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Method for preparing alpha-hydroxymethyl-beta-dicarbonyl compound under catalysis of disulfide excited by visible light

A technology for the preparation of dicarbonyl compounds and catalysis, which is applied in the preparation of organic compounds, chemical instruments and methods, and the formation/introduction of hydroxyl groups. It can solve the problems of narrow substrate types and achieve simple operation, low cost, and mild reaction conditions. Effect

Active Publication Date: 2018-11-06
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods all use metal catalysts or formaldehyde as methylolation reagents, which have certain toxicity and narrow substrate types.

Method used

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  • Method for preparing alpha-hydroxymethyl-beta-dicarbonyl compound under catalysis of disulfide excited by visible light
  • Method for preparing alpha-hydroxymethyl-beta-dicarbonyl compound under catalysis of disulfide excited by visible light
  • Method for preparing alpha-hydroxymethyl-beta-dicarbonyl compound under catalysis of disulfide excited by visible light

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1 Preparation of 5-chloro-2,3-dihydro-2-hydroxymethyl-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula VI, wherein R 1 , R 3 for H, R 2 for Cl, R 4 for OMe)

[0032] Add 5-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula II, wherein R1, R3 are H, R2 is Cl, R4 is OMe) in 4 mL of acetonitrile solution , 0.0224g, 0.1mmol), diphenyl disulfide (0.0011g, 0.005mmol) and styrene (0.0156g, 0.15mmol), 10W blue light irradiation for 8 hours to generate 5-chloro-2,3-dihydro-2 -Methyl hydroxymethyl-1-oxo-1H-indene-2-carboxylate, yield 91%. 1 H NMR (400MHz, Chloroform-d) δ7.70 (d, J = 8.2Hz, 1H), 7.51 (s, 1H), 7.41–7.37 (m, 1H), 4.12 (d, J = 11.2Hz, 1H) ,3.90(d,J=11.2Hz,1H),3.71(s,3H),3.54(d,J=17.5Hz,1H),3.39(d,J=17.5Hz,1H),2.53(s,1H) .

Embodiment 2

[0033] Example 2 Preparation of 5-bromo-2,3-dihydro-2-hydroxymethyl-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula VI, wherein R 1 , R 3 for H, R 2 for Br, R 4 for OMe)

[0034]Add 5-bromo-2,3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, where R 1 ,R 3 for H, R 2 for Br, R 4 Me, 0.0269g, 0.1mmol), diphenyl disulfide (0.0011g, 0.005mmol) and styrene (0.0156g, 0.15mmol), 10W blue light irradiation for 8 hours to generate 5-bromo-2,3-dihydro -2-Hydroxymethyl-1-oxo-1H-indene-2-carboxylic acid methyl ester, yield 89%. 1 H NMR (400MHz, Chloroform-d) δ7.63(s, 1H), 7.57(d, J=8.0Hz, 1H), 7.49(d, J=8.0Hz, 1H), 4.06(d, J=11.2Hz ,1H),3.82(d,J=11.2Hz,1H),3.65(s,3H),3.48(d,J=17.7Hz,1H),3.33(d,J=17.7Hz,1H),1.57(s ,1H).

Embodiment 3

[0035] Example 3 Preparation of 5-fluoro-2,3-dihydro-2-hydroxymethyl-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula VI, where R 1 for-F, R 2 R 3 for H, R 4 for OMe)

[0036] Add 5-fluoro-2,3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, where R 1 for-F, R 2 R 3 for H, R 4 OMe, 0.0208g, 0.1mmol), diphenyl disulfide (0.0011g, 0.005mmol) and styrene (0.0156g, 0.15mmol), 10W blue light irradiation for 8 hours to generate 5-fluoro-2,3-dihydro -2-Hydroxymethyl-1-oxo-1H-indene-2-carboxylic acid methyl ester, yield 90%. 1 H NMR (400MHz, Chloroform-d) δ7.74 (dd, J = 8.6, 5.2Hz, 1H), 7.13 (d, J = 8.6Hz, 1H), 7.07 (td, J = 8.6, 2.2Hz, 1H) ,4.09(d,J=11.3Hz,1H),3.83(d,J=11.3Hz,1H),3.68(s,2H),3.50(d,J=17.7Hz,1H),3.35(d,J= 17.8Hz, 1H).

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Abstract

The invention provides a method for preparing an alpha-hydroxymethyl-beta-dicarbonyl compound under catalysis of disulfide excited by visible light and belongs to the technical field of photocatalysissynthesis. The method comprises the following steps: in a solvent, by taking a disulfide compound as a photo-sensitive catalyst, a beta-dicarbonyl compound as a substrate, molecular oxygen as an oxidant, an olefin derivative for providing a 1C source, and visible light as an excitant light source, carrying out a photocatalysis reaction, thereby obtaining the alpha-hydroxymethyl-beta-dicarbonyl compound through preparation. The method is gentle in reaction condition, simple to operate, good in substrate applicability and environment protection, low in cost and applicable to industrial on-scaleproduction, and the alpha-hydroxymethyl-beta-dicarbonyl compound up to 90% or greater can be effectively prepared without external metal or alkali.

Description

technical field [0001] The invention belongs to the technical field of photocatalytic synthesis, and relates to a method for preparing α-hydroxymethyl-β-dicarbonyl compounds by using disulfide as a photosensitive catalyst under the action of visible light and molecular oxygen and using olefin as a 1C source. technical background [0002] Visible light-induced reaction systems provide a green and sustainable strategy for synthetic organic chemistry. The most commonly used visible light catalysts include bipyridyl complexes of metal ruthenium or rhodium (for example: Ru(bpy) 3 Cl 2 ,fac-Ir(ppy) 3 ) and organic dye molecules (eg eosin Y, rose bengal). In recent years, examples of disulfide-catalyzed photoreactions have been reported in which disulfides undergo photocleavage to catalyze the diboration of terminal alkynes (Chem. Eur. J. 2015, 21, 13930–13933 and C Reduction of halogen bonds (Adv.Synth.Catal.2013, 355, 3522–3526) and [3+2] cycloaddition reactions (Angew.Chem.I...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/757C07C67/343C07C235/82C07D295/182C07B41/02C07C231/12
CPCC07B41/02C07C67/343C07C231/12C07D295/182C07C2601/14C07C2602/08C07C69/757C07C235/82
Inventor 孟庆伟赵静喃杨帆刘广志唐晓飞武玉峰尹航冯世豪
Owner DALIAN UNIV OF TECH
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