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Ring alkylation of aniline or an aniline derivative using ionic liquid catalysts

A technology of aniline derivatives and ionic liquids, applied in the preparation of amino compounds from amines, organic chemistry, etc., can solve problems that do not involve cycloalkylation of aniline or aniline derivatives

Inactive Publication Date: 2011-09-14
CHEMTURA CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, neither study involved the cycloalkylation of aniline or aniline derivatives

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Alkylation of Aniline Using 1-Decene, Aluminum Chloride and 3-Butyl-1-methylimidazolium Chloride

[0028]To a 1 L 4-neck round bottom flask equipped with a heating mantle, temperature controller, water-cooled reflux condenser with positive nitrogen pressure inlet at the top, mechanical stirrer, and thermocouple was added aniline (46.52 g, 0.50 mol ), 1-decene (245.54 g, 1.75 moles, 3.5 equivalents relative to aniline), aluminum chloride (33.38 g, 0.25 moles, 50 mole % relative to aniline) and finally 3-butyl chloride -1-Methylimidazolium (BMIM chloride, 10.89 g, 0.0625 mol, 12.5 mol% relative to aniline). Stir at about 200-300 rpm and heat the mixture first to 100°C, then to 160°C and finally to 180°C. 1-Decene undergoes gentle reflux at this temperature. Heating was continued at 167-180°C for a total of 23.4 hours.

[0029] The reaction mixture was allowed to cool to room temperature and diluted with 400 mL of n-heptane. The reaction product separated into two phas...

Embodiment 2

[0031] Alkylation of Aniline Using Nonene, Aluminum Chloride, and Methyltributylammonium Chloride

[0032] To an apparatus similar to that described in Example 1, aniline, nonene, and aluminum chloride were sequentially added under a nitrogen atmosphere. Stirring at 200-300 rpm was started and then solid methyltributylammonium chloride was added. Then start heating to 160°C. Reflux started at a pot temperature of 137.5°C and steadily increased as the aniline was alkylated. Heating between 137-160°C was continued for 28.2 hours, then the reaction mixture was allowed to cool to room temperature.

[0033] The reaction mixture was diluted with 300 mL of n-heptane and 200 mL of dichloromethane, and the two phases were separated. When the heptane phase was washed with 500 mL of water, no reaction occurred. Careful addition of 500 mL of water to the lower dichloromethane phase resulted in a vigorous reaction, indicating that this phase contained the catalyst. After the reaction ...

Embodiment 3

[0036] Alkylation of Aniline Using Dodecene, Aluminum Chloride and Methyltributylammonium Chloride

[0037] Into an apparatus similar to that described in Example 1 was added aniline, dodecene, followed by aluminum chloride under positive nitrogen pressure, and slow stirring was started. After stirring with an exotherm of up to 46°C, methyltributylammonium chloride was added. The reaction mixture was heated to 160°C and maintained at this temperature for 27.8 hours. The reaction mixture was then allowed to cool to room temperature and diluted with 300 mL of n-heptane - 200 mL of dichloromethane.

[0038] The reaction mixture separated into a bulky upper phase and a dark red-orange lower phase. The upper layer was washed with 2×500 mL water, 500 mL ammonia water (400 mL water / 100 mL concentrated ammonia water), and then dried over anhydrous sodium sulfate.

[0039] The sodium sulfate was removed by suction filtration and the filtrate was evaporated in vacuo on a rotary evapo...

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PUM

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Abstract

A process for ring-alkylating aniline or an aniline derivative in which aniline or an aniline derivative is reacted with an alkylating agent in the presence of an ionic liquid which includes a Lewis acid and a quaternary cation, to produce a ring-alkylated alkylaniline or a ring-alkylated aniline derivative. The use of an ionic liquid permits convenient separation of the alkylated reaction product from the reactants.

Description

Background of the invention: [0001] The present invention relates to the cycloalkylation of aniline or alkylated aniline derivatives. [0002] Aniline is an important structural unit of rubber chemicals (such as diphenylamine, 4-aminodiphenylamine, mercaptobenzothiazole disulfide), dyes, polyaniline and petroleum additives, as well as agrochemicals. In applications where good hydrocarbon solubility of the compound is important, hydrocarbon chains must be introduced onto the aniline or alkylated aniline to improve solubility. [0003] The prior art has attempted to improve the cycloalkylation of aromatic amines such as aniline. For example, US Patent Nos. 4,740,620 and 4,876,377 disclose the selective cycloalkylation of aromatic amines to ortho-alkylated products using acidic crystalline molecular sieves and partially dealuminated zeolites, respectively. US Patent No. 5,081,302 discloses the selective cycloalkylation of aniline to p-alkylaniline in the presence of a zeolite c...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C209/68C07C211/45C07C211/47
CPCC07C209/68C07C211/45C07C211/47
Inventor S·J·霍布斯V·玛达布斯王金运J·F·斯蒂贝尔
Owner CHEMTURA CORP