CN109651114B - Method for synthesizing alkyl aromatic aldehyde - Google Patents
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Abstract
The present invention relates to a process for synthesizing alkyl aromatic aldehydes. The invention mainly solves the problems of low conversion rate of alkyl aromatic hydrocarbon and low selectivity of para-alkyl aromatic aldehyde in the prior art, and adopts the technical scheme that the method for synthesizing the alkyl aromatic aldehyde comprises the step of carrying out carbonylation reaction on the alkyl aromatic hydrocarbon and CO under the catalysis of a catalyst to obtain the alkyl aromatic aldehyde, wherein the catalyst comprises halogenated alkyl imidazole salt, aluminum halide and an accelerant, so that the technical problem is better solved, and the method can be used for industrial production of the alkyl aromatic aldehyde.
Description
Technical Field
The present invention relates to a process for synthesizing alkyl aromatic aldehydes.
Background
p-Tolualdehyde is one of alkyl aromatic aldehydes, namely 4-Tolualdehyde (PTAL), is colorless or light yellow transparent liquid, has mild flower fragrance and almond fragrance, and has certain irritation to eyes and skin. P-tolualdehyde can be used for oxidizing and synthesizing terephthalic acid with high selectivity, is an important organic synthesis intermediate, and is widely applied in the fields of fine chemical engineering and medicines.
The alkyl aromatic aldehyde is synthesized mainly by direct high-temperature oxidation, indirect electrosynthesis and carbonylation. Synthesis of PTAL as an example:
the direct high-temperature oxidation method is to prepare the PTAL by taking p-xylene as a raw material and carrying out photobromination, alkaline hydrolysis and oxidation of a hydrogen peroxide/hydrobromic acid mixed solution. Although the process has the advantages of easily obtained raw materials and simple operation, the process has low aromatic utilization rate, complicated process and lower total conversion rate (26.7 percent) (the synthesis research of p-tolualdehyde [ J ] proceedings of Zhejiang university, 1999,27 (4); 334-.
The indirect electrosynthesis method is to prepare PTAL by catalytic oxidation of p-xylene in an electrolytic bath, and has the advantages of simple process, high yield, less side reaction, less pollution discharge, environmental protection and resource saving, but the cost of the catalyst is high, and the equipment is complex, which restricts the industrial development (Tangdang, royal red, Liyanwei. process improvement of the indirect electrosynthesis of benzaldehyde/p-tolualdehyde by using on-line ultrasound outside the cell [ J ]. university of Tai principle, 2015,46(1): 6-10.).
The carbonylation method is to synthesize PTAL by catalyzing and carbonylating toluene and CO. The process takes CO as a carbonylation reagent, takes one of a B-L composite liquid acid catalyst, a solid super acid catalyst and an ionic liquid catalyst as a catalyst, and the reaction is essentially electrophilic substitution reaction of CO to toluene under the catalysis of acid, which is called as Gattermann-Koch synthesis reaction. The method has the advantages of high atom utilization rate, simple process, low cost of raw material CO and good market prospect. The process was successively investigated by DuPont, Mitsubishi gas, Inc., and Exxon Mobil, USA. Compared with B-L composite liquid acid and solid super strong acid catalysts, the catalytic activity of the selective carbonylation reaction of toluene and CO catalyzed by the ionic liquid is obviously improved. Saleh to [ emim]Cl/AlCl3(xAlCl30.75) as catalyst, IL/toluene mass ratio of 8.5/1.8, CO partial pressure of 8.2Mpa maintained at room temperature, reaction time of 1h, achieved 66% toluene conversion and 89.1% PTAL selectivity (Saleh RY, Rouge b. process for making aromatic aldehyde using ionic liquids [ P)]US 6320083,2001-11-20.). The further application is that the PTAL obtained by separation is oxidized to synthesize terephthalic acid, and the terephthalic acid is used as a monomer in the production of industrial polyester, and the demand is large. However, the above patents have problems of large amount of catalyst, low toluene conversion rate, and low selectivity to methylbenzaldehyde.
Disclosure of Invention
The invention aims to solve the technical problems of low conversion rate of alkyl aromatic hydrocarbon and low selectivity of para-alkyl aromatic aldehyde, and provides a novel method for synthesizing alkyl aromatic aldehyde, which has the characteristics of high conversion rate of alkyl aromatic hydrocarbon and high selectivity of para-alkyl aromatic aldehyde.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the method for synthesizing the alkyl aromatic aldehyde comprises the step of carrying out carbonylation reaction on alkyl aromatic hydrocarbon and CO under the catalysis of a catalyst to obtain the alkyl aromatic aldehyde, wherein the catalyst comprises halogenated alkyl imidazole salt, aluminum halide and a promoter.
In the technical scheme, the weight ratio of the catalyst to the alkyl aromatic hydrocarbon is preferably 1-12.
In the technical scheme, the reaction temperature is preferably 20-150 ℃.
In the technical scheme, the pressure of the reaction is preferably 1-8 MPa.
In the technical scheme, the reaction time is preferably 1-12 h.
In the above technical scheme, the halogenated alkyl imidazolium salt is selected from imidazolium salt a having the following structural formula a and/or imidazolium salt B having the following structural formula B:
wherein R is1And R2Independently selected from C1-C4 alkyl, R3Selected from C1-C6 alkylene radicals, R4And R5Independently selected from C1-C4 alkyl, and X and Y are independently selected from at least one of chlorine or bromine.
In the above technical scheme, R1And R2Preferably the same alkyl group, more preferably both methyl groups.
In the above technical scheme, R3C1-C6 alkylene or C6-C10 arylene is preferred. Such as but not limited to R3Is- (CH)2)k- (k ═ 1 to 6) or-C6H4- (wherein two substituents may be in ortho, meta or para positions in the phenyl ring).
In the above technical scheme, the halogenated alkyl imidazolium salt preferably includes both an imidazolium salt a and an imidazolium salt B, and the two halogenated alkyl imidazolium salts have a synergistic effect in improving conversion rate of alkyl aromatic hydrocarbons. In this case, the ratio between the imidazolium salt A and the imidazolium salt B is not particularly limited, and examples thereof include, but are not limited to, a weight ratio of the imidazolium salt A to the imidazolium salt B of 0.1 to 10, and more specific non-limiting ratios within this range are 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 8.0, 9.0, and the like.
In the above technical solution, the haloalkyl imidazolium salt a is preferably:
more preferably, the haloalkyl imidazolium salt A is an imidazolium salt a represented by the structural formula (a).
In the above technical solution, the imidazole salt B is one selected from 1-butyl-3-ethylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-N-propyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole chloride, N-dimethylimidazole chloride, 1-butyl-3-methylimidazole bromide, 1-N-propyl-3-methylimidazole bromide, 1-ethyl-3-methylimidazole bromide and N, N-dimethylimidazole bromide, and more preferably 1-ethyl-3-methylimidazole bromide.
In the above technical scheme, the aluminum halide is preferably selected from AlCl3And AlBr3Most preferably AlCl3。
In the above technical solution, the accelerator is preferably at least one of a nitrogen heterocyclic compound and an organic phosphine compound. More preferably, the compound simultaneously comprises a nitrogen heterocyclic compound and an organic phosphine compound, and the nitrogen heterocyclic compound and the organic phosphine compound have synergistic effect on improving the selectivity of para-alkyl aromatic aldehyde. In this case, the ratio between the two accelerators is not particularly limited, and examples thereof include, but are not limited to, a weight ratio of the nitrogen heterocyclic compound to the organic phosphine compound of 0.1 to 10, and more specific non-limiting ratios within the range of 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 8.0, 9.0, and the like.
In the above technical solution, the nitrogen heterocyclic compound is selected from at least one of azacyclo-carbene, alkyl pyridine and phenanthroline, and more preferably at least one of 4-benzyl pyridine and phenanthroline.
In the above technical solution, the organic phosphine compound is preferably at least one of triphenylphosphine and tricyclohexylphosphine.
In the above technical scheme, the promoter preferably comprises at least two of 4-benzylpyridine and phenanthroline, and the two promoters have a synergistic effect in improving the selectivity of the para-alkyl aromatic aldehyde. In this case, the ratio between the two promoters is not particularly limited, but is not limited to, for example, 0.1 to 10 in terms of the weight ratio of 4-benzylpyridine to phenanthroline, and more specific non-limiting ratios within this range are 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 8.0, 9.0, and the like.
In the technical scheme, the weight ratio of the halogenated alkyl imidazole salt to the aluminum halide to the accelerator is 100 to (50-300) to (1-50).
In the above technical scheme, the preparation method of the catalyst is not particularly limited, and the catalyst can be mixed according to the required components; the reaction system may be added separately or simultaneously with the desired components in the reaction for synthesizing the alkyl aromatic aldehyde, and if added separately, the order of addition of the components is not particularly limited.
By way of non-limiting example, when mixing according to the desired components, one skilled in the art will know that the catalyst component mixing atmosphere is preferably a CO atmosphere to increase the solubility of CO; the mixing and stirring speed of each component of the catalyst is preferably 100-800 rpm; the mixing time of the components of the catalyst is preferably 0.5 h-2 h.
In the above technical scheme, the alkyl aromatic hydrocarbon is preferably selected from monoalkyl substituted benzene.
In the above technical scheme, the alkyl group in the monoalkyl substituted benzene is an alkyl group of C1-C6, such as toluene, ethylbenzene, cumene, n-butylbenzene, tert-butylbenzene, n-hexylbenzene, but is not limited to the alkyl aromatic hydrocarbon. As known to those skilled in the art, the carbonylation reaction is electrophilic substitution, and alkyl mono-substituted aromatic hydrocarbon and CO are carbonylated according to the positioning rule of alkyl mono-substituted aromatic hydrocarbon, and the obtained product with predominant positioning is para-alkyl aromatic aldehyde, which is the target product of the present invention.
The specific steps for synthesizing the alkyl aromatic aldehyde may be:
(1) adding the components of the catalyst into the high-pressure reaction kettle;
(2) the air in the kettle is firstly used by N2Replacing for 3 times, then replacing for 3 times by CO gas, stirring and mixing;
(3) adding alkyl aromatic hydrocarbon, and then replacing for 3 times by CO gas;
(4) heating to reaction temperature, keeping constant reaction pressure, stirring, and reacting to obtain a mixture containing the product alkyl aromatic aldehyde.
In the present invention, unless otherwise specified, the pressure refers to gauge pressure.
The sample processing and analysis methods were as follows:
the product mixture was washed with 2 volumes of ice water, the aqueous phase was discarded and the organic phase was extracted three times with ether, the volume of ether used for each extraction being equal to the volume of the organic phase. Combining the three times of ether extraction liquid, performing rotary evaporation to obtain a residue, namely a crude product of the alkyl aromatic aldehyde, performing gas chromatography analysis on the crude product, and calculating the conversion rate of the alkyl aromatic hydrocarbon and the selectivity of para-alkyl aromatic aldehyde according to an analysis result, wherein the calculation formula is as follows:
after the technical scheme of the invention is adopted, the conversion rate of toluene can reach 85.3%, the selectivity of corresponding p-tolualdehyde can reach 92.1%, beneficial technical effects are obtained, and the method can be used for preparing alkyl aromatic aldehyde by carbonylation of alkyl aromatic hydrocarbon and CO.
Detailed Description
Preparation of imidazole salt a: reference is made to the preparation of imidazolium salts a described in the literature (Yanhong Wang, Tianying Zhang, Bin Li, et al Synthesis, chromatography, electrochemical properties and catalytic reactivity of the N-heterocyclic carbon-containing diene compounds [ J ] RSC Advances,2015,5(37): 29022-:
under the atmosphere of nitrogen, CH is added into a 1000mL three-neck flask in sequence3CN (400mL), 1-methylimidazole (49.8g, 0.6mol) and 1, 2-dibromoethane (56.4g, 0.3mol) were reacted at 80 ℃ with stirring for 72 h. Cooled to room temperature, filtered, the solid washed with THF (3X 200 mL/sec) and dried in vacuo at 30 ℃ to give the above imidazolium salt a (100.6g, 95.3%).
[ example 1 ]
The imidazole salt a 40g and AlCl are added into a 250mL high-pressure reaction kettle340g and triphenylphosphine 4g, the air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 2 ]
40g of 1-ethyl-3-methyl imidazole bromide and 40g of AlCl are added into a 250mL high-pressure reaction kettle340g and triphenylphosphine 4g, the air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 3 ]
250mL high-pressure reaction kettleAdding the imidazole salt a 40g and AlCl340g and 4g of phenanthroline, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 4 ]
40g of 1-ethyl-3-methyl imidazole bromide and 40g of AlCl are added into a 250mL high-pressure reaction kettle340g and 4g of phenanthroline, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 5 ]
The imidazole salt a 40g and AlCl are added into a 250mL high-pressure reaction kettle340g and 4g of 4-benzylpyridine, the air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 6 ]
40g of 1-ethyl-3-methyl imidazole bromide and 40g of AlCl are added into a 250mL high-pressure reaction kettle340g and 4g of 4-benzylpyridine, the air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain the p-methylbenzeneA product mixture of formaldehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 7 ]
20g of the imidazole salt a, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g and triphenylphosphine 4g, the air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 8 ]
20g of the imidazole salt a, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g and 4g of phenanthroline, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 9 ]
20g of the imidazole salt a, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g and 4g of 4-benzylpyridine, the air in the kettle is firstly N2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 10 ]
The imidazole salt a 40g and AlCl are added into a 250mL high-pressure reaction kettle340g of triphenylphosphine and 2g of 4-benzylpyridine, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 11 ]
40g of 1-ethyl-3-methyl imidazole bromide and 40g of AlCl are added into a 250mL high-pressure reaction kettle340g of triphenylphosphine and 2g of 4-benzylpyridine, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 12 ]
The imidazole salt a 40g and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of triphenylphosphine and 2g of phenanthroline, and N is firstly used for air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 13 ]
40g of 1-ethyl-3-methyl imidazole bromide and 40g of AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of triphenylphosphine and 2g of phenanthroline, and N is firstly used for air in the kettle2Displacing 3 times, then displacing 3 times with CO gas(ii) a Stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 14 ]
The imidazole salt a 40g and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of 4-benzyl pyridine and 2g of phenanthroline, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 15 ]
40g of 1-ethyl-3-methyl imidazole bromide and 40g of AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of 4-benzyl pyridine and 2g of phenanthroline, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 16 ]
20g of the imidazole salt a, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g of triphenylphosphine and 2g of 4-benzylpyridine, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 17 ]
20g of 1-ethyl-3-methyl imidazole bromide, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of triphenylphosphine and 2g of phenanthroline, and N is firstly used for air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 18 ]
20g of 1-ethyl-3-methyl imidazole bromide, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of 4-benzyl pyridine and 2g of phenanthroline, and N is firstly used as air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of toluene, and then replacing for 3 times by CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tolualdehyde.
For convenience of comparison and explanation, the catalyst formulation, the conversion of toluene and the selectivity to p-tolualdehyde are shown in table 1.
[ example 19 ]
20g of 1-ethyl-3-methyl imidazole bromide, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of triphenylphosphine and 2g of phenanthroline, and N is firstly used for air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of ethylbenzene, and then replacing for 3 times by using CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-ethylbenzaldehyde.
For convenience of comparison and illustration, the catalyst formulation, the conversion of ethylbenzene and the selectivity to p-ethylbenzaldehyde are shown in table 1.
[ example 20 ]
20g of 1-ethyl-3-methyl imidazole bromide, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of triphenylphosphine and 2g of phenanthroline, and N is firstly used for air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of isopropyl benzene, and then replacing 3 times with CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing the p-isopropyl benzaldehyde.
For ease of comparison and illustration, the catalyst formulation, cumene conversion and selectivity to p-isopropylbenzaldehyde are listed in table 1.
[ example 21 ]
20g of 1-ethyl-3-methyl imidazole bromide, 20g of 1-ethyl-3-methyl imidazole bromide and AlCl are added into a 250mL high-pressure reaction kettle340g, 2g of triphenylphosphine and 2g of phenanthroline, and N is firstly used for air in the kettle2Replacing for 3 times, and then replacing for 3 times by CO gas; stirring at 500rpm for 1 h; adding 30g of tert-butylbenzene, and then replacing for 3 times with CO gas; heating to 50 ℃, keeping CO pressure at 2.0MPa, stirring at 500rpm, and reacting for 5h to obtain a product mixture containing p-tert-butyl benzaldehyde.
For ease of comparison and illustration, the catalyst formulation, the conversion of t-butylbenzene and the selectivity to p-t-butylbenzaldehyde are listed in table 1.
TABLE 1
Note: the alkylaromatic hydrocarbon used in examples 1 to 18 was toluene, ethylbenzene in example 19, cumene in example 20, and tert-butylbenzene in example 21.
Claims (8)
1. The method for synthesizing the alkyl aromatic aldehyde comprises the step of carrying out carbonylation reaction on alkyl aromatic hydrocarbon and CO under the catalysis of a catalyst to obtain the alkyl aromatic aldehyde, wherein the catalyst comprises halogenated alkyl imidazolium salt, aluminum halide and an accelerator, and is characterized in that the halogenated alkyl imidazolium salt comprises imidazolium salt A with a structural formula A and imidazolium salt B with a structural formula B:
wherein R is1And R2Independently selected from C1-C4 alkyl, R3Selected from C1-C6 alkylene, R4And R5Independently selected from C1-C4 alkyl, X and Y are independently selected from at least one of chlorine or bromine; the accelerator is at least one of nitrogen heterocyclic compounds and organic phosphine compounds.
2. The process as set forth in claim 1, wherein the weight ratio of said catalyst to said alkylaromatic hydrocarbon is from 1 to 12.
3. The method according to claim 1, wherein the reaction temperature is 20 to 150 ℃.
4. The method according to claim 1, wherein the pressure of the reaction is 1 to 8 MPa.
5. The method according to claim 1, wherein the reaction time is 1 to 12 hours.
6. The method of claim 1, wherein R is1And R2Are the same alkyl groups.
7. The process according to claim 1, wherein the imidazolium salt B is selected from the group consisting of 1-butyl-3-ethylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-N-propyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, N-dimethylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-N-propyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium bromide, and N, N-dimethylimidazolium bromide.
8. The process as set forth in claim 1 wherein the aluminum halide is selected from AlCl3And AlBr3At least one of (1).
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| CN101209959A (en) * | 2006-12-26 | 2008-07-02 | 中国石油化工股份有限公司 | Method for preparing and separating alkyl aromatic aldehyde |
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