Preparation method of 2-chloro-4-methyl nicotinonitrile

A technology of methylnicotinonitrile and cyano group is applied in the field of preparation of 2-chloro-4-methylnicotinonitrile, and can solve the problems of low yield, triethyl orthoformate acetic anhydride solution reaction is not easy to carry out, etc.

Inactive Publication Date: 2014-01-15
上海品沃化工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The reaction between the product of Knoeveangel of WO0043365 and triethyl orthoformate acetic anhy

Method used

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  • Preparation method of 2-chloro-4-methyl nicotinonitrile
  • Preparation method of 2-chloro-4-methyl nicotinonitrile
  • Preparation method of 2-chloro-4-methyl nicotinonitrile

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] (1) Preparation of 2-cyano-5-(dimethylamino)-3-methyl-2,4-pentadienamide

[0019]

[0020] Add 100mL of methanol to a 250mL four-necked flask with mechanical stirring and a thermometer, then add 3g (0.05mol) of glacial acetic acid, 0.2g of β-alanine and 23.1g (0.204mol) of (E)-4-(dimethyl Amino) base-3-en-2-butanone, stir well and cool in a water bath. At room temperature, 13.2 g (0.2 mol) of malononitrile was added dropwise for about 1 to 2 hours. After the addition of malononitrile, the reaction was stirred at room temperature for 24h. After the reaction is completed, cool to 5-10°C with an ice-water bath. Suction filtration, the filter cake was washed with 10 mL ice methanol, and the filter cake was dried to obtain 47.5 g orange solid, namely 2-cyano-5-(dimethylamino)-3-methyl-2,4-dipentenamide . Yield: 88.4%; Purity: 98%.

[0021] (2) Preparation of 2-chloro-4-methylnicotinonitrile

[0022]

[0023] Add 17.9 g (0.1 mol) of 2-cyano-5-(dimethylamino)-3-met...

Embodiment 2

[0025] (1) Preparation of 2-cyano-5-(dimethylamino)-3-methyl-2,4-pentadienamide

[0026] Synthesize as in the method and conditions of Example 1 (1), only the catalyst is changed to piperidine acetate to obtain 2-cyano-5-(dimethylamino)-3-methyl-2,4-di Pentenamide, yield 75.5%, purity 98.3%.

[0027] (2) Preparation of 2-chloro-4-methylnicotinonitrile

[0028] Synthesize as in the method and condition of embodiment one (2), only change the mixture of phosphorus oxychloride (1.5eq) and phosphorus pentachloride (0.5eq) into the mixture of chlorination reagent phosphorus oxychloride, obtain 2-chloro- 4-Methylnicotinonitrile, yield 62%, purity 93%.

Embodiment 3

[0030] (1) Preparation of 2-cyano-5-(dimethylamino)-3-methyl-2,4-pentadienamide

[0031] Synthesized as in the method and conditions of Example 1 (1), only changing the catalyst to piperidine to obtain 2-cyano-5-(dimethylamino)-3-methyl-2,4-dipentenamide , yield 63%, purity 93.2%.

[0032] (2) Preparation of 2-chloro-4-methylnicotinonitrile

[0033] Synthesized as in the method and conditions of Example 1 (2).

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Abstract

The invention discloses a preparation method of 2-chloro-4-methyl nicotinonitrile. The preparation method disclosed by the invention comprises the following steps: with (E)-4-(dimethylamine) yl-3-butene-2-ketone and malononitrile as raw materials, catalyzing and condensing; and finally, chlorinating closed-loops to obtain 2-chloro-4-methyl nicotinonitrile under the effect of phosphorus oxychloride and phosphorus pentachloride. The total yield of the two reactions can reach 55.7%. The preparation method is simple in process, convenient to operate, low in equipment demand and very applicable to industrial production.

Description

technical field [0001] The invention relates to a preparation method of 2-chloro-4-methylnicotinonitrile. Background technique [0002] CN101157654 uses acetone, formate and sodium methylate as raw materials to obtain 4,4-dimethoxybutan-2-one through sodium salt addition, and then undergoes Knoevenagel reaction with malononitrile, hydrolysis and ring closure, and passes through phosphorus oxychloride Chlorination gave 2-chloro-4-methylnicotinonitrile with a total yield of 43.8% (calculated as malononitrile). [0003] US2002052507 uses 4,4-dimethoxybutan-2-one and malononitrile to undergo Knoevenagel reaction, hydrolysis and ring closure, and chlorination of phosphorus oxychloride to obtain 2-chloro-4-methylnicotinonitrile, with a total yield of 75.6% (calculated as malononitrile). [0004] WO0043365 reacts with acetone and malononitrile through Knoevenagel reaction, then reacts with triethyl orthoformate acetic anhydride solution, cyclizes under anhydrous NH3 / ethanol, and ...

Claims

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Application Information

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IPC IPC(8): C07D213/85
CPCC07D213/85
Inventor 吕建新
Owner 上海品沃化工有限公司
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