CN109320413A - A kind of preparation method of phenylacetic acid class compound - Google Patents
A kind of preparation method of phenylacetic acid class compound Download PDFInfo
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- CN109320413A CN109320413A CN201710648619.7A CN201710648619A CN109320413A CN 109320413 A CN109320413 A CN 109320413A CN 201710648619 A CN201710648619 A CN 201710648619A CN 109320413 A CN109320413 A CN 109320413A
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- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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Abstract
The invention discloses a kind of preparation methods of phenylacetic acid class compound.The preparation method of the phenylacetic acid class compound I, it includes the steps that following: in a solvent, in the gas phase system of CO, halogen benzyl class compound II, cobalt pyridine 2 carboxylate, palladium acetate and antalkali are subjected to carbonylation, obtain the phenylacetic acid class compound I.Mixed catalyst system of the invention has synergistic effect, substantially reduces the whole usage amount of catalyst.Better catalytic effect can achieve using mixed catalyst of the invention, have the characteristics that catalyst is easier to the production safeties risk such as obtain, avoid the toxic three wastes, reduces mild reaction pressure, reaction condition, reduction production risk, is more conducive to produce.
Description
Technical field
The present invention relates to a kind of preparation methods of phenylacetic acid class compound.
Background technique
Phenylacetic acid class compound is important fine-chemical intermediate, is widely used in medicine, pesticide, fragrance, dyestuff etc.
Field.
Such as 4-Chlorophenylacetic acid is the intermediate of the organic syntheses such as medicine, pesticide, fragrance.It is widely used in the industrial production
Under the chloro- 3,4- dihydro -1H-2- naphthalenone of S- fenvalerate, 6-, desinsection pyrethroids, 4- chlorophenethylol, fenvalerate, brofenxalerate etc.
Swim the production of product.
There are two types of the synthetic methods of phenylacetic acid analog derivative reported at present: the cyanalation method of benzyl chloride, benzyl chloride carbonylation method.
Cyanalation method is reported in patent CN102757337A, using adjacent chlorobenzyl chloride as starting material, one kettle way preparation is adjacent
Chlorobenzene acetic acid mixes adjacent chlorobenzyl chloride with triethylamine, and 80-100 DEG C of dropwise addition sodium cyanide solution of temperature control finishes 80-100 DEG C of heat preservation
It is stirred to react, then reaction solution is cooling, excessive sodium hydroxide is added and is warming up to 100-110 DEG C of insulated and stirred, obtains adjacent chlorobenzene
Sodium acetate.Reaction equation is as follows:
Benzyl chloride carbonylation is reported in patent CN1054584A prepares phenylacetic acid, Co2(CO)8For catalyst, alkali, alcohols
It is reaction medium with water, is passed through CO and prepares phenylacetic acid, yield 85-96%, purity is 98% or so.Reaction equation is as follows:
It is reported in patent CN1284406A using halogen benzyl as start material, is closed under the catalysis of cobalt pyridine 2 carboxylate
At phenylacetic acid, process is that catalyst is dissolved in organic solvent in autoclave, is passed through carbon monoxide, antalkali
It is added into the autoclave with reactant halogen benzyl by dropwise addition mode, in 2.5MPa, 100 DEG C, heat preservation 8hrs high pressure prepares phenylacetic acid.
Reaction equation is as follows:
In document Mendeleev Communications, 19 (5) are reported with halogen benzyl as reaction in 256-257,2009
Starting material, synthesizes phenylacetic acid under the catalysis of palladium acetate and tetrabutylammonium chloride and tetrabutylammonium bromide, and process is in height
Halogen benzyl, palladium acetate, tetrabutylammonium chloride/tetrabutylammonium bromide, water is added in pressure kettle and is warming up to 110 DEG C, pressure is maintained at
5.0MPa, insulation reaction 5h, high pressure prepare phenylacetic acid.
Existing cyanalation method uses the Cymag of severe toxicity for raw material, seriously polluted, and equipment corrosion is also very serious.And existing halogen
In benzyl carbonylation method, cobalt octacarbonyl method synthesizes phenylacetic acid method, and there are the preparations of catalyst difficulty and catalyst to be difficult to ensure the disadvantages of depositing;Vinegar
Sour palladium chtalyst synthesizes phenylacetic acid method, haves the shortcomings that catalyst amount is big, reaction pressure is excessively high, cobalt pyridine 2 carboxylate method is also deposited
In big, the at high cost disadvantage of catalyst amount.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome it is existing prepare phenylacetic acid class compound when, cyanalation method
It is middle to use this toxic material of Cymag, cause the generation and security risk of the toxic three wastes;When prepared by halogen benzyl carbonylation method, exist
Catalyst amount is big, the defects of pressure is big, cumbersome etc., and provide it is a kind of using cheap cobalt pyridine 2 carboxylate with
The mixed catalyst of palladium acetate can simple and direct, efficiently obtain the preparation method of phenylacetic acid class compound.
The present invention provides the preparation methods of phenylacetic acid class compound I a kind of comprising following steps: in a solvent,
In the gas phase system of CO, compound II, cobalt pyridine 2 carboxylate, palladium acetate and antalkali are subjected to carbonylation, obtained
To the phenylacetic acid class compound I,
Wherein, X F, Cl, Br or I;
R1、R2、R3、R4And R5It is each independently H, F, Cl, Br, I, C1~C4Alkyl, C1~C4Alkoxy, nitro
One of with cyano.
The X preferred Cl or Br.
The R1、R2、R3、R4And R5In preferred H independent, methyl, methoxyl group, F, Cl, Br, nitro and cyano
It is a kind of.
The antalkali can be conventional for such carbonylation of this field, such as alkali or alkaline earth metal
Hydroxide (such as NaOH, KOH, LiOH and Ca (OH)2), oxide (such as CaO) or carbonate (such as Na2CO3、K2CO3)
With organic amine (Et3N one of) or a variety of, the particularly preferred hydroxide and/or organic amine of alkali metal in the present invention, into one
Walk preferred NaOH and/or Et3N。
The solvent can be conventional for such carbonylation of this field, to be not involved in reaction, in the present invention
Particularly preferred organic solvent or organic solvent and water, the preferred methanol of the organic solvent, ethyl alcohol, propyl alcohol, isopropanol, positive fourth
One of alcohol, isobutanol, dimethyl sulfoxide and N,N-dimethylformamide are a variety of;The more preferable methanol of the solvent or first
The mixed liquor of alcohol and water.
The antalkali and the aqueous solvent can be the solution form of such carbonylation of this field routine,
The solution concentration of the antalkali can be such carbonylation of this field routine, for example, 20-40%'s is water-soluble
Liquid, preferably 30% aqueous solution.
In the carbonylation, the mass ratio of the cobalt pyridine 2 carboxylate and the palladium acetate can for 2:8~
2:3, preferably 2:5.
In the carbonylation, the mixed catalyst of the cobalt pyridine 2 carboxylate and palladium acetate composition
Total amount and the mass percent of the compound II can be 1~5%, preferably 3%.
The molar ratio of the antalkali and the compound II is that such carbonylation of this field is conventional,
Such as 1:1~10:1, the present invention in particularly preferably 1:1~3:1, most preferably 3:1.
The molar ratio of the organic solvent and the compound II is that such carbonylation is conventional in this field,
Not influence reaction;Particularly preferred 1:1~100:1, more preferable 4:1~25:1 in the present invention.
The temperature of the reaction can be conventional for such carbonylation of this field, such as 0 DEG C to 300 DEG C, in the present invention
Particularly preferred 100 DEG C to 180 DEG C, more preferable 150 DEG C.
The pressure of the reaction can be for such carbonylation of this field routine, particularly preferred 1~2MPa in the present invention,
Most preferably 1.5MPa.
The compound II, the cobalt pyridine 2 carboxylate, the palladium acetate, the antalkali and molten
Agent can mix in such a way that such carbonylation of this field is conventional, particularly preferably disposable mixing or described in the present invention
The aqueous solution of compound II and the antalkali in a manner of being added dropwise with the cobalt pyridine 2 carboxylate, the acetic acid
Palladium and solvent mixing.
In the carbonylation, the process of the reaction can be using the routine monitoring method (example in this field
Such as TLC, HPLC or NMR) it is monitored, as reaction end when generally being disappeared using the halogen benzyl class compound or no longer being reacted;
The reaction time such can react the conventional reaction time for this field, particularly preferred 3 hours to 8 hours in the present invention,
Further preferred 5 hours.
The carbonylation may also include following post-processing step: after the reaction was completed, remove solvent, filtering, with acid
Acidification adjusts pH value, controls the crude product 1~2 to get phenylacetic acid class compound shown in formula (I).
The acid can be such reaction routine in this field, such as hydrochloric acid and/or sulfuric acid;The concentration of the acid can
It is conventional for such reaction in this field, such as 10~40%, preferably 20~30% in the present invention.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: the present invention prepares phenylacetic acid class using mixed catalyst simple and easy to get
Object is closed, cyanalation method is avoided and uses the Cymag of severe toxicity for raw material, causes the generation and security risk of the toxic three wastes, and can be rotten
The shortcomings that losing equipment;Cobalt octacarbonyl catalyst is used alone in carbonylation method, price should not be prepared and should not be stored scarce
The disadvantages of cobalt pyridine 2 carboxylate is used alone in point, and the reaction time is long, catalyst usage amount is more, is used alone palladium acetate, technique
Hypertonia, the disadvantage that technological reaction condition is harsh, security risk is big.Mixed catalyst system of the invention has synergistic effect,
Substantially reduce the whole usage amount of catalyst.Better catalytic effect can achieve using mixed catalyst of the invention, have
Catalyst is easier to obtain, avoid the toxic three wastes etc. production safeties risk, reduces that reaction pressure, reaction condition are mild, reduce life
Wind-producing danger is more conducive to the features such as producing.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Embodiment 1
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added, 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.76%, yield 85%.
Embodiment 2
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added, 121g is added
(1.2mol) triethylamine, 73.7g methanol (1.6mol) are replaced system 3 times with CO, are warming up to 150 DEG C, pour pressure in CO to kettle
1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal and part triethylamine, filter out catalyst, add
30% hydrochloric acid adjusts PH to 1, filters, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.25%, yield 80%.
Embodiment 3
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.773g, palladium acetate 1.16g is added, 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.29%, yield 82%.
Embodiment 4
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added, 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 100 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.21%, yield 75%.
Embodiment 5
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added, 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 180 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.32%, yield 90%.
Embodiment 6
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 64.4g (0.4mol) p-chlorobenzylchloride and 160g (1.2mol) 30%NaOH being added in reaction kettle dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain 4-Chlorophenylacetic acid, purity are as follows: 99.32%, yield 90%.
Embodiment 7
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while chlorobenzyl chloride between 64.4g (0.4mol) and 160g (1.2mol) 30%NaOH being added in reaction kettle dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain a chlorobenzene acetic acid, purity are as follows: 99.28%, yield 81%.
Embodiment 8
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 57.8g (0.4mol) being added dropwise in reaction kettle fluorobenzyl chloride and 160g (1.2mol) 30%NaOH.It is small to react 5
Shi Hou, is cooled to room temperature, is evaporated under reduced pressure methanol removal, filters out catalyst, and 30% hydrochloric acid is added to adjust PH to 1, filtering, dry
To para-fluorophenylacetic acid, purity are as follows: 99.40%, yield 84%.
Embodiment 9
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 82.2g (0.4mol) adding in reaction kettle bromine benzyl chloride and 160g (1.2mol) 30%NaOH dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
It obtains to bromo-acid, purity are as follows: 99.25%, yield 88%.
Embodiment 10
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while the adjacent chlorobenzyl chloride of 64.4g (0.4mol) and 160g (1.2mol) 30%NaOH being added in reaction kettle dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain 4-Chlorophenylacetic acid, purity are as follows: 99.35%, yield 88%.
Embodiment 11
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.38g, palladium acetate 1.54g is added, 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.26%, yield 83%.
Embodiment 12
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.256g, palladium acetate 0.384g is added, be added
160g (1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle
Interior pressure 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, add 30% hydrochloric acid
PH to 1 is adjusted, filters, be dried to obtain 4-Chlorophenylacetic acid, purity are as follows: 99%, yield 73%.
Embodiment 13
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.18g, palladium acetate 0.46g is added, 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.26%, yield 78%.
Embodiment 14
Cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, and 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.6%, yield 95%.
Embodiment 15
Cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, and 121g is added
(1.2mol) triethylamine, 73.7g methanol (1.6mol) are replaced system 3 times with CO, are warming up to 150 DEG C, pour pressure in CO to kettle
1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal and part triethylamine, filter out catalyst, add
30% hydrochloric acid adjusts PH to 1, filters, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.25%, yield 92%.
Embodiment 16
Cobalt pyridine 2 carboxylate 0.773g, palladium acetate 1.16g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, and 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.2%, yield 93%.
Embodiment 17
Cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, and 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 100 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.21%, yield 85%.
Embodiment 18
Cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, and 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 180 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.3%, yield 94%.
Embodiment 19
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 82.2g (0.4mol) adding in reaction kettle chlorine bromobenzyl and 160g (1.2mol) 30%NaOH dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain 4-Chlorophenylacetic acid, purity are as follows: 99.32%, yield 95.2%.
Embodiment 20
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 82.2g (0.4mol) m-chloro bromobenzyl and 160g (1.2mol) 30%NaOH being added in reaction kettle dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain a chlorobenzene acetic acid, purity are as follows: 99.28%, yield 87%.
Embodiment 21
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 75.6g (0.4mol) being added dropwise in reaction kettle fluorine bromobenzyl and 160g (1.2mol) 30%NaOH.It is small to react 5
Shi Hou, is cooled to room temperature, is evaporated under reduced pressure methanol removal, filters out catalyst, and 30% hydrochloric acid is added to adjust PH to 1, filtering, dry
To para-fluorophenylacetic acid, purity are as follows: 99.40%, yield 86%.
Embodiment 22
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 100.0g (0.4mol) adding in reaction kettle bromine bromobenzyl and 160g (1.2mol) 30%NaOH dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
It obtains to bromo-acid, purity are as follows: 99.2%, yield 93%.
Embodiment 23
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while the adjacent chlorine bromobenzyl of 82.2g (0.4mol) and 160g (1.2mol) 30%NaOH being added in reaction kettle dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain o-chlorobenzene acetic acid, purity are as follows: 99.5%, yield 92%.
Embodiment 24
Cobalt pyridine 2 carboxylate 0.38g, palladium acetate 1.54g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, and 160g is added
(1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.3%, yield 86%.
Embodiment 25
Cobalt pyridine 2 carboxylate 0.256g, palladium acetate 0.384g is added to chlorine bromobenzyl 82.2g (0.4mol) in investment, is added
160g (1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle
Interior pressure 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, add 30% hydrochloric acid
PH to 1 is adjusted, filters, be dried to obtain 4-Chlorophenylacetic acid, purity are as follows: 99.1%, yield 80%.
Embodiment 26
It puts into p-chlorobenzylchloride 64.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added, 53.3g is added
(0.4mol) 30%NaOH, 73.7g methanol (1.6mol) is replaced system 3 times with CO, is warming up to 180 DEG C, is poured CO to kettle internal pressure
Power 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust
PH to 1 is filtered, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 99.02%, yield 85%.
Embodiment 27
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 180 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 64.4g (0.4mol) p-chlorobenzylchloride and 53.3g (0.4mol) 30%NaOH being added in reaction kettle dropwise.Reaction 5
After hour, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filtering, drying
Obtain 4-Chlorophenylacetic acid, purity are as follows: 99.32%, yield 86%.
Embodiment 28
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 74.0g (0.4mol) adding in reaction kettle methyl bromobenzyl and 30%NaOH 160g (1.2mol) dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain to methylphenyl acetic acid, purity are as follows: 98.95%, yield 85%.
Embodiment 29
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while methyl bromobenzyl between 74.0g (0.4mol) and 30%NaOH 160g (1.2mol) being added in reaction kettle dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain m-Tolylacetic acid, purity are as follows: 98.15%, yield 82%.
Embodiment 30
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while the adjacent methyl bromobenzyl of 74.0g (0.4mol) and 30%NaOH 160g (1.2mol) being added in reaction kettle dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain o-Tolylacetic acid, purity are as follows: 99.12%, yield 89%.
Embodiment 31
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 86.4g (0.4mol) adding in reaction kettle nitro bromobenzyl and 30%NaOH 160g (1.2mol) dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain paranitrophenylacetic acid, purity are as follows: 98.15%, yield 46%.
Embodiment 32
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while nitro bromobenzyl between 86.4g (0.4mol) and 30%NaOH 160g (1.2mol) being added in reaction kettle dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain m nitrophenylacetic acid, purity are as follows: 97.35%, yield 41%.
Embodiment 33
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 86.4g (0.4mol) adjacent nitro bromobenzyl and 30%NaOH 160g (1.2mol) being added in reaction kettle dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain o-nitrophenyl acetic acid, purity are as follows: 98.02%, yield 48%.
Embodiment 34
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while 78.4g (0.4mol) adding in reaction kettle cyano-benzyl bromide and 30%NaOH 160g (1.2mol) dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain to cyano phenylacetic acid, purity are as follows: 98.27%, yield 54%.
Embodiment 35
By 312ml methanol, cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g are added in autoclave reaction kettle, stirring 5
Minute catalyst is dissolved, with air 3 times in CO displacement kettle, be warming up to 150 DEG C, pouring CO, to pressure to rise to 1.5MPa. small 1
When it is interior, while the adjacent cyano-benzyl bromide of 78.4g (0.4mol) and 30%NaOH 160g (1.2mol) being added in reaction kettle dropwise.Instead
After answering 5 hours, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter,
It is dried to obtain adjacent cyano phenylacetic acid, purity are as follows: 98.56%, yield 61%.
Embodiment 36
By 312ml methanol, cobalt pyridine 2 carboxylate 1.92g is added in autoclave reaction kettle, and stirring makes catalyst in 5 minutes
Dissolution, with air 3 times in CO displacement kettle, is warming up to 150 DEG C, pours CO to pressure and rises to 1.5MPa. in 1 hour, simultaneously will
Nitro bromobenzyl and 30%NaOH160g (1.2mol) are added in reaction kettle dropwise between 86.4g (0.4mol).After reaction 5 hours, drop
It warms to room temperature, is evaporated under reduced pressure methanol removal, filters out catalyst, add 30% hydrochloric acid to adjust PH to 1, filter, be dried to obtain nitre
Base phenylacetic acid, purity are as follows: 97.05%, yield 27%.
Embodiment 37
By 312ml methanol, palladium acetate 1.92g is added in autoclave reaction kettle, and stirring dissolves catalyst in 5 minutes, is used
Air 3 times, is warming up to 150 DEG C in CO displacement kettle, pours CO to pressure and rises to 1.5MPa. in 1 hour, while by 78.4g
(0.4mol) adds in reaction kettle cyano-benzyl bromide and 30%NaOH 160g (1.2mol) dropwise.After reaction 5 hours, it is cooled to
Room temperature is evaporated under reduced pressure methanol removal, filters out catalyst, adds 30% hydrochloric acid to adjust PH to 1, filters, is dried to obtain to cyano benzene
Acetic acid, purity are as follows: 97.35%, yield 38%.
Embodiment 38
It puts into 3- chloro-4-methoxy benzyl chloride 76.4g (0.4mol) and cobalt pyridine 2 carboxylate 0.55g, palladium acetate 1.37g is added,
160g (1.2mol) 30%NaOH, 73.7g methanol (1.6mol) is added to be replaced system 3 times with CO, is warming up to 150 DEG C, pours CO
Pressure 1.5MPa in kettle, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, add 30%
Hydrochloric acid adjusts PH to 1, filters, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: and 96.16%, yield 32%
Embodiment 39
It puts into p-chlorobenzylchloride 6.44g (0.04mol) and cobalt pyridine 2 carboxylate 0.055g, palladium acetate 0.137g is added, be added
16g (0.12mol) 30%NaOH, 7.37g methanol (0.16mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured CO to kettle
Interior pressure 1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, add 30% hydrochloric acid
PH to 1 is adjusted, filters, be dried to obtain 4-Chlorophenylacetic acid, purity are as follows: 99.66%, yield 85.1%.
Embodiment 40
It puts into p-chlorobenzylchloride 161g (1mol) and cobalt pyridine 2 carboxylate 1.375g, palladium acetate 3.425g is added, 400g is added
(3mol) 30%NaOH, 184.3g methanol (4mol) is replaced system 3 times with CO, is warming up to 150 DEG C, is poured pressure in CO to kettle
1.5MPa, insulation reaction 5hrs are cooled to room temperature, are evaporated under reduced pressure methanol removal, filter out catalyst, and 30% hydrochloric acid is added to adjust PH
To 1, filters, is dried to obtain 4-Chlorophenylacetic acid, purity are as follows: 99.58%, yield 85.2%.
Comparative example 1
By 312ml methanol, 1.92g cobalt pyridine 2 carboxylate is added in autoclave reaction kettle, and stirring makes catalyst in 5 minutes
Dissolution, with air 3 times in CO displacement kettle, is warming up to 180 DEG C, pours CO to pressure and rises to 1.5MPa. in 1 hour, simultaneously will
64.4g (0.4mol) p-chlorobenzylchloride and 30%NaOH 160g (1.2mol) solution add in reaction kettle dropwise.Reaction 12 hours
Afterwards, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, adds 30% hydrochloric acid to adjust PH to 1, filters, is dried to obtain
4-Chlorophenylacetic acid, purity are as follows: 98.25%, yield 70%.
Comparative example 2
By 312ml methanol, 1.92g cobalt pyridine 2 carboxylate is added in autoclave reaction kettle, and stirring makes catalyst in 5 minutes
Dissolution, with air 3 times in CO displacement kettle, is warming up to 180 DEG C, pours CO to pressure and rises to 1.5MPa. in 1 hour, simultaneously will
64.4g (0.4mol) p-chlorobenzylchloride and 30%NaOH 160g (1.2mol) solution add in reaction kettle dropwise.After reaction 5 hours,
It is cooled to room temperature, is evaporated under reduced pressure methanol removal, filters out catalyst, 30% hydrochloric acid is added to adjust PH to 1, filter, be dried to obtain pair
Chlorobenzene acetic acid, purity are as follows: 98.32%, yield 68%.
Comparative example 3
By 312ml methanol, palladium acetate 1.92g is added in autoclave reaction kettle, and stirring dissolves catalyst in 5 minutes, is used
Air 3 times, is warming up to 180 DEG C in CO displacement kettle, pours CO to pressure and rises to 1.5MPa. in 1 hour, while by 64.4g
(0.4mol) p-chlorobenzylchloride and 30%NaOH 160g (1.2mol) solution add in reaction kettle dropwise.After reaction 12 hours, cooling
To room temperature, it is evaporated under reduced pressure methanol removal, filters out catalyst, added 30% hydrochloric acid to adjust PH to 1, filter, be dried to obtain to chlorobenzene
Acetic acid, purity are as follows: 98.05%, yield 69%.
Comparative example 4
By 312ml methanol, palladium acetate 1.92g is added in autoclave reaction kettle, and stirring dissolves catalyst in 5 minutes, is used
Air 3 times, is warming up to 180 DEG C in CO displacement kettle, pours CO to pressure and rises to 1.5MPa. in 1 hour, while by 64.4g
(0.4mol) p-chlorobenzylchloride and 30%NaOH 160g (1.2mol) are added in reaction kettle dropwise.After reaction 5 hours, it is cooled to room
Temperature is evaporated under reduced pressure methanol removal, filters out catalyst, adds 30% hydrochloric acid to adjust PH to 1, filters, is dried to obtain 4-Chlorophenylacetic acid,
Purity are as follows: 98.12%, yield 68%.
Comparative example 5
By 312ml methanol, 1.92g cobalt pyridine 2 carboxylate is added in autoclave reaction kettle, and stirring makes catalyst in 5 minutes
Dissolution, with air 3 times in CO displacement kettle, is warming up to 150 DEG C, pours CO to pressure and rises to 1.5MPa. in 1 hour, simultaneously will
82.2g (0.4mol) adds in reaction kettle chlorine bromobenzyl and 30%NaOH 160g (1.2mol) solution dropwise.Reaction 12 hours
Afterwards, it is cooled to room temperature, methanol removal is evaporated under reduced pressure, filters out catalyst, adds 30% hydrochloric acid to adjust PH to 1, filters, is dried to obtain
4-Chlorophenylacetic acid, purity are as follows: 98.8%, yield 78%.
Comparative example 6
By 312ml methanol, palladium acetate 1.92g is added in autoclave reaction kettle, and stirring dissolves catalyst in 5 minutes, is used
Air 3 times, is warming up to 180 DEG C in CO displacement kettle, pours CO to pressure and rises to 1.5MPa. in 1 hour, while by 82.2g
(0.4mol) neighbour's chlorine bromobenzyl and 30%NaOH 160g (1.2mol) are added in reaction kettle dropwise.After reaction 5 hours, it is cooled to room
Temperature is evaporated under reduced pressure methanol removal, filters out catalyst, adds 30% hydrochloric acid to adjust PH to 1, filters, is dried to obtain o-chlorobenzene acetic acid,
Purity are as follows: 98.5%, yield 70%.
Claims (10)
1. a kind of preparation method of phenylacetic acid class compound I comprising following step: in a solvent, in the gas phase system of CO
In, compound II, cobalt pyridine 2 carboxylate, palladium acetate and antalkali are subjected to carbonylation, obtain the phenylacetic acid
Class compound I,
Wherein, X F, Cl, Br or I;
R1、R2、R3、R4And R5It is each independently H, F, Cl, Br, I, C1~C4Alkyl, C1~C4Alkoxy, nitro and cyanogen
One of base.
2. the preparation method of phenylacetic acid class compound I as described in claim 1, which is characterized in that the X is Cl or Br;
The R1、R2、R3、R4And R5Independent is one of H, methyl, methoxyl group, F, Cl, Br, nitro and cyano;
And/or the antalkali is hydroxide, oxide or the carbonate and organic amine of alkali or alkaline earth metal
One of or it is a variety of;
And/or the solvent is organic solvent or organic solvent and water.
3. the preparation method of phenylacetic acid class compound I as claimed in claim 2, which is characterized in that the alkali metal or alkali
The hydroxide of earth metal is NaOH, KOH, LiOH and Ca (OH)2One of or it is a variety of;
And/or the oxide of the alkaline-earth metal is CaO;
And/or the carbonate of the alkali metal is Na2CO3And/or K2CO3;
And/or the organic amine is Et3N;
And/or the organic solvent be methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, dimethyl sulfoxide and N,
One of dinethylformamide is a variety of.
4. the preparation method of phenylacetic acid class compound I as claimed in claim 3, which is characterized in that the antalkali
For NaOH and/or Et3N;
And/or the solvent is the mixed liquor of methanol or first alcohol and water.
5. the preparation method of the phenylacetic acid class compound I as described in Claims 1 to 4, which is characterized in that the alkalinity neutralizes
Agent and the aqueous solvent are solution form;
And/or the cobalt pyridine 2 carboxylate and the mass ratio of the palladium acetate are 2:8~2:3;
And/or total amount and the chemical combination of the cobalt pyridine 2 carboxylate with the mixed catalyst of the palladium acetate composition
The mass percent of object II is 1~5%;
And/or the molar ratio of the antalkali and the compound II are 1:1~10:1;
And/or the molar ratio of the organic solvent and the compound II are 1:1~100:1.
6. the preparation method of phenylacetic acid class compound I as claimed in claim 5, which is characterized in that the antalkali
Solution concentration be 20-40% aqueous solution;
And/or the cobalt pyridine 2 carboxylate and the mass ratio of the palladium acetate are 2:5;
And/or total amount and the chemical combination of the cobalt pyridine 2 carboxylate with the mixed catalyst of the palladium acetate composition
The mass percent of object II is 3%;
And/or the molar ratio of the antalkali and the compound II are 1:1~3:1;
And/or the molar ratio of the organic solvent and the compound II are 4:1~25:1.
7. the preparation method of phenylacetic acid class compound I as claimed in claim 6, which is characterized in that the antalkali
Solution concentration be 30% aqueous solution;
And/or the molar ratio of the antalkali and the compound II are 3:1.
8. the preparation method of phenylacetic acid class compound I as claimed in claim 7, which is characterized in that the compound II, institute
Cobalt pyridine 2 carboxylate, the palladium acetate, the antalkali and the solvent once mixing stated or the chemical combination
The aqueous solution of object II and the antalkali in a manner of being added dropwise with the cobalt pyridine 2 carboxylate, the palladium acetate and
The solvent mixing;
And/or the temperature of the reaction is 0 DEG C to 300 DEG C;
And/or the pressure of the reaction is 1~2MPa.
9. the preparation method of phenylacetic acid class compound I as claimed in claim 8, which is characterized in that the temperature of the reaction is
100 DEG C to 180 DEG C;
And/or the pressure of the reaction is 1.5MPa;
And/or the reaction time is 3 hours to 8 hours.
10. the preparation method of phenylacetic acid class compound I as claimed in claim 9, which is characterized in that the temperature of the reaction is
150℃;
And/or the reaction time is 5 hours.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113548954A (en) * | 2021-07-30 | 2021-10-26 | 四川信乙化工有限公司 | Phenylacetic acid preparation system |
CN114394895A (en) * | 2022-01-21 | 2022-04-26 | 西安凯立新材料股份有限公司 | Preparation method of 2,4, 6-trimethylphenylacetic acid |
CN114835542A (en) * | 2021-02-02 | 2022-08-02 | 中国科学技术大学 | Method for synthesizing aryl acetic acid by directly carbonylating alkyl aromatic hydrocarbon and water |
CN114956983A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Production method of phenylacetic acid |
CN115073383A (en) * | 2021-03-16 | 2022-09-20 | 四川大学 | Synthetic method of aryl acetic acid compound |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0574082A2 (en) * | 1992-06-11 | 1993-12-15 | ENICHEM SYNTHESIS S.p.A. | Catalytic procedure for the prepartation of organic carbonates |
CN1284406A (en) * | 2000-06-21 | 2001-02-21 | 华中科技大学 | Catalyst for catalytic carboxylation to synthesize phenylacetic acid |
CN101249458A (en) * | 2008-04-09 | 2008-08-27 | 延安常泰药业有限责任公司 | Halogen compound carbonylation reaction catalyst and uses thereof |
CN102140062A (en) * | 2011-03-13 | 2011-08-03 | 联化科技股份有限公司 | Method for preparing 2,5-dimethyl phenylacetic acid |
-
2017
- 2017-08-01 CN CN201710648619.7A patent/CN109320413B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0574082A2 (en) * | 1992-06-11 | 1993-12-15 | ENICHEM SYNTHESIS S.p.A. | Catalytic procedure for the prepartation of organic carbonates |
CN1284406A (en) * | 2000-06-21 | 2001-02-21 | 华中科技大学 | Catalyst for catalytic carboxylation to synthesize phenylacetic acid |
CN101249458A (en) * | 2008-04-09 | 2008-08-27 | 延安常泰药业有限责任公司 | Halogen compound carbonylation reaction catalyst and uses thereof |
CN102140062A (en) * | 2011-03-13 | 2011-08-03 | 联化科技股份有限公司 | Method for preparing 2,5-dimethyl phenylacetic acid |
Non-Patent Citations (2)
Title |
---|
ALBERT L. LAPIDUS ET AL.: "Exceptionally simple catalytic system for the carbonylation of benzyl halides", 《MENDELEEV COMMUNICATIONS》 * |
MEI FU-MING ET AL.: "A New PdCl2-Co(Pyca)2 Catalyst System for Synthesis of Diphenyl Carbonate by Oxidative Carbonylation of Phenol", 《燃料化学学报》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114835542A (en) * | 2021-02-02 | 2022-08-02 | 中国科学技术大学 | Method for synthesizing aryl acetic acid by directly carbonylating alkyl aromatic hydrocarbon and water |
CN114835542B (en) * | 2021-02-02 | 2023-06-16 | 中国科学技术大学 | Method for synthesizing aryl acetic acid by directly carbonylating alkyl aromatic hydrocarbon and water |
CN114956983A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Production method of phenylacetic acid |
CN115073383A (en) * | 2021-03-16 | 2022-09-20 | 四川大学 | Synthetic method of aryl acetic acid compound |
CN115073383B (en) * | 2021-03-16 | 2023-07-18 | 四川大学 | Synthesis method of aryl acetic acid compound |
CN113548954A (en) * | 2021-07-30 | 2021-10-26 | 四川信乙化工有限公司 | Phenylacetic acid preparation system |
CN114394895A (en) * | 2022-01-21 | 2022-04-26 | 西安凯立新材料股份有限公司 | Preparation method of 2,4, 6-trimethylphenylacetic acid |
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