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Method for preparing 1,4,7,10-tetraaza-2,6-pyridinophane

A technology of pyridine ring and tetraazine, which is applied in the field of medicine, can solve the problems of large steric hindrance, low yield, and difficulty in removing by-products, and achieve the effects of low price, high safety, and simple operation

Active Publication Date: 2017-04-26
天津羲泽润科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The raw material diethylenetriamine of this route needs to protect the three amino groups in the molecule at the same time, the steric formation is relatively large, the yield is low, and it is easy to form a large amount of by-product S-phenylthio-o-nitrobenzene that is difficult to remove base sulfone; although the yield of the following cyclization step is slightly higher (86%), the highly toxic thiophenol is used in the step of removing nitrobenzenesulfonyl, and the yield is only 72%, so this method is not suitable for industrialization Production

Method used

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  • Method for preparing 1,4,7,10-tetraaza-2,6-pyridinophane
  • Method for preparing 1,4,7,10-tetraaza-2,6-pyridinophane

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Experimental program
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Effect test

Embodiment 1

[0030] S1: Add 115.7g (1.1mol, 1.1eq) of aminoethylene glycol and 80.0g (2.0mol, 2.0eq) of sodium hydroxide in 300L of water to a 2L four-neck flask with a mechanical stirrer and a thermometer and 1.2L of dichloromethane as a solvent, stirred for 1 hour, then added 221.6g of o-nitrobenzenesulfonyl chloride (1.0mol, 1.0eq) in three batches, slowly raised the temperature to between 25°C and 30°C, and continued to stir for 6h to complete reaction. Stand for stratification, separate the lower organic phase, wash the organic phase with 100mL 5% hydrochloric acid, concentrate the organic phase to about 500mL under reduced pressure, add 500mL n-heptane, a large amount of white solids are produced, filter with suction, and dry to obtain 274g of N,N-bis(2-hydroxyethyl)o-nitrobenzenesulfonamide, yield 94%, purity 99% (HPLC).

[0031] S2: Add 274g (0.944mol, 1.0eq) N,N-bis(2-hydroxyethyl)o-nitrobenzenesulfonate to a 2L dry four-necked flask equipped with a mechanical stirrer, a thermome...

Embodiment 2

[0038]S1: Add 126.2g (1.2mol, 1.2eq) of aminoethylene glycol, 60.0g (1.5mol, 1.5eq) of sodium hydroxide in 300L of water to a 2L four-neck flask with a mechanical stirrer and a thermometer and 1.2L of dichloromethane as a solvent, stirred for 1 hour, then added 221.6g of p-nitrobenzenesulfonyl chloride (1.0mol, 1.0eq) in three batches, slowly raised the temperature to between 25°C and 30°C, and continued to stir for 6h to complete reaction. Stand for stratification, separate the lower organic phase, wash the organic phase with 100mL 5% hydrochloric acid, concentrate the organic phase to about 500mL under reduced pressure, add 500mL n-heptane, a large amount of white solids are produced, filter with suction, and dry to obtain 280g of N,N-bis(2-hydroxyethyl)-p-nitrobenzenesulfonamide, yield 96%, purity 99% (HPLC).

[0039] S2: Add 435g (1.5mol, 1.0eq) N,N-bis(2-hydroxyethyl)p-nitrobenzenesulfonate to a 2L dry four-necked flask equipped with a mechanical stirrer, a thermometer, ...

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Abstract

The invention relates to a novel method for preparing 1,4,7,10-tetraaza-2,6-pyridinophane. 2,6-dimethylamino pyridine serving as a raw material is subjected to amino protection through o- / p-nitrobenzenesulfonyl and reacts with N,N-di(2-chloroethyl)-o- / p-nitrobenzenesulfonamide under the alkaline condition, nitrobenzenesulfonyl is removed under the action of lithium hydroxide / mercaptoacetic acid, and 1,4,7,10-tetraaza-2,6-pyridinophane is obtained. According to the preparation method, few side reactions are caused, the yield is high, operation is easier and more convenient, and industrial production is facilitated.

Description

technical field [0001] The invention belongs to the technical field of medicine, and relates to a new method for preparing 1,4,7,10-tetraaza-2,6-pyridine cyclofan. Background technique [0002] 1,4,7,10-tetraaza-2,6-pyridinecyclophane is a key intermediate in the synthesis of a variety of nuclear magnetic imaging imaging agents and diagnostic reagents (Tetrahedron, 2001, 57, 4713-4718), has very important Value. [0003] Patent US5834456 and literature (Tetrahedron 2001,57,4713-4718) report the following synthetic method: [0004] [0005] The raw material diethylenetriamine of this route needs to protect the three amino groups in the molecule at the same time, the steric formation is relatively large, the yield is low, and it is easy to form a large amount of by-product S-phenylthio-o-nitrobenzene that is difficult to remove base sulfone; although the yield of the following cyclization step is slightly higher (86%), the highly toxic thiophenol is used in the step of re...

Claims

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Application Information

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IPC IPC(8): C07D471/08
CPCC07D471/08
Inventor 马军礼
Owner 天津羲泽润科技有限公司
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