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An α-diphenylphosphine-substituted α, β-unsaturated carboxylic acid ester compound and its preparation and application method

A technology of carboxylate compound and diphenylphosphine, which is applied in the field of α-diphenylphosphine substituted α, to achieve the effect of simple and efficient synthesis method and high yield

Inactive Publication Date: 2017-03-15
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The α-diphenylphosphine-substituted α,β-unsaturated carboxylate compounds involved in the present invention have not been reported in the literature, and the phosphino-heteroatom catalysts connected by double bonds can be further transformed by them

Method used

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  • An α-diphenylphosphine-substituted α, β-unsaturated carboxylic acid ester compound and its preparation and application method
  • An α-diphenylphosphine-substituted α, β-unsaturated carboxylic acid ester compound and its preparation and application method
  • An α-diphenylphosphine-substituted α, β-unsaturated carboxylic acid ester compound and its preparation and application method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Synthesis of ethyl 3-phenyl-2-bromoacrylate (III-a):

[0042]In brominated triphenylphosphine ethyl acetate II-a (4.28g, 1.0mmol) (available through the document "Fine Organic Synthesis-Reaction and Synthesis in Organic Chemistry Practice", compiled by Zhang Jinqi, Nanjing University Press, P141) Dissolve in anhydrous dichloromethane, cool to -20°C, add NBS (1.78g, 1.1mmol), stir for 30 minutes, rise to room temperature and stir overnight. Then join K 2 CO 3 Solid and benzaldehyde (1.06g, 1.0mmol), react at room temperature for 48 hours, filter with suction, collect the filtrate, remove the organic solvent under reduced pressure, concentrate and column chromatography (petroleum ether: ethyl acetate (volume ratio) = 5:1) Obtain oil 1.8g, yield rate is 70.8%, and its NMR data is as follows:

[0043] 1 H NMR (300MHz, CDCl 3 ):δ7.39(s,1H),7.37–7.33(m,3H),7.32–7.27(m,2H),4.26(q,J=7.1Hz,2H),1.24(t,J=7.1Hz, 3H).

Embodiment 2

[0045] Synthesis of ethyl 3-phenyl-2-iodoacrylate:

[0046] In ethyl bromide triphenylphosphine acetate II-a (4.28g, 1.0mmol) (can refer to ("Fine Organic Synthesis-Reaction and Synthesis in Organic Chemistry Practice", compiled by Zhang Jinqi, Nanjing University Press, P141 ) was dissolved in anhydrous dichloromethane, cooled to -20°C, added NIS (2.25g, 1.1mmol), stirred for 30 minutes, rose to room temperature and stirred overnight. Then added K 2 CO 3 Solid and benzaldehyde (1.06g, 1.0mmol), react at room temperature for 24 hours, filter with suction, collect the filtrate, remove the organic solvent under reduced pressure, concentrate and column chromatography (petroleum ether: ethyl acetate (volume ratio) = 6:1) Obtain oil 2.4g, productive rate 79.5%, its nuclear magnetic analysis data are as follows:

[0047] 1 H NMR (300MHz, CDCl 3 ):δ8.26(s,1H),7.84–7.71(m,2H),7.41(dd,J=6.5,3.9Hz,3H),4.33(q,J=7.1Hz,2H),1.37(t, J=7.1Hz,3H).

[0048] Compounds III-b~III-k can be pre...

Embodiment 3

[0050] The synthetic method one of 3-phenyl-2-diphenylphosphinoethyl acrylate (I-a):

[0051] The compound 3-phenyl-2-bromoacrylate ethyl ester (2.56g, 1.01mmol) was dissolved in toluene, then Pd(PPh 3 ) 4 (0.0924g, 0.08mmol), add triethylamine 0.5mL and diphenylphosphine (1.86g, 1mmol), heat in an oil bath at 100°C for 24 hours, remove the solvent under reduced pressure, and filter the remaining solid with diatomaceous earth, The filtrate was concentrated to remove the solvent, and then separated by column chromatography (eluent, petroleum ether: ethyl acetate = 10:1) to obtain 0.21 g of an oily substance with a yield of 58%.

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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an alpha-diphenylphosphinesubstituted alpha, beta-unsaturated carboxylatecompound as well as preparation and application methods. A simple reagent phosphorus ylide and aromatic aldehyde are taken as raw materials, a Wittig reactionand a phosphorus ylidereaction of carboxylate ester are performed, a halogenating agent is added, halogenated alpha, beta-unsaturated carboxylate ester is generated and reacts with diphenylphosphine under catalysis of a palladium reagent, and a target product with high yield is generated. Carboxylate of the compound can be transformed into other groups, so that a novel organicphosphine catalyst is generated.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to an α, β-unsaturated carboxylic acid ester compound substituted by α-diphenylphosphine and a preparation and application method thereof. Background technique [0002] Organophosphorus compounds are not only widely used in fine chemicals such as pesticides and medicines, but in the past forty years, organophosphorus compounds have received more and more attention in the field of chiral synthesis, and many organophosphine reagents have been discovered and applied to various catalytic reactions. , some have been applied to industrial production, such as BINAP, JosiPhos and Du-Phos etc. (Science, 1992, 258, 584; Acc.Chem.Res.1983, 16, 106; 8518.) [0003] Phosphino-based compounds connected by different skeletons often exhibit different catalytic properties, and show unique characteristics in certain reactions. The present invention relates to α, β-unsaturated ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/50C07F9/6553C07F9/655B01J31/24
Inventor 傅滨谢磊麻红利张振华覃兆海
Owner CHINA AGRI UNIV