CN111039796A - Novel synthesis method of 4' -chloro-2-aminobiphenyl - Google Patents

Novel synthesis method of 4' -chloro-2-aminobiphenyl Download PDF

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CN111039796A
CN111039796A CN201911273111.9A CN201911273111A CN111039796A CN 111039796 A CN111039796 A CN 111039796A CN 201911273111 A CN201911273111 A CN 201911273111A CN 111039796 A CN111039796 A CN 111039796A
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chloro
aminobiphenyl
bromoaniline
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刘雷芳
李文波
王新芳
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Dezhou University
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton

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Abstract

The invention discloses a novel synthesis method of 4' -chloro-2-aminobiphenyl. It adopts o-bromoaniline and p-chlorobenzoic acid as starting materials. Placing o-bromoaniline, 1-2 equivalents of p-chlorobenzoic acid, 1-3 equivalents of alkali and 1-2 mol% of palladium catalyst into a reactor, adding water or a mixed solution of water and an organic solvent as a reaction solvent, and reacting at 60 DEG CoC‑100oCStirring for 12-24 hours. After the reaction, the reaction mixture was cooled to room temperature and then extracted with an organic solvent. And (4) after the organic solvent is dried in a spinning mode, separating to obtain the product. The invention has the advantages that: 1) adopting cheaper o-bromoaniline as a starting material; 2) the method adopts simple palladium salt as a catalyst, and does not need ligand participation; 3) the method can be carried out in the air without the protection of inert gas; 4) the preparation is completed in one step in water or a water phase system; 5) the method has simple post-treatment, and can separate the product from the reaction system by simple organic solvent extraction; 6) method for producing a composite materialThe yield of the 4' -chloro-2-aminobiphenyl is high.

Description

Novel synthesis method of 4' -chloro-2-aminobiphenyl
Technical Field
The invention relates to the technical field of synthesis of pesticide intermediates, relates to a synthesis method of an agricultural bactericide intermediate, and particularly relates to a synthesis method of a key boscalid intermediate 4' -chloro-2-aminobiphenyl.
Background
The boscalid is a novel broad-spectrum, low-toxicity and high-efficiency nicotinamide internal absorption bactericide which is firstly developed by Pasf company in Germany, can effectively prevent and treat various diseases such as powdery mildew, gray mold, sclerotinia, black spot and the like, and can be used for preventing and treating related diseases such as rape, grapes, fruit trees, tomatoes, vegetables, field crops and the like. Due to the limit of the administrative protection period of boscalid, the scale production of boscalid in China is only in the starting stage, and the market potential is very large.
4' -chloro-2-aminobiphenyl is a key intermediate of boscalid. According to the difference of raw materials, the current methods for synthesizing the key intermediate mainly comprise the following steps:
1. using o-chloronitrobenzene or p-chloroaniline as raw material
(1) The method is characterized in that o-chloronitrobenzene and p-chlorophenylboronic acid are used as raw materials, and the 4' -chloro-2-aminobiphenyl is synthesized through two steps of Suzuki coupling reaction and hydrogenation reduction (see:
Figure 261834DEST_PATH_IMAGE001
the invention has the following patent: patent nos. 201410828097.5, 201611022916.2, 201610103719.7, 201510053937. X;
Figure 905305DEST_PATH_IMAGE002
Adv. Synth. Catal., 2010,352, 3089-3097；
Figure 302788DEST_PATH_IMAGE003
EP0545099、DE19531813）。
although the o-chloronitrobenzene is abundant in source, cheap and easy to obtain, the first step of the coupling reaction is forced to require a large amount of expensive and highly active palladium catalyst and severe production conditions (such as high temperature, anhydrous and oxygen-free conditions and the like) due to the limited reactivity of the o-chloronitrobenzene. The method has the disadvantages of more impurities generated in the coupling reaction process, relatively low yield, long product synthesis period, generation of a large amount of iron mud pollutants in the nitro reduction step and the like, so that the method is greatly limited in actual production.
(2) P-chloroaniline is used as a raw material, and is subjected to diazotization and gang-Bakmann reaction to synthesize the 4' -chloro-2-aminobiphenyl (see the Chinese invention patent: patent No. 201610768463.1).
2. Takes o-iodoaniline and p-chlorobenzoic acid as raw materials
(1) With Pd (PPh)3)4Taking sodium carbonate as a catalyst, taking methylbenzene/water as a reaction solvent, and carrying out Suzuki coupling reaction on o-iodoaniline and p-chlorophenylboronic acid to synthesize 4' -chloro-2-ammoniaBiphenylene (see: fine chemical intermediates, 2007,37(4),14-16）。
(2) with Pd (OAc)2In the presence of 10% glucose, cesium carbonate is used as alkali, DMF/water is used as a reaction medium, and o-iodoaniline and p-chlorobenzeneboronic acid undergo a Suzuki coupling reaction to synthesize 4' -chloro-2-aminobiphenyl (see:RSC Adv., 2016,6, 16115-16121）。
the Suzuki coupling reaction is easy to realize by using the synthesis method of taking o-iodoaniline as the starting material. But the market price of iodobenzene is expensive, so that the production cost of the boscalid is high.
Compared with chlorinated aromatic hydrocarbon and iodo aromatic hydrocarbon, brominated aromatic hydrocarbon has higher activity than chlorinated aromatic hydrocarbon and lower price than iodo aromatic hydrocarbon, so the development of the method for synthesizing the 4' -chloro-2-aminobiphenyl by taking the brominated aromatic hydrocarbon as a starting material has important application value. However, there are only a few reports in the literature regarding this aspect.
2014, Sunjin and the like take 2-nitrobenzophenone and p-chlorobenzeneboronic acid as raw materials and Pd (OH)2The catalyst/C is subjected to Suzuki coupling reaction and nitro reduction reaction to synthesize the 4' -chloro-2-aminobiphenyl (see: chemical research and application: 2014,26(10), 1645-1649.）。
in the same year, Sunjin et al further used o-acetamidobromobenzene and p-chlorobenzeneboronic acid as raw materials, Pd (OH)2The catalyst/C is subjected to Suzuki coupling reaction and deprotection reaction to synthesize the 4' -chloro-2-aminobiphenyl (see the Chinese patent: 201410298571.8).
Disclosure of Invention
The invention aims to provide an economic and efficient synthetic method suitable for industrial production for boscalid key intermediate 4' -chloro-2-aminobiphenyl.
It adopts o-bromoaniline and p-chlorobenzoic acid as starting materials. Placing o-bromoaniline, 1-2 equivalents of p-chlorobenzoic acid, 1-3 equivalents of alkali and 1-2 mol% of palladium catalyst into a reactor, adding water or a mixed solution of water and an organic solvent as a reaction solvent, and reacting at 60 DEG CoC-100oStirring for 12-24 hours under C. Reaction junctionAfter completion, the mixture was cooled to room temperature and then extracted with an organic solvent. And (4) after the organic solvent is dried in a spinning mode, separating to obtain the product.
The invention has the advantages that:
1) adopting cheaper o-bromoaniline as a starting material;
2) the method adopts simple palladium salt as a catalyst, and does not need ligand participation;
3) the method can be carried out in the air without the protection of inert gas;
4) the preparation is completed in one step in water or a water phase system;
5) the method has simple post-treatment, and can separate the product from the reaction system by simple organic solvent extraction;
6) the method has high yield of the 4' -chloro-2-aminobiphenyl.
Detailed Description
The method adopts o-bromoaniline and p-chlorobenzoic acid as raw materials and simple palladium salt as a catalyst, and generates the 4' -chloro-2-aminobiphenyl through one-step reaction by Suzuki coupling reaction. The reaction equation is as follows:
Figure 31710DEST_PATH_IMAGE004
wherein the dosage of the p-chlorobenzoic acid is 1-2 equivalents of the o-bromoaniline, the dosage of the alkali is 1-3 equivalents of the o-bromoaniline, and the alkali is K2CO3、K3PO4、Na2CO3、NaOH、KOH、NaOAc、NaHCO3、K2HPO4. The dosage of the palladium catalyst is 1-2 mol%, and the palladium catalyst is Pd (OAc)2、PdCl2. The reaction solvent is water or a mixed solution of water and an organic solvent. The organic solvent is ethanol, acetone,N, N-dimethylformamide, methanol, dioxane, polyethylene glycol. The reaction temperature was 60 deg.CoC-100oAnd C, the reaction time is 12-24 hours. The organic solvent for extraction is ethyl acetate or diethyl ether.
The method adopts cheap o-bromoaniline as a raw material, is simple to operate, has high yield and has the potential of industrial production.
The following examples will aid in the understanding of the invention, but are not intended to limit the invention:
example 1
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1 mmol), sodium carbonate (1 mmol) and palladium chloride (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 60 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature, and then extracted with ethyl acetate. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 60 percent.
Example 2
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (2 mmol), sodium carbonate (3 mmol) and palladium acetate (2 mol%) in a 25mL round-bottom flask, adding 6 mL of water/ethanol (volume ratio 1: 1) mixed solution, 100oStirring for 24 h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 97%.
Example 3
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 24 h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 93 percent.
Example 4
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. And (4) after the organic solvent is dried in a spinning mode, separating to obtain the product, wherein the yield is 92%.
Example 5
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round bottom flask, addingAdding 6 mL of water, 80oStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 87%.
Example 6
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 8 mL, 80 mL of water/ethanol (volume ratio 3: 5) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 90 percent.
Example 7
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6.5 mL, 80 mL of water/ethanol (volume ratio 12: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 91 percent.
Example 8
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/acetone (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. And (4) after the organic solvent is dried in a spinning mode, separating to obtain the product, wherein the yield is 92%.
Example 9
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round bottom flask, adding waterN, N6 mL of a mixed solution of (1: 1 by volume) and (80)oStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 89%.
Example 10
O-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol) and sodium carbonate (2 mmol)l), palladium acetate (1 mol%) were placed in a 25mL round bottom flask, and water/methanol (volume ratio 1: 1) mixed solution 6 mL, 80oStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 88 percent.
Example 11
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL of water/dioxane (volume ratio 1: 1) mixed solution, 80 mLoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 68 percent.
Example 12
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/polyethylene glycol 2000 (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 87%.
Example 13
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), potassium carbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 84%.
Example 14
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), potassium phosphate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. And (4) after the organic solvent is dried in a spinning mode, separating to obtain the product, wherein the yield is 92%.
Example 15
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium hydroxide (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 90 percent.
Example 16
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), potassium hydroxide (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 89%.
Example 17
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), sodium bicarbonate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL, 80 mL of water/ethanol (volume ratio 1: 1) mixed solutionoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 86%.
Example 18
Placing o-bromoaniline (1 mmol), p-chlorobenzoic acid (1.5 mmol), potassium dihydrogen phosphate (2 mmol) and palladium acetate (1 mol%) in a 25mL round-bottom flask, adding 6 mL of water/ethanol (volume ratio 1: 1) mixed solution, 80 mLoStirring for 12h under C. After the reaction was completed, it was cooled to room temperature and then extracted with ether. After the organic solvent is dried by spinning, the product is obtained by separation, and the yield is 91 percent.

Claims (10)

  1. The new synthesis method of 1.4' -chloro-2-aminobiphenyl is characterized in that: it adopts o-bromoaniline and p-chlorobenzoic acid as initial material, and adopts o-bromoaniline, 1-2 equivalents of p-chlorobenzoic acid, 1-3 equivalents of alkali and 1-2 mol% of palladium catalyst as reaction solvent in a reactor, and adds water or mixed solution of water and organic solvent as reaction solvent, and makes the reaction solvent undergo the processes of reaction at 60 deg.CoC-100oStirring for 12-24 hours under C; after the reaction is finished, cooling to room temperature, and then extracting by using an organic solvent; after the organic solvent is dried by spinning, separating to obtain a product; the reaction equation is as follows:
    Figure 515177DEST_PATH_IMAGE001
    。
  2. 2. the novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the starting materials are o-bromoaniline and p-chlorobenzoic acid.
  3. 3. The novel synthesis method of 4' -chloro-2-aminobiphenyl according to claim 1, characterized by comprising the steps of:
    1) suzuki coupling reaction: placing o-bromoaniline, 1-2 equivalents of p-chlorobenzoic acid, 1-3 equivalents of alkali and 1-2 mol% of palladium catalyst into a reactor, adding water or a mixed solution of water and an organic solvent as a reaction solvent, and reacting at 60 DEG CoC-100oCStirring for 12-24 hours;
    2) and (3) post-treatment process: cooling the reaction liquid in the step 1) to room temperature, and then extracting with an organic solvent; and (4) after the organic solvent is dried in a spinning mode, separating to obtain the product.
  4. 4. The novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the dosage of the p-chlorobenzene boric acid is 1-2 equivalents of o-bromoaniline, and the dosage of the base is 1-3 equivalents of o-bromoaniline.
  5. 5. The novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the alkali is K2CO3、K3PO4、Na2CO3、NaOH、KOH、NaOAc、NaHCO3、K2HPO4。
  6. 6. 4' -chloro-2-ammonia according to claim 1The novel method for synthesizing the biphenyl is characterized by comprising the following steps: the dosage of the palladium catalyst is 1-2 mol%, and the palladium catalyst is Pd (OAc)2、PdCl2。
  7. 7. The novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the reaction solvent is a mixed solution of water and a water-organic solvent.
  8. 8. The novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the organic solvent is ethanol, acetone,N, N-dimethylformamide, methanol, dioxane, polyethylene glycol.
  9. 9. The novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the reaction temperature is 60 DEGoC-100oAnd C, the reaction time is 12-24 hours.
  10. 10. The novel method for synthesizing 4' -chloro-2-aminobiphenyl according to claim 1, wherein: the organic solvent for extraction is ethyl acetate or diethyl ether.
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CN110563649A (en) * 2019-08-27 2019-12-13 浙江工业大学 high-selectivity deuteration method of 2-methyl nitrogen heterocyclic compound

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1817829A (en) * 2006-03-10 2006-08-16 浙江大学 Production of aryl-group-aryl biphenyl compound
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
CN110563649A (en) * 2019-08-27 2019-12-13 浙江工业大学 high-selectivity deuteration method of 2-methyl nitrogen heterocyclic compound

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