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A method of using dast reagent as elimination reagent to synthesize conjugated nitroalkene substituted series derivatives

A compound and solvent technology, applied in the field of organic chemical synthesis, can solve problems such as potential safety hazards, unpleasant smells, and unfriendly environment

Active Publication Date: 2020-07-03
NANJING FURUN KAIDE BIOLOGICAL PHARMA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] This method uses thiophenol, which has an unpleasant smell and is not environmentally friendly, and the reaction uses highly toxic solvents such as benzene and carbon tetrachloride, and the peroxide m-CPBA is also used in the reaction, which has certain potential safety hazards , not suitable for mass production

Method used

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  • A method of using dast reagent as elimination reagent to synthesize conjugated nitroalkene substituted series derivatives
  • A method of using dast reagent as elimination reagent to synthesize conjugated nitroalkene substituted series derivatives
  • A method of using dast reagent as elimination reagent to synthesize conjugated nitroalkene substituted series derivatives

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044]

[0045] Preparation of compound III-1:

[0046] Put compound II-1 (50.0g, 0.29mol, 1.0e.q.), 60mL nitromethane, 0.25mL DBU, and 300mL ethanol into a 500mL four-necked flask, and stir overnight at 25°C for 15h. TLC showed that there were remaining raw materials, and an additional 0.5 mLDBU, 20mL nitromethane, stirred for another 4 hours, TLC showed that the reaction was complete, concentrated to remove the solvent, added 200mL PE to the residue, put it in the refrigerator overnight, filtered, rinsed with PE, and the dried compound III-1 was a light yellow solid 62.04g, yield 92%.

[0047] Preparation of Compound I-1:

[0048] Compound III-1 (20.0g, 0.086mol, 1.0e.q.) was dissolved in 200mL DCM, DAST (20.8g, 0.129mol, 1.5e.q.) was added dropwise at 0°C, and the reaction was continued for 30min after the addition was complete. TLC detection showed that the raw materials reacted Completely, add 200mL water to quench the reaction, add saturated Na 2 CO 3 The aqueous ...

Embodiment 2

[0050]

[0051] Preparation of Compound III-2:

[0052] Compound II-2 (50.0g, 0.24mol, 1.0e.q.) was dissolved in 300mL of methanol, 80mL of nitromethane and sodium methoxide (0.65g) were added, and stirred overnight at room temperature for 15h. TLC showed that the reaction of the raw materials was complete. Concentrate to remove methanol , Pour the remaining viscous material into water, extract with EA, combine the organic phases, dry and concentrate, PE crystallize and filter with suction, and dry to obtain 58.45 g of compound III-2 as a yellow solid, with a yield of 90.1%.

[0053] Preparation of Compound I-2:

[0054] Compound III-2 (20.0 g, 0.075 mol, 1.0 e.q.) was dissolved in 200 mL of DCM, and DAST (20.8 g, 0.129 mol, 1.0 e.q.) was added dropwise at -78°C, and the stirring reaction was continued at 0°C for 1 h after the addition was completed. TLC detection showed that the reaction of the raw materials was complete, adding 200mL of saturated sodium bicarbonate to qu...

Embodiment 3

[0056]

[0057] Preparation of compound III-3:

[0058]Compound II-3 (50.0g, 0.22mol, 1.0e.q.) was dissolved in 300mL of methanol, 80mL of nitromethane and DIPEA (1.43g) were added, and stirred overnight at 25°C for 15h. TLC showed that the reaction of the raw materials was complete. After concentration and removal of methanol , Pour the remaining viscous material into water, extract with EA, combine the organic phases, dry and concentrate, PE crystallize and filter with suction, and dry to obtain 56.62 g of compound III-3 as a yellow solid, with a yield of 89.1%.

[0059] Preparation of Compound I-3:

[0060] Compound III-3 (20.0g, 0.0698mol, 1.0e.q.) was dissolved in 200mL 1,2-dichloroethane, DAST (13.51g, 0.0838mol, 1.2e.q.) was added dropwise at 0°C, and the addition was completed at 10°C Continue to stir the reaction for 1 h, TLC detection shows that the raw materials are completely reacted, the reaction is quenched by adding saturated potassium carbonate aqueous solu...

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Abstract

The invention discloses a preparation method of taking a DAST reagent as a removing reagent to synthesize a conjugated nitroolefin substituted series derivative. The preparation method comprises the following steps that a carbonyl compound (compound II) is taken as a raw material to react with nitromethane under the alkaline condition to generate a compound III; and hydroxide radical of the compound III is substituted by DAST and removed, and the conjugated nitroolefin substituted series derivative (compound I) is prepared.

Description

technical field [0001] The invention relates to the field of organic chemical synthesis, in particular to a method for synthesizing conjugated nitroalkene substituted series derivatives by using DAST reagent as an elimination reagent. Background technique [0002] There are strong electron-withdrawing groups in the molecular structure of conjugated nitroalkenes, which makes the electron cloud of the conjugated olefins polarized, and is easy to add to nucleophilic or electrophilic reagents. The nitro group can also be transformed into A variety of functional groups to generate different types of chiral compounds, which are used in asymmetric Michael addition reaction, asymmetric D—A reaction, asymmetric Friedel-Crafts reaction, copolymerization reaction, etc., so the conjugated nitroalkene substitution series Compounds are a class of molecular building blocks with great application value. [0003] Literature Synlett, 27(1), 169-172; 2016 reported the synthesis method of simi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D205/06C07D307/28C07D309/20C07D211/70C07D305/10C07C201/12C07C205/03
CPCC07C201/12C07C2601/04C07C2601/08C07C2601/14C07D205/06C07D211/70C07D305/10C07D307/28C07D309/20C07C205/03Y02P20/55
Inventor 张雷亮方锐姜军
Owner NANJING FURUN KAIDE BIOLOGICAL PHARMA CO LTD
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