CN105017025B - The preparation method of one kind 4 '-chloro- 2 nitro biphenyl - Google Patents
The preparation method of one kind 4 '-chloro- 2 nitro biphenyl Download PDFInfo
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- CN105017025B CN105017025B CN201410164140.2A CN201410164140A CN105017025B CN 105017025 B CN105017025 B CN 105017025B CN 201410164140 A CN201410164140 A CN 201410164140A CN 105017025 B CN105017025 B CN 105017025B
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Abstract
The invention discloses a kind of preparation methods of 2 nitrobiphenyl of 4 ' chlorine, make rubigan magnesium halide and 2 nitro halogeno-benzenes that 4 ' chlorine, 2 nitrobiphenyl be obtained by the reaction in the presence of a nickel catalyst, in a solvent.Preparation method provided by the invention is not needed to using expensive palladium catalyst, at low cost, reaction step is few, reaction selectivity and high income.
Description
Technical field
The present invention relates to the preparation methods of one kind 4 '-chloro- 2 nitro biphenyl.
Background technology
4 '-chloro- 2 nitro biphenyl is the important intermediate of pesticide Boscalid, and the preparation method prior art has following report
Road：
Chinese patent CN97192942.4, which is disclosed, a kind of prepares 4 '-method of chloro- 2 nitro biphenyl：With rubigan boron
Acid or its Arrcostab, acid anhydrides and o-chloronitrobenzene are raw material, and suzuki coupling reactions occur under the action of palladium catalyst and are made
4 '-chloro- 2 nitro biphenyl.Chinese patent CN200680006706.2 improves the above method, uses two (4- chlorobenzenes
Base) boric acid replace rubigan boric acid carry out coupling reaction, reduce and prepare alkyl expensive used in rubigan boric acid
The dosage of borate simultaneously improves reactivity to reduce the dosage of palladium catalyst.The shortcomings that this two kinds of patented methods, is, former
Expect that boron alkyl acid esters and palladium catalyst are expensive.
The method that China profit CN200680021005.6 discloses another preparation 4 '-chloro- 2 nitro biphenyl：With adjacent nitro
Benzoic acid and para chlorobromobenzene are raw material, and coupling reaction occurs under the action of palladium catalyst and appropriate alkali, additive and is made
Target compound.This method is still needed to using expensive palladium catalyst, also needs addition mantoquita or silver salt, molecular sieve, potassium fluoride etc. more
Kind additive.
PCT Patent Application WO2010102980A1 discloses a kind of non-coupled method not needed to using noble metal catalyst
The method of preparation 4 '-chloro- 2 nitro biphenyl, using o-nitrobenzaldehyde as initial feed, through Aldol condensation reactions, Diels-
Target compound is made in the multistep reactions such as Alder reactions, oxidation aromatization.This method processing step is complicated, and aromatisation is received
Rate is extremely low, reagent nitromethane and 1,3-butadiene are inflammable and explosive.
Therefore, it is necessary to develop a kind of novel 4 '-preparation method of chloro- 2 nitro biphenyl.
Invention content
The purpose of the present invention is to provide a kind of novel 4 '-preparation method of chloro- 2 nitro biphenyl, without using your gold
Metal catalyst, at low cost, reaction step is few, reaction selectivity and high income.
In the prior art, Grignard Reagent is referred to as with the coupling reaction of alkenyl halide or halogenated aryl hydrocarbon under nickel or palladium chtalyst
Bear field (Kumada) coupling reaction.In general, Grignard Reagent cannot coexist with nitro compounds, so reaction is generally unsuitable for preparing nitre
Base joins benezene material.Present inventor creatively has found, at a lower temperature in the presence of a nickel catalyst, rubigan halogen
Coupling reaction generation 4 '-chloro- 2 nitro biphenyl can be occurred, and can reach higher selectivity by changing magnesium and 2- nitros halogeno-benzene
And yield.
It is to reach goal of the invention the technical solution adopted by the present invention：
The preparation method of one kind 4 '-chloro- 2 nitro biphenyl, it is characterised in that the method includes making rubigan magnesium halide
(I) with 2- nitros halogeno-benzene (II) in the presence of a nickel catalyst, 4 ' are obtained by the reaction in a solvent-chloro- 2 nitro biphenyl (III)：
It is described：X1And X2Independently selected from chlorine, bromine or iodine；
Reaction temperature is 0 DEG C~-78 DEG C.
As preferred mode, above-mentioned Raney nickel is preferably bis- (diphenylphosphine) the ethane chlorination nickel of 1,2-, bis- (triphenyls
Phosphine) Nickel Chloride, [bis- (diphenylphosphine) ferrocene of 1,1'-] Nickel Chloride or bis- (diphenylphosphine) the propyl nickel chlorides of 1,3-；Institute
The dosage for stating Raney nickel is preferably the 1%~100% of 2- nitros halogeno-benzene (II) molal quantity, and further preferably 5%~
30%, particularly preferably 10%~20%.
The solvent that the present invention uses can be the mixture of ethers or ethers and aprotic solvent.The ethers
It preferably is selected from tetrahydrofuran, methyltetrahydrofuran, ether, isopropyl ether, butyl oxide, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, diethyl
Glycol dimethyl ether, ethylene glycol diethyl ether or Isosorbide-5-Nitrae-dioxane；Further preferably tetrahydrofuran or methyltetrahydrofuran.It is described
Aprotic solvent preferably is selected from petroleum ether, n-hexane, normal heptane, toluene or dimethylbenzene；Further preferably toluene or dimethylbenzene.This
It is preferably that every mole of 2- nitros halogeno-benzene (II) uses 500~5000 grams of solvents to invent the dosage of solvent used；It is further excellent
It is selected as every mole of 2- nitros halogeno-benzene (II) and uses 1000~2500 grams of solvents.
In reaction of the present invention, 2- nitros halogeno-benzene (II) and the molar ratio of rubigan magnesium halide (I) are preferably 1:
0.5~1.The rubigan magnesium halide (I) preferably adds in reaction in the form of a solution, and the quality of rubigan magnesium halide solution is dense
Degree preferably 1%~30%, and further preferably 10%~15%.
Reaction temperature of the invention suitable is 0 DEG C~-78 DEG C, preferably -20~-70 DEG C, and further preferably -30 DEG C
~-50 DEG C；Reaction time is 0.5~24 hour, preferably 2~12 hours.
Compared with prior art, the present invention has the following advantages：
(1) cheap Raney nickel is used, is avoided low using noble metal catalysts, production costs such as expensive palladiums；
(2) 4 ' are obtained using the method single step reaction that is directly coupled-chloro- 2 nitro biphenyl, processing step is short, and need not make
With the aryl boric acid or aryl boric acid ester compounds for preparing cumbersome higher price；
(3) reaction selectivity and yield are relatively high.
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
In the examples below, unless otherwise specified, " % " representation quality percentage.
Embodiment 1
The 2- nitro-chlorobenzenes of 10.0g are dissolved in 180mL tetrahydrofurans, add in 3.4g1, bis- (diphenylphosphine) ethane chlorinations of 2-
Nickel is cooled to -45 DEG C, keeps -40 DEG C~-45 DEG C of system temperature in the rubigan chlorination magnesium that 11% is slowly added in about 2h
Tetrahydrofuran solution 98.7g, drip Bi Baowen 6h, after removing low-temperature receiver, be slowly warmed to room temperature, add in 30mL toluene and 30mL20%
Hydrochloric acid, stirring after static layering, takes organic layer to be evaporated to obtain grease crude product, using recrystallisation from isopropanol, obtains yellow solid
11.4g.After tested, yellow solid obtained for 4 '-chloro- 2 nitro biphenyl, purity 96.3%.Reaction yield 74%.
Embodiment 2
The 2- nitro iodobenzenes of 10.0g are dissolved in 150mL tetrahydrofurans, add in 2.3g1, bis- (diphenylphosphine) ethane chlorinations of 2-
Nickel is cooled to -78 DEG C, keeps -78 DEG C~-70 DEG C of system temperature in the rubigan chlorination magnesium that 15% is slowly added in about 4h
Tetrahydrofuran solution 45.7g, drip Bi Baowen 12h, after removing low-temperature receiver, be slowly warmed to room temperature, add in 30mL toluene with
The hydrochloric acid of 30mL20% stirs, after static layering, organic layer is taken to be evaporated to obtain grease crude product, using recrystallisation from isopropanol, is obtained yellow
Color solid 6.36g.After tested, yellow solid obtained for 4 '-chloro- 2 nitro biphenyl, purity 97.0%.Reaction yield 66%.
Embodiment 3
The 2- nitro-chlorobenzenes of 10.0g are dissolved in 200mL tetrahydrofurans, add in 6.8g1, bis- (diphenylphosphine) ethane chlorinations of 2-
Nickel is cooled to -50 DEG C, keeps -45 DEG C~-50 DEG C of system temperature in the rubigan chlorination magnesium that 10% is slowly added in about 3h
Tetrahydrofuran solution 108.5g, drip Bi Baowen 4h, after removing low-temperature receiver, be slowly warmed to room temperature, add in 30mL toluene with
The hydrochloric acid of 30mL20% stirs, after static layering, organic layer is taken to be evaporated to obtain grease crude product, using recrystallisation from isopropanol, is obtained light
Yellow solid 11.9g.After tested, yellow solid obtained for 4 '-chloro- 2 nitro biphenyl, purity 97.5%.Reaction yield
78%.
Embodiment 4
The 2- nitro-chlorobenzenes of 10.0g are dissolved in 200mL tetrahydrofurans, add in bis- (triphenylphosphine) Nickel Chlorides of 8.0g, drop
Temperature keeps -45 DEG C~-50 DEG C of system temperature in the four of the rubigan chlorination magnesium that 10% is slowly added in about 3h to -50 DEG C
Hydrogen tetrahydrofuran solution 108.5g drips Bi Baowen 4h, after removing low-temperature receiver, is slowly warmed to room temperature, and adds in 30mL toluene and 30mL20%
Hydrochloric acid stirs, after static layering, organic layer is taken to be evaporated to obtain grease crude product, using recrystallisation from isopropanol, obtains faint yellow solid
11.0g.After tested, yellow solid obtained for 4 '-chloro- 2 nitro biphenyl, purity 97.2%.Reaction yield 72%.
Embodiment 5
The 2- nitro-chlorobenzenes of 10.0g are dissolved in 150mL toluene, add in 10.0g [1,1'- bis- (diphenylphosphine) ferrocene] two
Nickel chloride is cooled to -40 DEG C, keeps -35 DEG C~-40 DEG C of system temperature in the parachlorobenzyl chloride that 11% is slowly added in about 2h
Change the tetrahydrofuran solution 99.0g of magnesium, drip Bi Baowen 5h, after removing low-temperature receiver, be slowly warmed to room temperature, add in the salt of 30mL20%
Reactant is removed catalyst by one section of silica gel after stirring, after static layering, organic layer is taken to be evaporated to obtain grease crude product by acid,
Using recrystallisation from isopropanol, yellow solid 10.1g is obtained.After tested, yellow solid obtained for 4 '-chloro- 2 nitro biphenyl, purity
95.8%.Reaction yield 65%.
Claims (10)
1. the preparation method of one kind 4 '-chloro- 2 nitro biphenyl, it is characterised in that the method includes making rubigan magnesium halide
(I) with 2- nitros halogeno-benzene (II) in the presence of a nickel catalyst, 4 ' are obtained by the reaction in a solvent-chloro- 2 nitro biphenyl (III)：
It is described：X1And X2Independently selected from chlorine, bromine or iodine；
Reaction temperature is -20~-70 DEG C；
The Raney nickel is selected from bis- (diphenylphosphine) the ethane chlorination nickel of 1,2-, bis- (triphenylphosphine) Nickel Chlorides, [1,1'- is bis-
(diphenylphosphine) ferrocene] Nickel Chloride or bis- (diphenylphosphine) the propyl nickel chlorides of 1,3-.
2. described in accordance with the claim 14 '-preparation method of chloro- 2 nitro biphenyl, it is characterised in that the Raney nickel
Dosage is the 1%~100% of 2- nitros halogeno-benzene (II) molal quantity.
3. described in accordance with the claim 24 '-preparation method of chloro- 2 nitro biphenyl, it is characterised in that the Raney nickel
Dosage is the 5%~30% of 2- nitros halogeno-benzene (II) molal quantity.
4. described in accordance with the claim 34 '-preparation method of chloro- 2 nitro biphenyl, it is characterised in that the Raney nickel
Dosage is the 10%~20% of 2- nitros halogeno-benzene (II) molal quantity.
5. described in accordance with the claim 14 '-preparation method of chloro- 2 nitro biphenyl, it is characterised in that the solvent is ethers
Or the mixture of ethers and aprotic solvent；The ethers is selected from tetrahydrofuran, methyltetrahydrofuran, ether, isopropyl ether, two fourths
Ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether or Isosorbide-5-Nitrae-dioxane；It is described non-
Proton solvent is selected from petroleum ether, n-hexane, normal heptane, toluene or dimethylbenzene；The dosage of the solvent is every mole of 2- nitro halogen
500~5000 grams of solvents are used for benzene (II).
6. according to the preparation method of 4 ' described in claim 5-chloro- 2 nitro biphenyl, it is characterised in that the ethers is selected from four
Hydrogen furans or methyltetrahydrofuran；The aprotic solvent is selected from toluene or dimethylbenzene；The dosage of the solvent is every mole of 2-
Nitro halogeno-benzene (II) uses 1000~2500 grams of solvents.
7. described in accordance with the claim 14 '-preparation method of chloro- 2 nitro biphenyl, it is characterised in that the 2- nitros are halogenated
The molar ratio of benzene (II) and rubigan magnesium halide (I) is 1:0.5~1；The rubigan magnesium halide (I) adds in the form of a solution
Enter reaction, the mass concentration of rubigan magnesium halide solution is 1%~30%.
8. according to the preparation method of 4 ' described in claim 7-chloro- 2 nitro biphenyl, it is characterised in that the rubigan halogen
The mass concentration for changing magnesium solution is 10%~15%.
9. described in accordance with the claim 14 '-preparation method of chloro- 2 nitro biphenyl, it is characterised in that the reaction time for 0.5~
24 hours.
10. according to the preparation method of 4 ' described in claim 9-chloro- 2 nitro biphenyl, it is characterised in that reaction temperature is-30
DEG C~-50 DEG C, the reaction time is 2~12 hours.
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| CN106397208B (en) * | 2016-08-30 | 2019-03-12 | 京博农化科技股份有限公司 | A kind of preparation method of Boscalid intermediate 2- (4- chlorphenyl) nitrobenzene |
| CN108046975A (en) * | 2017-12-27 | 2018-05-18 | 安徽金善化工科技有限公司 | A kind of preparation method of biphenyl |
| CN108083967A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of distillation recovery method of toluene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288895A (en) * | 1992-04-13 | 1994-02-22 | Elf Sanofi | Process for the preparation of a biphenyl derivative |
| CN101337895A (en) * | 2008-08-11 | 2009-01-07 | 武邑天大精细化工高新技术开发中心 | Method for preparing 2,2'-di(trifluoromethyl)-4,4'-benzidine |
| CN103360261A (en) * | 2013-07-12 | 2013-10-23 | 泰州百力化学股份有限公司 | Method for synthesizing nitrobiphenyl compound |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288895A (en) * | 1992-04-13 | 1994-02-22 | Elf Sanofi | Process for the preparation of a biphenyl derivative |
| CN101337895A (en) * | 2008-08-11 | 2009-01-07 | 武邑天大精细化工高新技术开发中心 | Method for preparing 2,2'-di(trifluoromethyl)-4,4'-benzidine |
| CN103360261A (en) * | 2013-07-12 | 2013-10-23 | 泰州百力化学股份有限公司 | Method for synthesizing nitrobiphenyl compound |
Non-Patent Citations (1)
| Title |
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| 联苯类化合物的合成;李文燕 等;《有机化学》;20111231;第31卷(第6期);第784-790页 * |
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