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Preparation method of 3,4,5-trifluoro-2'-nitro-1,1'-biphenyl

A technology for nitrobiphenyl and nitrobenzoate is applied in the field of preparation of 3,4,5-trifluoro-2'-nitrobiphenyl, and can solve the problems of high cost, complicated steps and high risk. , to achieve the effect of low production cost, short synthesis steps and low equipment requirements

Inactive Publication Date: 2017-11-14
SHANGHAI TAIHE INT TRADE CO LTD
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Problems solved by technology

[0004] At present, there are the following reports on the preparation method of 3,4,5-trifluoro-2'-nitrobiphenyl: CN104529786 and WO2009156359 respectively disclose a method for preparing 3,4,5-trifluoro-2'-nitrobiphenyl Benzene method: Using 3,4,5-trifluorophenylboronic acid and o-chloronitrobenzene as raw materials, the Suzuki coupling reaction was carried out under the action of palladium catalyst to synthesize 3,4,5-trifluoro-2'-nitro Biphenyl, however, aryl boronic acid usually needs to be synthesized from halogenated benzene through Grignard reagent, borate ester and hydrolysis in three steps. The synthetic route is complicated and the cost is high. There are more three wastes produced; and borate is a kind of relatively expensive chemical raw material. If trifluorophenylboronic acid is obtained through purchase, it will also greatly increase the cost of industrial production
[0005] WO2010102980 discloses a method for preparing 3,4,5-trifluoro-2'-nitrobiphenyl using a non-coupling method. The method uses 3,4,5-trifluorobromobenzene as a raw material, and forms The multi-step reactions such as oxidation, Aldol condensation reaction, Diels-Alder reaction, oxidative aromatization, etc. to prepare the target compound, the method steps are complicated, the yield is low, and the reagents n-butyllithium, nitromethane and 1,3-butanedi Oxygen is flammable, explosive and highly dangerous

Method used

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Embodiment 1

[0042] In this embodiment, 3,4,5-trifluoro-2'-nitrobiphenyl is prepared by the following method, which specifically includes the following steps:

[0043] (1) Preparation of o-nitrobenzoate

[0044] Add 100g of o-nitrobenzoic acid, 470mL of absolute ethanol to a 1L three-necked flask, and add potassium hydroxide ethanol solution dropwise at room temperature [41.2g potassium hydroxide (85% by mass) dissolved in 470mL of absolute ethanol] After stirring for 2 hours at room temperature, a large amount of light yellow solid precipitated during this process, filtered and dried to obtain 116 g of light yellow powdery solid potassium salt of o-nitrobenzoic acid.

[0045] (2) Preparation of 3,4,5-trifluoro-2'-nitrobiphenyl

[0046] Add 108g o-nitrobenzoic acid potassium salt, 105.5g 3,4,5-trifluorobromobenzene, 2.1g triphenylphosphine, 0.6g 1,10-phenanthroline, 0.28g sodium chloride in a 2L three-necked flask Copper, 65mg bis(dibenzylideneacetone)palladium and 500g N,N-dimethylformamide. Re...

Embodiment 2

[0048] Add 109g o-nitrobenzoic acid sodium salt, 105.5g 3,4,5-trifluorobromobenzene, 2.4g 2-(di-tert-butylphosphine)biphenyl, 0.6g 1,10-phenanthroline into a 2L three-necked flask, 0.53g cuprous iodide, 0.7g Pd / C and 500g trimethylbenzene. Replace nitrogen for three times, stir and warm to 150°C, react for 30 hours, then cool to room temperature, filter, recover the palladium catalyst from the filter cake, and wash the filtrate twice with 1% (w / w) hydrochloric acid solution to separate the organic phase and remove After the trimethylbenzene was dissolved and recovered, the crude product was obtained, which was recrystallized with isobutanol to obtain 101 g of 3,4,5-trifluoro-2'-nitrobiphenyl with a yield of 80%. The content of the product was 96% by quantitative HPLC analysis.

Embodiment 3

[0050] Add 108g o-nitrobenzoic acid potassium salt, 83.3g 3,4,5-trifluorochlorobenzene, 2.1g triphenylphosphine, 0.6g 1,10-phenanthroline, 0.4g bromide into a 2L three-necked flask Copper, 0.7g MS-Pd and 500g trimethylbenzene. Replace the nitrogen for three times, stir and raise the temperature to 160° C., react for 20 hours, then cool to room temperature, filter, and recover the palladium catalyst from the filter cake. The filtrate was washed twice with 1% (w / w) hydrochloric acid solution, the organic phase was separated, and the crude product was obtained after desolvation and recovery of trimethylbenzene, which was recrystallized with isobutanol to obtain 114g of 3,4,5-trifluoro-2'-nitrate The yield of biphenyl was 90%, and the content of the product was 97% by quantitative HPLC analysis.

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Abstract

The invention provides a preparation method of 3,4,5-trifluoro-2'-nitro-1,1'-biphenyl. The method comprises the following step: performing a decarboxylation coupling reaction on o-nitrobenzoate shown as a formula I and halogeno benzene shown as a formula II in the presence of a catalyst to obtain the 3,4,5-trifluoro-2'-nitro-1,1'-biphenyl, wherein X1 is a metal cation; X2 is any one of Cl, Br or I. The preparation method has the advantages of use of cheap and readily-available raw materials, avoidance of preparation of an arylboronic acid compound, short synthesis step, higher yield, high product purity, low production cost, no harsh reaction conditions, low equipment requirement, little emission of three wastes, only emission of carbon dioxide and inorganic salts, safety and environmental friendliness, and is suitable for industrial production.

Description

Technical field [0001] The invention belongs to the technical field of chemical synthesis and relates to a method for preparing 3,4,5-trifluoro-2'-nitrobiphenyl. Background technique [0002] 3,4,5-trifluoro-2'-nitrobiphenyl is an important intermediate for the preparation of the agricultural fungicide fluconazole (Fluxapyroxad), its molecular formula is: C 12 H 6 F 3 NO 2 ; CAS number is: 1056196-56-5; structural formula is: [0003] [0004] At present, there are the following reports on the preparation method of 3,4,5-trifluoro-2'-nitrobiphenyl: CN104529786 and WO2009156359 respectively disclose a method for preparing 3,4,5-trifluoro-2'-nitrobiphenyl Benzene method: 3,4,5-trifluorophenylboronic acid and o-chloronitrobenzene are used as raw materials, and 3,4,5-trifluoro-2'-nitro is synthesized by Suzuki coupling reaction under the action of palladium catalyst Biphenyl, but aryl boronic acid usually needs to be synthesized from halogenated benzene through three steps of Grignard...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C201/12C07C205/12
CPCC07C201/12C07C205/12
Inventor 张浩赵宏伟王淼张照军谢思勉田晓宏
Owner SHANGHAI TAIHE INT TRADE CO LTD
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