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Methods for preparing 1,4-dithiene and thiophene compounds from elemental sulfur and active internal alkyne through temperature regulation and control, and conversion reaction of 1,4-dithiene compounds into thiophene compounds

A compound, dithiene technology, applied in organic chemistry and other directions, can solve the problems of non-green environmental protection, single structure, harsh conditions, etc.

Active Publication Date: 2021-03-05
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there are few reports on the synthesis of 1,4-dithiene, but metal catalysts are usually required, the conditions are harsh, the structure is single, the synthesis method is complicated, and it is not environmentally friendly. Therefore, it is particularly necessary to develop a new, green, efficient and economical synthesis method (Synthesis2016,48,3107-3119; Chin.J.Org.Chem.2014,34,2021-2026;)

Method used

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  • Methods for preparing 1,4-dithiene and thiophene compounds from elemental sulfur and active internal alkyne through temperature regulation and control, and conversion reaction of 1,4-dithiene compounds into thiophene compounds
  • Methods for preparing 1,4-dithiene and thiophene compounds from elemental sulfur and active internal alkyne through temperature regulation and control, and conversion reaction of 1,4-dithiene compounds into thiophene compounds
  • Methods for preparing 1,4-dithiene and thiophene compounds from elemental sulfur and active internal alkyne through temperature regulation and control, and conversion reaction of 1,4-dithiene compounds into thiophene compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] The 2,5-dibenzoyl-3,6-difluorenyl-1,4-dithiene 3a and 2,6-dibenzoyl-3,5-difluorenyl-1,4-di Thiene 3b compound is prepared by direct reaction of acetylenone and elemental sulfur, and the reaction equation is as formula (1):

[0079]

[0080] Formula (1)

[0081] 1 is sublimed sulfur, which can be purchased from the market, in this example, it was purchased from Guangzhou brand chemical reagents. 2 is acetylene, and its synthesis method is as described in the literature (Macromolecules 2015,48,1941-1951);

[0082] The preparation steps of the 1,4-dithienes are as follows:

[0083] Add 0.32g (1.0mmol) of acetylene compound, 0.10g (3.0mmol) of elemental sulfur, and 0.06g (1.0mmol) of potassium hydroxide to a 10ml polymerization tube, and inject 2.0mL of dimethylmethylene Sulfone, react at room temperature for 2 hours, point the plate to detect the progress of the reaction, after the reaction is completed, add saturated NaCl solution to the reaction solution, extract w...

Embodiment 2

[0096] The thiophene compound is prepared by the direct reaction of acetylenone and elemental sulfur, and the reaction equation is as formula (2):

[0097]

[0098] Formula (2)

[0099] 1 is sublimed sulfur, which can be purchased from the market, in this example, it was purchased from Guangzhou brand chemical reagents. 2 is acetylene, and its synthesis method is as described in the literature (Macromolecules 2015,48,1941-1951);

[0100] The preparation steps of the 2,4-dibenzoyl-3,5-difluorenylthiophene 4a and 2,5-dibenzoyl-3,4-difluorenylthiophene 4b compounds are as follows:

[0101] Add 0.32g (1.0mmol) of acetylene compound, 0.10g (3.0mmol) of elemental sulfur, and 0.06g (1.0mmol) of potassium hydroxide to a 10ml polymerization tube, and inject 2.0mL of dimethylmethylene Sulfone, react at 80 degrees for 2 hours, point the plate to detect the progress of the reaction, after the reaction is completed, add saturated NaCl solution to the reaction solution, extract with wa...

Embodiment 3

[0114] The 1,4-dithienes can be converted to thiophenes by heating, and the reaction equation is as formula (3):

[0115]

[0116] Formula (3):

[0117] Experimental procedure for converting the 2,5-dibenzoyl-3,6-difluorenyl-1,4-dithiene 3a into 2,4-dibenzoyl-3,5-difluorenylthiophene 4a as follows:

[0118] Add 0.35g (0.5mmol) 1,4-dithiene 3a to a 10ml polymerization tube, inject 2.0mL dimethyl sulfoxide with a syringe, react at 80°C for 4 hours, spot the plate to detect the progress of the reaction, wait until After the reaction, extract with water and dichloromethane, remove the organic phase of the lower layer, dry the organic phase over anhydrous magnesium sulfate to remove water, filter to get the filtrate, distill off the dichloromethane under reduced pressure, obtain the crude product, and purify it by column chromatography , the eluent used was a mixed solvent of petroleum ether:dichloromethane with a volume ratio of 2:1, and the yield of thiophene 4a was 75%, and...

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Abstract

The invention discloses methods for preparing preparing 1,4-dithiene and thiophene compounds from elemental sulfur and active internal alkyne through temperature regulation and control, and a conversion reaction of 1,4-dithiene compounds into thiophene compounds. The invention discloses the thiophene compounds synthesized through temperature regulation and a synthesis method thereof, and disclosesa process for converting the 1,4-dithiene compounds into the thiophene compounds under a high-temperature condition. Benzoyl is broken by benzoyl-substituted thiophene under high-temperature and alkaline conditions, so a green, economical, high-selectivity and high-efficiency carbon-carbon bond breaking mode is realized. According to the invention, the conversion of elemental sulfur and acetylenic ketone into the 1,4-dithiene compounds can be realized through alkali induction without metal catalysis, and the synthesis of thiophene compounds from elemental sulfur and acetylenic ketone is realized through temperature regulation and control. The synthesis method is free of metal catalysis, mild in reaction conditions, safe and simple to operate, green, economical and good in selectivity, andthe sulfur-containing compounds have good biological activity and good application prospects in the aspects of natural products and drug synthesis.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing 1,4-dithienes and thiophenes by temperature-controlling elemental sulfur and active internal alkynes and a conversion reaction thereof. Background technique [0002] Sulfur-containing heterocyclic compounds are widely used in many natural products, bioactive molecules, drug molecules, pesticides, etc. 1,4-Dithiene is an important class of sulfur-containing six-membered heterocyclic compounds. Its molecule contains 2 carbon-carbon double bonds, 4 carbon-sulfur single bonds, and 8 π electrons. The six-membered heterocyclic ring in the molecule has a "boat-like" structure, which is non-aromatic and non-planar. Under certain conditions, it can be isomerized and transformed into other compounds. 1,4-Dithiene contains two sulfur atoms and is easily oxidized. Depending on the oxidation conditions and degree of oxidation, the boat-shaped stru...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D339/08C07D333/22
CPCC07D339/08C07D333/22
Inventor 唐本忠胡蓉蓉彭建文秦安军赵祖金
Owner SOUTH CHINA UNIV OF TECH
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