CN114524751B - Aryl nitrile compound and preparation method thereof - Google Patents
Aryl nitrile compound and preparation method thereof Download PDFInfo
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- CN114524751B CN114524751B CN202210214551.2A CN202210214551A CN114524751B CN 114524751 B CN114524751 B CN 114524751B CN 202210214551 A CN202210214551 A CN 202210214551A CN 114524751 B CN114524751 B CN 114524751B
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- C07C253/00—Preparation of carboxylic acid nitriles
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
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Abstract
The invention discloses an aryl nitrile compound and a synthesis method thereof, wherein aryl carboxylic acid and trimethyl cyano silane are used as main raw materials, under the action of a palladium catalyst, a phosphine ligand and an additive, the raw materials react in an organic solvent, and after the reaction is finished, the corresponding aryl nitrile is obtained through post-treatment. The method has the advantages of low cost, high yield, simple operation, no pollution and the like, and has potential industrial application prospect. The method provides a cheap and green way for preparing aryl alkyne compounds.
Description
[ field of technology ]
The invention belongs to the field of catalytic organic synthesis, and particularly relates to an aryl nitrile compound and a preparation method thereof.
[ background Art ]
Nitrile compounds are an important class of organic compounds, commonly found in fine chemicals, and are useful intermediates for the synthesis of amines, carboxylic acids, and the like [1] Plays an important role in the application of chemical technology, pharmacy, agrochemicals, fine chemicals and high-performance polymers, rubber and molecular electronics components. Nitrile is an important functional group in organic synthesis and is not only a multifunctional intermediate but also converted into amides, amines, ketones, carboxylic acids and oxazoles [2] But also are an important component of pesticides, dyes and pharmaceutical products. Along with the rapid development of technology, the demand and the added value of nitrile compounds are increased, so that more researches are reported, but the research is mainly focused on the improvement of the traditional production process, and the related synthesis routes of the nitrile compounds mainly comprise 1. Halocarbon cyanidation, 2. Ammoxidation, 3. Carboxynitrile and 4. AldehydeThe method comprises a cyanohydrination method, an electrolytic station formation method, an acetonitrile addition method, an acrylonitrile method and a diazotization method.
Generally, nitriles are prepared by nucleophilic substitution with toxic cyanide sources (e.g., KCN, naCN, or ZnCN). Along with the development of technology, the pollution to the environment is more and more serious, people now start to recognize the necessity of protecting the environment, and the production method is more faithful to pollution-free and zero-emission production modes. The traditional method generally adopts highly toxic cyanide as the cyanide reagent, which is extremely harmful to the environment and operators. In recent years, most scholars have sought pollution-free, non-toxic or low-pollution and low-toxicity cyanidation methods, and are now enthusiastic to develop various schemes for using less toxic cyanide sources in order to avoid the use of toxic metal cyanide; however, most processes rely on transition metal catalyzed cross-coupling of aryl halides, which are toxic and difficult to prepare. The aryl nitrile is prepared by decarboxylation coupling reaction of easily available and abundant aryl carboxylic acid compounds serving as starting materials and trimethyl cyano silane. The trimethyl cyano silane is used for replacing other cyano-derived compounds, so that the problems of unsafe experiment and the like caused by excessive toxicity due to the use of cyanide are effectively avoided, and the method has better step economy.
[ invention ]
The invention aims to obtain corresponding aryl nitrile through post-treatment after the reaction of aryl carboxylic acid and trimethyl cyano silane serving as raw materials in an organic solvent under the action of a catalyst, a ligand and an additive. The method has the advantages of low cost, high yield, simple operation, no pollution and the like, and has certain feasibility for realizing the industrialized production. In order to achieve the above purpose, the present invention proposes the following technical scheme:
an aryl nitrile compound and a synthesis method thereof, wherein the structural formula of the aryl nitrile compound 3 is as follows:
wherein Ar is 1-naphthyl, 2-naphthyl, independent or unsubstituted aryl. Wherein the substituents on the phenyl group include C 1 Phenyl, C 2 -C 4 Methyl, chlorine, C 4 Tertiary butyl, cyclohexyl, phenyl, phenoxy, dimethylamino. The synthesis method of the compound 3 is characterized in that under the action of a catalyst, a ligand, anhydride and alkali, aryl carboxylic acid 1 and trimethyl cyano silane 2 are used as raw materials to react in an organic solvent, and after the reaction is finished, the corresponding aryl nitrile 3 is obtained through post-treatment.
In the above synthesis method, the structural formulas of the raw materials aryl carboxylic acid 1 and trimethyl cyano silane 2 are as follows:
ar is 1-naphthyl, 2-naphthyl, independent or unsubstituted aryl. Wherein the substituents on the phenyl group include C 1 Phenyl, C 2 -C 4 Methyl, chlorine, C 4 Tertiary butyl, cyclohexyl, phenyl, phenoxy, dimethylamino.
In the synthesis method, under the action of a catalyst, a ligand and an additive, aryl carboxylic acid and trimethyl cyano silane are used as raw materials to react in an organic solvent, and after the reaction is finished, the corresponding aryl nitrile is obtained through post-treatment.
The synthesis method of the aryl nitrile compound provided by the invention opens up a new low-cost green path, and has the advantages that: the yield of the target product is high, the reaction condition is mild, and the reaction operation is simple.
[ description of the drawings ]
The drawing shows a route pattern for preparing aryl alkyne compounds.
[ embodiment 1 ]
The invention provides a synthesis method of aryl alkyne compounds, please refer to the accompanying drawings: aromatic carboxylic acid and trimethylcyano silane are used as raw materials, tetraphenylphosphine palladium is used as a catalyst, 1, 3-bis (diphenylphosphine) propane is used as a ligand, trimethylacetic anhydride is used as anhydride, cyclohexane is used as a solvent, the mixture is placed into a reaction vessel to react for 12 hours at 150 ℃, and the target product is obtained through column chromatography separation after the reaction is completed.
The invention is further illustrated below in connection with specific examples of preparation:
preparation example 1
To a reaction tube of 10 mL, 0.2 mmol of aryl carboxylic acid (Ar=2-naphthyl) and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=2-naphthyl) was obtained by separation by column chromatography, and a white solid was obtained in 94% yield.
Preparation example 2
To a reaction tube of 10 mL, 0.2 mmol of aryl carboxylic acid (Ar=1-naphthyl) and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=2-naphthyl) was obtained by separation by column chromatography, and a white solid was obtained in 88% yield.
Preparation example 3
To a 10 mL reaction tube was added 0.2 mmol of aryl carboxylic acid (ar=4-t-butylphenyl), 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane, 120 mol% of trimethylacetic anhydride, and cyclohexane as a solvent, and reacted at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-tert-butylphenyl) was obtained by separation by column chromatography, and a colorless liquid was obtained in a yield of 72%.
Preparation example 4
To a reaction tube of 10 mL, 0.2 mmol of aryl carboxylic acid (Ar=4-phenylphenyl) and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-phenylphenyl) was obtained by separation by column chromatography, and a white solid was obtained in 97% yield.
Preparation example 5
To a reaction tube of 10 mL, 0.2 mmol of aryl carboxylic acid (Ar=4-chlorophenyl) and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-chlorophenyl) was obtained by separation by column chromatography, and a white solid was obtained in 55% yield.
Preparation example 6
To a 10 mL reaction tube was added 0.2 mmol of aryl carboxylic acid (ar=4-acetylphenyl), 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane, 120 mol% of trimethylacetic anhydride, and cyclohexane as a solvent, and reacted at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-acetylphenyl) was obtained by separation by column chromatography, and a yellow solid was obtained in 78% yield.
Preparation example 7
To a 10 mL reaction tube was added 0.2 mmol of aryl carboxylic acid (ar=4-cyclohexylphenyl), 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane, 120 mol% of trimethylacetic anhydride, and cyclohexane as a solvent, and reacted at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-cyclohexylphenyl) was obtained by separation by column chromatography, and a white solid was obtained in 89% yield.
Preparation example 8
To a reaction tube of 10 mL, 0.2 mmol of aryl carboxylic acid (Ar=4-phenoxyphenyl) and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-phenoxyphenyl) was obtained by separation by column chromatography, and a colorless liquid was obtained in 88% yield.
Preparation example 9
To a reaction tube of 10 mL, 0.2 mmol of aryl carboxylic acid (Ar=3-phenylphenyl) and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=3-phenylphenyl) was obtained by separation by column chromatography, and a colorless liquid was obtained in 79% yield.
Preparation example 10
To a 10 mL reaction tube was added 0.2 mmol of aryl carboxylic acid (Ar=3-chloro-4 methoxyphenyl), 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane, 120 mol% of trimethylacetic anhydride and cyclohexane as a solvent, and the mixture was reacted at 150℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=3-chloro-4 methoxyphenyl) was obtained by separation by column chromatography to obtain a white solid with a yield of 77%.
[ embodiment 2 ]
The invention provides a synthesis method of aryl alkyne compounds, please refer to the accompanying drawings: aromatic carboxylic acid and trimethylcyano silane are used as raw materials, tetraphenylphosphine palladium is used as a catalyst, 1, 3-bis (diphenylphosphine) propane is used as a ligand, trimethylacetic anhydride is used as anhydride, cyclohexane is used as a solvent, the mixture is placed into a reaction vessel to react for 12 hours at 160 ℃, and the target product is obtained through column chromatography separation after the reaction is completed.
The invention is further illustrated below in connection with specific examples of preparation:
PREPARATION EXAMPLE 11
Into a 10 mL reaction tube, 0.2 mmol of quinoline-6-carboxylic acid, 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 160℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=6-quinolinyl) was obtained by separation by column chromatography to obtain a white solid with a yield of 79%.
Preparation example 12
0.2 mmol of alpha-phenyl cinnamic acid, 0.3 mmol of trimethyl cyano silane, 5 mol% of tetra-triphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenyl phosphine) propane and 120 mol% of trimethyl acetic anhydride are added into a reaction tube of 10 mL, cyclohexane is taken as a solvent, and the mixture is reacted at 160 ℃ for 12 h. After the reaction, the target compound, namely the arylnitrile compound (ar=α -phenylcinnamyl) was obtained by column chromatography separation, and a white solid was obtained in 98% yield.
Preparation example 13
Into a 10 mL reaction tube, 0.2 mmol of 4-dimethylaminobenzoic acid, 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 160℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=4-dimethylaminophenyl) was obtained by separation by column chromatography to obtain a yellow solid with a yield of 83%.
PREPARATION EXAMPLE 14
To a reaction tube of 10 mL, 0.2 mmol of 2-phenylbenzoic acid, 0.3 mmol of trimethylcyano silane, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 160℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=2-phenylphenyl) was obtained by separation by column chromatography, and a colorless liquid was obtained in 88% yield.
Preparation example 15
To a reaction tube of 10 mL, 0.2 mmol of 3,4, 5-trimethoxybenzoic acid and 0.3 mmol of trimethylcyano silane were added, 5 mol% of tetraphenylphosphine palladium, 10 mol% of 1, 3-bis (diphenylphosphine) propane and 120 mol% of trimethylacetic anhydride were added, and cyclohexane was used as a solvent to react at 160℃for 12 h. After the reaction was completed, the objective compound arylnitrile compound (ar=3, 4, 5-trimethoxyphenyl) was obtained by separation by column chromatography to obtain a white solid with a yield of 82%.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (2)
1. The synthetic method of the aryl nitrile compound comprises the following structural formulas of the aryl nitrile compound 3, the raw material aryl carboxylic acid 1 and the raw material trimethyl cyano silane 2:
wherein Ar is one of 1-naphthyl, 2-naphthyl, 4-tert-butylphenyl, 4-phenylphenyl, 4-chlorophenyl, 4-acetylphenyl, 4-cyclohexylphenyl, 4-phenoxyphenyl, 3-phenylphenyl, 3-chloro-4-methoxyphenyl, 6-quinolinyl, alpha-phenylcinnamyl, 4-dimethylaminophenyl, 2-phenylphenyl and 3,4, 5-trimethoxyphenyl, and the compound 3 is synthesized, and is characterized in that raw materials aryl carboxylic acid 1 and trimethylcyanosilane 2 react under the action of catalyst tetra-triphenylphosphine palladium, ligand 1, 3-bis (diphenylphosphine) propane and trimethylacetic anhydride, and corresponding aryl nitrile 3 is obtained through aftertreatment after the reaction.
2. The synthesis method according to claim 1, wherein the palladium tetraphenyl phosphine is used as a catalyst, the 1, 3-bis (diphenyl phosphine) propane is used as a ligand, the trimethyl acetic anhydride is used as an additive, the organic solvent is used as a reaction solvent, the reaction time is 12 hours, and the reaction temperature is 150-160 ℃.
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Non-Patent Citations (1)
| Title |
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| The Beckmann reactions: rearrangements, elimination-additions, fragmentations, and rearrangement-cyclizations;Gawley, Robert E.;《Organic reaction》;19881231;全文 * |
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