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Reducing dehalogenating method of organic halogenated compound

A compound and organohalogen technology, applied in the field of chemical synthesis, can solve the problems of expensive, poor group tolerance, narrow substrate application range, etc., and achieve the effects of fast reaction, less side reactions, and wide application range of reaction temperature

Active Publication Date: 2019-01-25
HUAZHONG UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] For the above defects or improvement needs of the prior art, the object of the present invention is to provide a method for reductive dehalogenation of organic halogenated compounds, wherein the type and proportion of each raw material adopted in the key reductive dehalogenation reaction ( Especially the specific types of accelerators) and corresponding reaction conditions are studied and improved. Compared with the prior art, it can effectively solve the problems of using highly toxic or expensive reagents, poor group tolerance, and narrow substrate application range. The present invention efficiently realizes various types of alkyl halogenated compounds and aromatic halogenated compounds by selecting cheap, easy-to-obtain, and easy-to-handle reaction reagents (especially non-noble metal promoters), mild reaction conditions, and simple operations. Reductive dehalogenation

Method used

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  • Reducing dehalogenating method of organic halogenated compound
  • Reducing dehalogenating method of organic halogenated compound
  • Reducing dehalogenating method of organic halogenated compound

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Experimental program
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Effect test

Embodiment 1

[0046] Embodiment 1: the synthesis of compound 1a

[0047]

[0048] a) Weigh iodo compound 1 (30mg), non-precious metal promoter (as shown in Table 1, 1-5mol%), p-toluenethiol (3-5equiv) in a 5mL reaction flask , then add the reaction solvent (dichloromethane or acetonitrile, 0.35ml) and N,N-diisopropylethylamine (3-5equiv) successively, and react under the irradiation of 1W blue LED light, and wait for iodo compound 1 or The reaction was terminated after p-methylthiophenol was consumed. The reaction solvent and volatile substances were removed by rotary evaporation, and compound 1a was obtained by separation and purification by column chromatography. The reaction results are shown in Table 1:

[0049] Table 1 The deiodination reaction of compound 1 promoted by various non-noble metal promoters

[0050]

[0051] [a]. Solvent: CH 2 Cl 2 , Promoter (1mol%), DIPEA (3equiv), p-Toluenethiol (3equiv);

[0052] [b]. Solvent: CH 3 CN, Promoter (5mol%), DIPEA (5equiv), p-T...

Embodiment 2

[0082] Embodiment 2: the synthesis of compound 2a

[0083]

[0084] a), weigh iodo compound 2 (30mg), bismuth trioxide (0.45mg, 1mol%), and p-methylthiophenol (36.1mg, 3equiv) in a 100mL reaction flask, and then add reaction solvent two successively Chloromethane (0.97ml) and N,N-diisopropylethylamine (50.7μL, 3equiv) were reacted under 1W blue LED light irradiation, and the reaction was terminated after the iodide compound 2 was consumed (1h). The reaction solvent and volatile substances were removed by rotary evaporation, and compound 2a (17.1 mg, 96%) was obtained by separation and purification by column chromatography.

[0085] b), weigh iodo compound 2 (3g), bismuth trioxide (4.5mg, 0.1mol%), and p-methylthiophenol (3.6g, 3equiv) in a 100mL reaction flask, and then add the reaction solvent in turn Dichloromethane (19.4ml) and N,N-diisopropylethylamine (1.68ml, 1 equiv) were reacted under 3W blue LED light irradiation, and the reaction was terminated after the iodide c...

Embodiment 3

[0087] Embodiment 3: the synthesis of compound 3a

[0088]

[0089] a), the iodo compound 3 (40mg), bismuth trioxide (0.5mg, 1mol%), N-acetyl-L-cysteine ​​methyl ester (2mg, 0.1equiv) were weighed in a 10mL reaction tube, After deoxygenation, add the reaction solvent dichloromethane (1.2ml) and N,N-diisopropylethylamine (0.2ml, 10equiv) in sequence, react under 1W blue LED light, and stop when the iodide compound 3 is consumed reaction. Compound 3a (20.1 mg, 79%) was obtained by separation and purification by column chromatography.

[0090] b), weigh iodo compound 3 (40mg), bismuth trioxide (0.5mg, 1mol%), N-acetyl-L-cysteine ​​methyl ester (6.1mg, 0.3equiv) in a 10mL reaction tube , after deoxygenation, the reaction solvent dichloromethane (1.2ml) and N,N-diisopropylethylamine (0.2ml, 10equiv) were added in sequence, and reacted under the irradiation of 1W blue LED light. The reaction was terminated when the iodo compound 3 was consumed. Compound 3a (24.6 mg, 97%) was ...

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Abstract

The invention discloses a reducing dehalogenating method of an organic halogenated compound. The reducing dehalogenating method comprises: mixing an organic halogenated compound R-X, a non-noble metalpromoter, a sulfide and an alkali, and carrying out a reducing dehalogenating reaction to obtain a reducing product R-H, wherein R is at least one selected from alkyl and aryl, and X is at least oneselected from iodine, bromine and chlorine. According to the present invention, the types and the ratio (especially the specific type of the promoter) of various raw materials used in the reducing dehalogenating reaction, the corresponding reaction conditions and the like are researched and improved, such that the problems of use of highly-toxic or expensive reagent, poor tolerance of the group, narrow application range of the substrate and the like in the prior art can be effectively solved.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and more specifically relates to a method for reductive dehalogenation of organic halogenated compounds, which is a method for reductive dehalogenation of organic halogenated compounds participated by non-precious metal promoters and sulfides . Background technique [0002] Organic halides are a very important class of compounds. They are commonly used solvents and reagents in organic synthesis reactions, and are important intermediates in the synthesis process. Dehalogenation reaction is an extremely important reaction type in organic synthesis reactions. New C-H bonds, C-C bonds, C-N bonds, C-O bonds, etc. can be generated through dehalogenation reactions. Conventional dehalogenation methods include radical reactions involving organic reagents such as organotin, azo, silane, alkyl boron compounds, and peroxy compounds; hydrogenation reactions catalyzed by transition metals (such as palladium,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07H13/06C07H17/08C07H9/04C07H1/00C07D307/00C07D493/04C07D305/14C07C67/317C07C69/78C07C69/80C07C69/38C07C49/637C07D205/04C07D309/30C07D295/205C07D209/08C07J1/00C07J71/00C07J9/00C07J7/00C07D473/34
CPCC07C45/65C07C67/317C07D205/04C07D209/08C07D295/205C07D305/14C07D307/00C07D309/30C07D473/34C07D493/04C07H1/00C07H9/04C07H13/06C07H17/08C07J1/0007C07J1/0055C07J7/0055C07J9/005C07J71/0005C07C69/78C07C69/80C07C69/38C07C49/637
Inventor 万谦曾静王浩孟令奎赵祥陈薇陶锦毅舒朋华
Owner HUAZHONG UNIV OF SCI & TECH
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