CN106631812A - Preparation method of 4'-chloro-2-nitro-1,1'-biphenyl serving as boscalid intermediate - Google Patents
Preparation method of 4'-chloro-2-nitro-1,1'-biphenyl serving as boscalid intermediate Download PDFInfo
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Abstract
The invention discloses a preparation method of 4'-chloro-2-nitro-1,1'-biphenyl serving as a boscalid intermediate. The 4'-chloro-2-nitro-1,1'-biphenyl is obtained by taking o-chloronitrobenzene and chlorobenzeneboronic acid as raw materials and carrying out Suzuki coupling reaction under the protection of nitrogen or other inert gases and under the action of an alkaline reagent, nickel catalysts or a CuI catalyst. In the preparation method disclosed by the invention, the raw materials are simple and easily obtained; the preparation method is simple and convenient in post treatment, and provides a basis for research and development of new pesticides.
Description
Technical field
The invention belongs to pesticide intermediate synthesis technical field, is related to the preparation method of disinfectant use in agriculture intermediate, especially
It is related to a kind of preparation method of Boscalid intermediate 4 '--1,1 '-biphenyl of chloro- 2- nitros.
Background technology
Boscalid is the new nicotinamide systemic fungicide developed by BASF Aktiengesellschaft, and its chemical name is
The chloro- N- of 2-（4- chlorodiphenyl -2- bases）Niacinamide, is butanedioic acid ubiquinone reductase inhibitor in mitochondrial respiratory chain, and its is main
For preventing and treating powdery mildew, gray mold, sclerotiniose and various rots.Its mechanism of action is more special, with carbendazim, Sukeling
Deng without cross resistance, the preventing and treating of the related disease that can be used to including the crop of the fruit such as the vegetables such as rape, tomato, grape.Base
In this, Boscalid has become a kind of important new type bactericide, and market potential is huge.
4 '-chloro- 2- nitro -1,1 '-biphenyl be synthesize Boscalid important intermediate, traditional synthesis 4 '-chloro- 2- nitre
Base -1, the method for 1 '-biphenyl has with o-iodonitrobenzene as raw material, for example CN 103073489A patents, with o-iodonitrobenzene and
It is raw material to chlorophenylboronic acid, the use of toluene and buck is mixed solvent, with Pd/C as catalyst, reaction obtains intermediate 4 '-chloro-
2- -1,1 '-biphenyl of nitro.Post processing is complex, and cost is also higher.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of low production cost, rear place
The synthetic method of easy Boscalid intermediate 4 '-- the 1,1 '-biphenyl of chloro- 2- nitros of reason.
A kind of described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that with
O-chloronitrobenzene, to chlorophenylboronic acid be raw material, in the presence of alkaline reagent and nickel class catalyst, in nitrogen or other indifferent gas
Under body protection, Jing coupling reactions and post processing obtain 4 '-chloro- 2- nitro -1,1 '-biphenyl, 4 '-chloro- 2- nitro -1,1 '-biphenyl
Structural formula such as（I）It is shown：
。
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that include as
Lower step：
1）Suzuki coupling reactions：Alkaline reagent is initially charged in reaction dissolvent, o-chloronitrobenzene is subsequently adding and to chlorobenzene boron
Acid, adds KI and nickel class catalyst after stirring and dissolving, under the protection of nitrogen or inert gas, 75-130 DEG C of reaction 5-20
Hour, 30-50 DEG C of filtration is cooled to, obtain filtrate；
2）Last handling process
By step 1）Filtrate first wash, then with dichloromethane extract, organic layer is rotated to be evaporated, and gained solid is washed with petroleum ether
Wash, suction filtration obtains product 4 '-chloro- 2- nitro -1,1 '-biphenyl.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that step 1）
In reaction dissolvent be organic solvent and water mixture.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that You Jirong
Agent is selected from DMF, DMAC, dioxane, dimethyl sulfoxide, THF, C2-C5Any one or a few mixture in monohydric alcohol, toluene,
C2-C5Monohydric alcohol is preferably ethanol or propyl alcohol.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that You Jirong
Agent volume is 3-8 with the mass ratio of o-chloronitrobenzene:1；Organic solvent is 5-20 with the volume ratio of water:1.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that step 1）
In one or more mixtures in NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, the cesium carbonate of alkaline reagent, alkali
Property reagent and o-chloronitrobenzene mol ratio be 1-2:1.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that step 1）
The 0.001-0.01% that quality is o-chloronitrobenzene quality that feeds intake of middle KI.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that step 1）
In catalyst be nickel class catalyst or CuI catalyst, its 0.01-1% that quality is o-chloronitrobenzene quality that feeds intake.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that step 1）
In nickel class catalyst be selected from nickel chloride, nickel acetate, bi triphenyl phosphine nickel chloride, [1,1 '-bis- (diphenylphosphine) ferrocene] two
Nickel chloride or 1,2- are double（Diphenylphosphino）Ethylmercury chloride nickel, its consumption is the 0.01-1% of o-chloronitrobenzene quality.
Described Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that adjacent chlorine nitre
Base benzene is 1 with the mol ratio to chlorophenylboronic acid:1-1.5.
The reaction mechanism of the present invention is as follows：
By the way that using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows：
1）The present invention is conducive to the molten of alkaline reagent by being used as coupling solvent with the mixing of water using the organic solvent of limited amount
Solution, using nitrogen or other inert gas shieldings after nickel class catalyst or CuI catalyst is added, is conducive to guard catalyst,
Make its not oxidized, so as to ensure the catalytic effect of catalyst；
2）Reaction temperature is defined to 75-130 DEG C by the present invention, in the temperature range reaction selectivity preferably and reaction speed compared with
Hurry up, it is to avoid reaction temperature is too high to be susceptible to side reaction, double couple crosslinking impurity occur, reaction temperature is too low to make reaction not exclusively,
Filtration temperature is also defined, filtration temperature is too high, make solvent volatilization serious, it is too low, product is separated out, affect reaction effect
Rate, therefore reaction temperature selects 30-50 DEG C；
3）The present invention needs the particularity for completely cutting off air according to Suzuki coupling reactions, using nitrogen or other inert gas conducts
Protective gas, improves its reaction effect；
4）The present invention 4 '-chloro- 2- nitro -1, the synthetic method of 1 '-biphenyl, using nickel class catalyst or CuI catalyst, its into
This is relatively low, by adding KI, can improve the activity of chlorine on o-chloronitrobenzene, shorten the reaction time and saved into
This, its raw material is simple and easy to get, and reaction process product are relatively easy, and the solvent after distilling can be reused, and realizes efficient
Recovery utilization rate, reduces environmental protection pressure.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1
Under room temperature and nitrogen protection, 20mlDMF and 2ml water, 7.8 grams of cesium carbonates and 0.3mg KI are added in four-hole bottle,
3.75g（99%, 0.024mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds after stirring and dissolving
0.3mg Ni(dppf)Cl2, stir and be warming up to 120 DEG C, 18h is reacted, reactant liquor is cooled to 40 DEG C, then filters to take filtrate then
Substantial amounts of washing is added, is extracted with dichloromethane, then organic layer revolving is obtained into solid, afterwards with petroleum ether twice,
Suction filtration obtains product 1.67g, yield 35.8%.
Embodiment 2
Under room temperature and nitrogen protection, 25ml DMF and 2ml water, 7.5g cesium carbonates and 0.4mg KI are added in four-hole bottle,
4.06g（99%, 0.026mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds after stirring and dissolving
0.2mg 1,2- are double（Diphenylphosphino）Ethylmercury chloride nickel, stirring is warming up to 110 DEG C, reacts 15 hours, and reactant liquor is cooled to 30
DEG C then filtering to take filtrate then adds substantial amounts of washing, is extracted with dichloromethane, then organic layer revolving is obtained into solid, it
Afterwards with petroleum ether twice, suction filtration obtains product 1.37g, yield 29.3%.
Embodiment 3
Under room temperature and nitrogen protection, 20ml DMF and 1ml water, 4.14g potassium carbonate and 0.35mg are added in four-hole bottle
KI, 4.68g（99%, 0.03mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds after stirring and dissolving
5mgNi(Ac)2.4H2O, stirring is warming up to 130 DEG C, reacts 17 hours, and reactant liquor is cooled to 30 DEG C and then filters to take filtrate then
Substantial amounts of washing is added, is extracted with dichloromethane, then organic layer revolving is obtained into solid, afterwards with petroleum ether twice,
Suction filtration obtains product 0.97g, yield 20.8%.
Embodiment 4
Under room temperature and nitrogen protection, 25ml DMF and 1.5ml water, 3.18g sodium carbonate and 0.33mg are added in four-hole bottle
KI, 3.43g（99%, 0.022mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds after stirring and dissolving
0.8mgNi(dppf)Cl2, stirring is warming up to 130 DEG C, reacts 19 hours, reactant liquor be cooled to 35 DEG C then filter to take filtrate and
After add substantial amounts of washing, with dichloromethane extract, then by organic layer revolving obtain solid, afterwards with petroleum ether two
Secondary, suction filtration obtains product 1.97g, yield 42.2%.
Embodiment 5
Room temperature and nitrogen protection under, in four-hole bottle add 25ml DMAC and 1.5ml water, 1.2g NaOH and
0.25mg KI, 3.75g（99%, 0.028mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, stirring and dissolving
Add 0.6mg bi triphenyl phosphine nickel chlorides, stirring to be warming up to 125 DEG C afterwards, react 20 hours, reactant liquor is cooled to 35 DEG C of then mistakes
Leaching filtrate then adds substantial amounts of washing, is extracted with dichloromethane, then organic layer revolving is obtained into solid, and oil is used afterwards
Ether is washed twice, and suction filtration obtains product 1.63g, yield 34.9%.
Embodiment 6
Under room temperature and nitrogen protection, 25ml dioxane and 1.5ml water, 1.12g potassium hydroxide are added in four-hole bottle
With 0.26mg KI, 3.12g（99%, 0.02mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, stirs molten
Add 1.2mg nickel chlorides, stirring to be warming up to 130 DEG C after solution, react 20 hours, reactant liquor is cooled to 45 DEG C and then filters to take filtrate
Substantial amounts of washing is then added, is extracted with dichloromethane, then organic layer revolving is obtained into solid, afterwards with petroleum ether two
Secondary, suction filtration obtains product 0.62g, yield 13.3%.
Embodiment 7
Under room temperature and nitrogen protection, 20mlDMF and 2ml water, 7.8 grams of cesium carbonates and 0.35mg KI are added in four-hole bottle,
3.75g（99%, 0.024mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds 1.0 after stirring and dissolving
Mg CuI, stirring is warming up to 120 DEG C, reacts 18h, and reactant liquor is cooled to 40 DEG C, then filter to take filtrate then add it is substantial amounts of
Washing, is extracted with dichloromethane, then organic layer revolving is obtained into solid, and afterwards with petroleum ether twice, suction filtration is produced
Product 1.38g, yield 29.5%.
Embodiment 8
Under room temperature and nitrogen protection, 25ml DMF and 2ml water, 7.5g cesium carbonates and 0.33mg KI are added in four-hole bottle,
4.06g（99%, 0.026mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds 1.5 after stirring and dissolving
Mg CuI, stirring is warming up to 110 DEG C, reacts 15 hours, and reactant liquor is cooled to 30 DEG C and then filters to take filtrate and then adds in a large number
Washing, with dichloromethane extract, then by organic layer revolving obtain solid, afterwards with petroleum ether twice, suction filtration is obtained
Product 1.53g, yield 32.7%.
Embodiment 9
Under room temperature and nitrogen protection, 20ml DMF and 1ml water, 4.14g potassium carbonate and 0.35mg are added in four-hole bottle
KI, 4.68g（99%, 0.03mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds 2 after stirring and dissolving
Mg CuI, stirring is warming up to 130 DEG C, reacts 17 hours, and reactant liquor is cooled to 30 DEG C and then filters to take filtrate and then adds in a large number
Washing, with dichloromethane extract, then by organic layer revolving obtain solid, afterwards with petroleum ether twice, suction filtration is obtained
Product 1.02g, yield 21.8%.
Embodiment 10
Under room temperature and nitrogen protection, 25ml DMF and 1.5ml water, 3.18g sodium carbonate and 0.38mg are added in four-hole bottle
KI, 3.43g（99%, 0.022mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, adds after stirring and dissolving
2.5mgCuI, stirring is warming up to 130 DEG C, reacts 19 hours, and reactant liquor is cooled to 35 DEG C and then filters to take filtrate and then adds greatly
The washing of amount, is extracted with dichloromethane, then organic layer revolving is obtained into solid, and afterwards with petroleum ether twice, suction filtration is obtained
To product 1.52g, yield 32.4%.
Embodiment 11
Room temperature and nitrogen protection under, in four-hole bottle add 25ml DMAC and 1.5ml water, 1.2g NaOH and
0.25mg KI, 3.75g（99%, 0.028mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, stirring and dissolving
After add 3.0mgCuI, stirring is warming up to 125 DEG C, reacts 20 hours, and reactant liquor is cooled to 35 DEG C and then filters to take filtrate then
Substantial amounts of washing is added, is extracted with dichloromethane, then organic layer revolving is obtained into solid, afterwards with petroleum ether twice,
Suction filtration obtains product 1.60g, yield 34.2%.
Embodiment 12
Under room temperature and nitrogen protection, 25ml dioxane and 1.5ml water, 1.12g potassium hydroxide are added in four-hole bottle
With 0.26mg KI, 3.12g（99%, 0.02mol）To chlorophenylboronic acid, 3.15g（99%, 0.02mol）O-chloronitrobenzene, stirs molten
Add 3.5mgCuI after solution, stirring is warming up to 130 DEG C, react 20 hours, reactant liquor be cooled to 45 DEG C then filter to take filtrate and
After add substantial amounts of washing, with dichloromethane extract, then by organic layer revolving obtain solid, afterwards with petroleum ether two
Secondary, suction filtration obtains product 1.59g, yield 34.1%.
Claims (10)
1. a kind of Boscalid intermediate 4 '-chloro- 2- nitro -1, the preparation method of 1 '-biphenyl, it is characterised in that with adjacent chlorine nitro
Benzene, to chlorophenylboronic acid be raw material, in the presence of alkaline reagent and nickel class catalyst, in nitrogen or other inert gas shieldings
Under, Jing coupling reactions and post processing obtain 4 '-chloro- 2- nitro -1,1 '-biphenyl, 4 '-chloro- 2- nitro -1, the structure of 1 '-biphenyl
Formula is such as（I）It is shown：
。
2. a kind of Boscalid intermediate 4 ' according to claim 1-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that comprising the steps：
1）Suzuki coupling reactions：Alkaline reagent is initially charged in reaction dissolvent, o-chloronitrobenzene is subsequently adding and to chlorobenzene boron
Acid, adds KI and catalyst after stirring and dissolving, under the protection of nitrogen or inert gas, 75-130 DEG C of reaction 5-20 is little
When, 30-50 DEG C of filtration is cooled to, obtain filtrate；
2）Last handling process
By step 1）Filtrate first wash, then with dichloromethane extract, organic layer is rotated to be evaporated, and gained solid is washed with petroleum ether
Wash, suction filtration obtains product 4 '-chloro- 2- nitro -1,1 '-biphenyl.
3. a kind of Boscalid intermediate 4 ' according to claim 2-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that step 1）In reaction dissolvent be organic solvent and water mixture.
4. a kind of Boscalid intermediate 4 ' according to claim 3-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that organic solvent is selected from DMF, DMAC, dioxane, dimethyl sulfoxide, THF, C2-C5It is any in monohydric alcohol, toluene
One or more mixtures.
5. the preparation side of a kind of Boscalid intermediate 4 ' according to claim 3 or 4-- 1,1 '-biphenyl of chloro- 2- nitros
Method, it is characterised in that organic solvent volume is 3-8 with the mass ratio of o-chloronitrobenzene:1；Organic solvent is 5- with the volume ratio of water
20:1。
6. a kind of Boscalid intermediate 4 ' according to claim 2-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that step 1）In alkaline reagent in NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, the cesium carbonate one
Plant or several mixtures, alkaline reagent is 1-2 with the mol ratio of o-chloronitrobenzene:1.
7. a kind of Boscalid intermediate 4 ' according to claim 2-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that step 1）The 0.001-0.01% that quality is o-chloronitrobenzene quality that feeds intake of middle KI.
8. a kind of Boscalid intermediate 4 ' according to claim 2-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that step 1）In catalyst be nickel class catalyst or CuI catalyst, it feeds intake quality for o-chloronitrobenzene quality
0.01-1%.
9. a kind of Boscalid intermediate 4 ' according to claim 8-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that step 1）In nickel class catalyst selected from nickel chloride, nickel acetate, bi triphenyl phosphine nickel chloride, [1,1 '-bis- (two
Phenylphosphine) ferrocene] Nickel Chloride or 1,2- be double（Diphenylphosphino）Ethylmercury chloride nickel, its consumption is o-chloronitrobenzene quality
0.01-1%。
10. a kind of Boscalid intermediate 4 ' according to claim 2-chloro- 2- nitro-1, the preparation method of 1 '-biphenyl,
It is characterized in that o-chloronitrobenzene is 1 with the mol ratio to chlorophenylboronic acid:1-1.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912425A (en) * | 2018-12-29 | 2019-06-21 | 京博农化科技有限公司 | A kind of preparation method of the chloro- 2 nitro biphenyl of 4`- |
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|---|---|---|---|---|
| CN102701964A (en) * | 2012-05-09 | 2012-10-03 | 江西师范大学 | Method for synthesizing 4, 4' -biphenyldicarboxylic acid |
| CN103073489A (en) * | 2013-02-06 | 2013-05-01 | 利民化工股份有限公司 | Preparation method of Boscalid |
| CN104478797A (en) * | 2014-12-09 | 2015-04-01 | 苏州至善化学有限公司 | Preparation method of nicotinamide fungicide namely boscalid |
-
2016
- 2016-11-29 CN CN201611072538.9A patent/CN106631812B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701964A (en) * | 2012-05-09 | 2012-10-03 | 江西师范大学 | Method for synthesizing 4, 4' -biphenyldicarboxylic acid |
| CN103073489A (en) * | 2013-02-06 | 2013-05-01 | 利民化工股份有限公司 | Preparation method of Boscalid |
| CN104478797A (en) * | 2014-12-09 | 2015-04-01 | 苏州至善化学有限公司 | Preparation method of nicotinamide fungicide namely boscalid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109912425A (en) * | 2018-12-29 | 2019-06-21 | 京博农化科技有限公司 | A kind of preparation method of the chloro- 2 nitro biphenyl of 4`- |
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Application publication date: 20170510 Assignee: Yichang Hanping Decoration Engineering Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980035918 Denomination of invention: Preparation method of 4 '- chloro-2-nitro-1,1' - biphenyl, an intermediate of pyrimidine Granted publication date: 20190305 License type: Common License Record date: 20230525 |
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