CN113845427A - 芳基醇、芳基酮、芳基羧酸化合物及其合成方法和应用 - Google Patents
芳基醇、芳基酮、芳基羧酸化合物及其合成方法和应用 Download PDFInfo
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- CN113845427A CN113845427A CN202111044426.3A CN202111044426A CN113845427A CN 113845427 A CN113845427 A CN 113845427A CN 202111044426 A CN202111044426 A CN 202111044426A CN 113845427 A CN113845427 A CN 113845427A
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- phenyl
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- -1 Aryl alcohol Chemical compound 0.000 title claims abstract description 147
- 238000001308 synthesis method Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 197
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 128
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 117
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 97
- 239000001301 oxygen Substances 0.000 claims abstract description 97
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 23
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000005284 excitation Effects 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 177
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 88
- COQLPRJCUIATTQ-UHFFFAOYSA-N Uranyl acetate Chemical compound O.O.O=[U]=O.CC(O)=O.CC(O)=O COQLPRJCUIATTQ-UHFFFAOYSA-N 0.000 claims description 87
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 62
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 30
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000001555 benzenes Chemical group 0.000 claims description 9
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 229910002007 uranyl nitrate Inorganic materials 0.000 claims description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000384 uranyl sulfate Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229940013688 formic acid Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960000443 hydrochloric acid Drugs 0.000 claims 1
- 238000005286 illumination Methods 0.000 claims 1
- 229960004319 trichloroacetic acid Drugs 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 3
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- 239000012530 fluid Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
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- 239000000758 substrate Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 168
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 82
- 238000003756 stirring Methods 0.000 description 79
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- MOZHUOIQYVYEPN-UHFFFAOYSA-N 1-bromo-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(Br)C=C1 MOZHUOIQYVYEPN-UHFFFAOYSA-N 0.000 description 4
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- FHBSIIZALGOVLM-UHFFFAOYSA-N 1-chloro-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(Cl)C=C1 FHBSIIZALGOVLM-UHFFFAOYSA-N 0.000 description 3
- KWSHGRJUSUJPQD-UHFFFAOYSA-N 1-phenyl-4-propan-2-ylbenzene Chemical compound C1=CC(C(C)C)=CC=C1C1=CC=CC=C1 KWSHGRJUSUJPQD-UHFFFAOYSA-N 0.000 description 3
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- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 3
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- 230000005611 electricity Effects 0.000 description 1
- YWKVMGDEOUPQGN-UHFFFAOYSA-N ethyl 2-[4-[2-(3-hydroxy-1-azabicyclo[2.2.2]octan-3-yl)ethynyl]phenyl]acetate Chemical compound C1=CC(CC(=O)OCC)=CC=C1C#CC1(O)C(CC2)CCN2C1 YWKVMGDEOUPQGN-UHFFFAOYSA-N 0.000 description 1
- ZPUKPAPWEWUPTC-UHFFFAOYSA-N ethyl 4-ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(CC)C=C1 ZPUKPAPWEWUPTC-UHFFFAOYSA-N 0.000 description 1
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 1
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- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- RWWYLEGWBNMMLJ-YSOARWBDSA-N remdesivir Chemical compound NC1=NC=NN2C1=CC=C2[C@]1([C@@H]([C@@H]([C@H](O1)CO[P@](=O)(OC1=CC=CC=C1)N[C@H](C(=O)OCC(CC)CC)C)O)O)C#N RWWYLEGWBNMMLJ-YSOARWBDSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/19—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种式(4)芳基醇化合物、式(5)芳基酮化合物、式(6)芳基羧酸化合物的合成方法,分别以烷基苯(1)、烷基苯(2)、烷基苯(3)为反应原料,在氧气氛围中,在可见光激发光催化剂催化作用下,在有机溶剂中,反应合成得到相应芳基化合物。本发明合成方法原料廉价易得,反应操作简单,反应条件温和,反应收率较高,底物官能团兼容性好。本发明可以实现精细化工品的合成;还可以通过流体反应,实现基础化工品芳基醇化合物(4)、芳基酮化合物(5)和芳基羧酸化合物(6)的放大。
Description
技术领域
本发明属于有机化合物工艺应用技术领域,涉及芳基醇、芳基酮、芳基羧酸化合物及其合成方法和应用。
背景技术
芳基醇、芳基酮、芳基羧酸是三类非常重要的化合物。作为基础化工原料,它们大量用于香料、食品添加剂、化妆品等,且用于合成医药、农药、材料等;另外本身可以用于增塑剂、防腐剂、药物、农药等。因此,利用简单、廉价、商业可大宗量获得的原料构建芳基醇、芳基酮、芳基羧酸化合物显得尤为重要。
含芳基醇、酮、羧酸化合物药物以及农药分子
芳基醇、芳基酮、芳基羧酸化合物的传统合成中需要用到当量有机或者无机氧化剂,如高锰酸钾、三氧化铬、过氧化叔丁醇、间氯过氧化苯甲酸、过氧化氢等,兼容性差、污染大;在绿色环保原子经济性等概念驱动下,化学工作者随后发展了一系列其它氧化策略,如利用氧气等来充当氧化剂,另外还尝试利用光、电等新型手段。虽然取得了一系列的进展,但是始终没有解决一些问题:如常温常压下苄位逐级氧化分别得到芳基醇、酮、羧酸化合物;温和条件下强吸电子底物氧化。
因此,寻找一种更加普适性,更加绿色高效的氧化策略显得尤其重要。
发明内容
为了解决现有技术存在的不足,本发明的目的是提供一种芳基醇化合物(4)、芳基酮化合物(5)、芳基羧酸化合物(6)的合成方法。本发明为实现大量基础化工品以及一些医药的合成提供了一条操作简单、高效、绿色的合成方法,同时也为含苄位药物、天然产物、活性分子等的修饰提供了一个策略。
本发明提供了一种芳基醇化合物的合成方法,以烷基苯(1)为反应原料,在氧气氛围中,在可见光激发光催化剂催化作用下,在溶剂中,反应合成得到芳基醇化合物(4),所述反应过程如反应式(a)所示:
其中,Ar1选自苯环、取代苯环;
R1选自烷基、环状烷基;
R2选自烷基、环状烷基。
优选地,
Ar1选自苯基、硝基取代的苯基、氰基取代的苯基、酰基取代的苯基、羧酸乙酯基取代的苯基、羧基取代的苯基、卤素取代的苯基、烷氧基取代的苯基、苯并环己基酮基、联苯;
R1选自C1-C10烷基、C3-C10环状烷基;
R2选自C1-C10烷基、C3-C10环状烷基。
进一步优选地,
Ar1选自对硝基苯基、对氰基苯基、间氰基苯基、对乙酰基苯基、对羧酸乙酯基苯基、对羧基苯基、间溴苯基、间氯苯基、邻氯苯基、3,5-二氯苯基、3,4-二氯苯基、苯基、间甲氧基苯基、苯并环己基酮基、对溴苯基、对氯苯基、联苯;
R1、R2分别选自甲基、环己基。
Ar1、R1、R2可以是但是不仅仅局限于如上取代基。
本发明中,利用烷基苯(1)为反应原料,在氧气氛围中,可见光激发光催化剂催化作用下,在溶剂中,反应合成得到芳基醇化合物(4)。
本发明芳基醇化合物(4)合成中,所述氧气压力为1个大气压。
本发明芳基醇化合物(4)合成中,所述溶剂为甲醇、丙酮、乙腈、氯仿、二氯甲烷之任意一种或者任意组合;优选地,所述溶剂为甲醇。
本发明芳基醇化合物(4)合成中,所述溶剂的用量为1-1.2mL;优选地,为1mL。
本发明芳基醇化合物(4)合成中,所述反应的温度为0-50℃;优选地,室温25℃下进行。
本发明芳基醇化合物(4)合成中,所述光催化剂为醋酸铀酰、硝酸铀酰、醋酸氧铀锌、硫酸氧铀中任意一种;优选地,所述光催化剂是醋酸铀酰。
本发明芳基醇化合物(4)合成中,所述光催化剂的摩尔用量为烷基苯(1)的2mol%。
本发明芳基醇化合物(4)合成中,所述光为温和的可见光,光源可采用23W紧凑型节能灯、1-20W蓝色LED灯(460nm)、1-20W蓝色LED灯(430nm)中的一种或多种;优选地,所述光源为3个同时使用的3W蓝色LED灯(460nm)。
本发明芳基醇化合物(4)合成中,所述反应的时间为1-96小时;优选地,是30小时。
本发明合成反应包括以下步骤:在反应容器中加入式(1)所示的原料烷基苯、光催化剂、溶剂,抽空换氧在可见光照射下,在室温下搅拌反应得到式(4)所示的芳基醇化合物。
在一个合成芳基醇化合物(4)的具体实例中,本发明合成反应是在反应瓶A中,加入烷基苯(Xmmol),光催化剂醋酸铀酰(Ymmol),溶剂(ZmL),使用水泵抽取体系内的空气置换为氧气,重复多次,在可见光照射下室温搅拌30小时;反应完毕后,直接加硅胶旋干,经柱层析分离得到芳基醇化合物(4)。
本发明还提供了一种芳基酮化合物的合成方法,以烷基苯(2)为反应原料,在氧气氛围中,在可见光激发光催化剂催化作用下,在溶剂中,反应合成得到芳基酮化合物(5),所述反应过程如反应式(b)所示:
其中,Ar2选自苯环、取代苯环、吡啶环;
R3选自烷基、取代烷基、芳基。
优选地,Ar2选自苯基、硝基苯基、羧酸乙酯基苯基、卤素取代的苯基、对(环丙基亚甲基氧)苯基、吡啶;
R3选自C1-C10烷基、卤素取代的C1-C10烷基、丁酸酯乙基、氰基取代的C1-C10烷基、乙酸酯取代的C1-C10烷基、苯基。
进一步优选地,Ar2选自对硝基苯基、邻硝基苯基、对羧酸乙酯基苯基、对溴苯基、间溴苯基、邻溴苯基、2-溴-4-氯苯基、对氯苯基、苯基、对(环丙基亚甲基氧)苯基、吡啶;
R3选自甲基、正丙基、溴甲基、溴乙基、异丁酸酯乙基、氰基乙基、乙酸酯乙基、苯基。
Ar2、R3可以是但是不仅仅局限于如上取代基。
本发明中,利用烷基苯(2)为反应原料,在氧气氛围中,可见光激发光催化剂催化作用下,在溶剂中,反应合成得到芳基酮化合物(5)。
本发明芳基酮化合物(5)合成中,所述氧气压力为1个大气压。
本发明芳基酮化合物(5)合成中,所述溶剂为丙酮、乙腈、氯仿、二氯甲烷之任意一种或者任意组合。优选地,所述溶剂为丙酮。
本发明芳基酮化合物(5)合成中,所述溶剂的用量为1-1.2mL;优选地,为1mL。
本发明芳基酮化合物(5)合成中,所述反应的温度为0-50℃;优选地,室温25℃下进行。
本发明芳基酮化合物(5)合成中,所述光催化剂为醋酸铀酰、硝酸铀酰、醋酸氧铀锌、硫酸氧铀中任意一种;优选地,所述光催化剂是醋酸铀酰。
本发明芳基酮化合物(5)合成中,所述光催化剂的摩尔用量为烷基苯(2)的2mol%。
本发明芳基酮化合物(5)合成中,所述光为温和的可见光,光源可采用23W紧凑型节能灯、1-20W蓝色LED灯(460nm)、1-20W蓝色LED灯(430nm)中的一种或多种;优选地,所述光源为3个同时使用的2W蓝色LED灯(460nm)。
本发明芳基酮化合物(5)合成中,所述反应时间为1-96小时;优选地,是24小时。
本发明合成反应包括以下步骤:在反应容器中加入式(2)所示的原料烷基苯、光催化剂、溶剂,抽空换氧在可见光照射下,在室温下搅拌反应得到式(5)所示的芳基酮化合物。
在一个合成芳基酮化合物(5)的具体实例中,本发明合成反应是在反应瓶A中,加入烷基苯(Xmmol),光催化剂醋酸铀酰(Ymmol),溶剂(ZmL),使用水泵抽取体系内的空气置换为氧气,重复多次,在可见光照射下室温搅拌24小时;反应完毕后,直接加硅胶旋干,经柱层析分离得到芳基酮化合物(5)。
本发明还提供了一种芳基羧酸化合物的合成方法,以烷基苯(3)为反应原料,在氧气氛围中,在可见光激发光催化剂催化作用下,在溶剂中,以添加剂为辅助,反应合成得到芳基羧酸化合物(6),所述反应过程如反应式(c)所示:
其中,Ar3选自苯环、取代苯环、苯并噁唑环。
优选地,
Ar3选自硝基苯基、氰基苯基、三氟甲基苯基、乙酰基苯基、羧酸乙酯基苯基、卤素取代的苯基、苯基、联苯、(环丁基亚甲基氧)苯基、(环丙基亚甲基氧)苯基、(环氧乙烷亚甲基氧)苯基、(3,5-二氯苯基)苯并噁唑基。
进一步优选地,
Ar3选自对硝基苯基、间硝基苯基、对氰基苯基、间氰基苯基、邻氰基苯基、对三氟甲基苯基、对乙酰基苯基、对羧酸乙酯基苯基、对氯苯基、苯基、联苯、2-氯-4-氟苯基、对(环丁基亚甲基氧)苯基、对(环丙基亚甲基氧)苯基、对(环氧乙烷亚甲基氧)苯基、邻(对三氟甲基苯基)苯基(新那利平衍生物)、邻(3,5-二氯苯基)苯并噁唑基。Ar3可以是但是不仅仅局限于如上取代基。
本发明中,利用烷基苯(3)为反应原料,在氧气氛围中,可见光激发光催化剂催化作用下,有添加剂(质子酸)辅助,反应合成得到芳基羧酸化合物(6)。
本发明芳基羧酸化合物(6)合成中,所述氧气压力为1个大气压。
本发明芳基羧酸化合物(6)合成中,所述溶剂为丙酮、乙腈、氯仿、二氯甲烷、叔丁醇之任意一种或者任意组合;优选地,所述溶剂为丙酮。
本发明芳基羧酸化合物(6)合成中,所述有机溶剂的用量为1-1.2mL;优选地,为1mL。
本发明芳基羧酸化合物(6)合成中,所述反应的温度为0-50℃;优选地,室温25℃下进行。
本发明芳基羧酸化合物(6)合成中,所述光催化剂为醋酸铀酰、硝酸铀酰、醋酸氧铀锌、硫酸氧铀中任意一种;优选地,所述光催化剂是醋酸铀酰。
本发明芳基羧酸化合物(6)合成中,所述光催化剂的摩尔用量为烷基苯(3)的2mol%。
本发明芳基羧酸化合物(6)合成中,所述添加剂为质子酸,选自醋酸、甲酸、甲磺酸、三氟乙酸、三氯乙酸、氢溴酸、三氟甲磺酸、磷酸、三氯化铁、氯化锌、三氟化硼乙醚、盐酸、硫酸的一种或者多种;优选地,所述添加剂是盐酸。
本发明芳基羧酸化合物(6)合成中,所述添加剂的摩尔用量为烷基苯(3)的1个当量。
本发明芳基羧酸化合物(6)合成中,所述光为温和的可见光,光源可采用23W紧凑型节能灯、1-20W蓝色LED灯(460nm)、1-20W蓝色LED灯(430nm);优选地,所述光源为3个同时使用的2W蓝色LED灯(460nm)。
本发明芳基羧酸化合物(6)合成中,所述反应的时间为1-120小时;优选地,是36小时。
本发明合成反应包括以下步骤:在反应容器中加入式(3)所示的原料烷基苯、光催化剂、质子酸、溶剂,抽空换氧在可见光照射下,在室温下搅拌反应得到式(6)芳基羧酸化合物。
在一个合成芳基羧酸化合物(6)的具体实例中,本发明合成反应是在反应瓶A中,加入烷基苯(Xmmol),光催化剂醋酸铀酰(Ymmol),盐酸(Zmmol),溶剂(PmL),使用水泵抽取体系内的空气置换为氧气,重复多次,在可见光照射下室温搅拌36小时;反应完毕后,直接加硅胶旋干,经柱层析分离得到芳基羧酸化合物(6)。
本发明还提供了通过上述方法获得的芳基醇化合物、芳基酮化合物、芳基羧酸化合物,分别如下式(4)、式(5)、式(6)所示:
其中,式(4)式(5)式(6)中基团的定义分别同反应式(a)、(b)、(c)中基团的定义。
本发明还提供了上述芳基醇化合物、芳基酮化合物、芳基羧酸化合物在药物、农药、材料、香料等领域中的应用。
本发明具有以下优点:a)所使用的各原料简单易得,来源广泛;b)可见光在室温下催化反应,绿色环保,操作简单,条件温和,收率较高;c)使用简单的添加剂、溶剂就可以微调光催化剂的活性,实现不同烷基苯得到芳基醇化合物、芳基酮化合物、芳基羧酸化合物;d) 普适性广、官能团耐受性强,兼容性好;e)合成方法成功实现了多个药物分子(包括新那利平、氯苯唑酸等)的合成,为药物合成以及药物化学研究提供了新的合成策略;f)合成方法可以通过流体反应器进行放大,为工业化应用奠定了基础。
具体实施方式
结合以下具体实施例,对本发明作进一步的详细说明。实施本发明的过程、条件、实验方法等,除以下专门提及的内容之外,均为本领域的普遍知识和公知常识,本发明没有特别限制内容。
实施例中产物纯度通过核磁鉴定。
本发明芳基醇化合物合成反应包括以下步骤:在反应瓶A中,加入烷基苯(1),光催化剂醋酸铀酰,溶剂,使用水泵抽取体系内的空气置换为氧气,重复多次,在可见光照射下室温搅拌30小时;反应完毕后,直接加硅胶旋干,经柱层析分离得到芳基醇化合物(4)。
本发明芳基酮化合物合成反应包括以下步骤:在反应瓶A中,加入烷基苯(2),光催化剂醋酸铀酰,溶剂,使用水泵抽取体系内的空气置换为氧气,重复多次,在可见光照射下室温搅拌24小时;反应完毕后,直接加硅胶旋干,经柱层析分离得到芳基酮化合物(5)。
本发明芳基羧酸化合物合成反应包括以下步骤:在反应瓶A中,加入烷基苯(3),光催化剂醋酸铀酰,盐酸,溶剂,使用水泵抽取体系内的空气置换为氧气,重复多次,在可见光照射下室温搅拌36小时;反应完毕后,直接加硅胶旋干,经柱层析分离得到芳基羧酸化合物(6)。
实施例1
化合物4a的合成
在25mL反应管中,加入对硝基异丙基苯(33.0mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),甲醇(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌30小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得黄色液体4a(21.7mg,60%);1H NMR(400MHz,CDCl3)δ8.09(d,J=8.0Hz,2H),7.61(d,J=8.0Hz,2H),2.62(brs,1H), 1.57(s,6H).13C NMR(100MHz,CDCl3)δ156.5,146.4,125.4,123.3,72.3,31.5.IR(neat)3396,1599,1514,1346,1175,1107,1092.GCMS(EI)m/z,[M]+=181.
实施例2
化合物4b的合成
在25mL反应管中,加入对氰基异丙基苯(29.0mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),甲醇(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得黄色液体4b(16.4mg,51%);1H NMR(400MHz,CDCl3)δ7.62-7.58(m,4H),2.00(brs,1H),1.57(s,6H).13C NMR(100MHz, CDCl3)δ154.4,132.0,125.3,118.9,110.4,72.4,31.6.IR(neat)2956,1691,1402,1363,1261,1186,1080.GCMS(EI)m/z,[M]+=161.
实施例3
化合物4c的合成
在25mL反应管中,加入间氰基异丙基苯(29.0mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),甲醇(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得棕色液体4c(15.5mg,48%);1H NMR(400MHz,CDCl3)δ7.80(s,1H),7.72(d,J=8.0Hz,1H),7.52(d,J=8.0Hz,1H),7.44(t, J=8.0Hz,1H),1.99(brs,1H),1.58(s,6H).13C NMR(100MHz,CDCl3)δ150.5,130.3,129.1,129.0,128.3,119.0,112.1,72.1,31.7.IR(neat)3442,2229,1419,1366,1263,1173,1090.GCMS (EI)m/z,[M]+=161.
实施例4
化合物4d的合成
在25mL反应管中,加入对乙酰基异丙基苯(32.4mg,0.2mmol),醋酸铀酰水合物(3.4 mg,8*10-3mmol),甲醇(1.2mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得黄色液体4d(20.6mg,58%);1H NMR(400MHz,CDCl3)δ7.92(d,J=8.0Hz,2H),7.58(d,J=8.0Hz,2H),2.59(s,3H),2.03 (brs,1H),1.59(s,6H).13C NMR(100MHz,CDCl3)δ197.9,154.4,135.6,128.4,124.6,72.5,31.7,26.6.IR(neat)3447,1676,1607,1406,1358,1271,1176.GCMS(EI)m/z,[M]+=178.
实施例5
化合物4e的合成
在25mL反应管中,加入对羧酸乙酯基异丙基苯(38.4mg,0.2mmol),醋酸铀酰水合物 (1.7mg,4*10-3mmol),甲醇(1.0mL),抽空换氧,在三个1瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得黄色液体4e(30.4mg, 73%);1H NMR(400MHz,CDCl3)δ7.99(d,J=8.0Hz,2H),7.54(d,J=8.0Hz,2H),4.35(q,J= 8.0Hz,2H),2.06(s,1H),1.58(s,6H),1.38(t,J=7.2Hz,3H).13C NMR(100MHz,CDCl3)δ 166.5,154.1,129.5,128.8,124.4,72.5,60.8,31.6,14.3.IR(neat)3462,2976,1717,1697,1408, 1367,1173.GCMS(EI)m/z,[M]+=208.
实施例6
化合物4f的合成
在25mL反应管中,加入对羧基异丙基苯(32.8mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),甲醇(1.0mL),抽空换氧,在三个1瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=1/1)分离得白色固体4f(19.8mg,55%);1H NMR(400MHz,d6-DMSO)δ7.88(d,J=8.0Hz,2H),7.57(d,J=8.0Hz,2H),5.18(brs,1H), 1.43(s,6H).13C NMR(100MHz,d6-DMSO)δ167.4,155.7,129.0,128.5,124.8,70.9,31.8.IR(neat)2976,1647,1423,1315,1167,1089,1051.GCMS(EI)m/z,[M]+=180.
实施例7
化合物4g的合成
在25mL反应管中,加入间溴异丙基苯(39.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),三氟乙酸(22.8mg,0.2mmol),甲醇(1.2mL),抽空换氧,在三个3瓦LED 灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得无色液体4g(27.4mg,64%);1H NMR(400MHz,CDCl3)δ7.65(t,J=2.0Hz,1H),7.40-7.35 (m,2H),7.19(t,J=8.0Hz,1H),2.02(brs,1H),1.55(s,6H).13C NMR(100MHz,CDCl3)δ151.4, 129.8,129.7,127.8,123.1,122.4,72.2,31.6.IR(neat)3383,2976,1412,1364,1248,1171,1142.GCMS(EI)m/z,[M]+=214.
实施例8
化合物4h的合成
在25mL反应管中,加入间氯异丙基苯(30.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),氢溴酸(40wt%inH2O,5ul,0.01mmol),甲醇(1.2mL),抽空换氧,在三个 2瓦LED灯(460nm)照射下室温搅拌12小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1) 分离得无色液体4g(26.5mg,78%);1H NMR(400MHz,CDCl3)δ7.49(t,J=1.6Hz,1H),7.36 (d,J=8.0Hz,1H),7.27(t,J=8.0Hz,1H),7.22(d,J=8.0Hz,1H),1.72(brs,1H),1.57(s,6H). 13CNMR(100MHz,CDCl3)δ151.2,134.1,129.5,126.8,124.9,122.6,72.3,31.7.IR(neat)3447,2978,1772,1683,1362,1252,1173.GCMS(EI)m/z,[M]+=170.
实施例9
化合物4i的合成
在25mL反应管中,加入邻氯异丙基苯(30.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),氢溴酸(40wt%inH2O,5ul,0.01mmol),甲醇(1.2mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌12小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1) 分离得无色液体4i(20.7mg,61%);1H NMR(500MHz,CDCl3)δ7.69(d,J=7.5Hz,1H),7.38 (d,J=7.5Hz,1H),7.28(t,J=7.5Hz,1H),7.21(t,J=7.5Hz,1H),2.68(brs,1H),1.76(s,6H). 13CNMR(125MHz,CDCl3)δ144.7,131.3,131.2,128.2,126.9(2C),73.1,29.3.IR(neat)2936,2249,1682,1595,1290,1211,746.GCMS(EI)m/z,[M]+=170.
实施例10
化合物4j的合成
在25mL反应管中,加入3,5-二氯异丙基苯(37.6mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),氢溴酸(40wt%inH2O,5ul,0.01mmol),甲醇(1.2mL),抽空换氧,在三个1瓦LED灯(460nm)照射下室温搅拌24小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得无色液体4j(29.4mg,72%);1H NMR(400MHz,CDCl3)δ7.36(d,J=1.6Hz, 1H),7.23(t,J=1.6Hz,1H),1.84(brs,1H),1.55(s,6H).13C NMR(100MHz,CDCl3)δ152.5, 134.8,126.7,123.3,72.2,31.6.IR(neat)3392,1472,1431,1364,1273,1172,1034.GCMS(EI) m/z,[M]+=204.
实施例11
化合物4k的合成
在25mL反应管中,加入3,4-二氯异丙基苯(37.6mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),氢溴酸(40wt%inH2O,5ul,0.01mmol),甲醇(1.2mL),抽空换氧,在三个1瓦LED灯(460nm)照射下室温搅拌24小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得无色液体4k(27.7mg,68%);1H NMR(400MHz,CDCl3)δ7.58(d,J=4.0Hz, 1H),7.39(d,J=8.0Hz,1H),7.30(dd,J1=8.0Hz,J2=4.0Hz,1H),1.80(brs,1H),1.56(s,6H). 13C NMR(100MHz,CDCl3)δ149.4,132.2,130.5,130.1,126.8,124.0,72.0,31.7.IR(neat)3381,2976,1469,1385,1242,1173,1139.GCMS(EI)m/z,[M]+=204.
实施例12
化合物4l的合成
在25mL反应管中,加入异丙基苯(24.0mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),甲醇(1.2mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得无色液体4l(12.2mg,45%);1H NMR (400MHz,CDCl3)δ7.50(d,J=8.0Hz,2H),7.36(t,J=8.0Hz,2H),7.26(t,J=8.0Hz,1H),1.88 (brs,1H),1.60(s,6H).13C NMR(100MHz,CDCl3)δ149.1,128.2,126.6,124.3,72.5,31.7.IR(neat)3394,1688,1495,1447,1362,1259,1175.GCMS(EI)m/z,[M]+=136.
实施例13
化合物4m的合成
在25mL反应管中,加入间甲氧基异丙基苯(30.0mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),氢溴酸(40wt%inH2O,5ul,0.01mmol),甲醇(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌24小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得无色液体4m(17.6mg,53%);1H NMR(400MHz,CDCl3)δ7.27(d,J=8.0Hz, 1H),7.07(t,J=8.0Hz,2H),6.80(dd,J1=8.0Hz,J2=2.4Hz,1H),3.82(s,3H),2.15(brs,1H), 1.58(s,6H).13C NMR(100MHz,CDCl3)δ159.4,150.9,129.1,116.8,111.7,110.5,72.4,55.1, 31.6.IR(neat)2963,1601,1487,1431,1288,1267,1230.GCMS(EI)m/z,[M]+=166.
实施例14
化合物4n的合成
在25mL反应管中,加入4-甲基-3,4-二氢萘酮(32.0mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),甲醇(1mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌 24小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得白色固体4n(21.1mg,60%);1H NMR(400MHz,CDCl3)δ7.98(d,J=12.0Hz,1H),7.71(t,J=12.0Hz,2H),7.60(t,J=8.0 Hz,1H),7.39(t,J=8.0Hz,1H),2.92-2.82(m,1H),2.75-2.64(m,1H),2.31-2.26(m,2H),1.85(brs,1H),1.64(s,3H).13C NMR(100MHz,CDCl3)δ197.3,149.5,134.3,130.5,127.8,127.0,125.2,70.2,38.3,35.8,29.0.IR(neat)3416,2970,1599,1450,1287,1194,1089.GCMS(EI)m/z, [M]+=176.
实施例15
化合物4o的合成
在25mL反应管中,加入对溴异丙基苯(39.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),甲醇(1.2mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌 21小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得棕色液体4o(34.2mg,80%);1H NMR(400MHz,CDCl3)δ7.44(d,J=8.0Hz,2H),7.34(d,J=8.0Hz,2H),2.14(brs,1H), 1.54(s,6H).13C NMR(100MHz,CDCl3)δ148.1,131.1,126.3,120.5,72.2,31.6.IR(neat)3379,1481,1396,1364,1169,1142,1107.GCMS(EI)m/z,[M]+=214.
实施例16
化合物4p的合成
在25mL反应管中,加入对氯异丙基苯(30.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),氢溴酸(40wt%inH2O,5ul,0.01mmol),甲醇(1.0mL),抽空换氧,在三个 2瓦LED灯(460nm)照射下室温搅拌12小时,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1) 分离得无色液体4p(20.7mg,61%);1H NMR(400MHz,CDCl3)δ7.41(d,J=8.0Hz,2H), 7.29(d,J=8.0Hz,2H),1.89(brs,1H),1.56(s,6H).13C NMR(100MHz,CDCl3)δ147.6,132.5, 128.3,125.9,72.3,31.8.IR(neat)2961,1491,1398,1363,1209,1188.GCMS(EI)m/z,[M]+=170.
实施例17
化合物4q的合成
在25mL反应管中,加入对苯基异丙基苯(39.2mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),甲醇(1.0mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌24小时,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体4q(21.2mg,50%);1HNMR(400MHz,CDCl3)δ7.62-7.58(m,6H),7.45(t,J=8.0Hz,2H),7.36(t,J=7.6Hz,1H),1.82(brs,1H),1.64(s,6H).13C NMR(100MHz,CDCl3)δ148.1,140.8,139.6,128.7,127.2,127.0,126.9,124.8,72.4,31.7.IR(neat)3408,1487,1398,1265,1167,1117,1097.GCMS(EI) m/z,[M]+=212.
实施例18
化合物5a的合成
在25mL反应管中,加入对硝基乙基苯(30.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌 24小时,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色固体5a(26.7mg,81%);1H NMR(400MHz,CDCl3)δ8.29(d,J=8.0Hz,2H),8.10(d,J=8.0Hz,1H),2.67(s,3H).13C NMR(100MHz,CDCl3)δ196.3,150.3,141.3,129.3,123.8,26.9.IR(neat)3107,1708,1693,1602,1527,1346,1242.
实施例19
化合物5b的合成
在25mL反应管中,加入邻硝基乙基苯(30.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2 天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5b(17.8mg,54%);1H NMR(400MHz,CDCl3)δ8.06-8.03(m,1H),7.72-7.68(m,1H),7.61-7.56(m,1H),7.42(d,J =8.0Hz,1H),2.53(s,3H).13C NMR(100MHz,CDCl3)δ199.7,145.7,137.7(d,J=4Hz),134.1, 130.6,127.2,124.2,30.0.IR(neat)3007,1710,1575,1529,1348,1222,1001.
实施例20
化合物5c的合成
在25mL反应管中,加入对乙基苯甲酸乙酯(35.6mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5c(31.1mg,81%);1H NMR(400MHz,CDCl3)δ8.08(d,J=8.8Hz,2H),7.95(d,J=8.8Hz,2H),4.37(q,J=7.2 Hz,2H),2.60(s,3H),1.37(t,J=7.2Hz,3H).13C NMR(100MHz,CDCl3)δ197.4,165.6,140.0, 134.1,129.6,128.0,61.3,26.7,14.2.IR(neat)2959,1718,1676,1435,1277,1111,955.
实施例21
化合物5d的合成
在25mL反应管中,加入对溴乙基苯(36.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5d(26.9mg,68%);1H NMR (400MHz,CDCl3)δ7.79(d,J=8.0Hz,2H),7.57(d,J=8.0Hz,2H),2.56(s,3H).13C NMR(100 MHz,CDCl3)δ196.9,135.7,131.8,129.7,128.2,26.5.IR(neat)1683,1583,1230,1070,1008,821,590.
实施例22
化合物5e的合成
在25mL反应管中,加入间溴乙基苯(36.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5e(31.7mg,80%);1H NMR (400MHz,CDCl3)δ8.06(t,J=2.0Hz,1H),7.87-7.84(m,1H),7.68-7.65(m,1H),7.33(t,J=8.0 Hz,1H),2.57(s,3H).13C NMR(100MHz,CDCl3)δ196.6,138.7,135.9,131.3,130.1,126.8,122.9,26.6.IR(neat)1685,1566,1419,1246,997,781,680.
实施例23
化合物5f的合成
在25mL反应管中,加入邻溴乙基苯(36.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5f(27.7mg,70%);1H NMR (400MHz,CDCl3)δ7.61(d,J=8.0Hz,1H),7.46(d,J=8.0Hz,1H),7.37(t,J=8.0Hz,1H), 7.29(t,J=8.0Hz,1H),2.63(s,3H).13C NMR(100MHz,CDCl3)δ201.3,141.5,133.8,131.8, 128.9,127.4,118.9,30.3.IR(neat)1737,1697,1425,1357,1242,1026,758.
实施例24
化合物5g的合成
在25mL反应管中,加入2-溴-4-氯乙基苯(43.6mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5g(32.5mg,70%);1H NMR(400MHz,CDCl3)δ7.63-7.61(m,1H),7.44-7.42(m,1H),7.36-7.33(m,1H),2.61(s, 3H).13CNMR(125MHz,CDCl3)δ199.8,139.4,137.3,133.6,130.1,127.7,119.7,30.2.IR(neat)1697,1578,1466,1356,1269,1234,1101.
实施例25
化合物5h的合成
在25mL反应管中,加入对氯正丁基苯(33.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2 天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5h(24.7mg,68%);1H NMR(400MHz,CDCl3)δ7.87(d,J=8.0Hz,2H),7.39(d,J=8.0Hz,2H),2.89(t,J=7.6Hz, 2H),1.78-1.69(m,2H),0.98(t,J=7.2Hz,3H).13C NMR(125MHz,CDCl3)δ198.9,139.2, 135.3,129.4,128.7,40.4,17.6,13.7.IR(neat)1716,1684,1213,1155,1091,1024,1003.
实施例26
化合物5i的合成
在25mL反应管中,加入乙基苯(21.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5i(18.5mg,77%);1H NMR (400MHz,CDCl3)δ7.97-7.95(m,2H),7.58-7.54(m,1H),7.48-7.44(m,2H),2.61(s,3H).13C NMR(100MHz,CDCl3)δ198.1,137.1,133.1,128.5,128.3,26.6.IR(neat)1712,1683,1448, 1423,1359,1222,761.
实施例27
化合物5j的合成
在25mL反应管中,加入4-(O-环丙基亚甲基醚)乙基苯(35.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm) 照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色液体5j(19.8 mg,52%);1H NMR(400MHz,CDCl3)δ7.91(d,J=12.0Hz,2H),6.91(d,J=12.0Hz,2H),3.86 (d,J=8.0Hz,2H),2.54(s,3H),1.32-1.24(m,1H),0.69-0.64(m,2H),0.38-0.34(m,2H).13C NMR(100MHz,CDCl3)δ196.8,162.9,130.5,130.1,114.1,72.9,26.3,10.1,3.2.IR(neat)1674,1598,1247,1168,1002,835,588.HRMS(EI)CalcdforC12H14O2190.0994,Found190.0995.
实施例28
化合物5k的合成
在25mL反应管中,加入2-苯乙基溴(36.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得棕色固体5k(27.7mg,70%);1H NMR (400MHz,CDCl3)δ8.00-7.98(m,2H),7.61(t,J=6.0Hz,1H),7.50(t,J=8.0Hz,2H),4.46(s, 2H).13CNMR(100MHz,CDCl3)δ191.3,133.9,128.9,128.8,30.9.IR(neat)1685,1579,1448, 1388,1280,991,744.HRMS(EI)CalcdforC8H7BrO197.9680,Found197.9678.
实施例29
化合物5l的合成
在25mL反应管中,加入3-苯丙基溴(39.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得棕色固体5l(28.8mg,68%);1H NMR (400MHz,CDCl3)δ7.95(d,J=8.0Hz,2H),7.59(t,J=8.0Hz,1H),7.48(t,J=8.0Hz,2H),3.74 (t,J=8.0Hz,2H),3.57(t,J=6.0Hz,2H).13C NMR(100MHz,CDCl3)δ196.9,136.2,133.5,128.7,128.0,41.5,25.7.IR(neat)1681,1361,1228,1112,974,756,688.HRMS(EI)Calcdfor C9H9BrO211.9837,Found211.9835.
实施例30
化合物5m的合成
在25mL反应管中,加入异丁酸苯丙基酯(41.2mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5m(22.0mg,50%);1H NMR(400MHz,CDCl3)δ7.95(d,J=12.0Hz,2H),7.58(t,J=8.0Hz,1H),7.48(t,J=8.0 Hz,2H),4.52(t,J=8.0Hz,2H),3.31(t,J=6.0Hz,2H),2.56-2.47(m,1H),1.13(d,J=8.0Hz, 6H).13C NMR(100MHz,CDCl3)δ197.1,177.1,136.6,133.3,128.7,128.1,59.6,37.4,33.9,18.9. IR(neat)2974,1734,1686,1389,1265,1157,746.
实施例31
化合物5n的合成
在25mL反应管中,加入4-苯丁氰(29.0mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得白色固体5n(16.2mg,51%);1H NMR (400MHz,CDCl3)δ7.92(d,J=8.0Hz,2H),7.59(t,J=8.0Hz,1H),7.44(t,J=8.0Hz,2H),3.34 (t,J=8.0Hz,2H),2.73(t,J=8.0Hz,2H).13C NMR(100MHz,CDCl3)δ195.3,135.4,133.7,128.7,127.8,119.2,34.0,11.6.IR(neat)1682,1447,1369,1284,1207,1053,976.
实施例32
化合物5o的合成
在25mL反应管中,加入异色满(26.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得无色液体5o(17.2mg,58%);1H NMR (400MHz,CDCl3)δ8.09(dd,J1=8.0Hz,J2=0.8Hz,1H),7.53(td,J1=8.0Hz,J2=1.6Hz,1H), 7.39(t,J=8.0Hz,1H),7.26(d,J=8.0Hz,1H),4.53(t,J=6.0Hz,2H),3.06(t,J=6.0Hz,2H). 13C NMR(100MHz,CDCl3)δ165.1,139.5,133.6,130.4,127.7,127.2,125.3,67.3,27.8.IR(neat)1716,1678,1602,1392,1292,1118,1028.
实施例33
化合物5p的合成
在25mL反应管中,加入芴(33.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10- 3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5p(27.7mg,77%);1H NMR(400MHz,CDCl3)δ7.65(d,J=8.0Hz,2H),7.51-7.44(m,4H),7.28(t,J=8.0Hz,2H).13C NMR(100MHz,CDCl3)δ193.8,144.3,134.6,134.0,128.9,124.2,120.2.IR(neat)1717,1612,1452,1300,1192, 1148,737.
实施例34
化合物5q的合成
在25mL反应管中,加入氧杂蒽(36.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5q(33.3mg,85%);1H NMR (400MHz,CDCl3)δ8.33(d,J=8.0Hz,2H),7.71(t,J=8.0Hz,2H),7.48(t,J=8.0Hz,2H),7.37 (t,J=8.0Hz,2H).13C NMR(100MHz,CDCl3)δ177.2,156.1,134.8,126.7,123.9,121.8,117.9. IR(neat)1674,1589,1304,1283,968,746,690.
实施例35
化合物5r的合成
在25mL反应管中,加入9-氧杂-1-氮杂蒽(36.6mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得白色固体5r(33.3mg,85%);1H NMR(400MHz,CDCl3)δ8.73-8.68(m,2H),8.28(d,J=8.0Hz,1H),7.76(t,J=8.0Hz,1H), 7.69(d,J=8.0Hz,1H),7.44-7.38(m,2H).13C NMR(100MHz,CDCl3)δ177.5,160.3,155.6,154.1,137.3,135.6,126.6,124.6,121.4,121.0,118.4,116.7.IR(neat)1670,1614,1418,1348, 1199,937,760.
实施例36
化合物5s的合成
在25mL反应管中,加入1,4-二乙基苯(26.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2 天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得无色液体5s(25.9mg,80%);1H NMR(400MHz,CDCl3)δ7.98(s,4H),2.60(s,6H).13C NMR(100MHz,CDCl3)δ197.3,140.0, 128.4,26.8.IR(neat)1676,1566,1423,1348,1246,1166,1010.
实施例37
化合物5t的合成
在25mL反应管中,加入1,3,5-三乙基苯(16.2mg,0.1mmol),醋酸铀酰水合物(0.85mg, 2*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5t(15.7mg,77%);1H NMR(400MHz,CDCl3)δ8.70(s,3H),2.71(s,9H).13C NMR(100MHz,CDCl3)δ196.7, 137.9,131.7,26.8.IR(neat)1683,1419,1361,1226,1022,904,684.HRMS(EI)CalcdforC12H12O3204.0786,Found204.0789.
实施例38
化合物5u的合成
在25mL反应管中,加入2-乙基吡啶(21.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1)分离得无色液体5u(16.2mg,67%);1H NMR (400MHz,CDCl3)δ8.65(d,J=4.0Hz,1H),8.00(d,J=8.0Hz,1H),7.79(td,J1=8.0Hz,J2= 1.6Hz,1H),7.45-7.41(m,1H),2.69(s,3H).13C NMR(100MHz,CDCl3)δ200.0,153.5,148.9, 136.7,127.0,121.5,25.7.IR(neat)1697,1355,1280,1238,1043,777,588.
实施例39
化合物5v的合成
在25mL反应管中,加入对氯异丙基苯(30.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2 天,反应完毕后,浓缩,经柱层析(VPE/VEA=20/1)分离得无色液体5v(22.5mg,73%);1H NMR(400MHz,CDCl3)δ7.89(d,J=8.0Hz,2H),7.43(d,J=8.0Hz,2H),2.59(s,3H).13C NMR(100MHz,CDCl3)δ196.8,139.5,135.4,129.7,128.9,26.5.IR(neat)1684,1587,1396, 1356,1258,1093,1012.
实施例40
化合物5w的合成
在25mL反应管中,加入4-苯基异丙基苯(39.2mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5w(21.2mg,54%);1H NMR(400MHz,CDCl3)δ8.04(d,J=8.0Hz,2H),7.69(d,J=8.0Hz,2H),7.63(d,J=8.0 Hz,2H),7.48(t,J=8.0Hz,2H),7.41(t,J=8.0Hz,1H),2.65(s,3H).13C NMR(100MHz, CDCl3)δ197.8,145.8,139.9,135.8,128.94,128.90,128.2,127.3,127.2,26.7.IR(neat)1676,1600,1359,1261,1004,677,592.
实施例41
化合物5x的合成
在25mL反应管中,加入乙酸苯丙酯(35.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5x(23.4mg,61%);1H NMR (400MHz,CDCl3)δ7.96(d,J=8.0Hz,2H),7.59(t,J=6.0Hz,1H),7.48(t,J=8.0Hz,2H),4.52 (t,J=6.0Hz,2H),3.32(t,J=6.0Hz,2H),2.03(s,3H).13C NMR(100MHz,CDCl3)δ197.0, 171.0,136.6,133.4,128.7,128.1,59.7,37.4,20.9.IR(neat)2926,1728,1670,1249,1176,1049,744.HRMS(EI)CalcdforC11H12O3192.0786,Found192.0787.
实施例42
化合物5y的合成
在25mL反应管中,加入对溴正丁基苯(42.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2 天,反应完毕后,浓缩,经柱层析(VPE/VEA=20/1)分离得棕色液体5y(28.5mg,63%);1H NMR(400MHz,CDCl3)δ7.80(d,J=8.0Hz,2H),7.58(d,J=8.0Hz,2H),2.89(t,J=8.0Hz, 2H),1.79-1.70(m,2H),0.99(t,J=8.0Hz,2H).13C NMR(100MHz,CDCl3)δ199.2,135.8, 131.8,129.5,127.9,40.4,17.6,13.8.IR(neat)1686,1587,1379,1271,1091,1045,879.
实施例43
化合物5z的合成
在25mL反应管中,加入对乙基苯甲酸(30.0mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.0mL),抽空换氧,在三个2瓦LED灯(460nm)照射下室温搅拌2 天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体5z(32.5mg,99%);1H NMR(400MHz,DMSO-d6)δ13.31(brs,1H),8.05(s,4H),2.62(s,3H).13C NMR(100MHz, DMSO-d6)δ197.7,166.6,139.9,134.5,129.5,128.3,27.0.IR(neat)3005,1716,1670,1570, 1425,1288,1224.
实施例44
化合物6a的合成
在25mL反应管中,加入对硝基甲苯(27.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm) 照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得黄色固体6a(27.0mg,81%);1H NMR(400MHz,DMSO-d6)δ13.66(brs,1H),8.31(d,J=8.0Hz,2H), 8.16(d,J=8.0Hz,2H).13C NMR(100MHz,DMSO-d6)δ165.8,150.0,136.4,130.7,123.7.IR (KBr)3392,1685,1598,1539,1425,1350,1278.
实施例45
化合物6b的合成
在25mL反应管中,加入间硝基甲苯(27.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm) 照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得黄色固体 6b(25.4mg,76%);1H NMR(400MHz,DMSO-d6)δ13.66(brs,1H),8.61(s,1H),8.46(d,J=8.0Hz,1H),8.34(d,J=8.0Hz,1H),7.81(t,J=8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ165.5,147.9,135.4,132.5,130.5,127.3,123.7.IR(neat)3367,1705,1618,1527,1417,1350, 1228.
实施例46
化合物6c的合成
在25mL反应管中,加入对氰基甲苯(23.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),三氯乙酸(0.2mmol,32.4mg),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460 nm)照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6c(20.0mg,68%);1H NMR(400MHz,DMSO-d6)δ13.56(brs,1H),8.08(d,J=8.0Hz, 2H),7.98(d,J=8.0Hz,2H).13C NMR(100MHz,DMSO-d6)δ166.3,135.0,132.9,130.1,118.4,115.2.IR(KBr)3410,2231,1714,1566,1429,1286,927.
实施例47
化合物6d的合成
在25mL反应管中,加入间氰基甲苯(23.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm) 照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6d(15.3mg,52%);1H NMR(400MHz,DMSO-d6)δ13.74(brs,1H),8.48-8.45(m,1H), 8.36-8.33(m,1H),7.81(t,J=8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ165.5,147.9,135.4, 132.5,130.6,127.4,123.7.IR(KBr)2924,2233,1689,1616,1435,1298,675.
实施例48
化合物6e的合成
在25mL反应管中,加入邻氰基甲苯(23.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm) 照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6e(21.5mg,73%);1H NMR(400MHz,DMSO-d6)δ8.09(d,J=8.0Hz,1H),7.95-7.94(m, 1H),7.79-7.78(m,2H).13C NMR(100MHz,DMSO-d6)δ165.3,135.1,133.24,133.16,133.1,131.0,117.8,111.8.IR(neat)2976,1697,1417,1275,1093,1082,1051.
实施例49
化合物6f的合成
在25mL反应管中,加入对三氟甲基甲苯(32.0mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6f(26.2mg,69%);1H NMR(500MHz,acetone-d6)δ11.58(brs,1H),8.24(d,J= 8.0Hz,2H),7.87(d,J=8.0Hz,2H).13C NMR(126MHz,acetone-d6)δ166.5,135.1(d,J= 1.26Hz),134.5(q,J=32.76Hz),131.2,126.4(q,J=3.90Hz),124.9(q,J=272.16Hz).19F NMR(376MHz,acetone-d6)δ-63.59.IR(KBr)2926,1689,1583,1425,1284,1166,700.
实施例50
化合物6g的合成
在25mL反应管中,加入对甲基苯甲酸乙酯(32.8mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),三氯乙酸(0.2mmol,32.4mg),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6g(24.8mg,64%);1H NMR(400MHz,DMSO-d6)δ13.33(brs,1H),8.05(s, 4H),4.34(q,J=6.7Hz,2H),1.33(t,J=8.0Hz,3H).13C NMR(100MHz,DMSO-d6)δ166.6, 165.1,134.8,133.4,129.6,129.3,61.2,14.1.IR(KBr)3005,1712,1573,1427,1224,1014,729.
实施例51
化合物6h的合成
在25mL反应管中,加入对氯甲苯(25.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm) 照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体 6h(24.0mg,77%);1H NMR(400MHz,DMSO-d6)δ13.16(brs,1H),7.93(d,J=8.0Hz,2H), 7.54(d,J=8.0Hz,2H).13C NMR(100MHz,DMSO-d6)δ166.5,137.8,131.2,129.7,128.8.IR (KBr)3008,1716,1678,1423,1365,1224,1091.
实施例52
化合物6i的合成
在25mL反应管中,加入甲苯(18.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10- 3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VPE/VEA=2/1)分离得白色固体6i(16.3mg,67%);1H NMR(400MHz,DMSO-d6)δ12.96(brs,1H),7.96-7.94-7.98(m,2H),7.63-7.59(m,1H),7.51-7.48(m,2H).13C NMR(100MHz,DMSO-d6)δ167.4,132.9,130.8,129.3,128.6.IR(KBr)3007,1716,1681,1421,1224,923,704.
实施例53
化合物6j的合成
在25mL反应管中,加入4-甲基联苯(33.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm) 照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6j(36.4mg,92%);1H NMR(400MHz,DMSO-d6)δ12.99(brs,1H),8.03(d,J=8.0Hz,2H), 7.79(d,J=8.0Hz,2H),7.72(d,J=8.0Hz,2H),7.49(t,J=8.0Hz,2H),7.42(t,J=8.0Hz,1H).13C NMR(100MHz,DMSO-d6)δ167.2,144.3,139.0,129.9,129.6,129.1,128.3,126.9,126.8.IR(KBr)2547,1712,1674,1421,1298,1286,746.
实施例54
化合物6k的合成
在25mL反应管中,加入2-氯-4-氟甲苯(28.8mg,0.2mmol),醋酸铀酰水合物(1.7mg, 4*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(460nm)照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6k(21.2mg,61%);1H NMR(400MHz,DMSO-d6)δ7.91-7.88(m,1H),7.54-7.51 (m,1H),7.33-7.28(m,1H).13C NMR(100MHz,DMSO-d6)δ165.8,163.22(d,J=251Hz), 133.7(d,J=22Hz),133.4(d,J=10Hz),127.7(d,J=3Hz),118.2(d,J=25Hz),114.7(d,J=21 Hz).19FNMR(376MHz,DMSO-d6)δ-106.72.IR(neat)2955,1703,1599,1500,1427,1294, 1269.
实施例55
化合物6l的合成
在25mL反应管中,加入对二甲苯(21.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在三个3瓦LED灯(430nm) 照射下室温搅拌4天,反应完毕后移除溶剂,加入碳酸氢钠水溶液溶解(20mL),然后加入乙酸乙酯萃取,收集水相,加入盐酸(2N)酸化,过滤,利用水和乙醚洗涤,干燥得白色固体6l(18.9mg,57%);1H NMR(400MHz,DMSO-d6)δ8.03(s,4H).13C NMR(100MHz, DMSO-d6)δ166.9,134.6,129.6.IR(neat)2820,2534,2359,1670,1508,1419,1279.
实施例56
化合物6m的合成
在25mL反应管中,加入4-(环丁基亚甲氧基)甲苯(35.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),冰乙酸(0.2mmol,12mg),丙酮(1mL),抽空换氧,在9瓦 LED灯(460nm)照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1) 分离得白色固体6m(21.0mg,51%);1H NMR(400MHz,DMSO-d6)δ12.60(brs,1H),7.87(d, J=8.0Hz,2H),7.00(d,J=8.0Hz,2H),4.01(d,J=8.0Hz,2H),2.76-2.68(m,1H),2.10-2.03(m, 2H),1.93-1.79(m,4H).13C NMR(100MHz,DMSO-d6)δ167.0,162.4,131.3,122.8,114.3,71.7,33.8,24.3,18.1.IR(KBr)2922,1674,1600,1423,1286,1238,1166.HRMS(EI)CalcdforC12H14O3206.0943,Found206.0947.
实施例57
化合物6n的合成
在25mL反应管中,加入4-(环丙基亚甲氧基)甲苯(32.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),冰乙酸(0.2mmol,12mg),丙酮(1mL),抽空换氧,在9瓦 LED灯(460nm)照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1) 分离得白色固体6n(20.7mg,54%);1H NMR(400MHz,CDCl3)δ8.05(d,J=8.0Hz,2H),6.94 (d,J=8.0Hz,2H),3.88(d,J=4.0Hz,2H),1.32-1.26(m,1H),0.70-0.65(m,2H),0.39-0.36(m,2H).13C NMR(100MHz,CDCl3)δ171.6,163.5,132.3,121.4,114.2,73.0,10.1,3.2.IR(neat)2924,1741,1672,1575,1406,1242,1001.HRMS(EI)CalcdforC11H12O3192.0786,Found192.0788.
实施例58
化合物6o的合成
在25mL反应管中,加入4-(环氧乙基亚甲氧基)甲苯(32.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),冰乙酸(0.2mmol,12mg),丙酮(1mL),抽空换氧,在9 瓦LED灯(460nm)照射下室温搅拌36小时,反应完毕后,浓缩,经柱层析(VDCM/VMeOH= 20/1)分离得白色固体6o(23.3mg,60%);1H NMR(400MHz,DMSO-d6)δ12.66(brs,1H),7.89 (d,J=8.0Hz,2H),7.04(d,J=8.0Hz,2H),4.43-4.40(m,1H),3.92-3.88(m,1H),3.37-3.34(m, 2H),2.86-2.84(m,1H),2.73-2.71(m,1H).13C NMR(100MHz,DMSO-d6)δ167.0,161.8,131.4,123.3,114.4,69.2,49.6,43.8.IR(KBr)2920,1674,1602,1425,1246,1170,916.HRMS(EI)CalcdforC10H10O4194.0579,Found194.0582.
实施例59
化合物6p的合成
在25mL反应管中,加入2-(4-三氟甲基苯)甲苯(23.6mg,0.1mmol),醋酸铀酰水合物(0.85mg,2*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在9瓦LED灯(460nm)照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1) 分离得白色固体6p(15.4mg,58%);1H NMR(400MHz,DMSO-d6)δ12.86(brs,1H),7.83(dd, J1=7.6Hz,J2=1.2Hz,1H),7.76(d,J=8.0Hz,2H),7.63(dt,J1=7.6Hz,J2=1.6Hz,1H), 7.55-7.51(m,3H),7.42-7.40(m,1H).13C NMR(100MHz,DMSO-d6)δ168.9,145.3,140.0, 131.8,131.3,130.6,129.6,129.2,128.1,127.6(d,J=31Hz),124.9(q,J=4Hz),124.4(d,J=270 Hz).19F NMR(376MHz,DMSO-d6)δ-60.81.IR(KBr)2926,1697,1404,1290,1155,1107,1006.HRMS(EI)CalcdforC14H9F3O2266.0555,Found266.0552.
实施例60
化合物6q的合成
在25mL反应管中,加入2-(3,5-二氯苯基)-6-甲基苯并噁唑(27.7mg,0.1mmol),醋酸铀酰水合物(0.85mg,2*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在9瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6q(15.4mg,50%);1H NMR(400MHz,DMSO-d6)δ8.29(d,J=1.2 Hz,1H),8.17(d,J=1.6Hz,2H),8.05(dd,J1=8.4Hz,J2=1.6Hz,1H),7.96(t,J=2.0Hz,1H), 7.93(d,J=8.4Hz,1H).13C NMR(100MHz,DMSO-d6)δ166.8,162.1,150.2,144.7,135.2, 131.8,129.3,126.6,126.0,120.0,112.3.IR(KBr)2924,1743,1703,1267,1242,1049,1004. HRMS(EI)CalcdforC14H7Cl2NO3306.9803,Found306.9807.
实施例61
化合物6r的合成
在25mL反应管中,加入对溴异丙基苯(39.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),硫酸(2N,0.2mmol,100ul),丙酮(1.2mL),抽空换氧,在12瓦LED灯(460 nm)照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6r(18.8mg,47%);1H NMR(400MHz,DMSO-d6)δ13.21(brs,1H),7.86(d,J=8.0Hz, 2H),7.71(d,J=8.0Hz,2H).13C NMR(100MHz,DMSO-d6)δ166.7,131.7,131.3,130.1,126.9. IR(neat)2546,1670,1570,1421,1234,925,754.
实施例62
化合物6s的合成
在25mL反应管中,加入对甲氧基异丙基苯(24.4mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在9瓦LED灯(460nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6s(24.6mg,81%);1H NMR(400MHz,DMSO-d6)δ12.62(brs,1H),7.89(d,J=8.0 Hz,2H),7.01(d,J=8.0Hz,2H),3.82(s,3H).13C NMR(100MHz,DMSO-d6)δ167.0,162.9, 131.4,123.0,113.8,55.4.IR(neat)2926,1705,1678,1575,1425,1230,1022.
实施例63
化合物6t的合成
在25mL反应管中,加入2-甲氧基-4-氰基甲苯(29.4mg,0.2mmol),醋酸铀酰水合物(1.7 mg,4*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在9瓦LED灯(460nm)照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6t(24.8mg,70%);1H NMR(400MHz,DMSO-d6)δ7.89(d,J=8.0Hz,1H),7.62 (d,J=0.8Hz,1H),7.46(dd,J1=8.0Hz,J2=1.6Hz,1H),3.87(s,3H).13C NMR(100MHz, DMSO-d6)δ166.5,157.4,130.8,126.6,124.1,118.2,116.0,114.6,56.4.IR(neat)2951,1458, 1375,1169,1092,1051,881.
实施例64
化合物5d的合成
在25mL反应管中,加入对溴异丙基苯(39.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),丙酮(1.2mL),抽空换氧,在9瓦LED灯(460nm)照射下室温搅拌30小时,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得白色固体5d(23.8mg,60%)。
实施例65
化合物5z的合成
在25mL反应管中,加入对甲基苯乙酮(26.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),盐酸(2N,0.2mmol,100ul),丙酮(1mL),抽空换氧,在9瓦LED灯(460 nm)照射下室温搅拌2天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体5z(19.7mg,60%)。
实施例66
化合物6h的合成
在25mL反应管中,加入对氯异丙基苯(30.8mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),硫酸(2N,0.2mmol,100ul),丙酮(1.2mL),抽空换氧,在12瓦LED灯(460 nm)照射下室温搅拌5天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6h(18.4mg,59%)。
实施例67
化合物6i的合成
在25mL反应管中,加入乙酸苯丙酯(35.6mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),叔丁醇(1.2mL),抽空换氧,在12瓦LED灯(460nm)照射下室温搅拌5天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6i(15.9mg,65%)。
实施例68
化合物6j的合成
在25mL反应管中,加入对异丙基联苯(39.2mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),硫酸(2N,0.2mmol,100ul),丙酮(1.2mL),抽空换氧,在12瓦LED灯(430 nm)照射下室温搅拌4天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6j(24.1mg,61%)。
实施例69
化合物6l的合成
在25mL反应管中,加入对乙基苯甲酸(30.0mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),叔丁醇(1.2mL),抽空换氧,在12瓦LED灯(460nm)照射下室温搅拌3 天,反应完毕后移除溶剂,加入碳酸氢钠水溶液溶解(20mL),然后加入乙酸乙酯萃取,收集水相,加入盐酸(2N)酸化,过滤,利用水和乙醚洗涤,干燥得白色固体6l(17.3mg,52%)
实施例70
化合物6r的合成
在25mL反应管中,加入对溴正丁基苯(42.4mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3mmol),叔丁醇(1.2mL),抽空换氧,在12瓦LED灯(460nm)照射下室温搅拌3 天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体6r(22.4mg,56%)。
实施例71
化合物6r的合成
在25mL反应管中,加入对溴甲苯(34.0mg,0.2mmol),醋酸铀酰水合物(1.7mg,4*10-3 mmol),盐酸(2N,0.2mmol,100ul),丙酮(1.2mL),抽空换氧,在9瓦LED灯(460nm) 照射下室温搅拌3天,反应完毕后,浓缩,经柱层析(VDCM/VMeOH=20/1)分离得白色固体 6r(22.0mg,55%)。
实施例72
化合物4o的合成
在100mL三口烧瓶中,加入对溴异丙基苯(3.96g,20.0mmol),硝酸铀酰水合物(200mg, 0.4mmol),甲醇(60mL),在氧气氛围下搅拌。在泵的作用下,使得液体在聚四氟乙烯管道 (O.D.=2mm,I.D.=1mm,length=31.4m,volume=24.65mL)中循环流动(流速0.5mL/min),同时90瓦蓝色LED灯(435nm)照射聚四氟乙烯管道,在空气中室温反应4天,反应完毕后,浓缩,经柱层析(VPE/VEA=5/1到2/1)分离得棕色液体4o(2.19g,51%,0.111 mmol/h)。
实施例73
化合物5a的合成
在100mL三口烧瓶中,加入对硝基乙基苯(3.02g,20.0mmol),硝酸铀酰水合物(200mg, 0.4mmol),丙酮(60mL),在氧气氛围下搅拌。在泵得作用下,使得液体在聚四氟乙烯管道 (O.D.=2mm,I.D.=1mm,length=31.4m,volume=24.65mL)中循环流动(流速0.5mL/min),同时90瓦蓝色LED灯(435nm)照射聚四氟乙烯管道,在空气中室温反应4天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色固体5a(2.15g,65%,0.135mmol/h)。
实施例74
化合物6a的合成
在100mL三口烧瓶中,加入对硝基甲苯(2.74g,20.0mmol),硝酸铀酰水合物(200mg, 0.4mmol),盐酸(2N,20mmol,10mL),丙酮(60mL),在氧气氛围下搅拌。在泵得作用下,使得液体在聚四氟乙烯管道(O.D.=2mm,I.D.=1mm,length=31.4m,volume=24.65mL) 中循环流动(流速0.5mL/min),同时90瓦蓝色LED灯(435nm)照射聚四氟乙烯管道,在空气中室温反应5天,反应完毕后,浓缩,经柱层析(VPE/VEA=10/1)分离得黄色固体6a(2.67g,80%,0.133mmol/h)。
除上述实施例外,本发明在温度为0-50℃范围内,都能实现上述制备芳基醇化合物(4)、芳基酮化合物(5)、芳基羧酸化合物(6)的技术效果。
本发明的保护内容不局限于以上实施例。在不背离本发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求书为保护范围。
Claims (15)
4.如权利要求1所述的合成方法,其特征在于,Ar1选自苯基、硝基取代的苯基、氰基取代的苯基、酰基取代的苯基、羧酸乙酯基取代的苯基、羧基取代的苯基、卤素取代的苯基、烷氧基取代的苯基、苯并环己基酮基、联苯;R1选自C1-C10烷基、C3-C10环状烷基;R2选自C1-C10烷基、C3-C10环状烷基。
5.如权利要求2所述的合成方法,其特征在于,Ar2选自苯基、硝基苯基、羧酸乙酯基苯基、卤素取代的苯基、对(环丙基亚甲基氧)苯基、吡啶;R3选自C1-C10烷基、卤素取代的C1-C10烷基、丁酸酯乙基、氰基取代的C1-C10烷基、乙酸酯取代的C1-C10烷基、苯基。
6.如权利要求3所述的合成方法,其特征在于,Ar3选自硝基苯基、氰基苯基、三氟甲基苯基、乙酰基苯基、羧酸乙酯基苯基、卤素取代的苯基、苯基、联苯、(环丁基亚甲基氧)苯基、(环丙基亚甲基氧)苯基、(环氧乙烷亚甲基氧)苯基、(3,5-二氯苯基)苯并噁唑基。
7.如权利要求1-3之任一项所述的合成方法,其特征在于,所述氧气压力为1个大气压;
和/或,所述溶剂为甲醇、丙酮、叔丁醇、乙腈、氯仿、二氯甲烷中的一种或多种;
和/或,所述溶剂的用量为1~1.2毫升;
和/或,所述反应均在0-50℃下进行;
和/或,所述光催化剂为醋酸铀酰、硝酸铀酰、醋酸氧铀锌、硫酸氧铀中的一种;
和/或,所述光催化剂的摩尔用量为各自烷基苯用量的2mol%;
和/或,所述光照采用23W紧凑型节能灯、1-20W 460nm波长蓝色LED灯、1-20W 430nm波长蓝色LED灯中的一种或多种。
8.如权利要求1或2所述的合成方法,其特征在于,所述合成反应的时间为1-96小时。
9.如权利要求3所述的合成方法,其特征在于,所述添加剂为质子酸,选自甲酸、甲磺酸、盐酸、三氯乙酸、冰乙酸、三氟乙酸、硫酸、氢溴酸、三氟甲磺酸、磷酸、三氯化铁、氯化锌、三氟化硼乙醚中的其中一种;
和/或,所述添加剂的摩尔用量为烷基苯(3)的1个当量;
和/或,所述合成反应时间为1-120小时。
11.如权利要求10所述的芳基醇化合物,其特征在于,Ar1选自苯基、硝基取代的苯基、氰基取代的苯基、酰基取代的苯基、羧酸乙酯基取代的苯基、羧基取代的苯基、卤素取代的苯基、烷氧基取代的苯基、苯并环己基酮基、联苯;R1选自C1-C10烷基、C3-C10环状烷基;R2选自C1-C10烷基、C3-C10环状烷基。
13.如权利要求12所述的芳基酮化合物,其特征在于,Ar2选自苯基、硝基苯基、羧酸乙酯基苯基、卤素取代的苯基、对(环丙基亚甲基氧)苯基、吡啶;R3选自C1-C10烷基、卤素取代的C1-C10烷基、丁酸酯乙基、氰基取代的C1-C10烷基、乙酸酯取代的C1-C10烷基、苯基。
15.如权利要求14所述的芳基羧酸化合物,其特征在于,Ar3选自硝基苯基、氰基苯基、三氟甲基苯基、乙酰基苯基、羧酸乙酯基苯基、卤素取代的苯基、苯基、联苯、(环丁基亚甲基氧)苯基、(环丙基亚甲基氧)苯基、(环氧乙烷亚甲基氧)苯基、(3,5-二氯苯基)苯并噁唑基。
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CN101362680A (zh) * | 2008-09-28 | 2009-02-11 | 华东师范大学 | 一种苯乙酮的制备方法 |
WO2019232715A1 (en) * | 2018-06-06 | 2019-12-12 | Rhodia Operations | Selective oxidation of alcohols |
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CN101362680A (zh) * | 2008-09-28 | 2009-02-11 | 华东师范大学 | 一种苯乙酮的制备方法 |
WO2019232715A1 (en) * | 2018-06-06 | 2019-12-12 | Rhodia Operations | Selective oxidation of alcohols |
Non-Patent Citations (9)
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