2H)；13C NMR(100MHz,CDCl3)δ157.13,148.87,140.26,110.17,108.47；HRMS(m/z):calcd.for C5H5BrN2[M+H+],172.9714；found,172.9711。
21.的合成
取一反应管，添加0.2mmol 6-硝基香豆素，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，
在氮气氛围中，400nm光照下，30℃条件下反应20h，反应结束后，旋干，柱层析分离，得到分离产率87％。
1H NMR(400MHz,CDCl3)δ7.57(d,J＝9.5Hz,1H),7.14(d,J＝8.8Hz,1H),6.87(dd,J＝8.8,2.7Hz,1H),6.71(d,J＝2.7Hz,1H),6.37(d,J＝9.5Hz,1H),3.73(s,2H)；13C NMR(100MHz,CDCl3)δ161.41,147.47,143.29,143.21,119.80,119.48,117.71,117.06,111.77；HRMS(m/z):calcd.for C9H7NO2[M+H+],162.0549；found,162.0546。
22.的合成
取一反应管，添加0.2mmol 5-硝基吲哚，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率92％。
1H NMR(400MHz,CDCl3δ8.00(s,1H),7.19(d,J＝8.5Hz,1H),7.12(t,J＝2.9Hz,1H),6.96(d,J＝2.2Hz,1H),6.67(dd,J＝8.5,2.2Hz,1H),6.39-6.37(m,1H),3.20(br s,2H)；13CNMR(100MHz,CDCl3)δ139.60,130.82,128.90,124.84,113.09,111.64,105.70,101.67；HRMS(m/z):calcd.for C8H8N2[M+H+],133.0760；found,133.0755。
23.的合成
取一反应管，添加0.2mmol 6-硝基苯并噻唑，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率84％。
1H NMR(400MHz,CDCl3)δ8.66(s,1H),7.86(d,J＝8.7Hz,1H),7.09(d,J＝2.3Hz,1H),6.81(dd,J＝8.7,2.3Hz,1H),3.87(br s,2H)；13C NMR(100MHz,CDCl3)δ149.76,146.61,144.94,135.46,123.84,115.73,105.59；HRMS(m/z):calcd.for C7H6N2S[M+H+],151.0325；found,151.0322。
24.的合成
取一反应管，添加0.2mmol 5-硝基苯并呋喃-2-甲酸乙酯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率69％。
1H NMR(400MHz,CDCl3)δ7.38-7.36(m,2H),6.89-6.88(m,1H),6.84-6.81(m,1H),4.42(q,J＝7.02Hz,2H),3.65(br s,2H),1.41(t,J＝7.02Hz,3H)；13C NMR(100MHz,CDCl3)δ159.81,150.53,146.14,142.98,127.95,117.62,113.46,112.85,106.36,61.52,14.48；HRMS(m/z):calcd.for C11H11NO3[M+H+],206.0805；found,206.0812。
25.的合成
取一反应管，添加0.2mmol 5-硝基吲哚-1-氢-1-甲酸叔丁酯，0.4mmol四羟基二硼，0.5mL异丙醇溶剂，在氮气氛围中，400nm光照下，30℃条件下反应18h，反应结束后，旋干，柱层析分离，得到分离产率78％。
1H NMR(400MHz,CDCl3)δ7.91(d,J＝8.7Hz,1H),7.51(d,J＝3.5Hz,1H),6.84(d,J＝2.2Hz,1H),6.71(dd,J＝8.7,2.2Hz,1H),6.40(d,J＝3.5Hz,1H),3.61(s,2H),1.65(s,9H)；13CNMR(101MHz,CDCl3)δ149.90,142.03,131.74,129.36,126.40,115.81,113.75,106.84,106.10,83.33,28.34；HRMS(m/z):calcd.for C13H16N2O2[M+H+],233.1285；found,233.1271。

Claims (6)

1.一种芳香胺的合成方法，其特征在于在光诱导条件下，硝基芳香化合物经还原剂还原而成，所述还原剂为异丙醇和联硼试剂，所述硝基芳香化合物为被一个或多个硝基，以及被一个或多个H、F、Cl、Br、I、NH2、-CN、-COOH、-CHO、C1-C10烷基、C2-C10烯基、C3-C10炔基、C1-C10烷氧基、C1-C10卤代烷基、C2-C10烷硫基、C3-C10酯基、C4-C10酰烷基、C5-C10酰胺基、C6-C10酰氯基、C7-C10硼酸基、硼酸酯基中的一种或几种取代的芳香烃或者芳杂环，所述芳香烃选自苯、联苯、萘，所述芳杂环选自呋喃、吡咯、噻吩、噻唑、咪唑、噁唑、吡喃、吡啶、嘧啶、吲哚、嘌呤、喹啉、异喹啉、哒嗪、苯并噻吩，苯并噻唑，苯并呋喃，苯并吡喃或1,2-苯并吡喃酮，所述联硼试剂选自双（新戊基乙二醇）二硼、联硼酸频那醇酯、双联邻苯二酚硼酸酯、四羟基二硼中的一种或几种，所述光诱导条件为395-500nm波长光照。
2.根据权利要求1所述的合成方法，其特征在于所述波长为400nm。
3.根据权利要求1所述的合成方法，其特征在于所述联硼试剂为双（新戊基乙二醇）二硼和/或四羟基二硼。
4.根据权利要求1所述的合成方法，其特征在于反应溶剂选自二氯甲烷、二氯乙烷、乙腈、甲醇、乙醇、异丙醇、环己醇、二甲基亚砜、N,N-二甲基甲酰胺中的一种或几种。
5.根据权利要求1所述的合成方法，其特征在于反应溶剂为异丙醇。
6.根据权利要求1所述的合成方法，其特征在于反应条件为氮气保护下，0℃-50℃条件下反应1-48小时。
CN202110778130.8A 2021-07-09 2021-07-09 一种可见光诱导的合成芳香胺的方法 Active CN115594602B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110778130.8A CN115594602B (zh) 2021-07-09 2021-07-09 一种可见光诱导的合成芳香胺的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110778130.8A CN115594602B (zh) 2021-07-09 2021-07-09 一种可见光诱导的合成芳香胺的方法

Publications (2)

Publication Number Publication Date
CN115594602A CN115594602A (zh) 2023-01-13
CN115594602B true CN115594602B (zh) 2024-01-30

Family

ID=84841272

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110778130.8A Active CN115594602B (zh) 2021-07-09 2021-07-09 一种可见光诱导的合成芳香胺的方法

Country Status (1)

Country Link
CN (1) CN115594602B (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101072758A (zh) * 2004-10-12 2007-11-14 阿斯利康(瑞典)有限公司 喹唑啉衍生物
CN106800493A (zh) * 2017-01-16 2017-06-06 三峡大学 一种芳硝基还原为芳胺的方法
CN108546253A (zh) * 2018-06-23 2018-09-18 大连正邦信息咨询有限公司 多步合成2-苄基-1,5-二氢苯并[e][1,4]氧氮杂卓的方法
CN111635288A (zh) * 2020-06-03 2020-09-08 新乡市润宇新材料科技有限公司 一种利用碱土金属氢化物催化还原硝基化合物制备氨基化合物的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101072758A (zh) * 2004-10-12 2007-11-14 阿斯利康(瑞典)有限公司 喹唑啉衍生物
CN106800493A (zh) * 2017-01-16 2017-06-06 三峡大学 一种芳硝基还原为芳胺的方法
CN108546253A (zh) * 2018-06-23 2018-09-18 大连正邦信息咨询有限公司 多步合成2-苄基-1,5-二氢苯并[e][1,4]氧氮杂卓的方法
CN111635288A (zh) * 2020-06-03 2020-09-08 新乡市润宇新材料科技有限公司 一种利用碱土金属氢化物催化还原硝基化合物制备氨基化合物的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A Mild, DNA-Compatible Nitro Reduction Using B2(OH)4;Huang-Chi Du等;《Org. Lett.》;第21卷;2194−2199 *
Metal-free Reduction of Nitro Aromatics to Amines with B2(OH)4/H2O;Danyi Chen等;《Synlett》;第29卷;1765–1768 *

Also Published As

Publication number Publication date
CN115594602A (zh) 2023-01-13

Similar Documents

Publication Publication Date Title
Ishihara et al. 3, 5-Bis (perfluorodecyl) phenylboronic acid as an easily recyclable direct amide condensation catalyst
Schmidt et al. Mizoroki–Heck Reactions with 4‐Phenoldiazonium Salts
Lee et al. Nickel-catalyzed decarbonylative silylation, borylation, and amination of arylamides via a deamidative reaction pathway
Esguerra et al. Unified synthesis of 1, 2-oxy-aminoarenes via a bio-inspired phenol-amine coupling
Cheng et al. Lewis acid-catalyzed 2-arylquinazoline formation from N′-arylbenzimidamides and paraformaldehyde
Kumar et al. Microwave-assisted and Yb (OTf) 3-promoted one-pot multicomponent synthesis of substituted quinolines in ionic liquid
Chen et al. Palladium‐Catalyzed Reaction of Arylamine and Diarylacetylene: Solvent‐Controlled Construction of 2, 3‐Diarylindoles and Pentaarylpyrroles
Han et al. Synthesis of acridines and persubstituted phenols from cyclobutenones and active methylene ketones
Jie et al. Phase-Transfer-Catalyzed Intramolecular Hydroaryloxylation and Hydroamination of C≡ C Triple Bonds: An Efficient Synthesis of Benzo [b] furan and 3-Methyleneisoindoline-1-one Derivatives
Kondoh et al. Novel Methodology for the Efficient Synthesis of 3-Aryloxindoles:[1, 2]-Phospha-Brook Rearrangement–Palladium-Catalyzed Cross-Coupling Sequence
Bachon et al. Synthesis of 1, 2-disubstituted indoles from α-aminonitriles and 2-halobenzyl halides
Zhang et al. Regiospecific Synthesis of Substituted 2‐Nitrobenzaldehydes from Benzaldehydes through Palladium‐Catalyzed Chelation‐Assisted C–H Nitration
CN115594602B (zh) 一种可见光诱导的合成芳香胺的方法
Ferreira et al. Synthesis of diarylamines in the benzo [b] thiophene series bearing electron donating or withdrawing groups by Buchwald–Hartwig C–N coupling
Xie et al. Sodium persulfate-promoted site-selective synthesis of mononitroarylamines under transition-metal-free conditions
Dvorko et al. Superbase‐Catalyzed Steric‐Hindrance‐Induced Dimerization of Alkynones to Highly Functionalized Furans
CN115043770B (zh) 一种吲哚/氮杂吲哚类化合物的光诱导合成方法
Cheng et al. Ligand-free copper-catalyzed direct amidation of diaryliodonium salts using nitriles as amidation reagents
Hajare et al. The p-toluenesulfonic acid catalyzed single pot synthesis of tetracyclic 1, 2-dihydroquinolines: a metal free approach
CN110028422B (zh) 一种咪唑盐酸盐催化氨基保护的方法
Heo et al. Organocatalytic enantioselective conjugate addition–cyclization domino reactions of oN-protected aminophenyl α, β-unsaturated aldehydes
Tan et al. Mild and Efficient Cobalt-Catalyzed Cross-Coupling of Aliphatic Amides and Aryl Iodides in Water
Du et al. Copper (II)-Catalyzed C–N Coupling of Aryl Halides and N-Nucleophiles Promoted by Quebrachitol or Diethylene Glycol
Liu et al. Cyclization and Oxidation of o-Bromophenylacetamides for the Synthesis of Oxindoles and Isoindigoes
Grigg et al. Palladium catalysed tandem cyclisation–anion capture. Part 8: Cascade hydrostannylation—cyclisation–anion capture and cascade hydroboration—cyclisation–anion capture on solid phase

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