CN113801037A - 硝基芳烃和烷基或苯基硼酸一步法制备c-n偶联产物 - Google Patents
硝基芳烃和烷基或苯基硼酸一步法制备c-n偶联产物 Download PDFInfo
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- CN113801037A CN113801037A CN202110976337.6A CN202110976337A CN113801037A CN 113801037 A CN113801037 A CN 113801037A CN 202110976337 A CN202110976337 A CN 202110976337A CN 113801037 A CN113801037 A CN 113801037A
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000008878 coupling Effects 0.000 title claims abstract description 31
- 238000010168 coupling process Methods 0.000 title claims abstract description 31
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000005580 one pot reaction Methods 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000004440 column chromatography Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 5
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 5
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical group [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004809 thin layer chromatography Methods 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910003091 WCl6 Inorganic materials 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical group Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000001543 aryl boronic acids Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 34
- -1 amine compounds Chemical class 0.000 abstract description 7
- 239000004327 boric acid Substances 0.000 abstract description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003480 eluent Substances 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 230000001678 irradiating effect Effects 0.000 description 6
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWMIVCCXDVRXST-UHFFFAOYSA-N (4-benzoylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C(=O)C1=CC=CC=C1 CWMIVCCXDVRXST-UHFFFAOYSA-N 0.000 description 1
- IBRBMZRLVYKVRF-UHFFFAOYSA-N 1,2,4-trichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C=C1Cl IBRBMZRLVYKVRF-UHFFFAOYSA-N 0.000 description 1
- GMUWJDVVXLBMEZ-UHFFFAOYSA-N 1-nitro-3,5-bis(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 GMUWJDVVXLBMEZ-UHFFFAOYSA-N 0.000 description 1
- VHADYSUJZAPXOW-UHFFFAOYSA-N 1h-indol-5-ylboronic acid Chemical compound OB(O)C1=CC=C2NC=CC2=C1 VHADYSUJZAPXOW-UHFFFAOYSA-N 0.000 description 1
- OFCBNMYNAHUDGE-UHFFFAOYSA-N 2-chloro-5-nitropyrimidine Chemical compound [O-][N+](=O)C1=CN=C(Cl)N=C1 OFCBNMYNAHUDGE-UHFFFAOYSA-N 0.000 description 1
- USZINSZJSVMICC-UHFFFAOYSA-N 2-methyl-5-nitropyridine Chemical compound CC1=CC=C([N+]([O-])=O)C=N1 USZINSZJSVMICC-UHFFFAOYSA-N 0.000 description 1
- NBHKYBWIGBFSRE-UHFFFAOYSA-N 5-nitropyridine-2-carbaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)N=C1 NBHKYBWIGBFSRE-UHFFFAOYSA-N 0.000 description 1
- YZDHDHMJKCKESU-UHFFFAOYSA-N 5-nitropyridine-2-carbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)N=C1 YZDHDHMJKCKESU-UHFFFAOYSA-N 0.000 description 1
- RNWGZXAHUPFXLL-UHFFFAOYSA-N 6-nitro-3h-2-benzofuran-1-one Chemical compound [O-][N+](=O)C1=CC=C2COC(=O)C2=C1 RNWGZXAHUPFXLL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- XDRVAZAFNWDVOE-UHFFFAOYSA-N cyclohexylboronic acid Chemical compound OB(O)C1CCCCC1 XDRVAZAFNWDVOE-UHFFFAOYSA-N 0.000 description 1
- VTTDFSNKIMAQTB-UHFFFAOYSA-N cyclopentylboronic acid Chemical compound OB(O)C1CCCC1 VTTDFSNKIMAQTB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- 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
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- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
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Abstract
本发明公开了硝基芳烃和烷基或苯基硼酸一步法制备C‑N偶联产物，所述方法将硝基芳烃、烷基或苯基硼酸、还原剂、催化剂均加至极性溶剂中，然后置于反应器内，室温光照条件反应，反应过程中采用TLC薄层色谱跟踪反应进程，最终经柱层析获得偶联产物。与现有技术相比，本发明具有以下优点：(1)本发明所述方法以商品化、价低的硝基芳烃为氮源，以有机硼酸为底物，在还原剂和催化剂存在条件下一步反应合成系列新型C‑N偶联产物，为传统方法难以合成的有机胺类化合物提供了一种实用的方法；(2)所述反应是在室温条件下进行，因此反应条件温和、方法操作简单、经济高效、产率高，具有重要的应用价值。
Description
技术领域
本发明属于有机化学技术领域，涉及一种通过有机合成方法制备系列化合物的技术，具体为硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物。
背景技术
钯催化芳基卤化物的布赫瓦尔德-哈特威格胺化和铜催化的乌尔曼偶联已成为现代有机化学中最广泛使用的反应之一，且前者是药物化学中最常用的20个反应之一。近几年，随着光化学策略的出现，大大提高了C-N交叉偶联的效率和范围。虽然这些开创性的工作为进一步发展C-N偶联提供了创新的思路，但迄今为止报道的所有构筑多级胺类化合物大多使用胺,特别是苯胺,作为氮源。而胺类化合物通常经过硝基化合物的还原获得。如果将硝基芳烃作为氮源，这样将扩大C-N偶联的适用范围，绕过硝基芳烃还原为胺的步骤，同时潜在地改善偶联中官能团的相容性。虽然硝基化合物与苯基硼酸的偶联已有报道，但是还存在反应温度高(>100℃)、底物适用范围有限等问题。
发明内容
解决的技术问题：为了克服现有技术的不足，获得一种经济的C-N偶联产物合成路线，本发明提供了一种在室温条件下实现硝基芳烃和烷基或苯基硼酸经一步反应制得系列C-N偶联产物的方法。
技术方案：硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，所述方法将硝基芳烃、烷基或苯基硼酸、还原剂、催化剂均加至极性溶剂中，然后置于反应器内，室温光照条件反应，反应过程中采用TLC薄层色谱跟踪反应进程，最终经柱层析获得偶联产物；
硝基芳烃的结构式如式1所示：
苯基硼酸的结构式如式2所示，烷基硼酸的结构式如式3所示：
由苯基硼酸制得的偶联产物结构式如式4所示，由烷基硼酸制得的偶联产物结构式如式5所示：
其中，R1为-Br、-Cl、-Et、-COOMe、-CF3、-CHO或-COOMe，且R1在苯环上任一位置；X为碳原子或氮原子，且X在苯环上任一位置；R2为-H、-CH3、-OPh、-COOMe或-OCH3；R3为-iPr、-Cy、环丙基、环戊基或-nBu。
优选的，一步法反应方程式为式(1)或式(2)：
优选的，硝基芳烃、烷基或芳基硼酸、还原剂、催化剂的摩尔比为0.5:0.75-1:1-2:0.05-0.20。
优选的，还原剂为苯基硅烷、二苯基硅烷、三乙氧基硅烷、三苯基膦、三环己基膦、三甲基膦或三乙氧基膦。
优选的，催化剂为钨盐或钨氧化物。
优选的，催化剂为WCl6、WCl4、WCl5、WO3或W(CO)6。
优选的，极性溶剂为乙醚、四氢呋喃、环戊己甲醚、甲醇、乙醇、异丙醇或甲苯。
优选的，反应条件具体为：紫外线灯波长为254-500nm，反应时间为24-48小时。
由以上任一所述方法制备获得的C-N偶联产物。
优选的，所述产物的化学式为：
不同硝基底物范围
不同硼酸底物范围
有益效果：(1)本发明所述方法以商品化、价低的硝基芳烃为氮源，以有机硼酸为底物，在还原剂和催化剂存在条件下一步反应合成系列新型C-N偶联产物，为传统方法难以合成的有机胺类化合物提供了一种实用的方法；(2)所述反应是在室温条件下进行，因此反应条件温和、方法操作简单、反应温和、经济高效、产率高，具有重要的应用价值。
附图说明
图1是实施例8制得的偶联产物12液相扩散培养晶体的X-射线单晶结构图；
图2是实施例12制得的偶联产物34液相扩散培养晶体的X-射线单晶结构图；
图3是化合物3的核磁共振氢谱(400M，CDCl3，25℃)；
图4是化合物3的核磁共振碳谱(126MHz,CDCl3，25℃)；
图5是化合物5的核磁共振氢谱(400M，CDCl3，25℃)；
图6是化合物5的核磁共振碳谱(126MHz,CDCl3，25℃)；
图7是化合物7的核磁共振氢谱(400M，CDCl3，25℃)；
图8是化合物7的核磁共振碳谱(126MHz,CDCl3，25℃)；
图9是化合物10的核磁共振氢谱(400M，CDCl3，25℃)；
图10是化合物10的核磁共振碳谱(126MHz,CDCl3，25℃)；
图11是化合物12的核磁共振氢谱(400M，CDCl3，25℃)；
图12是化合物12的核磁共振碳谱(126MHz,CDCl3，25℃)；
图13是化合物21的核磁共振氢谱(400M，CDCl3，25℃)；
图14是化合物21的核磁共振碳谱(126MHz,CDCl3，25℃)；
图15是化合物23的核磁共振氢谱(400M，CDCl3，25℃)；
图16是化合物23的核磁共振碳谱(126MHz,CDCl3，25℃)；
图17是化合物30的核磁共振氢谱(400M，CDCl3，25℃)；
图18是化合物30的核磁共振碳谱(126MHz,CDCl3，25℃)；
图19是化合物37的核磁共振氢谱(400M，CDCl3，25℃)；
图20是化合物37的核磁共振碳谱(126MHz,CDCl3，25℃)。
具体实施方式
以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
实施例1
碳氮偶联产物，通式为：
具体结构可以是:
不同硝基底物范围
不同硼酸底物范围
其中，化合物3、5、7、10、12、21、23、30、37的核磁共振氢谱、碳谱结果如图3-20所示。
实施例2
偶联产物1的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 2-氯-5-硝基嘧啶、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WCl6、6mL环戊己甲醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用365nm紫外灯光照，反应24小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:5,v:v)为洗脱剂，柱层析后得纯产品1，产率90％。
实施例3
偶联产物3的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 5-硝基吡啶甲腈、0.75mmol苯硼酸、1mmol苯基硅烷、0.05mmol WO3、6mL四氢呋喃，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用410nm紫外灯光照，反应24小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:10,v:v)为洗脱剂，柱层析后得纯产品3，产率92％。
实施例4
偶联产物5的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 5-硝基吡啶甲醛、0.75mmol苯硼酸、1mmol三乙氧基硅烷、0.05mmol W(CO)6、6mL乙醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用400nm紫外灯光照，反应24小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:20,v:v)为洗脱剂，柱层析后得纯产品5，产率89％。
实施例5
偶联产物7的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 2-甲基-5-硝基吡啶、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WCl5、6mL环戊己甲醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用254nm紫外灯光照，反应24小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:15,v:v)为洗脱剂，柱层析后得纯产品7，产率82％。
实施例6
偶联产物9的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 1,2,4-三氯-5-硝基苯、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WO3、6mL环戊己甲醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用254nm紫外灯光照，反应36小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:50,v:v)为洗脱剂，柱层析后得纯产品9，产率95％。
实施例7
偶联产物11的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 4-氟-2-硝基-9H-芴、0.75mmol苯硼酸、1mmol苯基硅烷、0.05mmol WCl4、6mL环戊己甲醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用365nm紫外灯光照，反应48小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂，柱层析后得纯产品11，产率93％。
实施例8
偶联产物12的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 6-硝基异苯并呋喃-1(3H)-one、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WCl6、6mL甲苯，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用400nm紫外灯光照，反应24小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂，柱层析后得纯产品12，产率90％。该产品可通过液相扩散法培养其晶体，X-射线单晶结构如图1所示。
实施例9
偶联产物15的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 1-硝基-3,5-双(三氟甲基)苯、0.75mmol苯硼酸、1mmol三苯基膦、0.05mmol WO3、6mL异丙醇，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用254nm紫外灯光照，反应35小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂，柱层析后得纯产品15，产率88％。
实施例10
偶联产物23的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.75mmol(4-苯甲酰基苯基)硼酸、1mmol三苯基硅烷、0.05mmol WCl6、6mL环戊己甲醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用365nm紫外灯光照，反应24小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂，柱层析后得纯产品23，产率86％。
实施例11
偶联产物33的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.65mmol环戊基硼酸、1.3mmol三苯基膦、0.02mmol W(CO)6、6mL乙醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用254nm紫外灯光照，反应36小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:50,v:v)为洗脱剂，柱层析后得纯产品33，产率90％。
实施例12
偶联产物34的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.75mmol 5-吲哚硼酸、1.2mmol三苯基膦、0.04mmol WCl6、6mL乙醇，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用400nm紫外灯光照，反应48小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂，柱层析后得纯产品34，产率92％。该产品可通过液相扩散法培养其晶体，X-射线单晶结构如图2所示。
实施例13
偶联产物37的制备：在氮气氛围中，向10mL的反应管中加入0.5mmol 4-氯硝基苯、0.75mmol环己基硼酸、1.5mmol三苯基膦、0.01mmol WCl4、6mL环戊己甲醚，然后使用双排管将反应管抽真空再通入氮气，此操作重复三次后，在磁力搅拌下用400nm紫外灯光照，反应36小时。结束光照，将反应液移入烧瓶，用二氯甲烷清洗反应管，再将清洗后的溶液移入反应液烧瓶。加入4mL硅胶粉溶液于反应液烧瓶，旋干。旋干后用乙酸乙酯和石油醚(1:100,v:v)为洗脱剂，柱层析后得纯产品37，产率85％。
Claims (10)
1.硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，所述方法将硝基芳烃、烷基或苯基硼酸、还原剂、催化剂均加至极性溶剂中，然后置于反应器内，室温光照条件反应，反应过程中采用TLC薄层色谱跟踪反应进程，最终经柱层析获得偶联产物；
硝基芳烃的结构式如式1所示：
苯基硼酸的结构式如式2所示，烷基硼酸的结构式如式3所示：
由苯基硼酸制得的偶联产物结构式如式4所示，由烷基硼酸制得的偶联产物结构式如式5所示：
其中，R1为-Br、-Cl、-Et、-COOMe、-CF3、-CHO或-COOMe，且R1在苯环上任一位置；X为碳原子或氮原子，且X在苯环上任一位置；R2为-H、-CH3、-OPh、-COOMe或-OCH3；R3为-iPr、-Cy、环丙基、环戊基或-nBu。
2.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，一步法反应方程式为式(1)或式(2)：
3.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，硝基芳烃、烷基或芳基硼酸、还原剂、催化剂的摩尔比为0.5:0.75-1:1-2:0.05-0.20。
4.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，还原剂为苯基硅烷、二苯基硅烷、三乙氧基硅烷、三苯基膦、三环己基膦、三甲基膦或三乙氧基膦。
5.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，催化剂为钨盐或钨氧化物。
6.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，催化剂为WCl6、WCl4、WCl5、WO3或W(CO)6。
7.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，极性溶剂为乙醚、四氢呋喃、环戊己甲醚、甲醇、乙醇、异丙醇或甲苯。
8.根据权利要求1所述的硝基芳烃和烷基或苯基硼酸一步法制备C-N偶联产物，其特征在于，反应条件具体为：紫外线灯波长为254-500nm，反应时间为24-48小时。
9.由权利要求1-8任一所述方法制备获得的C-N偶联产物。
10.根据权利要求9所述的C-N偶联产物，其特征在于，所述产物的化学式为：
不同硝基底物范围
不同硼酸底物范围
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