CN116102453A - Method for preparing diphenyl hydrazine or 2H-indazole compound by utilizing azobenzene compound - Google Patents
Method for preparing diphenyl hydrazine or 2H-indazole compound by utilizing azobenzene compound Download PDFInfo
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- CN116102453A CN116102453A CN202211535667.2A CN202211535667A CN116102453A CN 116102453 A CN116102453 A CN 116102453A CN 202211535667 A CN202211535667 A CN 202211535667A CN 116102453 A CN116102453 A CN 116102453A
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- compound
- indazole
- azobenzene
- phenyl
- hydrazine
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- -1 2H-indazole compound Chemical class 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 53
- YBQZXXMEJHZYMB-UHFFFAOYSA-N 1,2-diphenylhydrazine Chemical compound C=1C=CC=CC=1NNC1=CC=CC=C1 YBQZXXMEJHZYMB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003960 organic solvent Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 229940124530 sulfonamide Drugs 0.000 claims description 7
- 150000003456 sulfonamides Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical class C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 18
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- 238000001228 spectrum Methods 0.000 description 27
- 238000000926 separation method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 241000282326 Felis catus Species 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000000746 purification Methods 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- QZEWCQGGAIGUPS-UHFFFAOYSA-N benzene-1,2-diol;boric acid Chemical compound OB(O)O.OC1=CC=CC=C1O.OC1=CC=CC=C1O QZEWCQGGAIGUPS-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 239000010453 quartz Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000005286 illumination Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DXFUKGOIQHQVRL-UHFFFAOYSA-N 2,3-diphenylindazole Chemical class C1=CC=CC=C1C1=C2C=CC=CC2=NN1C1=CC=CC=C1 DXFUKGOIQHQVRL-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- OXAFDXWMDZZORA-UHFFFAOYSA-N 1,2-bis(4-bromophenyl)hydrazine Chemical compound C1=CC(Br)=CC=C1NNC1=CC=C(Br)C=C1 OXAFDXWMDZZORA-UHFFFAOYSA-N 0.000 description 3
- WLIHKOXMZBJACE-UHFFFAOYSA-N 1-phenyl-2-[4-(trifluoromethyl)phenyl]hydrazine Chemical compound C1=CC(C(F)(F)F)=CC=C1NNC1=CC=CC=C1 WLIHKOXMZBJACE-UHFFFAOYSA-N 0.000 description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical group NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 3
- YERVDRGMKDTBDL-UHFFFAOYSA-N 1-[4-[2-(4-acetylphenyl)hydrazinyl]phenyl]ethanone Chemical compound C1=CC(C(=O)C)=CC=C1NNC1=CC=C(C(C)=O)C=C1 YERVDRGMKDTBDL-UHFFFAOYSA-N 0.000 description 2
- VWHCYGDZGLKYIK-UHFFFAOYSA-N 1-phenyl-2-(4-phenylphenyl)hydrazine Chemical compound N(NC1=CC=C(C=C1)C1=CC=CC=C1)C1=CC=CC=C1 VWHCYGDZGLKYIK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- NMCIPMLLSDPYDL-UHFFFAOYSA-N (2-iodophenyl)-phenyldiazene Chemical compound IC1=CC=CC=C1N=NC1=CC=CC=C1 NMCIPMLLSDPYDL-UHFFFAOYSA-N 0.000 description 1
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- YLDZLMYBCBYPPZ-UHFFFAOYSA-N 1-[4-[(4-acetylphenyl)diazenyl]phenyl]ethanone Chemical compound C1=CC(C(=O)C)=CC=C1N=NC1=CC=C(C(C)=O)C=C1 YLDZLMYBCBYPPZ-UHFFFAOYSA-N 0.000 description 1
- 125000001088 1-naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- 125000003541 2-chlorobenzoyl group Chemical group ClC1=C(C(=O)*)C=CC=C1 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- LTPLLZWVPBTAMH-UHFFFAOYSA-N bis(4-bromophenyl)diazene Chemical compound C1=CC(Br)=CC=C1N=NC1=CC=C(Br)C=C1 LTPLLZWVPBTAMH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- PKXRSRRXINHVGC-UHFFFAOYSA-N phenyl-(2-phenyldiazenylphenyl)methanone Chemical compound C=1C=CC=C(N=NC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 PKXRSRRXINHVGC-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic compound preparation, and particularly relates to a method for preparing diphenyl hydrazine or 2H-indazole compounds by utilizing an azobenzene compound. The method comprises the following steps: mixing an azobenzene compound, biboronate, water and an organic solvent, and reacting to obtain a diphenyl hydrazine or 2H-indazole compound; the reaction is carried out under visible light; the reaction time is less than 2 hours. According to the invention, azobenzene compound is used as a raw material, water is used as a hydrogen source, biboronate is added, the reaction is carried out under the irradiation of visible light under the condition of no metal catalyst, and the diphenyl hydrazine or 2H-indazole compound product with the yield of not less than 70% can be prepared after the reaction time of less than 1 hour. The method of the invention has wide functional group compatibility, so that various azobenzene compounds can be converted into diphenyl hydrazine or 2H-indazole compounds.
Description
Technical Field
The invention belongs to the technical field of organic compound preparation, and particularly relates to a method for preparing diphenyl hydrazine or 2H-indazole compounds by utilizing an azobenzene compound.
Background
The diphenyl hydrazine and 2H-indazole compounds are used as important organic chemical raw materials, and can be widely applied to the fields of synthesizing various fine chemical products such as organic dyes, pigments, pesticides, medicines and functional materials. The current methods for preparing the diphenyl hydrazine compounds mainly comprise the following steps: (1) an azobenzene or azoxybenzene compound reduction method; (2) a transition metal reduction method of nitro or nitrosyl benzene; (3) an arylamine compound oxidation method; (4) phenylhydrazine substituted halogenated aromatic hydrocarbon method; (5) an aryl hydroxylamine compound oxidation method. The preparation method of the 2H-indazole compound mainly comprises the following steps: (1) A cross coupling method of ortho halogen substituted benzaldehyde and phenylhydrazine; (2) 1, 3-dipolar cycloaddition of diazo compounds; (3) C-H bond amination synthesis method of phenylhydrazone.
The existing methods for preparing the diphenyl hydrazine compounds are many, and most of the traditional laboratory and industrial preparation methods are to use aryl nitro compounds as raw materials and reduce the aryl nitro compounds by zinc powder in a strong alkaline medium. Such conventional methods require the use of a large amount of organic transition metal as a catalyst, alcohol as a hydrogen source in the presence of an excessive amount of strong base, and reaction at a relatively high temperature, and require a reaction time of more than 12 hours, so that the substrate has a narrow application range. There have been attempts in the prior art to prepare a diphenyl hydrazine compound without using a metal catalyst, but it is often required to heat to a higher temperature and react for up to 24 hours or even longer to obtain the diphenyl hydrazine compound. The method for synthesizing the 2H-indazole compound is reported to be more in the past, noble metal catalysis is generally needed or expensive ligands are needed, and the method is not friendly to the environment, has higher cost and is difficult to apply to industrial production. There are also attempts to synthesize 2H-indazoles using non-metal catalyzed methods, but usually use large amounts of additives to aid the reaction, which do not meet the requirements of atomic economy.
Therefore, there is a need to provide a new preparation method of diphenyl hydrazine and 2H-indazole compounds, which does not need to use metal catalysts, does not need to be heated, and has short reaction time (less than 24 hours) and high product yield.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. To this end, the present invention proposes a process for preparing a diphenylhydrazine or 2H-indazole compound using an azobenzene compound. The method of the invention does not need to use metal catalyst and heating, only needs visible light illumination under normal temperature condition, has short reaction time (less than 24 hours and even less than 2 hours or 1 hour) and high product yield.
The invention is characterized in that: according to the invention, azobenzene compound is used as a raw material, water is used as a hydrogen source, biboronate is added, and under the condition of no metal catalyst, under the irradiation of visible light (preferably 400nm-500 nm), the reaction time is less than 1 hour, so that the diphenyl hydrazine or 2H-indazole compound product with the yield not less than 70% can be prepared. Furthermore, the method of the present invention exhibits a wide range of functional group compatibility, allowing various types of azobenzene compounds to be converted into diphenylhydrazine or 2H-indazole compounds.
In a first aspect, the present invention provides a process for preparing a diphenylhydrazine or 2H-indazole compound using an azobenzene compound.
Specifically, the method for preparing the diphenyl hydrazine or 2H-indazole compound by utilizing the azobenzene compound comprises the following steps:
mixing an azobenzene compound, biboronate, water and an organic solvent, and reacting to obtain the diphenyl hydrazine or 2H-indazole compound;
the reaction is carried out under visible light;
the reaction time is less than 2 hours.
Preferably, the reaction is carried out under light of 400nm to 500 nm; further preferably, the reaction is carried out under light of 400nm to 450 nm.
Preferably, the reaction time is less than 1 hour; further preferably, the reaction time is 30 minutes to 1 hour.
Preferably, the structural general formula of the azobenzene compound is Ar 1 -N＝N-Ar 2 Wherein Ar is 1 And Ar is a group 2 Each independently represents an aryl group or a substituted aryl group.
Preferably, the aryl group is an aromatic ring of 6 to 16 carbon atoms; further preferably, the aryl group is an aromatic ring of 6 to 10 carbon atoms.
Further preferably, the aryl group is at least one selected from phenyl and naphthyl.
Preferably, the substituted aryl group has one or more substituent groups (where the plurality of substituent groups means two or more substituent groups, the plurality of substituent groups may be the same or different when the plurality of substituent groups are the plurality of substituent groups), and the substituent groups are at least one selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, halo, nitro, alkoxy, ester, sulfonamide, cyano, carbonyl, and trifluoromethyl.
Preferably, the carbon number of the alkyl and alkoxy is 1-15; further preferably, the carbon number of the alkyl group or the alkoxy group is 2 to 8.
Preferably, the azobenzene compound is selected from any one of the following:
preferably, the diphenyl hydrazine compound is selected from any one of the following:
preferably, the 2H-indazole compound is selected from any one of the following:
preferably, the bisborate is selected from the group consisting of biscatechol borates (the biscatechol borates abbreviated as B) 2 cat 2 . The structure is that
)。
Preferably, the organic solvent is selected from at least one of Tetrahydrofuran (THF), acetonitrile (MeCN), methanol (MeOH) or Dichloromethane (DCM); further preferably, the organic solvent is Tetrahydrofuran (THF).
Preferably, the molar ratio of the azobenzene compound, the biboronate and the water is 1: (0.5-5): (10-100); it is further preferable that the molar ratio of the azobenzene compound, the diboronate, and water is 1: (1-1.5): (10-50).
Preferably, the dosage ratio of the azobenzene compound to the organic solvent is 0.1mmol:0.5-5mL; preferably 0.1mmol:0.5-1mL.
Preferably, the mixing process is simultaneous feed mixing of the components or stepwise mixing.
Preferably, the reaction is carried out by mixing the components under a closed condition and an inert atmosphere (such as nitrogen and argon), and irradiating with light.
Preferably, after the reaction is finished, removing the organic solvent, and separating to obtain the diphenyl hydrazine or the 2H-indazole compound.
Preferably, the organic solvent is removed by rotary evaporation.
Preferably, the diphenyl hydrazine or the 2H-indazole compound is obtained by separation through column chromatography and high performance liquid chromatography.
The use of the above method according to the second aspect of the invention.
In particular, the method is applied to the field of organic synthesis.
Preferably, the organic synthesis field includes the fields of organic dye, pigment, pesticide, medicine or functional material synthesis.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, azobenzene compound is used as a raw material, water is used as a hydrogen source, biboronate is added, the reaction is carried out under the irradiation of visible light under the condition of no metal catalyst, and the diphenyl hydrazine or 2H-indazole compound product with the yield of not less than 70% can be prepared after the reaction time of less than 1 hour. The method of the invention has wide functional group compatibility, so that various azobenzene compounds can be converted into diphenyl hydrazine or 2H-indazole compounds.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1: preparation of 1, 2-diphenyl hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in the preparation of the 1, 2-diphenyl hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) Mixing 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of azobenzene and 0.1mL of water to obtain a mixture, taking out a sealed test tube from a glove box, placing the test tube under 450nm of light for stirring reaction for 30 minutes, removing the organic solvent under reduced pressure, separating and purifying by column chromatography, wherein the developing agent used in the separating and purifying process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and separating to obtain the product 1, 2-diphenyl hydrazine, wherein the yield of the 1, 2-diphenyl hydrazine is 92.0%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 1 are characterized by: 1 H-NMR(CDCl 3 ,400MHz)δ(ppm)7.26-7.22(t,4H),6.89 -6.87(m,6H),5.63(s,2H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.85,129.36,119.91,112.33。
example 2: preparation of 1-phenyl-2- [4- (trifluoromethyl) phenyl ] -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 1-phenyl-2- [4- (trifluoromethyl) phenyl ] -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) Mixing 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 4-trifluoromethyl azobenzene and 0.1mL of water to obtain a mixture, taking out a sealed test tube from a glove box, placing the test tube under 450nm of light for stirring and reacting for 30 minutes, removing the organic solvent under reduced pressure, separating and purifying by column chromatography, wherein a developing agent used in the separating and purifying process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and separating to obtain a product 1-phenyl-2- [4- (trifluoromethyl) phenyl]-hydrazine, 1-phenyl-2- [4- (trifluoromethyl) phenyl ]]The yield of hydrazine was 91.5%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in this example 2 are characterized as follows: 1 H-NMR(CDCl 3 ,400MHz)δ(ppm)7.50-7.47(d,2H)7.29-7.25(m,2H),6.94-6.89(m,3H),6.86-6.83(q,2H),5.85-5.73(d,2H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)151.55,148.05,129.49,126.83,126.79,126.76,126.72,126.04,123.34,121.76,121.43,120.50,112.40,111.60。
example 3: preparation of 1-phenyl-2- [4- (benzoyl) phenyl ] -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 1-phenyl-2- [4- (benzoyl) phenyl ] -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) Mixing 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 4-benzoylazobenzene and 0.1mL of water to obtain a mixture, taking out a sealed test tube from a glove box, placing the test tube under 450nm of light for stirring and reacting for 30 minutes, removing the organic solvent under reduced pressure, separating and purifying by column chromatography, wherein a developing agent used in the separating and purifying process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 5:1), and separating to obtain a product 1-phenyl-2- [4- (benzoyl) phenyl]-hydrazine, 1-phenyl-2- [4- (benzoyl) phenyl ]]The yield of hydrazine was 97.6%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in this example 3 are characterized by: 1 H-NMR(CDCl 3 ,400MHz)δ(ppm)7.79-7.74(m,4H),7.58-7.54(t,1H),7.49-7.45(t,2H),7.28-7.24(q,2H),6.92-6.84(m,5H),6.09(s,1H),5.79(s,1H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)195.36,152.87,147.99,138.73,132.84,131.55,129.59,129.47,128.81,128.11,120.51,112.45,111.05。
example 4: preparation of 1-phenyl-2- (2-iodophenyl) -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 1-phenyl-2- (2-iodophenyl) -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) Mixing 1.5mL of tetrahydrofuran as an organic solvent, 0.2mmol of 2-iodoazobenzene and 0.1mL of water to obtain a mixture, taking out a sealed test tube from a glove box, placing the test tube under 450nm of light for stirring reaction for 30 minutes, removing the organic solvent under reduced pressure, and passing through a columnThe chromatography is carried out for separation and purification, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 1-phenyl-2- (2-iodinated phenyl) -hydrazine is obtained by separation, and the yield of the 1-phenyl-2- (2-iodinated phenyl) -hydrazine is 82.0%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in this example 4 are characterized by: 1 H-NMR(CDCl 3 ,400MHz)δ(ppm)7.72-7.70(d,1H),7.27-7.19(m,3H),6.99-6.97(d,1H),6.90-6.87(t,1H),6.84-6.82(d,2H),6.03(s,1H),5.73(s,1H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.17,147.26,138.98,129.51,129.43,121.33,120.28,112.89,112.40,81.34。
example 5: 1-phenyl-2- (4-biphenyl) -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in the preparation of 1-phenyl-2- (4-biphenyl) -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 4-biphenylazobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out of a glove box, the sealed test tube is placed under illumination of 450nm and stirred for reaction for 30 minutes, then the organic solvent is removed under reduced pressure, separation and purification are carried out by column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 1-phenyl-2- (4-biphenylyl) -hydrazine is obtained by separation, wherein the yield of the 1-phenyl-2- (4-biphenylyl) -hydrazine is 96.0%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 5 are characterized by: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.65-7.63(d,2H),7.57-7.55(d,2H),7.52-7.48(t,2H),7.40-7.36(t,1H),7.35-7.31(t,2H),6.99-6.93(m,5H),5.67-5.64(d,2H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.88,148.38,141.08,132.92,129.48,128.81,128.13,126.57,126.53,120.08,112.76,112.48。
example 6: preparation of 1-phenyl-2- [4- (sulfonamide) phenyl ] -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 1-phenyl-2- [4- (sulfonamide) phenyl ] -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) Mixing 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 4-sulfonamide azobenzene and 0.1mL of water to obtain a mixture, taking out a sealed test tube from a glove box, placing the test tube under 450nm of light for stirring and reacting for 30 minutes, removing the organic solvent under reduced pressure, separating and purifying by column chromatography, wherein a developing agent used in the separating and purifying process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and separating to obtain a product 1-phenyl-2- [4- (sulfonamide) phenyl]-hydrazine, 1-phenyl-2- [4- (sulfonamide) phenyl ]]The yield of hydrazine was 81.0%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 6 are characterized by: 1 H-NMR(DMSO,400MHzδ(ppm)8.30(s,1H),7.83(s,1H),7.58-7.56(d,2H),7.16-7.12(t,2H),6.98(s,2H),6.81-6.79(d,2H),6.72-6.67(q,3H)； 13 C-NMR(DMSO,125MHz)δ(ppm)153.21,149.61,132.74,129.41,127.86,118.71,112.26,110.81。
example 7: preparation of 1, 2-bis (4-bromophenyl) -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in the preparation of 1, 2-bis (4-bromophenyl) -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 4,4' -dibromoazobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out of a glove box, the sealed test tube is placed under illumination of 450nm and stirred for reaction for 30 minutes, then the organic solvent is removed under reduced pressure, separation and purification are carried out through column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 1, 2-bis (4-bromophenyl) -hydrazine is obtained through separation, and the yield is 92.4%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 7 are characterized by: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.34-7.30(m,4H),6.75-6.71(m,4H),5.64(s,2H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)147.46,132.20,113.98,111.92。
example 8: preparation of 1, 2-bis [4- (acetyl) phenyl ] -hydrazine
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 1, 2-bis [4- (acetyl) phenyl ] -hydrazine is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of tetrahydrofuran, 0.2mmol of 4,4' -diacetylazobenzene, and 0.1mL of water were mixed to obtain a mixture, and the mixture was prepared fromTaking out the sealed test tube from the glove box, placing the test tube under 450nm light, stirring and reacting for 30 minutes, removing the organic solvent under reduced pressure, separating and purifying by column chromatography, wherein the developing agent used in the separating and purifying process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and separating to obtain the product 1, 2-bis [4- (acetyl) phenyl]-hydrazine, 1, 2-bis [4- (acetyl) phenyl ]]The yield of hydrazine was 93.9%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in this example 8 are characterized by: 1 H-NMR(DMSO,400MHzδ(ppm)8.63(s,2H),7.80-7.78(d,4H),6.76.-6.73(d,4H),3.36(s,6H)； 13 C-NMR(DMSO,125MHz)δ(ppm)195.91,153.86,130.90,127.87,110.89,26.48。
example 9: preparation of 2, 3-diphenyl-2H-indazoles
The reaction equation (only the target product is shown in the reaction equation) involved in preparing the 2, 3-diphenyl 2H-indazole is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 2-benzoylazobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out of a glove box, the sealed test tube is placed under illumination of 450nm and stirred for reaction for 30 minutes, then the organic solvent is removed under reduced pressure, separation and purification are carried out through column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 2, 3-diphenyl-2H-indazole is obtained through separation, wherein the yield of the 2, 3-diphenyl-2H-indazole is 89.5%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in this example 9 are characterized as follows: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.84-7.82(d,1H),7.76-7.73(d,1H),7.48-7.38(m,11H),7.19-7.15(q,1H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)149.02,140.28,135.42,129.96,129.70,128.97,128.76,128.31,128.25,126.98,126.04,122.51,121.77,120.51,117.78。
example 10: preparation of 2-phenyl-3- (2-fluorophenyl) -5-chloro-2H-indazole
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 2-phenyl-3- (2-fluorophenyl) -5-chloro-2H-indazole is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of tetrahydrofuran as an organic solvent, 0.2mmol of 4-chloro-2- (2-fluorobenzoyl) azobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out from a glove box, stirred and reacted for 30 minutes under 450nm of light, then the organic solvent is removed under reduced pressure, separation and purification are carried out by column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 2-phenyl-3- (2-fluorophenyl) -5-chloro-2H-indazole is obtained by separation, wherein the yield of the 2-phenyl-3- (2-fluorophenyl) -5-chloro-2H-indazole is 97.8%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 10 are characterized as follows: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.79-7.77(d,1H),7.59(s,1H),7.46-7.30(m,8H),7.24-7.20(m,1H),7.15-7.11(t,1H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)160.79,158.30,147.30,140.14,131.79,131.77,131.31,131.23,129.36,129.07,128.56,128.40,128.34,125.05,124.66,124.62,123.11,119.52,119.11,117.61,117.46,116.60,116.39。
example 11: preparation of 2-phenyl-3-naphthyl-2H-indazoles
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 2-phenyl-3-naphthyl-2H-indazole is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 2- (1-naphthoyl) azobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out from a glove box, the sealed test tube is placed under illumination of 450nm and stirred for reaction for 1 hour, then the organic solvent is removed under reduced pressure, separation and purification are carried out by column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 2-phenyl-3-naphthyl-2H-indazole is obtained by separation, wherein the yield of the 2-phenyl-3-naphthyl-2H-indazole is 99.4%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in this example 11 are characterized by: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.96-7.92(m,3H),7.71-7.69(d,2H),7.54-7.38(m,8H),7.25-7.23(t,3H),7.12-7.08(q,1H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.91,140.28,134.01,133.77,132.08,129.65,129.53,128.82,127.08,126.84,126.34,125.65,125.32,125.06,123.45,122.33,120.87,117.87。
example 12: preparation of 2-phenyl-3- (2-chlorophenyl) -2H-indazole
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 2-phenyl-3- (2-chlorophenyl) -2H-indazole is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of tetrahydrofuran as an organic solvent, 0.2mmol of 2- (2-chlorobenzoyl) azobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out from a glove box, the mixture is placed under illumination of 450nm and stirred for reaction for 1 hour, then the organic solvent is removed under reduced pressure, separation and purification are carried out by column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the yield of the product 2-phenyl-3- (2-chlorophenyl) -2H-indazole is 96.9 percent.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 12 are characterized as follows: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.84-7.82(d,1H),7.70-7.68(d,1H),7.45-7.38(m,8H),7.31-7.29(d,2H),7.19-7.16(q,1H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.99,140.00,134.50,134.13,130.86,129.15,129.14,128.51,128.40,127.12,126.04,122.89,121.73,120.12,117.91。
example 13: preparation of 2-phenyl-3-cyclohexyl-2H-indazoles
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 2-phenyl-3-cyclohexyl-2H-indazole is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of tetrahydrofuran as an organic solvent, 0.2mmol of 2-cyclohexylformylazobenzene and 0.1mL of water, and the mixture was mixed to obtain a mixture, the sealed test tube was taken out of the glove box, and the mixture was stirred under 450nm light for 1 hourThen removing the organic solvent under reduced pressure, separating and purifying by column chromatography, wherein the developing agent used in the separating and purifying process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and separating to obtain the product 2-phenyl-3-cyclohexyl-2H-indazole, wherein the yield of the 2-phenyl-3-cyclohexyl-2H-indazole is 96.6%.
The nmr hydrogen spectrum and nmr carbon spectrum of the product obtained in example 13 are characterized by: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.90-7.88(d,1H),7.76-7.73(d,1H),7.54-7.51(m,5H),7.34-7.30(m,1H),7.09-7.05(m,1H),3.04-2.96(m,1H),2.03-1.85(m,6H),1.45-1.22(m,4H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.88,141.14,140.23,129.14,128.98,126.45,126.32,121.24,120.55,119.53,117.84,37.32,32.60,26.59,25.88。
example 14: preparation of 2-phenyl-3-undecyl-2H-indazoles
The reaction equation (only the target product is shown in the reaction equation) involved in preparing 2-phenyl-3-undecyl-2H-indazole is as follows:
a method for preparing diphenyl hydrazine or 2H-indazole compounds by using an azobenzene compound, comprising the following steps:
in a glove box under nitrogen atmosphere, 0.3mmol of the bis-catechol borate (B) was added in sequence to a 10mL quartz tube equipped with a stirrer 2 cat 2 ) 1.5mL of organic solvent tetrahydrofuran, 0.2mmol of 2-dodecanoylazobenzene and 0.1mL of water are mixed to obtain a mixture, a sealed test tube is taken out of a glove box, the sealed test tube is placed under illumination of 450nm, stirring reaction is carried out for 40min, then the organic solvent is removed under reduced pressure, separation and purification are carried out through column chromatography, the developing agent used in the separation and purification process is a mixed solution of n-hexane/ethyl acetate (volume ratio is 15:1), and the product 2-phenyl-3-undecyl-2H-indazole is obtained through separation, wherein the yield of the 2-phenyl-3-undecyl-2H-indazole is 70.5%.
Nuclear magnetic resonance hydrogen Spectrometry and Nuclear magnetic resonance of the product obtained in example 14The carbon spectrum characterization results are: 1 H-NMR(CDCl 3 ,400MHzδ(ppm)7.76-7.74(d,1H),7.70-7.68(d,1H),7.55-7.48(m,5H),7.35-7.32(t,1H),7.11-7.07(q,1H),3.07-3.03(t,2H),1.70-1.63(m,2H),1.31-1.22(m,16H),0.92-0.89(t,3H)； 13 C-NMR(CDCl 3 ,125MHz)δ(ppm)148.64,140.16,136.93,129.14,128.85,126.63,126.21,121.09,120.89,120.24,117.62,31.90,29.57,29.55,29.38,29.37,29.31,29.28,29.10,25.29,22.68,14.10。
comparative example 1
In comparison with example 1, comparative example 1 differs only in that the biscatechol borate (B) in example 1 was replaced by an equivalent amount of pinacol borate 2 cat 2 ) The yield of 1, 2-diphenyl hydrazine was 15%.
Claims (10)
1. A process for preparing a diphenyl hydrazine or 2H-indazole compound using an azobenzene compound, comprising the steps of:
mixing an azobenzene compound, biboronate, water and an organic solvent, and reacting to obtain the diphenyl hydrazine or 2H-indazole compound;
the reaction is carried out under visible light;
the reaction time is less than 2 hours.
2. The method according to claim 1, wherein the reaction is carried out under light of 400nm to 500 nm.
3. The method of claim 1, wherein the reaction time is less than 1 hour.
4. The method according to claim 1, wherein the azobenzene compound has a structural formula of Ar 1 -N＝N-Ar 2 Wherein Ar is 1 And Ar is a group 2 Each independently represents an aryl group or a substituted aryl group.
5. The method according to claim 4, wherein the aryl group is at least one selected from the group consisting of phenyl and naphthyl.
6. The method of claim 4, wherein the substituted aryl group has one or more substituents thereon, and wherein the substituents are at least one selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, halo, nitro, alkoxy, ester, sulfonamide, cyano, carbonyl, and trifluoromethyl.
7. The method according to claim 1, wherein the molar ratio of azobenzene compound, biboronate, water is 1: (0.5-5): (10-100).
8. The method according to claim 1 or 4, wherein the azobenzene compound is selected from any one of the following:
the diphenyl hydrazine compound is selected from any one of the following:
the 2H-indazole compound is selected from any one of the following:
9. use of the method according to any one of claims 1-8 in the field of organic synthesis.
10. The use according to claim 9, characterized in that the field of organic synthesis is comprised in the field of organic dye, pigment, pesticide, pharmaceutical or functional material synthesis.
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| FÉLIX MATADAMAS-MARTÍNEZ, ET AL.: "Synthesis and Antitumor Activity of 2, 3-Diphenyl-2Hindazole Derivatives as Potent Antitubulin Agents", 《MEDICINAL CHEMISTRY & DRUG DISCOVERY》, 18 July 2022 (2022-07-18), pages 202202056 * |
| 张高举 等: "锌-琥珀酸铵还原体系用于氢化偶氮苯的合成", 《精细化工》, vol. 46, no. 2, 31 December 2015 (2015-12-31), pages 44 - 46 * |
| 杨国坤: "硝基苯催化加氢制二苯肼的研究", 《湖北民族学院学报（自然科学版）》, no. 2, 31 December 1989 (1989-12-31), pages 89 - 91 * |
| 甘景镐: "《农药药剂学》", 31 July 1952, 中国科学图书仪器公司, pages: 26 * |
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