Synthetic method of alpha-hydroxyl carbonyl compound

A technology of carbonyl compounds and hydroxycarbonyl compounds, which is applied in the field of synthesizing α-hydroxycarbonyl compounds, can solve the problems such as the narrow scope of application of substrates, and achieve the effects of easy industrial production, high yield and simple conditions

Inactive Publication Date: 2014-03-05
PEKING UNIV
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Problems solved by technology

[0003] However, there are not many reports on the synthesis methods directly converted from carbonyl compounds to α-hydroxycarbonyl compounds, although the literature B.-C.Chen, P.Zhou, F.A.Davis, E.Ciganek, Organic Reactions; L.E.Overman, Ed.; John Wiley&Sons, Inc.: New York, 2003, 62, 1; G.J.Chuang, W.Wang, E.Lee, T.Ritter, J.Am.Chem.Soc.2011, 133, 1760. Synthesis of such compounds The methods have been reported in detail, but these methods have the following limitations: 1. The scope of substrate application is narrow; 2. Use expensive and complex palladium as a catalyst; 3. Reaction needs to be carried out at low temperature or under heating conditions

Method used

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  • Synthetic method of alpha-hydroxyl carbonyl compound
  • Synthetic method of alpha-hydroxyl carbonyl compound
  • Synthetic method of alpha-hydroxyl carbonyl compound

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Experimental program
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Effect test

Embodiment 12

[0014] The synthesis of embodiment 12-hydroxyl-2-methyl-1-phenylacetone

[0015]

[0016] a): Take a 25mL Schlenk reaction tube, add 33mg of cesium carbonate, 74mg of 2-methyl-1-phenylacetone, 167mg of triethyl phosphite, 2mL of dimethyl sulfoxide, connect a 200mL oxygen balloon, and put it at room temperature Stir at 25°C for 24 hours. After the reaction was completed, 15 mL of ethyl acetate was added to quench the reaction, washed with 5 mL of brine, the organic phase was separated, the aqueous phase was extracted 3 times with ethyl acetate, the organic phases were combined, and separated by column chromatography to obtain 2-hydroxy-2-methyl- Pure 1-phenylacetone 71mg, yield 87%.

[0017] b): Take a 25mL Schlenk reaction tube, add 33mg of cesium carbonate, 74mg of 2-methyl-1-phenylacetone, 167mg of triethyl phosphite, 2mL of dimethyl sulfoxide, and stir at room temperature at 25°C under normal air pressure 48 hours. After the reaction was completed, 15 mL of ethyl acet...

Embodiment 2

[0033] The synthesis of embodiment 22-hydroxyl-4'-(2-hydroxyethoxy)-2-methylpropiophenone

[0034]

[0035] Take a 25mL Schlenk reaction tube, add 33mg of cesium carbonate, 105mg of 4'-(2-hydroxyethoxy)-2-methylpropiophenone, 167mg of triethyl phosphite, 2mL of dimethyl sulfoxide, and connect a 200mL Oxygen balloon, stirred at room temperature 25°C for 24 hours. Add 15 mL of ethyl acetate to quench the reaction after the reaction is finished, add 5 mL of brine to wash, separate the organic phase, extract the aqueous phase with ethyl acetate for 3 times, combine the organic phases, and separate by column chromatography to obtain 2-hydroxy-4'-(2 -Hydroxyethoxy)-2-methylpropiophenone pure product 84mg, productive rate 75%.

[0036] 1 H NMR (400MHz, CDCl 3 ):δ7.97(d,J=8.8Hz,2H),6.84(d,J=8.0Hz,2H),4.04(t,J=4.4Hz,2H),3.88(t,J=4.0Hz,2H ),3.57(s,2H),1.52(s,6H); 13 CNMR (100MHz, CDCl 3 ): δ202.5, 162.4, 132.3, 126.1, 114.0, 75.9, 69.3, 60.8, 28.4 ppm; IR (neat): ν=3404.8, 2932...

Embodiment 3

[0037] The synthesis of embodiment 3α-hydroxycyclohexyl benzophenone

[0038]

[0039] Take a 25mL Schlenk reaction tube, add 163mg cesium carbonate, 95mg cyclohexyl benzophenone, 167mg triethyl phosphite, 2mL dimethyl sulfoxide, connect a 200mL oxygen balloon, and stir at room temperature 25°C for 72 hours. Add 15 mL of ethyl acetate to quench the reaction after the reaction, add 5 mL of brine to wash, separate the organic phase, extract the aqueous phase with ethyl acetate for 3 times, combine the organic phases, and separate by column chromatography to obtain pure α-hydroxycyclohexylbenzophenone. Product 98mg, yield 96%.

[0040] 1 H NMR (400MHz, CDCl 3 ):δ8.00(d,J=7.6Hz,2H),7.53(t,J=7.2Hz,1H),7.43(d,J=8.0Hz,2H),3.40(s,1H),2.08-2.00 (m,2H),1.82-1.65(m,7H),1.39-1.29(m,1H); 13 C NMR (100MHz, CDCl 3 ): δ205.5, 135.1, 132.3, 129.4, 128.2, 78.6, 35.3, 25.3, 21.4ppm; IR (neat): ν=3460.2, 2930.8, 1675.4, 1261.9cm -1 ;MS(70ev):m / z(%):99.0(100),105(30),176.0(M + ,5).

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Abstract

The invention relates to a synthetic method of an alpha-hydroxyl carbonyl compound. The method is as below: mixing a carbonyl compound (I) with an organic phosphorus compound in an organic solvent; adding a catalyst cesium carbonate; and reacting under aerobic conditions to obtain the alpha-hydroxyl carbonyl compound (II). R1 is selected from the group consisting of hydrogen, alkyl, alkoxy, amino, aromatic base, substituted aromatic base and heterocyclic aromatic base; R2 is selected from alkyl, carbonyl, ester and phenyl; R3 is selected from alkyl, carbonyl, ester group and phenyl. Or, R1 combines with R2 to form naphthenic group or substituted cycloalkyl, benzo cycloalkyl base or substituted benzo cycloalkyl base, indole ring or substituted indole ring. Or, R2 combines with R3 to form the cycloalkyl or substituted cycloalkyl. The organic phosphorus compound is triphenylphosphine or triethyl phosphate. The organic solvent is dimethyl sulphoxide, N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methyl pyrrolidone.

Description

technical field [0001] The invention relates to a method for synthesizing α-hydroxycarbonyl compounds. Background technique [0002] α-hydroxycarbonyl compounds such as ketones, esters, amides, and aldehydes containing hydroxyl structural units in the α position are widely used in biologically active natural products and pharmaceutical intermediates. At the same time, α-hydroxycarbonyl compounds are widely used in organic synthesis. synthesis factor. Hydroxyl is a mild reaction precursor of double bonds, ester groups, halogenated hydrocarbons and other groups. Heterocyclic compounds can also be derived from α-hydroxycarbonyl structures. Therefore, the α-hydroxyl located at the active site of the molecular structure is a The introduction of this group has greater research significance; in addition, α-hydroxy ketones can be used as photoinitiators and are widely used in UV-curable coatings. [0003] However, there are not many reports on the synthesis methods directly conver...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/02C07C45/64C07C49/82C07C49/84C07C49/83C07C49/17C07C49/747C07C49/245C07C67/31C07C69/732C07C47/27C07C49/497C07C69/675C07C69/716C07C69/757C07D333/22C07D213/50C07D277/24C07D209/38
Inventor 焦宁梁雨锋
Owner PEKING UNIV
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