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Deoxidizing reduction method for phenolic compound

A technology of phenolic compounds and reducing agents, applied in the field of deoxygenation and reduction of phenolic compounds, can solve the problems of uneconomical, narrow scope of substrate application, harsh reaction conditions, etc., and achieve the advantages of simple operation, short reaction time and high reaction conversion rate Effect

Inactive Publication Date: 2017-10-24
WUHAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Most of the deoxygenation and reduction methods of phenolic compounds reported so far use strong reducing agents such as lithium aluminum hydride and sodium borohydride to reduce or use H2 to reduce under high temperature and high pressure conditions. The reaction conditions are harsh, the scope of substrate application is narrow, and it is not economical. shortcoming

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] 4-tert-butylphenol (100mmol, 15g) was dissolved in dimethyl sulfoxide, adding Et 3 N (1.2eq), cover with a brine plug, insert a balloon filled with sulfuryl fluoride gas, use a TLC plate to detect the reaction, remove the sulfuryl fluoride balloon after the conversion of the raw materials is complete, and then add Pd(OAc) to the reaction solution 2 (2mol%), dppp (2.4mol%), Et 3 N (4eq), HCOOH (4eq), continue to react at room temperature, TCL plate detection, when the reaction is complete, add water to quench, extract three times with dichloromethane, combine organic phase, then backwash with water three times, add anhydrous sodium sulfate to dry , dichloromethane was removed under vacuum at low temperature, and the product was distilled off to obtain 10.5 g of a colorless oily liquid with a yield of 78%.

[0028] Gained product is carried out NMR analysis, and data are as follows: 1 H NMR (500MHz, CDCl 3 )δ7.39(d, J=7.5Hz, 2H), 7.29(t, J=7.4Hz, 2H), 7.16(t, J=7.3Hz, ...

Embodiment 2

[0030] Resorcinol (100mmol, 11g) was dissolved in dimethyl sulfoxide, adding Et 3 N (2.4eq), cover with a brine plug, insert a balloon filled with sulfuryl fluoride gas, use a TLC plate to detect the reaction, remove the sulfuryl fluoride balloon after the conversion of the raw materials is complete, and then add Pd(OAc) to the reaction solution 2 (4mol%), dppp (4.8mol%), Et 3 N (8eq), HCOOH (8eq), continue to react at room temperature, TCL plate detection, when the reaction is complete, add water to quench, dichloromethane extract three times, combine the organic phase, then backwash with water three times, add anhydrous sodium sulfate to dry , dichloromethane was removed under vacuum at low temperature, and then the product was distilled off to obtain 5.5 g of a colorless oily liquid with a yield of 70%.

[0031] Gained product is carried out NMR analysis, and data are as follows: 1 H NMR (500MHz, CDCl 3 )δ7.62(s,6H). 13 CNMR (126MHz, CDCl 3 )δ128.6. It can be seen that...

Embodiment 3

[0033] Benzyloxyphenol (20mmol, 4g) was dissolved in dimethyl sulfoxide, adding Et 3 N (1.2eq), cover with a brine plug, insert a balloon filled with sulfuryl fluoride gas, use a TLC plate to detect the reaction, remove the sulfuryl fluoride balloon after the conversion of the raw materials is complete, and then add Pd(OAc) to the reaction solution 2 (2mol%), dppp (2.4mol%), Et 3 N (4eq), HCOOH (4eq), continue to react at room temperature, TCL plate detection, when the reaction is complete, add water to quench, extract three times with dichloromethane, combine organic phase, then backwash with water three times, add anhydrous sodium sulfate to dry , remove dichloromethane under vacuum and low temperature, use silica gel for column separation, and obtain 3.2 g of white solid, and the separation yield is 88%.

[0034] Gained product is carried out NMR analysis, and data are as follows: 1 H NMR (500MHz, CDCl 3 )δ7.43(d, J=7.2Hz, 2H), 7.37(t, J=7.1Hz, 2H), 7.32-7.26(m, 3H), 6.9...

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Abstract

The invention discloses a deoxidizing reduction method for a phenolic compound. The method comprises the following steps: reacting the phenolic compound with sulfuryl fluoride, thereby generating aryl fluorosulfonate; adding palladium acetate as a catalyst, 1,3-diphenylphosphine propane ligand and NH3 / HCOOH as transferring hydrogen reducing agent; acquiring the corresponding arene after completing the reaction. On the basis of the molar weight of the raw material phenol, the dosage of the palladium acetate catalyst is 2mol%-5mol%; the dosage of the 1,3-diphenylphosphine propane ligand is 1.2 times of the dosage of the palladium acetate catalyst; the removal of monomolecular hydroxy requires 4 times of equivalent transferring hydrogen reducing agent. Most reagents used according to the invention are low-cost and are easily acquired. The dosage of the high-cost palladium acetate catalyst is less and the low-toxicity dimethyl sulfoxide is used as the solvent, so that the method is green and economical. Besides, the reaction time according to the invention is short and the whole process requires no heating and can be completed under room temperature, so that the method has the characteristics of high speed, energy-saving effect, and the like.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a method for deoxidation and reduction of phenolic compounds. Background technique [0002] With the development of the global economy, the contradictions between human demand for fossil energy and energy shortage and greenhouse effect are becoming more and more intense. Therefore, the development of renewable energy is an inevitable choice to alleviate the contradiction. Lignocellulose is the cheapest biomass raw material with the widest distribution and the most storage, and bio-oil can be obtained by rapid pyrolysis of it. Due to the high content of phenolic compounds in lignocellulose, the bio-oil produced after direct decomposition has defects such as high viscosity, severe corrosion, and poor calorific value. is particularly important. [0003] Phenolic compounds are important raw materials and intermediates for drug synthesis, and the reductive deoxygenation o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/24C07C305/26C07C1/32C07C15/02C07C15/04C07C15/52C07C41/26C07C43/205C07J1/00
CPCC07C1/322C07C41/26C07C303/24C07J1/0059
Inventor 秦华利王晓燕冷静
Owner WUHAN UNIV OF TECH