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Preparation method of 2-methyl-8-aminoquinoline

An aminoquinoline and methyl technology, which is applied in the field of preparation of 2-methyl-8-aminoquinoline, can solve the problems of difficulty in preparing 2-methyl-8-aminoquinoline, difficulty in carrying out amino substitution reaction, and the like, To achieve the effect of novel preparation process, increased activity, and cheap catalyst

Inactive Publication Date: 2009-12-16
HUNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the amino substitution reaction of follow-up 2-methyl-8-hydroxyquinoline and 2-methyl-8-chloroquinoline is difficult to carry out, it is difficult to prepare 2-methyl-8-aminoquinoline

Method used

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  • Preparation method of 2-methyl-8-aminoquinoline
  • Preparation method of 2-methyl-8-aminoquinoline
  • Preparation method of 2-methyl-8-aminoquinoline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] The preparation of embodiment 1 2-methyl-8-aminoquinoline

[0021] (1) Preparation of 2-methyl-8-bromoquinoline

[0022]

[0023] 8.60g (0.05mol) o-bromoaniline, heat up to about 40°C, add 50mL 18% HCl solution and 3.10g (0.05mol) boric acid, stir and heat up to about 100°C, add dropwise 2.02g (0.01mol) 2-nitro The mixture of bromobenzene and 4.20g (0.06mol) crotonaldehyde reacted for about 3.5h. The reaction solution was post-treated to obtain 2-methyl-8-bromoquinoline with a yield of 52.0% and a melting point of 69-71°C. 1 H NMR (CDCl 3 , 400MHz) δ: 2.82 (s, 3H, CH 3 ), 7.33 (m, 2H, quinoline ring), 7.73 (dd, J=8.0, J=1.2Hz, 1H, quinoline ring), 8.02 (m, 2H, quinoline ring).

[0024] (2) Preparation of 2-methyl-8-aminoquinoline

[0025]

[0026] 4.44g (20mmol) 2-methyl-8-bromoquinoline, 0.53g (2mmol) copper acetylacetonate, Cs 2 CO 3 Add 13.04g (40mmol), 0.80g (8mmol) acetylacetone and 80mL N-methylpyrrolidone into the reaction tank, quickly add 12mL 25%...

Embodiment 2

[0027] The preparation of embodiment 2 2-methyl-8-aminoquinoline

[0028] (1) Preparation of 2-methyl-8-bromoquinoline

[0029]

[0030] 8.60g (0.05mol) o-bromoaniline, heat up to about 40°C, add 50mL 18% HCl solution and 0.05mol glacial acetic acid, stir and heat up to about 100°C, add dropwise 0.015mol 2-nitrobromobenzene and 4.20g (0.06 mol) a mixture of crotonaldehyde, the reaction is about 4.0h. The reaction solution was post-treated to obtain 2-methyl-8-bromoquinoline with a yield of 62.1% and a melting point of 69-71°C.

[0031] (2) Preparation of 2-methyl-8-aminoquinoline

[0032]

[0033] 4.44g (20mmol) 2-methyl-8-bromoquinoline, 0.53g (2mmol) copper acetylacetonate, 40mmol cesium hydroxide, 0.80g (8mmol) acetylacetone and 80mL N, N-dimethylformamide were added to the reaction In the tank, add 12mL of 25% concentrated ammonia water, stir, slowly raise the temperature to 85°C, and keep it warm for 36h. The reaction solution was post-treated to obtain 2-methyl...

Embodiment 3

[0034] The preparation of embodiment 3 2-methyl-8-aminoquinoline

[0035] (1) Preparation of 2-methyl-8-bromoquinoline

[0036]

[0037]8.60g (0.05mol) o-bromoaniline, heat up to about 40°C, add 50mL 18% HCl solution, 5mL sulfuric acid and 0.05mol ferric sulfite, stir and heat up to about 100°C, add 0.012mol cerium ammonium nitrate and dropwise add 4.20g (0.06mol) a mixture of crotonaldehyde, the reaction is about 3.0h. The reaction solution was post-treated to obtain 2-methyl-8-bromoquinoline with a yield of 61.0% and a melting point of 69-71°C.

[0038] (2) Preparation of 2-methyl-8-aminoquinoline

[0039]

[0040] Add 4.44g (20mmol) 2-methyl-8-bromoquinoline, 2mmol iron acetylacetonate, 40mmol potassium carbonate, 0.80g (8mmol) acetylacetone and 80mL dimethyl sulfoxide into the reaction tank, add 12mL 25% concentrated ammonia water , stirred, and slowly heated to 120°C. Insulation reaction 48h. The reaction solution was post-treated to obtain 2-methyl-8-aminoquin...

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Abstract

The invention discloses a preparation method of 2-methyl-8-aminoquinoline. The preparation method of 2-methyl-8-aminoquinoline comprises the step of ammoniating 2-methyl-8-bromoquinoline in a solvent at 60-120 DEG C under the action of catalyst and strong alkali to obtain the 2-methyl-8-aminoquinoline, wherein the catalyst is one or more selected out of copper acetylacetonate, iron acetylacetonate, cobalt acetylacetonate and zinc acetylacetonate, the solvent used is one or more selected out of dimethylsulfoxide, N, N-dimethylformamide, acetylacetone, tetrahydrofuran and N-methylpyrrolidone, and the strong alkali is one or more selected out of caesium carbonate, caesium hydroxide, potassium carbonate and potassium hydroxide. The preparation method of the intermediate 2-methyl-8-bromoquinoline comprises the step of performing a cyclization reaction on o-bromoaniline and crotonic aldehyde in a solvent in the presence of oxidant and mollient, so as to obtain the 2-methyl-8-bromoquinoline, wherein the oxidant is selected out of one or more of nitrobenzene, 2-nitrobromobenzene, ammonium ceric nitrate, vanadic acid and iron oxide, the mollient is selected out of one or more of glacial acetic acid, hydrochloric acid, ferrous sulfate and boric acid, and the solvent is selected out of one or more of hydrochloric acid, sulfuric acid and chlorobenzene.

Description

technical field [0001] The invention relates to a preparation method of a fine chemical intermediate, in particular to a preparation method of 2-methyl-8-aminoquinoline. Background technique [0002] 2-methyl-8-aminoquinaldine (also known as 8-aminoquinaldine) is an important intermediate in organic synthesis, mainly used in dye production, and can also be used in the preparation of pharmaceutical intermediates (CN1918244, CN1763013, EP0463477A1, US3622583 , US5106980, US5030717). [0003] 2-Methyl-8-aminoquinoline is an important intermediate for the synthesis of quinophthalone pigment-C.I Pigment Yellow 138: 2-Methyl-8-aminoquinoline and tetrachlorophthalic anhydride are used to prepare organic pigment C.I P.Y138. This yellow pigment is one of the few high-grade yellow pigments in the world at present. It has bright color tone, low toxicity, and excellent properties such as light resistance, heat resistance, migration resistance, and solvent resistance. It can replace hea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/18B01J31/20
Inventor 胡艾希吴天泉王健华沈芳
Owner HUNAN UNIV
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