A kind of synthetic method of thermosensitive chromogenic agent 4,4'-sulfonylbis[2-(2-propenyl)]phenol

A technology for the synthesis of sulfonyl bis, which is applied in the field of synthesis of heat-sensitive chromogenic agents, can solve the problems of large equipment investment, many side reactions, and high prices, and achieve the goal of reducing safety accidents, production costs, and equipment investment Effect

Active Publication Date: 2022-02-22
WEIFANG DAYOU BIOLOGICAL CHEM CO LTD
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  • Abstract
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  • Claims
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AI Technical Summary

Problems solved by technology

Japanese patent (Japanese Patent Application No. 2005-75757, patent No. 4248915) prepared 4,4'-diallyloxydiphenyl sulfone by microwave Claisen rearrangement under the catalysis of heterocyclic compounds to prepare 4,4'- Sulfonyl bis[2-(2-propenyl)]phenol, but microwave reaction is difficult to scale up production
Japanese patent (Japanese Patent Laid-Open No. 2002-30064) discloses a method for synthesizing 4,4'-sulfonyl bis[2-(2-propenyl)]phenol under the catalysis of amino compounds, but the yield of this method is low and there are many side reactions , the post-processing is complicated and the production cost is high
Subsequently, including Korean patent KR101597659, US patent US20180118672, Chinese patent CN106397283, CN109928902, etc., although various process improvements have been made by replacing solvents or adding various catalysts to suppress by-products, they inevitably require high temperature and high pressure conditions above 200 degrees. Carrying out Claisen rearrangement, such a high temperature can easily induce various safety accidents. High-temperature reactions, especially reactions above 200 degrees, are a great challenge to industrial production. It is necessary to use particularly high-quality heat-conducting oil for heating, and the price It is very high, and it needs to be replaced regularly, with high energy consumption and safety problems. The equipment needs to use high-temperature and high-pressure stainless steel reactors, which are expensive and require high requirements for operators.
[0003] In addition, although the high-temperature reaction suppresses the formation of high-temperature by-products as much as possible by adding various catalysts and controlling the alkali content, the post-treatment still needs to remove impurities by means of a large amount of activated carbon adsorption, and the cost of the high-boiling solvent used is relatively high, and the required equipment investment Larger, resulting in high cost of the developer

Method used

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  • A kind of synthetic method of thermosensitive chromogenic agent 4,4'-sulfonylbis[2-(2-propenyl)]phenol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Example 1 The synthetic method of 4,4'-sulfonyl bis[2-(2-propenyl)]phenol

[0034] Add 4,4'-diallyloxydiphenyl sulfone (33.0 g, 0.10 mol) and zinc chloride (0.33 g) into dichloromethane (100 mL), heat to 40°C and stir for 20 hours. After the reaction is complete, Cool down to room temperature and pour into 100mL 10%NaOH solution, stir to dissolve, then use 30%H 2 SO 4 Adjust the pH to about 9, continue to stir for 15 minutes, let stand and separate, recover the organic phase and use it mechanically, continue to adjust the pH to about 6 in the water phase at room temperature, filter, and dry to obtain 30g of white solid with a yield of 90.9% and a purity of 97%. .

[0035] The organic phase was recycled according to the above reaction conditions. After 10 times of recycling, the overall yield was 96%, and the purity was 96.5%.

[0036] ESI-MS: (m / z, %)=331(M+).

[0037] 1 H NMR (DMSO- d 6 ): δ=3.28(d, 4H, J = 8), 5.02 (d, 4H, J = 12), 5.85 (m, 2H), 6.90 (d, 2H...

Embodiment 2

[0038] Example 2 The synthetic method of 4,4'-sulfonyl bis[2-(2-propenyl)]phenol

[0039] Add 4,4'-diallyloxydiphenyl sulfone (33.0 g, 0.10 mol) and aluminum trichloride (0.66 g) into dichloromethane (100 mL), heat to 40°C and stir for 20 hours, the reaction is complete , pour it into 100mL 10%NaOH solution at room temperature, stir to dissolve, then use 30%H 2 SO 4 Adjust the pH to about 9, continue to stir for 15 minutes, let stand and separate, recover the organic phase and use it mechanically, continue to adjust the pH to about 6 in the water phase at room temperature, filter, and dry to obtain 28g of white solid, with a yield of 84.8% and a purity of 97.5%. .

[0040] The organic phase was recovered and applied mechanically according to the above reaction conditions. After 10 times of recovery and applied mechanically, the comprehensive yield was 94%, and the purity was 97%.

[0041] 1 H NMR and MS are consistent with Example 1.

Embodiment 3

[0042] Example 3 The synthetic method of 4,4'-sulfonyl bis[2-(2-propenyl)]phenol

[0043] Add 4,4'-diallyloxydiphenylsulfone (33.0 g, 0.10 mol) and ferric chloride (1.5 g) into 1,2-dichloroethane (100 mL), heat to 60°C and stir to react After 15 hours, the reaction was completed, lowered to room temperature and poured into 100mL 10%NaOH solution, stirred and dissolved, then washed with 30%H 2 SO 4 Adjust the pH to about 9, continue to stir for 15 minutes, let stand and separate, recover the organic phase and use it mechanically, continue to adjust the pH to about 6 in the water phase at room temperature, filter, and dry to obtain 31g of white solid, with a yield of 93.9% and a purity of 98%. .

[0044] The organic phase was recovered and applied mechanically according to the above reaction conditions. After 10 times of recovery and applied mechanically, the comprehensive yield was 98%, and the purity was 97.5%.

[0045] 1 H NMR and MS are consistent with Example 1.

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Abstract

The invention provides a synthetic method of 4,4'-sulfonyl bis[2-(2-propenyl)]phenol, a thermal display agent, 4,4'-diallyl diphenyl sulfone is directly in the 4,4'-sulfonylbis[2-(2-propenyl)]phenol is prepared by heating rearrangement in an organic solvent. In the process of preparing 4,4'-sulfonylbis[2-(2-propenyl)]phenol in the present invention, by using a Lewis acid catalyst, high-temperature reactions above 200 degrees can be avoided, safety accidents can be greatly reduced, energy can be saved, consumption can be reduced, and Reduce equipment investment. The catalyst zinc chloride, aluminum trichloride, iron trichloride and titanium tetrachloride used in the process of preparing 4,4'-sulfonyl bis[2-(2-propenyl)]phenol in the present invention have low cost and can be post-treated convenient. In the process of preparing 4,4'-sulfonyl bis[2-(2-propenyl)]phenol, the present invention can avoid the use of high-boiling point solvents and heat-conducting oil, and greatly reduce production costs.

Description

technical field [0001] The invention belongs to the technical field of synthesis of heat-sensitive color developer, and in particular relates to a synthesis method of heat-sensitive color developer 4,4'-sulfonylbis[2-(2-propenyl)]phenol. Background technique [0002] 4,4'-sulfonylbis[2-(2-propenyl)]phenol is a color developer widely used in thermal paper coating. Generally, 4,4'-diallyloxydiphenyl sulfone is subjected to Claisen rearrangement reaction to obtain 4,4'-sulfonyl bis[2-(2-propenyl)]phenol. Japanese patent (Japanese Patent Application No. 2005-75757, patent No. 4248915) prepared 4,4'-diallyloxydiphenyl sulfone by microwave Claisen rearrangement under the catalysis of heterocyclic compounds to prepare 4,4'- Sulfonyl bis[2-(2-propenyl)]phenol, but microwave reaction is difficult to scale up production. Japanese patent (Japanese Patent Laid-Open No. 2002-30064) discloses a method for synthesizing 4,4'-sulfonyl bis[2-(2-propenyl)]phenol under the catalysis of amino ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C315/04C07C317/22
CPCC07C315/04
Inventor 李峰冯树海耿红军
Owner WEIFANG DAYOU BIOLOGICAL CHEM CO LTD
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