Method for preparing quinoline derivative

A technology of derivatives and quinoline, which is applied in the field of preparation of quinoline derivatives, can solve the problems of difficult post-processing of glycerin, inconvenient follow-up processing, and low yield of quinoline, etc., and achieve easy product, mild reaction conditions, and reaction selectivity Good results

Inactive Publication Date: 2011-05-25
北京成宇化工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The yield of quinoline in this method is low, and the use of a large amount of glycerol brings difficulties to post-processing
[0004] In U.S. Patent (US: 3697400), a method for preparing quinoline derivatives from aniline and acrolein in the presence of nitrobenzene, using copper sulfate or ferrous sulfate as a catalyst, in concentrated sulfuric acid or concentrated hydrochloric acid is introduced. , this method improves the yield of the reaction, but the use of a large amount of nitrobenzene brings many disadvantages in the purification process
[0005] In the U.S. Patent (US: 5130434), the above-mentioned method is improved, and the method for preparing quinoline derivatives from anilines and acrolein is introduced with alumum pentoxide as a catalyst in concentrated sulfuric acid or concentrated nitric acid. The yield of the reaction is improved, but a large amount of strong acid is still used, which brings inconvenience to the subsequent treatment of the reaction, leads to a large amount of industrial waste, and causes environmental pollution

Method used

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  • Method for preparing quinoline derivative
  • Method for preparing quinoline derivative
  • Method for preparing quinoline derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Preparation of 2-methylquinoline

[0028] In a 0.5 liter reaction flask, add aniline (93 grams, 1 mole), 1-methyl-3-sulfonic acid propylimidazolium bisulfate (100 grams), sodium iodide (5 grams), at 100 ~ 105 ° C Next, crotonaldehyde (77 g, 1.1 mol) was added dropwise, and the addition was completed in 1.5 hours, and the reaction was continued for 1 hour at this temperature. After cooling, water (300 ml) was added to the reaction solution, neutralized with 30% sodium hydroxide to pH=9-10, stirred for 30 minutes, and extracted with toluene.

[0029] The filtrate was adjusted to acidity with sulfuric acid, concentrated, and the ionic liquid was recovered.

[0030] The toluene solution was concentrated and distilled under reduced pressure to collect fractions at 118-120° C. / 10 mmHg to obtain 133 g of 2-methylquinoline (93% yield).

[0031] The product has a purity of 99.5% as determined by gas chromatography.

Embodiment 2

[0033] Preparation of 3-methylquinoline

[0034] In a 0.5-liter reaction flask, add aniline (93 grams, 1 mole), (3-sulfonic acid propyl) triethylammonium bisulfate (100 grams), potassium iodide (3 grams), drop at 95 ~ 100 ° C α-Methacrolein (77 g, 1.1 mol) was added over 1 hour and the reaction was continued at this temperature for 1 hour. After cooling, water (300 ml) was added to the reaction solution, neutralized with 30% sodium hydroxide to pH=9-10, stirred for 30 minutes, and extracted with toluene. The filtrate was adjusted to acidity with sulfuric acid, concentrated, and the ionic liquid was recovered.

[0035] The toluene solution was concentrated and distilled under reduced pressure to collect fractions at 120-123° C. / 10 mmHg to obtain 126 grams of 3-methylquinoline (88% yield).

[0036] The purity of the product as determined by gas chromatography is 99.4%.

Embodiment 3

[0038] Preparation of 4-methylquinoline

[0039] In a 0.5-liter reaction flask, add aniline (93 grams, 1 mole), 1-methyl-3-sulfonic acid propylimidazolium bisulfate (100 grams), iodine (3 grams), and drop at 90 to 95 ° C Methyl ketene (91 g, 1.3 moles) was added over 1.5 hours and the reaction was continued at this temperature for 2 hours. After cooling, water (300 ml) was added to the reaction solution, neutralized with 30% sodium hydroxide to pH=9-10, stirred for 30 minutes, and extracted with toluene. The filtrate was adjusted to acidity with sulfuric acid, concentrated, and the ionic liquid was recovered.

[0040] The toluene solution was concentrated and distilled under reduced pressure to collect fractions at 130-132° C. / 5 mmHg to obtain 131.5 g of 4-methylquinoline (92% yield).

[0041] The purity of the product as determined by gas chromatography is 99.7%.

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Abstract

The invention discloses a method for preparing a quinoline derivative. The quinoline derivative serving as a goal product is prepared by cyclizing aniline or an aniline derivative with alpha, beta-unsaturated aldehyde and ketone in acidic ionic liquid under the catalysis of iodine or iodide. A synthesis method provided by the invention has the characteristics of high reaction selectivity, high yield, mild reaction conditions, environmental friendliness and the like, and is suitable for industrial production; a product is easy to separate; and the ionic liquid can be recycled.

Description

technical field [0001] The invention belongs to the field of chemical industry, and more specifically relates to a preparation method of quinoline derivatives. Background technique [0002] Quinoline derivatives are important intermediates for the synthesis of medicines, pesticides, photosensitive materials and dyes. As an existing method for preparing quinoline derivatives, in the literature (A.Weissberger and E.C Taylor, Heterocyclic Compounds, 32(1), 100-117), it is introduced that in concentrated sulfuric acid, anilines are similar to glycerol or α, The preparation method of β-unsaturated aldehydes and ketones in the presence of oxidizing agents such as iron oxide and phosphorus pentoxide has many side reactions, poor selectivity, low yield, and a large amount of wastewater generated, making it difficult to achieve large-scale production. [0003] Introduced in British Patent (GB: 549502), use iodine as oxidant in concentrated sulfuric acid, utilize anilines and glyceri...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/04C07D215/18
Inventor 宋也王道林
Owner 北京成宇化工有限公司
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