CN117447362A - Green synthesis method of azoxybenzene compound - Google Patents
Green synthesis method of azoxybenzene compound Download PDFInfo
- Publication number
- CN117447362A CN117447362A CN202311383296.5A CN202311383296A CN117447362A CN 117447362 A CN117447362 A CN 117447362A CN 202311383296 A CN202311383296 A CN 202311383296A CN 117447362 A CN117447362 A CN 117447362A
- Authority
- CN
- China
- Prior art keywords
- aromatic
- catalyst
- synthesis method
- green synthesis
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 azoxybenzene compound Chemical class 0.000 title claims description 30
- 238000001308 synthesis method Methods 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000004280 Sodium formate Substances 0.000 claims abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 4
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 81
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 239000007787 solid Substances 0.000 description 31
- 235000013024 sodium fluoride Nutrition 0.000 description 28
- 239000011775 sodium fluoride Substances 0.000 description 28
- 238000005481 NMR spectroscopy Methods 0.000 description 26
- 238000010586 diagram Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- 238000010898 silica gel chromatography Methods 0.000 description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- 238000004293 19F NMR spectroscopy Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical class C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 2
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 description 1
- YNOOQIUSYGWMSS-UHFFFAOYSA-N 2,5-difluoroaniline Chemical compound NC1=CC(F)=CC=C1F YNOOQIUSYGWMSS-UHFFFAOYSA-N 0.000 description 1
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 1
- AXNUZKSSQHTNPZ-UHFFFAOYSA-N 3,4-difluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1 AXNUZKSSQHTNPZ-UHFFFAOYSA-N 0.000 description 1
- KQOIBXZRCYFZSO-UHFFFAOYSA-N 3,5-difluoroaniline Chemical compound NC1=CC(F)=CC(F)=C1 KQOIBXZRCYFZSO-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- YSEMCVGMNUUNRK-UHFFFAOYSA-N 3-chloro-4-fluoroaniline Chemical compound NC1=CC=C(F)C(Cl)=C1 YSEMCVGMNUUNRK-UHFFFAOYSA-N 0.000 description 1
- RQKFYFNZSHWXAW-UHFFFAOYSA-N 3-chloro-p-toluidine Chemical compound CC1=CC=C(N)C=C1Cl RQKFYFNZSHWXAW-UHFFFAOYSA-N 0.000 description 1
- LJWAPDSCYTZUJU-UHFFFAOYSA-N 3-fluoro-4-methoxyaniline Chemical compound COC1=CC=C(N)C=C1F LJWAPDSCYTZUJU-UHFFFAOYSA-N 0.000 description 1
- XUJFOSLZQITUOI-UHFFFAOYSA-N 4-(trifluoromethoxy)aniline Chemical compound NC1=CC=C(OC(F)(F)F)C=C1 XUJFOSLZQITUOI-UHFFFAOYSA-N 0.000 description 1
- CSFDTBRRIBJILD-UHFFFAOYSA-N 4-chloro-2-fluoroaniline Chemical compound NC1=CC=C(Cl)C=C1F CSFDTBRRIBJILD-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- XAACOEWSHBIFGJ-UHFFFAOYSA-N 4-fluoro-3-methoxyaniline Chemical compound COC1=CC(N)=CC=C1F XAACOEWSHBIFGJ-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/08—Azoxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In an organic solvent, aromatic amine or aromatic hybrid amine is used as a raw material, and the aromatic amine is selectively oxidized into a corresponding azo oxide compound by a reaction system consisting of an oxidant and a catalyst; wherein the catalyst is NaOAc, sodium formate or KF, naF, csF, caF 2 、R″ 4 One or more of NF, wherein R' is one of alkyl, methyl, ethyl and butyl; compared with the metal catalyst in the prior art, the catalyst adopted by the invention has the advantages of low cost, high activity, good selectivity and small environmental pollution, and accords with the environment-friendly concept; meanwhile, the catalyst is less in dosage, the problems of catalyst recovery treatment and the like are not needed to be considered, and the operation steps are greatly simplified.
Description
Technical Field
The invention belongs to the field of synthesis of organic chemical raw materials and intermediates, and particularly relates to a green synthesis method for selectively catalyzing and oxidizing aromatic amine or aromatic hybrid amine into corresponding azoxybenzene compounds.
Background
The azoxybenzene compound has special 1, 3-dipole O-N=N bond, can be widely applied to the fields of medicines, dyes, resins, food additives, liquid crystal materials and the like, and has very broad market application prospect. Currently, azoxybenzene compounds are selectively prepared mainly through two paths of aromatic amino compound oxidation and aromatic nitro compound reduction, and the synthetic route is specifically shown in fig. 1; however, both processes require severe reaction conditions, and the selectivity of the target product is poor, which is challenging.
Typical reducing agents used in the reduction of aromatic nitro compounds include borohydride, hydrazine hydrate, alcohols and CO, such as: yufang Liu et al (molecular 2011,16,3563-3568) reduced several nitroaromatics to the corresponding azoxybenzenes in water using potassium borohydride under conditions of PEG-400 as a phase transfer catalyst. The method has simple experimental steps and high reaction efficiency. Ruiping Wei et al (Synth. Commun.2019,49:5, 688-696) developed a catalyst-free system for the reductive conversion of nitrobenzene to a variety of products. Nitrobenzene is used as a raw material, alcohol is used as a reducing agent, and KOH is utilized to promote the nitrobenzene to be selectively reduced into azoxybenzene and aniline. The method can complete selective conversion by only changing alcohols and changing temperature, and is simple to operate, economical and practical.
Hydrogen peroxide is commonly used as the oxidant in the oxidation process of aromatic amino compounds, and a few use oxygen or air as the oxidant. Such as: qin et al (Angew. Chem. Int. Ed.2022,61, e 202112907) developed a low cost, multifunctional Zr (OH) 4 Heterogeneous catalyst for use in H 2 O 2 Or O 2 The selective aniline oxide in the system is azoxybenzene. Song Yuwan et al (organic chemistry, 2019,39 (04): 1181-1186) report a method for improving the efficient, highly selective conversion of aniline to the corresponding azoxybenzene by adjusting the molar ratio of titanium silicon of TS-1. At a Si/Ti molar ratio of TS-1 of 80, H is used as 2 O 2 As an oxidizing agent, aryl anilines are converted in good yields and with high selectivity to the corresponding azoxybenzenes.
At present, a plurality of methods for synthesizing azoxybenzene are available, but the methods still need to be improved, for example, the requirements on equipment and other conditions in the synthesis process are high, a noble metal or a toxic catalyst is adopted in a reaction system, the environment is damaged, and some catalysts are difficult to recover, the required cost is high, and the application limitation is high. Therefore, the development of a green, efficient and safe way for obtaining the azoxybenzene product with high added value has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a green synthesis method of an azoxybenzene compound.
The invention adopts the following technical scheme:
in an organic solvent, aromatic amine or aromatic hybrid amine is used as a raw material, and the aromatic amine is selectively oxidized into a corresponding azo oxide compound by a reaction system consisting of an oxidant and a catalyst;
wherein the catalyst is NaOAc, sodium formate or KF, naF, csF, caF 2 、R″ 4 One or more of NF, wherein R' is one of alkyl, methyl, ethyl and butyl.
Further, the molar amount of the catalyst is 0.1-3equiv of the aromatic amine or the aromatic hetero amine.
Further, the catalyst is NaF.
Further, the molar amount of the oxidizing agent is 3-20equiv of the aromatic amine or the aromatic hetero amine.
Further, the oxidizing agent is hydrogen peroxide.
Further, the mass concentration of the hydrogen peroxide is more than or equal to 30%.
Further, the R, R' is selected from hydrogen, halogen, -CF 3 、-OCF 3 、-CHF 2 -one or more of CN, ester group, alkyl, alkoxy, aryl; ar is an aromatic groupAromatic rings or heteroaromatic rings, the aromatic rings being selected from benzene rings or naphthalene rings, the heteroaromatic rings being selected from pyridine, thiophene, furan, pyridazine, pyrimidine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, quinoline, benzothiazole or isoquinoline.
Further, the organic solvent is MeCN, DMF, DMSO, DCE, etOH, H 2 One or more of O.
Further, the reaction temperature is rt-100 ℃.
Further, the reaction time is 1h-36h.
As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following beneficial effects:
firstly, the method takes aromatic amine or aromatic hybrid amine as raw material, and uses hydrogen peroxide as oxidant through screening catalyst and solvent, so as to realize the efficient and selective oxidation of the aromatic amine or aromatic hybrid amine into corresponding azoxybenzene compounds under mild conditions; the oxidant selected by the method is green, environment-friendly, pollution-free, the catalyst is common and easy to obtain, the price is low, the catalytic effect is obvious, the reaction condition is mild, the operation is simple, the cost is low, the rate is high, the selectivity is high, the product yield is high, and the method is a novel synthesis method of the azoxybenzene compound with good scientific research value and industrialization potential;
secondly, compared with the traditional metal catalyst, the catalyst adopted by the invention has the advantages of low cost, high activity, good selectivity and small environmental pollution, and accords with the environment-friendly concept; meanwhile, the catalyst consumption is small, the problems of catalyst recovery treatment and the like are not needed to be considered, and the operation steps are greatly simplified;
thirdly, the acetonitrile solvent adopted by the invention has excellent performance, simple post-reaction treatment, high-yield target product can be quickly obtained, and the whole catalytic system has strong universality, good scientific research value and great industrial application potential;
fourth, the oxidant adopted in the invention is hydrogen peroxide, and the byproduct after the reaction is only water, so that the method has no pollution, and has low requirements on reaction equipment and conditions, and compared with the traditional oxidant, the method has the advantages of greatly reduced cost and improved safety;
fifth, the raw material aromatic amine or aromatic hybrid amine adopted by the invention is used as industrial basic raw material, and is cheap and easy to obtain.
Drawings
FIG. 1 is a schematic diagram of the oxidation reaction mechanism of aromatic amino compounds and the reduction reaction mechanism of aromatic nitro compounds;
FIG. 2 is a synthetic route diagram of the azoxybenzene compound of the present invention;
FIG. 3 is a synthetic route diagram of example 1;
FIG. 4 is a synthetic route diagram of example 4;
FIG. 5 is a synthetic route diagram of example 5;
FIG. 6 is a synthetic route diagram of example 6;
FIG. 7 is a synthetic route diagram of example 7;
FIG. 8 is a synthetic route diagram of example 8;
FIG. 9 is a synthetic route diagram of example 9;
FIG. 10 is a synthetic route diagram of example 10;
FIG. 11 is a synthetic route diagram of example 11;
FIG. 12 is a synthetic route diagram of example 12;
FIG. 13 is a synthetic route diagram of example 13;
FIG. 14 is a synthetic route diagram of example 14;
FIG. 15 is a synthetic route diagram of example 15;
FIG. 16 is a synthetic route diagram of example 16;
FIG. 17 is a synthetic route diagram of example 17;
FIG. 18 is a synthetic route diagram of example 18;
FIG. 19 is a synthetic route diagram of example 19;
FIG. 20 is a synthetic route diagram of example 20;
FIG. 21 is a synthetic route diagram of example 21;
FIG. 22 is a synthetic route diagram of example 22;
FIG. 23 is a synthetic route diagram of example 23;
FIG. 24 is a synthetic route diagram of example 24;
FIG. 25 is a synthetic route diagram of example 25;
FIG. 26 is a synthetic route diagram of example 26;
FIG. 27 is a chart of hydrogen nuclear magnetic resonance spectra of example 1;
FIG. 28 is a chart of the hydrogen nuclear magnetic resonance spectrum of example 4.
Detailed Description
The invention is further described below by means of specific embodiments.
In an organic solvent, aromatic amine or aromatic hybrid amine is taken as a raw material, and the aromatic amine is selectively oxidized into a corresponding azoxybenzene compound by utilizing a reaction system consisting of an oxidant and a catalyst, wherein the synthetic route is shown in a figure 2; specifically, the reaction temperature is rt-100 ℃; the reaction time is 1h-36h.
Wherein R, R' is selected from hydrogen, halogen, -CF 3 、-OCF 3 、-CHF 2 -one or more of CN, ester group, alkyl, alkoxy, aryl; ar is an aromatic ring or an aromatic heterocyclic ring, wherein the aromatic ring is selected from benzene ring or naphthalene ring, and the aromatic heterocyclic ring is selected from pyridine, thiophene, furan, pyridazine, pyrimidine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, quinoline, benzothiazole or isoquinoline.
The catalyst is NaOAc, sodium formate, KF, naF, csF, caF 2 、R″ 4 One or more of NF, wherein R' is one of alkyl, methyl, ethyl and butyl; specifically, the molar amount of the catalyst is 0.1-3equiv of the aromatic amine or the aromatic hetero amine.
The oxidant is hydrogen peroxide, and the mass concentration of the hydrogen peroxide is more than or equal to 30%; specifically, the molar amount of the oxidizing agent is 3-20equiv of the aromatic amine or the aromatic hetero amine.
The organic solvent is MeCN, DMF, DMSO, DCE, etOH, H 2 One or more of O.
The present invention will be further described in detail with reference to the following specific examples, but the content of the present invention is not limited thereto. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
Example 1
See FIG. 3 for a synthetic route.
Aniline (2 mmol,186 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (0.2 eq,17 mg) was added, and 2mL of 30% hydrogen peroxide was added to react at 80℃for 1h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give a yellow oil in 91% yield.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.34–8.29(m,2H),8.20–8.15(m,2H),7.60–7.46(m,5H),7.43–7.37(m,1H)。
comparative examples 1 to 6 were set for example 1, and the effect of the catalyst amount and the reaction time on the reaction was examined, and the catalytic results of aniline are shown in table 1, except that the catalyst amount and the reaction time were the same as those of example 1.
TABLE 1
As is clear from Table 1, when NaF was added in an amount of 0.2eq, the yield of the target product was 90% or more, and the reaction time was shortened as the yield of the product increased with increasing catalyst amount, so that the system was selectively charged with 2eq of catalyst.
Example 2
Aniline (2 mmol,186 mg) was dissolved in 4mL of DMF, sodium fluoride (2 eq,168 mg) was added, hydrogen peroxide 2mL was added, and the reaction was carried out at 80℃for 1h. The yield of the target product was 92% by GC monitoring.
For example 2, comparative examples 7-15 were set to examine the effect of different catalysts on the reaction, the catalyst amounts were all 4mmol, the remaining conditions were the same as in example 2, and the catalytic oxidation results of aniline are shown in Table 2.
TABLE 2
Example 3
Amplification reaction: aniline (53.7 mmol,5 g) was dissolved in 20mL acetonitrile, sodium fluoride (1 eq,2.25 g) was added, hydrogen peroxide (5 eq,27 mL) was slowly added dropwise to the reaction solution, and the reaction was carried out at 80 ℃ for 4 hours; the yield of the target product was 96% by GC monitoring. Namely, the reaction system has strong universality and can be used for large-scale industrial production.
Example 4
See FIG. 4 for synthetic routes.
Para-fluoroaniline (2 mmol,222 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 2 hours. After the reaction, the reaction solution was concentrated, and the product was precipitated, washed with water three times, filtered, and the solid was dried to obtain 210mg of yellow powder with a yield of 96%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.35–8.29(m,2H),8.29–8.23(m,2H),7.22–7.13(m,4H).19F NMR(376MHz,Chloroform-d)δ-108.03(q,J=6.3Hz),-108.59(q,J=6.9Hz)。
example 5
See FIG. 5 for synthetic routes.
P-chloroaniline (2 mmol,254 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 2 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 260mg of a yellow solid with a yield of 98%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.28–8.23(m,2H),8.19–8.13(m,2H),7.51–7.42(m,4H)。
example 6
See FIG. 6 for synthetic routes.
Para-methoxyaniline (2 mmol,246 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 2h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 253mg of a yellow solid in 98% yield.
The structural data are confirmed by nuclear magnetic resonance:
1 H NMR(400MHz,Chloroform-d)δ8.31–8.18(m,4H),7.00–6.93(m,4H),3.92–3.86(m,6H)。
example 7
See FIG. 7 for synthetic routes.
Para-tert-butylaniline (2 mmol,298 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 2 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 285mg of yellow crystals in 92% yield.
The structural data are confirmed by nuclear magnetic resonance:
1 H NMR(400MHz,Chloroform-d)δ8.23–8.18(m,2H),8.17–8.12(m,2H),7.53–7.48(m,4H),1.37(d,J=2.9Hz,18H)。
example 8
See FIG. 8 for synthetic routes.
Para-trifluoromethoxy aniline (2 mmol,354 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 3h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 348mg of white crystals with a yield of 95%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.40–8.34(m,2H),8.28–8.22(m,2H),7.34(dd,J=12.5,8.7Hz,4H).19F NMR(376MHz,Chloroform-d)δ-57.69,-57.79。
example 9
See FIG. 9 for synthetic routes.
4-alkynylaniline (2 mmol,234 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 2 hours. After the reaction, the reaction solution was concentrated to precipitate a solid, which was rinsed three times with water, filtered, and the solid was dried to give a yellow solid with a yield of 96%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.31–8.24(m,1H),8.18–8.13(m,1H),7.65–7.56(m,2H),3.27(s,1H),3.21(s,0H)。
example 10
See FIG. 10 for synthetic routes.
O-fluoroaniline (2 mmol,222 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 12 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 166mg of a yellow solid in 71% yield.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.25–8.19(m,1H),7.86(td,J=7.9,1.8Hz,1H),7.44(tdd,J=8.1,4.6,1.7Hz,1H),7.34–7.28(m,1H),7.24–7.12(m,4H).19F NMR(376MHz,Chloroform-d)δ-115.92(dt,J=11.9,6.1Hz),-120.70(dt,J=11.4,5.4Hz)。
example 11
See FIG. 11 for synthetic routes.
O-chloroaniline (2 mmol,254 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 12 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 215mg of a yellow solid in 81% yield.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.01(dd,J=8.0,1.7Hz,1H),7.76(dd,J=7.5,2.1Hz,1H),7.57–7.51(m,2H),7.48–7.42(m,2H),7.39(td,J=7.7,1.4Hz,1H),7.31(td,J=7.7,1.7Hz,1H)。
example 12
See FIG. 12 for synthetic routes.
O-methylaniline (2 mmol,214 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 12 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 199mg of a yellow solid with a yield of 88%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.03(dd,J=7.5,2.3Hz,1H),7.68(dd,J=8.1,1.5Hz,1H),7.42–7.37(m,1H),7.35–7.30(m,4H),7.29–7.27(m,1H),2.53(s,3H),2.38(s,3H)。
example 13
See FIG. 13 for synthetic routes.
2, 6-difluoroaniline (2 mmol,258 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 12h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 227mg of a yellow solid with a yield of 84%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ7.48(tt,J=8.6,5.9Hz,1H),7.33(tt,J=8.5,6.0Hz,1H),7.12(t,J=8.0Hz,2H),7.04(t,J=8.4Hz,2H).19F NMR(376MHz,Chloroform-d)δ-113.50(t,J=7.3Hz),-120.53(t,J=7.3Hz)。
example 14
See FIG. 14 for synthetic routes.
Methylaniline (2 mmol,214 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, hydrogen peroxide 2mL was added, and the mixture was reacted at 80℃for 12 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 219mg of a yellow oil in 97% yield.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.24(dd,J=13.3,2.3Hz,1H),8.10–8.04(m,2H),7.99(ddd,J=9.0,2.4,1.5Hz,1H),7.02(td,J=8.9,2.0Hz,2H),3.97(d,J=3.9Hz,6H)。
example 15
See FIG. 15 for synthetic routes.
M-trifluoromethylaniline (2 mmol,322 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 1.5h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 311mg of a yellowish green solid in 93% yield.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.63(s,1H),8.54(d,J=8.3Hz,1H),8.48(s,1H),8.38(d,J=7.8Hz,1H),7.87(d,J=7.7Hz,1H),7.67(dt,J=24.7,8.1Hz,3H).19F NMR(376MHz,Chloroform-d)δ-62.69,-62.74。
example 16
See FIG. 16 for synthetic routes.
2, 4-difluoroaniline (2 mmol,258 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 5h. After the reaction was completed, the reaction solution was concentrated, rinsed three times with water, filtered, and the solid was dried to give 248mg of yellow solid with a yield of 92%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.61–8.52(m,1H),8.02–7.93(m,1H),7.06–6.93(m,4H).19F NMR(376MHz,Chloroform-d)δ-103.46,-105.16,-110.83,-114.45。
example 17
See FIG. 17 for synthetic routes.
2, 5-difluoroaniline (2 mmol,258 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 12h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 251mg of a yellow solid with a yield of 93%.
The structural data are confirmed by nuclear magnetic resonance: 1H NMR (400 MHz, chloroform-d) delta 8.25-8.18 (m, 1H), 7.72-7.66 (m, 1H), 7.31-7.26 (m, 1H), 7.24 (dd, J=4.4, 1.9Hz, 1H), 7.19 (td, J=9.4, 4.8Hz, 1H), 7.15-7.08 (m, 1H).
Example 18
See FIG. 18 for synthetic routes.
3, 5-difluoroaniline (2 mmol,258 mg) was dissolved in 4mL acetonitrile, sodium fluoride (4 mmol,168 mg) was added, hydrogen peroxide 2mL was added, and the reaction was carried out at 80℃for 13h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 259mg of yellow solid in 96% yield.
The structural data are confirmed by nuclear magnetic resonance: 1H NMR (400 MHz, chloroform-d) delta 7.91-7.84 (m, 2H), 7.79-7.72 (m, 2H), 7.07 (tt, J=8.2, 2.4Hz, 1H), 6.91 (tt, J=8.5, 2.4Hz, 1H) 19F NMR (376MHz, chloroform-d) delta-106.55 (t, J=7.6 Hz), -108.67 (t, J=8.2 Hz).
Example 19
See FIG. 19 for the synthetic route.
3, 4-difluoroaniline (2 mmol,258 mg) was dissolved in 4mL acetonitrile, sodium fluoride (4 mmol,168 mg) was added, hydrogen peroxide 2mL was added, and the reaction was carried out at 80℃for 8h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 262mg of a yellow solid with a yield of 97%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.33(ddd,J=12.2,7.7,2.4Hz,1H),8.22–8.16(m,1H),8.14–8.09(m,1H),7.89(ddt,J=8.7,4.3,2.1Hz,1H),7.36–7.23(m,2H).19F NMR(376MHz,Chloroform-d)δ-131.16(dt,J=20.7,10.4Hz),-131.77–-131.98(m),-133.85(dt,J=19.5,9.2Hz),-135.17(dt,J=20.9,10.5Hz)。
example 20
See FIG. 20 for synthetic routes.
3-methoxy-4-fluoroaniline (2 mmol,282 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 10 hours. After the reaction, the reaction solution was concentrated to precipitate a solid, and the solid was suction-filtered, rinsed three times with water, and the filter cake was dried to obtain 288mg of yellow solid with a yield of 98%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.06(dd,J=8.3,2.3Hz,1H),7.95(dd,J=7.6,2.6Hz,1H),7.92–7.88(m,1H),7.79(ddd,J=8.9,4.4,2.4Hz,1H),7.18(ddd,J=10.7,8.8,3.4Hz,2H),4.00(s,3H),3.96(s,3H).19F NMR(376MHz,Chloroform-d)δ-129.34(t,J=10.3Hz),-129.55(dd,J=14.3,8.4Hz)。
example 21
See FIG. 21 for synthetic routes.
3-chloro-4-fluoroaniline (2 mmol,290 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 2 hours. After the reaction, the reaction solution was concentrated to precipitate a solid, and the solid was filtered, rinsed three times with water, and the cake was dried to obtain 296mg of a white solid with a yield of 98%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.47(dd,J=7.2,2.4Hz,1H),8.42(dd,J=6.5,2.7Hz,1H),8.23(ddd,J=9.0,4.2,2.7Hz,1H),8.08(ddd,J=9.0,4.6,2.4Hz,1H),7.31–7.26(m,1H),7.24(d,J=8.8Hz,1H).19F NMR(376MHz,Chloroform-d)δ-109.32,-110.21。
example 22
See FIG. 22 for synthetic routes.
2-fluoro-4-chloroaniline (2 mmol,290 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 14h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 260mg of a yellow solid in 86% yield.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.43(dd,J=9.1,7.9Hz,1H),7.95–7.88(m,1H),7.34–7.26(m,2H),7.25–7.20(m,2H).19F NMR(376MHz,Chloroform-d)δ-112.98(t,J=9.0Hz),-116.67(t,J=8.9Hz)。
example 23
See FIG. 23 for synthetic routes.
3-fluoro-4-methoxyaniline (2 mmol,282 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 12h. After the reaction, the reaction solution was concentrated to precipitate a solid, and the solid was filtered, rinsed three times with water, and the cake was dried to give 276mg of a yellow solid with a yield of 94%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.24(dd,J=13.3,2.3Hz,1H),8.11–8.04(m,2H),7.99(ddt,J=8.9,2.5,1.5Hz,1H),7.02(td,J=8.9,1.6Hz,2H),3.97(d,J=3.8Hz,6H).19F NMR(376MHz,Chloroform-d)δ-132.53(t,J=9.8Hz),-133.55(dd,J=13.4,9.1Hz)。
example 24
See FIG. 24 for synthetic routes.
2, 5-dimethylaniline (2 mmol,242 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 8 hours. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 199mg of a yellow solid with a yield of 88%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ7.75(s,1H),7.47(s,1H),7.22–7.17(m,3H),7.07(d,J=9.8Hz,1H),2.47(s,3H),2.39(d,J=5.6Hz,6H),2.31(s,3H).
example 25
See FIG. 25 for synthetic routes.
3-chloro-4-methylaniline (2 mmol,282 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, and 2mL of hydrogen peroxide was added to react at 80℃for 4h. After the reaction was completed, the reaction solution was concentrated to precipitate a solid, and the solid was filtered and rinsed three times with water, and dried to give 282mg of a yellow solid with a yield of 96%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ8.33–8.29(m,2H),8.09(dd,J=8.3,2.3Hz,1H),7.97(dd,J=8.3,2.0Hz,1H),7.35(dd,J=10.5,7.9Hz,2H),2.47(s,3H),2.44(s,3H)。
example 26
See FIG. 26 for synthetic routes.
3-aminopyridine (2 mmol,188 mg) was dissolved in 4mL of acetonitrile, sodium fluoride (4 mmol,168 mg) was added, hydrogen peroxide 2mL was added, and the mixture was reacted at 80℃for 12h. After the completion of the reaction, the reaction mixture was poured into 10mL of water, extracted three times with methylene chloride, and the organic phase was concentrated and purified by silica gel column chromatography (gradient 0 to 5% PE: EA) to give 196mg of a white solid with a yield of 98%.
The structural data are confirmed by nuclear magnetic resonance:
1H NMR(400MHz,Chloroform-d)δ9.58(d,J=2.5Hz,1H),9.27(d,J=2.3Hz,1H),8.84(dd,J=4.8,1.5Hz,1H),8.79(ddd,J=8.3,2.4,1.5Hz,1H),8.64(dd,J=4.9,1.5Hz,1H),8.61(ddd,J=8.4,2.6,1.5Hz,1H),7.50(dddd,J=14.3,8.4,4.8,0.7Hz,2H)。
according to the invention, aromatic amine or aromatic hybrid amine is used as a raw material, and through screening a catalyst and a solvent, hydrogen peroxide is used as an oxidant, and the efficient and selective oxidation of the aromatic amine or aromatic hybrid amine into corresponding azoxybenzene compounds is realized under mild conditions; the oxidant selected by the method is green and environment-friendly, has no pollution, the catalyst is common and easy to obtain, the price is low, the catalytic effect is obvious, the reaction condition is mild, the operation is simple, the cost is low, the rate is high, the selectivity is high, the product yield is high, and the method is a novel synthesis method of the azoxybenzene compound with good scientific research value and industrialization potential.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the claims and the description, but rather is to cover all modifications which are within the scope of the invention.
Claims (10)
1. A green synthesis method of an azoxybenzene compound is characterized in that: in an organic solvent, aromatic amine or aromatic hybrid amine is taken as a raw material, and the aromatic amine is selectively oxidized into a corresponding azo oxide compound by utilizing a reaction system consisting of an oxidant and a catalyst, wherein the synthetic route is as follows:
wherein the catalyst is NaOAc, sodium formate or KF, naF, csF, caF 2 、R″ 4 One or more of NF, wherein R' is one of alkyl, methyl, ethyl and butyl.
2. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the molar amount of the catalyst is 0.1-3equiv of aromatic amine or aromatic hetero amine.
3. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the catalyst is NaF.
4. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the molar amount of the oxidant is 3-20equiv of aromatic amine or aromatic hetero amine.
5. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the oxidizing agent is hydrogen peroxide.
6. The green synthesis method of the azoxybenzene compound according to claim 5, wherein the method comprises the following steps: the mass concentration of the hydrogen peroxide is more than or equal to 30 percent.
7. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the R, R' is selected from hydrogen, halogen, -CF 3 、-OCF 3 、-CHF 2 -one or more of CN, ester group, alkyl, alkoxy, aryl; ar is an aromatic ring or an aromatic heterocyclic ring, wherein the aromatic ring is selected from benzene ring or naphthalene ring, and the aromatic heterocyclic ring is selected from pyridine, thiophene, furan, pyridazine, pyrimidine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, quinoline, benzothiazole or isoquinoline.
8. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the organic solvent is MeCN, DMF, DMSO, DCE, etOH, H 2 One or more of O.
9. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the reaction temperature is rt-100 ℃.
10. The green synthesis method of the azoxybenzene compound according to claim 1, which is characterized in that: the reaction time is 1h-36h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311383296.5A CN117447362A (en) | 2023-10-24 | 2023-10-24 | Green synthesis method of azoxybenzene compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311383296.5A CN117447362A (en) | 2023-10-24 | 2023-10-24 | Green synthesis method of azoxybenzene compound |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117447362A true CN117447362A (en) | 2024-01-26 |
Family
ID=89592213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311383296.5A Pending CN117447362A (en) | 2023-10-24 | 2023-10-24 | Green synthesis method of azoxybenzene compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117447362A (en) |
-
2023
- 2023-10-24 CN CN202311383296.5A patent/CN117447362A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111269129B (en) | Method for preparing 5,5 '-disubstituted-2, 2' -diaminobiphenyl and hydrochloride thereof by continuous flow oxidation coupling method | |
CN117447362A (en) | Green synthesis method of azoxybenzene compound | |
CN108276261B (en) | Method for preparing 2-bromofluorenone by catalyzing molecular oxygen oxidation in aqueous phase | |
WO2017177531A1 (en) | Method for preparing 9-fluorenone from fluorene | |
CN114516817B (en) | Chemical intermediate and preparation method thereof | |
CN112778351B (en) | Preparation method of beta-dimethylphenyl silicon substituted aromatic nitro compound | |
CN108003031A (en) | A kind of method for preparing nitro compound using graphene catalysis nitrogen dioxide | |
CN104447391A (en) | Methylenebisamide derivative and preparation method thereof | |
CN111269149B (en) | Production process of 5- (3,3-dimethylguanidino) -2-oxopentanoic acid | |
CN108299384A (en) | Trifluoromethylthio transfering reagent compound and its synthetic method | |
CN114436846A (en) | Nitrate transesterification reagent and preparation method and application thereof | |
CN102180794B (en) | Method for synthesizing nitrobenzene compounds | |
CN109438349A (en) | 6- (alpha-cyano imines) base phenanthridines class compound and its synthetic method | |
CN115340485B (en) | Method for synthesizing indole terpene analogues by palladium-catalyzed cascade Heck/carbonyl ortho-alkylation reaction | |
CN111875534B (en) | Safe and efficient preparation method of 1, 8-diformylcarbazole | |
CN110372633B (en) | Method for catalyzing reduction of iminodibenzyl carbonyl derivative | |
CN114832862B (en) | Catalytic composition for coupling reaction and application of catalytic composition in preparation of isoquinoline-1, 3-dione compounds | |
CN110467558B (en) | Reaction method for synthesizing 3-aminoisoindolinone under catalysis of nickel | |
CN110015987B (en) | Preparation method of 2,3 '-dimethoxy- [2,4' ] bipyridyl | |
CN111499539B (en) | Aryl cyanide synthesis method using aryl carboxylic acid as raw material | |
CN114874105B (en) | Preparation method of visible light and water promoted homoallylic amine compound | |
CN110041285B (en) | Preparation method of 2, 4, 5-trisubstituted oxazole compound | |
CN102093354B (en) | Indolizine Mannich base compound and preparation method thereof | |
CN118146116A (en) | Method for preparing imine from nitrobenzene | |
CN116041376A (en) | Preparation method of 2-fluoro-4-pyridine boric acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |