CN113527107A - 一类烷基芳胺类化合物及其制备方法 - Google Patents
一类烷基芳胺类化合物及其制备方法 Download PDFInfo
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- CN113527107A CN113527107A CN202110577819.4A CN202110577819A CN113527107A CN 113527107 A CN113527107 A CN 113527107A CN 202110577819 A CN202110577819 A CN 202110577819A CN 113527107 A CN113527107 A CN 113527107A
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- Prior art keywords
- alkyl
- compound
- ethyl acetate
- solvent
- hydrogen
- Prior art date
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- -1 Alkyl arylamine compounds Chemical class 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 183
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- 238000004440 column chromatography Methods 0.000 claims abstract description 18
- 230000002829 reductive effect Effects 0.000 claims abstract description 17
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 68
- 239000003208 petroleum Substances 0.000 claims description 34
- 125000005843 halogen group Chemical group 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 125000005842 heteroatom Chemical group 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 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
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 8
- 150000003456 sulfonamides Chemical class 0.000 claims description 8
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 8
- 125000005296 thioaryloxy group Chemical group 0.000 claims description 8
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 8
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 claims description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000005190 thiohydroxy group Chemical group 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- BUZRUIZTMOKRPB-UHFFFAOYSA-N carboxycarbamic acid Chemical compound OC(=O)NC(O)=O BUZRUIZTMOKRPB-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229940071870 hydroiodic acid Drugs 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- ZBQZBWKNGDEDOA-UHFFFAOYSA-N eosin B Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C(O)C(Br)=C1OC1=C2C=C([N+]([O-])=O)C(O)=C1Br ZBQZBWKNGDEDOA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 125000005289 uranyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 28
- 230000015572 biosynthetic process Effects 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 8
- 239000003814 drug Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 38
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- AEBJDOTVYMITIA-UHFFFAOYSA-N 1,3,5-trichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C=C(Cl)C=C1Cl AEBJDOTVYMITIA-UHFFFAOYSA-N 0.000 description 13
- 239000012230 colorless oil Substances 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一类烷基芳胺类化合物及其制备方法，所述制备方法主要包括以下步骤：将烷基类化合物、硝基类化合物、酸、光催化剂溶于溶剂中，于室温下光照反应，反应结束后，经碱中和，乙酸乙酯萃取，减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物。相比于已经被广泛研究报道的烷基芳胺类化合物，该发明涵盖的烷基芳胺类化合物不仅具有操作简单，步骤简洁，原子利用率高，化学性质稳定、成本低、易提纯等优点以外，且由于直接活化烷基，可以实现低附加值化学品向高附加值化学品的转化，这为有机合成化学和药物合成提供了便利。
Description
技术领域
本发明属于有机合成和应用领域，具体涉及一类烷基芳胺类化合物的制备方法和应用。
背景技术
在有机合成和药物化学中，利用光催化产生的自由基具有很好的反应活性和底物适用性。光催化作为一种绿色高效的合成手段，被很多工业生产和药物开发合成广泛利用，避免大量的氧化还原剂和金属试剂对环境的污染和反应体系的干扰，尤其适合多官能团的敏感分子的合成。
此外，碳氮键的有效合成在有机合成中具有重要的意义，因为碳氮键是构成天然产物、药物和功能材料中的基本结构。烷基芳胺类化合物是重要的有机合成中间体，在天然产物、药物合成中具有广泛的应用价值，在众多的药物中可以发现烷基芳胺的结构。例如，ezogabine(A)是上市销售的抗癫痫了药物有效成份；盐酸丁卡因amethocainehydrochloride(B)是一类重要的局部麻醉药物；氟比他班florbetaben 18F(C)是由PiramalImaging公司开发的一种放射性诊断试剂，于2014年2月24日获得欧盟委员会批准在欧洲上市，同年3月19日获得美国FDA批准在美国上市，用于诊断阿尔茨海默病(AlzheimerDisease)或其他认知障碍疾病；恩曲替尼entrectinib(D)是一种口服、选择性酪氨酸激酶抑制药(TRKI),靶向治疗携带原肌球蛋白受体激酶(NTRK)1/2/3或原癌基因酪氨酸蛋白激酶1(ROS1)的局部晚期或转移性实体瘤。因此合成烷基芳胺类化合物具有十分重要意义。
目前，在过去的几十年里烷基芳胺类化合物的构建得到了极大发展和提高。例如含氮化合物与卤代烷的偶联，醛酮类化合物与芳胺还原胺化，钯催化下卤代芳烃与烷基胺偶联等。但是目前这类方法构建烷基芳胺都是依附于原料预官能团化。这极大增加了合成步骤，合成成本，以及原料的浪费和对环境的污染。因此，为解决上述问题，我们开发了一种直接利用烷烃类化合物与廉价易得的硝基苯作为原料合成烷基芳胺类化合物。
发明内容
本发明的目的在于提供一类烷基芳胺类化合物的制备方法，主要包括：将烷基类化合物、硝基类化合物、酸、光催化剂溶于溶剂中，于室温下光照反应，反应结束后，经碱中和，乙酸乙酯萃取，减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物，相比于已经被广泛研究报道的烷基芳胺类化合物，该发明涵盖的烷基芳胺类化合物不仅具有操作简单，步骤简洁，原子利用率高，化学性质稳定、成本低、易提纯等优点以外，且由于直接活化烷基。可以实现低附加值化学品向高附加值化学品的转化，这为有机化学和药物合成提供了便利。
为了实现上述目的，本发明采用的技术方案为：一类烷基芳胺类化合物的制备方法，所述制备方法包括以下步骤：
(1)将烷基类化合物、硝基类化合物、酸、多聚钨酸盐溶于溶剂中，于室温下光照反应；优选地，烷基类化合物和硝基类化合物的摩尔比为(5-10):1；
(2)反应结束后，经碱中和、萃取、干燥、除去溶剂、分离，获得烷基芳胺类化合物；优选地，所述萃取方式采用乙酸乙酯萃取；优选地，所述干燥方式为通过无水硫酸镁对有机相进行干燥；优选地，采用减压蒸馏除去溶剂；优选地，经石油醚/乙酸乙酯作为淋洗溶剂柱层析分离。。
优选地，所述步骤(1)的反应条件为：惰性气体保护环境下，室温条件下搅拌反应6-24h。
优选地，所述步骤(1)中，硝基类化合物与溶剂的用量比为0.2mmol:1mL。
优选地，所述步骤(2)中，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为20-80:1；优选地，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
优选地，步骤(1)中，所述烷基类化合物为选自1～5个R取代基取代或未取代的C2至C15烷烃，或选自1～5个R取代基取代或未取代的C3至C15环烷烃，其中每个R取代基选自氢、烷基、烯基、炔基、环烷基、芳基、杂芳基、卤素、三卤甲基、羟基、烷氧基、芳氧基、硫代羟基、硫代烷氧基、硫代芳氧基、膦酸酯、磷酸酯、氧膦基、磺酰基、亚磺酰基、磺酰胺、酰胺、羰基、硫代羰基、羧基、羧基、氨基甲酸酯、氨基甲酸酯、硫代羧基、硫代羧基和氨基中的一种多种；或
所述烷基类化合物为式I或式II化合物，其中R1～R3选自氢、烷基、烯基、炔基、环烷基、芳基、杂芳基、卤素、三卤甲基、羟基、烷氧基、芳氧基、硫代羟基、硫代烷氧基、硫代芳氧基、膦酸酯、磷酸酯、氧膦基、磺酰基、亚磺酰基、磺酰胺、酰胺、羰基、硫代羰基、羧基、羧基、氨基甲酸酯、氨基甲酸酯、硫代羧基、硫代羧基和氨基中的一种多种；
其中，n为独立的选自阿拉伯数字0至15任意一个，R1，R2，R3，R4，为独立的选自氢、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种；R5，R6，R7，R8，为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种。
优选地，步骤(1)中，所述硝基类化合物的结构式为：
其中，R9，R10，R11，R12，R13为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种。
优选地，所述酸为盐酸(HCl)，硫酸(H2SO4)，硝酸(HNO3)，高氯酸(HClO4)，醋酸(AcOH)，三氟乙酸(TFA)，氢溴酸(HBr)，氢碘酸(HI)，对甲苯磺酸(TsOH)中的一种或多种，酸与硝基类化合物的摩尔比为(1-6):1。
优选地，所述溶剂选自：甲醇，乙醇，乙腈，苯腈，1,2-二氯乙烷、甲苯、氯苯、N，N二甲基甲酰胺、N，N二甲基乙酰胺、1,4-二氧六环中的一种或多种。
优选地，所述光催化剂选自：多聚钨酸盐、4CzIPN,、Eosin B、Eosin Y、Uranyl、[Ru(bpy)3]Cl2、Ir(dF(CF3)ppy)3(dtbbpy)PF6中的一种或多种；优选地，光催化剂与硝基类化合物的摩尔比为1:100。
所述烷基芳胺类化合物的结构为
其中，n为独立的选自阿拉伯数字0至15任意一个，R1，R2，R3，R4，为独立的选自氢、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种；R5，R6，R7，R8，为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种。R9，R10，R11，R12，R13为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种。
上述技术方案的反应过程可表示为：
本发明的有益效果：与现有方法相比，相比于已经被广泛研究报道的烷基芳胺类化合物，该发明涵盖的烷基芳胺类化合物不仅具有操作简单，步骤简洁，原子利用率高，化学性质稳定、成本低、易提纯等优点以外，且由于直接活化烷基。可以实现低附加值化学品向高附加值化学品的转化。这为有机合成化学和药物合成提供了便利。
附图说明
图1化合物3的1H NMR
图2化合物4的1H NMR
图3化合物5的1H NMR
图4化合物6的1H NMR
图5化合物7的1H NMR
图6化合物8的1H NMR
图7化合物9的1H NMR
图8化合物10的1H NMR
图9化合物11的1H NMR
图10化合物12的1H NMR
图11化合物13的1H NMR
图12化合物14的1H NMR
图13化合物15的1H NMR
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不局限于这些实施例。实施例中，所有反应原料和溶剂等都为安耐吉试剂产品。
实施例1：烷基芳胺类化合物(3)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂十聚钨酸盐(TBADT)(1mol％)和乙烷(10mmol)混合加入反应管中。然后加入溶剂乙腈。随后加入盐酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为30:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(20％).
1H NMR(400MHz,CDCl3):δ7.24(s,2H),3.36(q,J＝7.2Hz,3H),1.20(t,J＝7.2Hz,3H)ppm.
13C NMR(101MHz,CDCl3):δ141.71,128.51,126.40,125.47,42.36,16.04(s)ppm.
HRMS(EI):calculated for C8H9Cl3N[M+H]+:223.9801,found:223.9800.
实施例2：烷基芳胺类化合物(4)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂四咔唑间苯二腈(4CzIPN)(1mol％)和丙烷(10mmol)混合加入反应管中。然后加入溶剂甲醇。随后加入硫酸(0.6mmol)。将反应管置于450nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为80:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(62％).
Rf＝0.71(Hexane:ethyl acetate＝20:1).
1H NMR(400MHz,CDCl3):δ7.25(s,2H),4.03–3.86(m,1H),3.55(br,1H),1.17(d,J＝6.4Hz,6H)ppm.
13C NMR(101MHz,CDCl3):δ140.96,128.51,127.11,125.71,48.39,23.66(s)ppm.
HRMS(EI):calculated for C9H11Cl3N[M+H]+:237.9957,found:237.9958.
实施例3：烷基芳胺类化合物(5)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂薯红B(Eosin B)(1mol％)和正丁烷(10mmol)混合加入反应管中。然后加入溶剂苯腈。随后加入硝酸(0.6mmol)。将反应管置于450nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钾水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸镁干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(53％).
Rf＝0.71(Hexane:ethyl acetate＝20:1).
1H NMR(400MHz,CDCl3):δ7.24(s,2H),3.87–3.70(m,1H),3.44(br,1H),1.58(ddd,J＝13.3,7.5,5.8Hz,1H),1.51–1.40(m,1H),1.12(d,J＝6.4Hz,3H),0.95(t,J＝7.4Hz,3H)ppm.
13C NMR(101MHz,CDCl3):δ140.96,128.56,126.69,125.36,53.63,30.62,20.73,10.34(s)ppm.
HRMS(EI):calculated for C10H13Cl3N[M+H]+:252.0114,found:252.0114.
实施例4：烷基芳胺类化合物(6)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂硝酸铀酰(1mol％)和环戊烷(5mmol)混合加入反应管中。然后加入溶剂丙酮。随后加入高氯酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水氯化钙干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(61％).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.23(s,2H),4.34–4.09(m,1H),3.47(br,1H),1.96–1.82(m,2H),1.80–1.68(m,2H),1.70–1.53(m,2H),1.46(tdd,J＝7.4,5.7,1.8Hz,2H)ppm.
13C NMR(126MHz,CDCl3):δ141.13,128.51,126.34,125.18,58.30,33.65,23.39(s)ppm.
HRMS(EI-TOF):calculated for C11H13Cl3N[M+H]+:264.0114,found:264.0113.
实施例5：烷基芳胺类化合物(7)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂三吡啶二氯化钌([Ru(bpy)3]Cl2)(1mol％)和环己烷(5mmol)混合加入反应管中。然后加入溶剂二氯甲烷。随后加入三氟乙酸(0.6mmol)。将反应管置于450nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3二氯甲烷萃取，合并有机相。无水硫酸镁干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，正己烷/乙酸乙酯混合溶剂中正己烷和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(65％).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.23(s,2H),4.04–2.66(m,2H),1.93(dd,J＝8.5,4.0Hz,2H),1.80–1.67(m,2H),1.69–1.49(m,1H),1.33–1.24(m,2H),1.24–1.12(m,3H)ppm.
13C NMR(126MHz,CDCl3):δ140.84,128.45,126.82,125.36,55.36,34.30,25.72,25.04(s)ppm.
HRMS(ESI-TOF):calculated for C12H15Cl3N[M+H]+:278.0270,found:278.0268.
实施例6：烷基芳胺类化合物(8)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂(Ir(df(CF3)ppy)3(dtbbpy)PF6)(1mol％)和环庚烷(5mmol)混合加入反应管中。然后加入溶剂甲苯。随后加入氢溴酸(0.6mmol)。将反应管置于450nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为60:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(65％).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.24(s,2H),3.82(dt,J＝8.5,4.2Hz,1H),3.48(br,1H),2.01–1.86(m,2H),1.74–1.49(m,6H),1.48–1.35(m,4H)ppm.
13C NMR(101MHz,CDCl3):δ140.74,128.53,126.91,125.38,57.49,35.66,28.25,23.87(s)ppm.
HRMS(ESI-TOF):calculated for C13H17Cl3N[M+H]+:292.0427,found:292.0427.
实施例7：烷基芳胺类化合物(9)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂十聚钨酸钠(NaDT)(1mol％)和环辛烷(5mmol)混合加入反应管中。然后加入溶剂N,N-二甲基乙酰胺。随后加入氢碘酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为80:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(72％).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.23(s,2H),3.89(td,J＝8.5,4.1Hz,1H),3.51(br,1H),1.92–1.79(m,2H),1.67(ddd,J＝9.9,6.4,3.9Hz,2H),1.62–1.43(m,10H)ppm.
13C NMR(101MHz,CDCl3):δ140.76,128.53,126.78,125.23,56.20,32.62,27.34,25.64,23.64(s)ppm.
HRMS(EI-TOF):calculated for C14H19Cl3N[M+H]+:306.0583,found:306.0584.
实施例8：烷基芳胺类化合物(10)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂十聚钨酸盐(TBADT)(1mol％)和环十二烷(5mmol)混合加入反应管中。然后加入溶剂乙腈。随后加入盐酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(43％).
Rf＝0.70(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.23(s,1H),3.93(dd,J＝6.6,3.8Hz,1H),2.87(br,1H),1.61(d,J＝6.2Hz,2H),1.51–1.27(m,20H)ppm.
13C NMR(101MHz,CDCl3):δ141.14,128.57,126.36,124.90,53.10,30.99,24.35,23.79,23.40,23.30,21.32(s)ppm.
HRMS(EI-TOF):calculated for C18H27Cl3N[M+H]+:362.1209,found:362.1208.
实施例9：烷基芳胺类化合物(11)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂四咔唑间苯二腈(4CzIPN)(1mol％)和相应的烷烃(5mmol)混合加入反应管中。然后加入溶剂1，4-二氧六环。随后加入盐酸乙醇溶液(0.6mmol)。将反应管置于450nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为100:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(50％,dr＝1:1).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(400MHz,CDCl3):δ7.22(s,2H),7.21(s,1H),4.13(dd,J＝6.6,3.2Hz,0.77H),3.74(s,1.29H),3.37(ddd,J＝11.2,10.2,3.9Hz,1H),1.80–1.69(m,3H),1.61(dddd,J＝17.8,14.0,6.5,3.5Hz,2H),1.45–1.36(m,3H),1.32–1.24(m,2H),1.08(d,J＝6.4Hz,3H),0.97(d,J＝6.9Hz,3H),0.87(d,J＝4.6Hz,3H),0.85(d,J＝4.6Hz,2H)ppm.
13C NMR(126MHz,CDCl3):δ141.50,141.44,128.73,128.56,125.93,124.79,124.55,123.63,60.84,55.39,43.28,40.02,39.92,39.67,35.88,34.68,34.60,34.41,32.15,28.66,26.23,22.25,19.27,18.47(s)ppm.
HRMS(ESI-TOF):calculated for C14H19Cl3N[M+H]+:306.0583,found:306.0584.
实施例10：烷基芳胺类化合物(12)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂十聚钨酸盐(TBADT)(1mol％)和降砍烷(5mmol)混合加入反应管中。然后加入溶剂乙腈。随后加入盐酸乙酸乙酯溶液(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸钾水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(63％).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.23(s,2H),3.90(s,1H),3.78(dd,J＝7.7,3.1Hz,1H),2.29(br,1H),2.09–2.03(m,1H),1.78(ddd,J＝13.2,7.8,2.4Hz,1H),1.55–1.44(m,3H),1.23(dd,J＝6.4,3.7Hz,1H),1.18(ddd,J＝10.2,2.3,1.3Hz,1H),1.11(dd,J＝7.9,2.2Hz,2H)ppm.
13C NMR(126MHz,CDCl3):δ140.84,128.53,126.04,124.96,59.59,42.00,41.12,35.87,35.12,28.26,26.44(s)ppm.
HRMS(ESI-TOF):calculated for C13H15Cl3N[M+H]+:290.0270,found:290.0265.
实施例11：烷基芳胺类化合物(13)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂醋酸铀酰(1mol％)和溴代降砍烷(10mmol)混合加入反应管中。然后加入溶剂甲醇。随后加入醋酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为30:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(60％,dr>20:1).
Rf＝0.60(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.27(s,1H),3.98–3.89(dt,1H),3.74–3.66(dd,1H),3.54(br,1H),2.61(d,J＝4.6Hz,1H),2.19(d,J＝4.7Hz,1H),2.09–2.03(dt,1H),1.99(ddd,J＝14.7,7.3,2.0Hz,1H),1.95–1.90(m,1H),1.82(ddd,J＝14.1,7.7,2.4Hz,1H),1.73–1.67(m,1H),1.42(dt,J＝14.1,4.0Hz,1H)ppm.
13C NMR(126MHz,CDCl3):δ140.37,128.65,126.29,125.69,58.31,51.83,46.12,42.62,40.58,38.82,32.47(s)ppm.
HRMS(ESI-TOF):calculated for C13H14BrCl3N[M+H]+:367.9375,found:367.9366.
实施例12：烷基芳胺类化合物(14)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂十聚钨酸盐(TBADT)(1mol％)和金刚烷(5mmol)混合加入反应管中。然后加入溶剂乙腈和二氯甲烷(体积比20：1)。随后加入盐酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(45％).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.22(s,2H),3.94(dd,1H),3.31(br,1H),1.95(d,J＝15.5Hz,4H),1.90–1.83(m,4H),1.81–1.70(m,4H),1.65–1.56(m,2H)ppm.
13C NMR(126MHz,CDCl3):δ140.61,128.60,125.63,124.39,60.12,37.62,37.44,32.46,31.25,27.31,27.21(s)ppm.
HRMS(ESI-TOF):calculated for C16H19Cl3N[M+H]+:330.0583,found:330.0581.
实施例13：烷基芳胺类化合物(15)的合成
将1,3,5-三氯-2-硝基苯(0.2mmol)、光催化剂十聚钨酸盐(TBADT)(1mol％)和3-甲基戊烷(5mmol)混合加入反应管中。然后加入溶剂乙腈。随后加入盐酸(0.6mmol)。将反应管置于395nm LED之间，并在室温下搅拌(用风扇冷却反应)24小时。反应完成后，添加5mL饱和碳酸氢钠水溶液，用100mL×3乙酸乙酯萃取，合并有机相。无水硫酸钠干燥有机相。减压蒸馏除去溶剂，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
所得烷基芳胺类化合物的产品结构式为：
Physical State:colorless oil(47％,dr＝1:1).
Rf＝0.75(Hexane:ethyl acetate＝20:1).
1H NMR(500MHz,CDCl3):δ7.23(d,J＝2.2Hz,2H),3.97–3.59(m,2H),1.57–1.41(m,2H),1.21(dd,J＝21.5,7.7Hz,2H),0.95–1.05(m,4.2Hz,4H),0.94–0.85(m,4H)ppm.
13C NMR(101 MHz,CDCl3):13C NMR(126 MHz,CDCl3)δ141.24,141.01,128.59,126.22,124.82,124.77,55.49,55.14,40.40,39.67,29.73,26.53,24.87,17.91,16.16,14.91,13.60,12.05(s)ppm.
HRMS(ESI-TOF):calculated for C12H17Cl3N[M+H]+:280.0427,found:280.0429.
Claims (10)
1.一类烷基芳胺类化合物的制备方法，其特征在于，所述制备方法包括以下步骤：
(1)将烷基类化合物、硝基类化合物、酸、光催化剂溶于溶剂中，于室温下光照反应；优选地，烷基类化合物和硝基类化合物的摩尔比为(5-10):1；
(2)反应结束后，经碱中和、萃取、干燥、除去溶剂、分离，获得烷基芳胺类化合物；优选地，所述萃取方式采用乙酸乙酯萃取；优选地，所述干燥方式为通过无水硫酸镁对有机相进行干燥；优选地，采用减压蒸馏除去溶剂；优选地，经石油醚/乙酸乙酯作为淋洗溶剂柱层析分离。
2.根据权利要求1所述的一类烷基芳胺类化合物的制备方法，其特征在于：所述步骤(1)的反应条件为：惰性气体保护环境下，室温条件下搅拌反应6-24h。
3.根据权利要求1所述的一类烷基芳胺类化合物的制备方法，其特征在于：所述步骤(1)中，硝基类化合物与溶剂的用量比为0.2mmol:1mL。
4.根据权利要求1所述的一类烷基芳胺类化合物的制备方法，其特征在于：所述步骤(2)中，经柱层析分离，获得烷基芳胺类化合物衍生物；其中，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为20-80:1；优选地，石油醚/乙酸乙酯混合溶剂中石油醚和乙酸乙酯的用量体积比为50:1。
5.根据权利要求1所述的一类烷基芳胺类化合物的制备方法，其特征在于：步骤(1)中，所述烷基类化合物为选自1～5个R取代基取代或未取代的C2至C15烷烃，或选自1～5个R取代基取代或未取代的C3至C15环烷烃，其中每个R取代基选自氢、烷基、烯基、炔基、环烷基、芳基、杂芳基、卤素、三卤甲基、羟基、烷氧基、芳氧基、硫代羟基、硫代烷氧基、硫代芳氧基、膦酸酯、磷酸酯、氧膦基、磺酰基、亚磺酰基、磺酰胺、酰胺、羰基、硫代羰基、羧基、羧基、氨基甲酸酯、氨基甲酸酯、硫代羧基、硫代羧基和氨基中的一种多种；或所述烷基类化合物为式I或式II化合物，其中R1～R3选自氢、烷基、烯基、炔基、环烷基、芳基、杂芳基、卤素、三卤甲基、羟基、烷氧基、芳氧基、硫代羟基、硫代烷氧基、硫代芳氧基、膦酸酯、磷酸酯、氧膦基、磺酰基、亚磺酰基、磺酰胺、酰胺、羰基、硫代羰基、羧基、羧基、氨基甲酸酯、氨基甲酸酯、硫代羧基、氨基中的一种多种；
其中，n为独立的选自阿拉伯数字0至15任意一个，R1，R2，R3，R4，为独立的选自氢、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种；R5，R6，R7，R8，为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种。
6.根据权利要求1所述的一类烷基芳胺类化合物的制备方法，其特征在于：步骤(1)中，所述硝基类化合物的结构式为
其中，R9，R10，R11，R12，R13为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种。
7.根据权利要求1所述烷基芳胺类化合物的制备方法制备方法，其特征在于：所述酸为盐酸(HCl)，硫酸(H2SO4)，硝酸(HNO3)，高氯酸(HClO4)，醋酸(AcOH)，三氟乙酸(TFA)，氢溴酸(HBr)，氢碘酸(HI)，对甲苯磺酸(TsOH)中的一种或多种；优选地，酸与硝基类化合物的摩尔比为(1-6):1。
8.根据权利要求1所述烷基芳胺类化合物的制备方法，其特征在于：所述溶剂选自：甲醇，乙醇，乙腈，苯腈，1,2-二氯乙烷、甲苯、氯苯、N，N二甲基甲酰胺、N，N二甲基乙酰胺、1,4-二氧六环中的一种或多种。
9.根据权利要求1所述烷基芳胺类化合物的制备方法，其特征在于：所述光催化剂选自：多聚钨酸盐、4CzIPN,、Eosin B、Eosin Y、Uranyl、[Ru(bpy)3]Cl2、Ir(dF(CF3)ppy)3(dtbbpy)PF6中的一种或多种；优选地，光催化剂与硝基类化合物的摩尔比为1:100。
10.一种采用权利要求1-9任意一项所述的方法制备的烷基芳胺类化合物，其特征在于：所述烷基芳胺类化合物的结构为
R9，R10，R11，R12，R13为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种，R14选自1～5个R取代基取代或未取代的C2至C15烷烃，或选自1～5个R取代基取代或未取代的C3至C15环烷烃，其中每个R取代基选自氢、烷基、烯基、炔基、环烷基、芳基、杂芳基、卤素、三卤甲基、羟基、烷氧基、芳氧基、硫代羟基、硫代烷氧基、硫代芳氧基、膦酸酯、磷酸酯、氧膦基、磺酰基、亚磺酰基、磺酰胺、酰胺、羰基、硫代羰基、羧基、羧基、氨基甲酸酯、氨基甲酸酯、硫代羧基、硫代羧基和氨基中的一种多种；或所述烷基芳胺类化合物的结构为
其中R1～R3选自氢、烷基、烯基、炔基、环烷基、芳基、杂芳基、卤素、三卤甲基、羟基、烷氧基、芳氧基、硫代羟基、硫代烷氧基、硫代芳氧基、膦酸酯、磷酸酯、氧膦基、磺酰基、亚磺酰基、磺酰胺、酰胺、羰基、硫代羰基、羧基、羧基、氨基甲酸酯、氨基甲酸酯、硫代羧基、硫代羧基和氨基中的一种多种，R9，R10，R11，R12，R13为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种；或
烷基芳胺类化合物的结构为
其中，n为独立的选自阿拉伯数字0至15任意一个，R1，R2，R3，R4，为独立的选自氢、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种；R5，R6，R7，R8，为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种；R9，R10，R11，R12，R13为独立的选自氢、卤原子(-F、-Cl、-Br、-I)、-NO2、-OCH3、-CN、-CF3、-CH3、-CH2CH3、-tBu、-OTs、-N3、-SPh、C1至C15的烷基、C1至C15的含杂原子或卤原子(N,O,F,Cl,Br,I,S,P)的烷基中的任意一种或多种。
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