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Preparation method of azacyclo

A technology of nitrogen heterocycles and heterocycles, which is applied in the field of preparation of nitrogen heterocycles, can solve problems that have not been reported, and achieve the effects of reducing reaction steps, reducing costs, and enhancing reactivity

Active Publication Date: 2013-08-07
浙江凯普化工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Substituting methanesulfonyl chloride for p-toluenesulfonyl chloride does not need to first synthesize methanesulfonamide sodium salt, and then carry out cyclization reaction to prepare nitrogen heterocyclic rings.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Example 1: Preparation of 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane

[0020] Add 5000g of pyridine as a base and solvent to the reaction flask, and add 260g of triethylenetetramine, cool to 0-5 degrees, stir, slowly add 600g of methanesulfonyl chloride dropwise, warm up to room temperature, and concentrate to dryness under reduced pressure after 15 hours. After adding 2000g of deionized water, adjust the pH to 4-5 with concentrated hydrochloric acid, filter, wash the filter cake with 1000g of water and dry to obtain 660g of the product tetramethanesulfonyltriethylenetetramine.

[0021] Add 218g of tetramethanesulfonyltriethylenetetramine, 15g of benzyltriethylammonium chloride, 40g of 15-crown-5, 42g of sodium hydroxide, 1000g of water and 1000g of toluene into the reaction flask, slowly raise the temperature to 90 degrees, and keep the temperature for reaction Slowly add 103g of 1,2-diethanol dimethanesulfonate under stirring for half an hour; after the addi...

Embodiment 2

[0023] Example 2: Preparation of 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane

[0024] Add 5000g of pyridine as a base and solvent to the reaction flask, and add 260g of triethylenetetramine, cool to 0-5 degrees, stir, slowly add 600g of methanesulfonyl chloride dropwise, warm up to room temperature, and concentrate to dryness under reduced pressure after 15 hours. After adding 2000g of deionized water, adjust the pH to 4-5 with concentrated hydrochloric acid, filter, wash the filter cake with 1000g of water and dry to obtain 660g of the product tetramethanesulfonyltriethylenetetramine.

[0025] Add 218g of tetramethanesulfonyltriethylenetetramine, 19g of benzyltriethylammonium iodide, 40g of 15-crown-5, 42g of sodium hydroxide, 1000g of water and 1000g of toluene into the reaction flask. Slowly raise the temperature to reflux, and keep the reaction for half an hour. 120 g of 1,2-bromoethane were added slowly with stirring. After the addition, keep the temperature a...

Embodiment 3

[0027] Example 3: Preparation of 1,4,7-trimethyl-1,4,7-triazacyclononane

[0028] Add 5000g of pyridine and 180g of diethylenetriamine into the reaction kettle, cool to 0-5°C, stir, slowly add 600g of methanesulfonyl chloride dropwise, warm up to room temperature, and concentrate to dryness under reduced pressure after 15 hours. After adding 2000g of deionized water, adjust the pH to 4-5 with concentrated hydrochloric acid, filter, wash the filter cake with 1000g of water and dry to obtain 555g of the product N,N-bis(2-methanesulfonamidoethyl)methanesulfonamide.

[0029] Add 160g N,N-bis(2-methanesulfonamidoethyl) methanesulfonamide, 14g benzyltriethylammonium hydroxide, 40g 15-crown-5, 42g sodium hydroxide, 1000g water and 1000g xylene. Slowly raise the temperature to 90°C, and keep the reaction for half an hour. 175 g of 1,2-diethanol di-p-toluenesulfonate was added slowly with stirring. After the addition, keep the temperature at 90°C for 10 hours, then cool down to ro...

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PUM

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Abstract

The invention discloses a preparation method of azacyclo. The preparation method comprises the following steps of: (1) reacting diethylenetriamine or triethylene tetramine with methylsulfonyl chloride to generate methanesulfonamide; (2) during two-phase reaction, cyclizing compound catalytic cyclization on methanesulfonamide and a compound having the structure shown in a chemical formula (a) under the composite catalysis of benzyl triethylanmine compound and 15-crown-5 at 90 DEG C under a backflow condition; and (3) removing methylsulfonyl from methanesulfonamide azacyclo and performing methylation treatment, wherein X represents bromine, iodine or sulphonate. The preparation method has the advantages that raw materials are low in cost, atom economy is high, and operation is easy and safe. The preparation method is suitable for industrial production.

Description

technical field [0001] The invention relates to a preparation method of nitrogen heterocycle, which belongs to the field of organic chemistry. Background technique [0002] The nitrogen heterocyclic compound is a compound having a ring structure, and the atoms on the ring contain nitrogen atoms in addition to carbon atoms. Nitrogen heterocyclic compounds are important organic compounds, widely used in medicine, pesticides, materials and other fields. Zhejiang Kaipu Chemical Co., Ltd. has recently introduced 1,4,7-trimethyl-1,4,7-triazacyclononane and 1,4,7,10-tetramethyl-1,4,7, 10-Tetraazacyclododecane has been successfully used in organic synthesis as a metal ion chelating agent. [0003] Existing 1,4,7-trimethyl-1,4,7-triazacyclononane and 1,4,7,10-tetramethyl-1,4,7,10-tetraazacycle The synthesis of dodecane usually needs to react with amine and p-toluenesulfonyl chloride to generate p-toluenesulfonamide, and then prepare it through cyclization, desulfonyl and methylati...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D257/02C07D255/02
Inventor 黄建谭翔晖周忱
Owner 浙江凯普化工有限公司
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