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Gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative and preparation method thereof

A technology of ethyl alkenyl fluoroacetate and tetra-substitution, which is applied in the field of γ-bromo-β, γ-tetra-substituted ethyl alkenyl fluoroacetate derivatives and the preparation thereof, and can solve the problems of low reactivity of alkynes and the like , to achieve the effect of good industrial production prospects, mild reaction conditions and high yields

Pending Publication Date: 2021-11-05
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In the field of organic fluorine chemistry, the addition reaction of different fluoroalkyl reagents and alkynes to prepare fluorine-containing alkenes with various structures has been developed rapidly. However, intramolecular alkynes are constrained by their low reactivity and have not been used in organic Fluorine chemistry is widely used in the field of synthetic chemistry

Method used

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  • Gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative and preparation method thereof
  • Gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative and preparation method thereof
  • Gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Preparation of ethyl 4-bromo-2-fluoro-3,4-diphenyl-3-butenoate

[0032]

[0033] Its preparation method is as follows:

[0034] Add CoBr sequentially to a 10ml standard opening reaction tube 2 (11mg, 0.05mmol), 1,2-bis(diphenylphosphino)benzene (22.3mg, 0.05mmol), zinc powder (33mg, 0.5mmol), and then replace the nitrogen three times, add an appropriate amount of solvent, at room temperature Stirred at low temperature for 2 minutes, added ethyl bromofluoroacetate (222mg, 1.2mmol) and toluene (178mg, 1mmol) and stirred at room temperature for 1-2h, TLC detected that the reaction was complete, filtered through diatomaceous earth, collected the organic phase and evaporated Concentrate, then use petroleum ether: ethyl acetate = (200-100): 1 eluent for column chromatography separation, and finally obtain 272 mg of milky white liquid (yield 75%, Z / E = 1:0.54).

[0035] 1 H NMR (500MHz, CDCl 3 ,ppm):(E):δ7.31-7.46(m,3H),7.21-7.01(m,7H),5.56(d,J=50Hz,1H),4.17-4.04(m,2H),...

Embodiment 2

[0040] Preparation of ethyl 4-bromo-2-fluoro-3-butyl-4-phenyl-3-butenoate

[0041]

[0042] Add CoBr sequentially to a 10ml standard opening reaction tube 2 (11mg, 0.05mmol), 1,2-bis(diphenylphosphino)benzene (22.3mg, 0.05mmol), zinc powder (33mg, 0.5mmol), and then replace the nitrogen three times, add an appropriate amount of solvent, at room temperature After stirring at low temperature for 2 minutes, ethyl bromofluoroacetate (185mg, 1mmol) and 1-phenyl-1-hexyne (190mg, 1.2mmol) were added and the reaction was stirred at room temperature for 1-2h. TLC detected that the reaction was complete. Filter, collect the organic phase and concentrate by evaporation, then carry out column chromatography separation with petroleum ether:ethyl acetate=(200-100):1 eluent, finally obtain 209mg of light yellow liquid (yield 61%, Z / E= 0.41:1).

[0043]1 H NMR (400MHz, CDCl 3 ,ppm):(E):δ7.36(m,5H),5.32(d,J=48Hz,1H),4.34–4.23(m,2H),2.39–1.95(m,2H),1.77–1.47( m,2H),1.46-1.36(m,2H),1.31(t...

Embodiment 3

[0048] Preparation of ethyl 4-bromo-2-fluoro-3-methyl-4-phenyl-3-butynoate

[0049]

[0050] Add CoBr sequentially to a 10ml standard opening reaction tube 2 (11mg, 0.05mmol), 1,2-bis(diphenylphosphino)benzene (22.3mg, 0.05mmol), zinc powder (33mg, 0.5mmol), and then replace the nitrogen three times, add an appropriate amount of solvent, at room temperature After stirring at low temperature for 2 minutes, ethyl bromofluoroacetate (185mg, 1mmol) and 1-phenyl-1-propyne (139mg, 1.2mmol) were added and the reaction was stirred at room temperature for 1-2h. TLC detected that the reaction was complete. Filter, collect the organic phase and concentrate by evaporation, then carry out column chromatography separation with petroleum ether:ethyl acetate=(200-100):1 eluent, finally obtain 217mg of light yellow liquid (yield 72%, Z / E= 0.82:1).

[0051] 1 H NMR (500MHz, CDCl 3 ):(E):δ7.30–7.41(m,5H),5.33(d,J=45Hz,1H),4.25–4.34(m,2H),1.71(s,3H),1.30–1.36(m, 3H); (Z): δ7.30–7.41(m,5H)...

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Abstract

The invention relates to a gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative and a preparation method thereof. The method comprises the following steps of: mixing a compound 1, a compound 2, a cobalt salt catalyst, a phosphine ligand and a metal reducing agent in a solvent; stirring the materials for a reaction at room temperature under the protection of N2 until the reaction is complete, so as to obtain are action liquid; and performing filtration and column chromatography purification on the obtained reaction liquid to obtain a compound 3, namely the gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative. Compared with the prior art, monofluoro tetra-substituted olefin can be obtained through efficient free radical addition reaction with intramolecular alkyne; the reaction time is short, the yield is high, and the reaction condition is mild; and the derivative has a good industrial production prospect.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a gamma-bromo-beta, gamma-tetrasubstituted alkenyl fluoroethyl acetate derivative and a preparation method thereof. Background technique [0002] Fluorine-containing multi-substituted olefins have a wide range of applications in the fields of medicinal chemistry and material chemistry. The free radical addition of cheap and readily available alkynes to obtain multi-substituted alkenes is a relatively economical method. [0003] In the field of organic fluorine chemistry, the addition reaction of different fluoroalkyl reagents and alkynes to prepare fluorine-containing alkenes with various structures has been developed rapidly. However, intramolecular alkynes are constrained by their low reactivity and have not been used in organic Fluorine chemistry is widely used in the field of synthetic chemistry. [0004] Therefore, it is necessary to develop an efficient catalytic system f...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/65C07C69/63C07C69/738C07C69/732C07C67/347
CPCC07C67/347C07C69/65C07C69/63C07C69/738C07C69/732
Inventor 吴晶晶胡朝明任洁吴范宏
Owner SHANGHAI INST OF TECH