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Preparation method of alpha-beta-unsaturated carbonyl compound

A carbonyl compound and unsaturated technology, applied in the α field, can solve the problems that have not been reported in the literature, and achieve the effects of wide application range, high reaction yield and high safety performance

Inactive Publication Date: 2016-04-20
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, cation-modified montmorillonite has been used in many fields, but there is no literature report on its use as a catalyst in the preparation of α, β-unsaturated carbonyl compounds

Method used

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  • Preparation method of alpha-beta-unsaturated carbonyl compound
  • Preparation method of alpha-beta-unsaturated carbonyl compound
  • Preparation method of alpha-beta-unsaturated carbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Now take 1-phenyl-2-hepten-1-ol as an example to prepare (E)-1-phenyl-1-hepten-3-one as follows:

[0033] Dissolve 1-phenyl-2-hepten-1-ol (188 mg, 1 mmol) in 5 mL of 1,2-dichloroethane, add Fe 3+ - Montmorillonite (200mg) and ethanol (5mmol, 0.29mL), stirred and heated, reacted at 80°C for 12 hours, filtered to remove Fe 3+ -Montmorillonite, concentrate the filtrate, and the concentrate is separated by column chromatography to obtain 177 mg of product (E)-1-phenyl-1-hepten-3-one, with a yield of 94%;

[0034] The reaction equation is

[0035]

[0036] 1 H-NMR (CDCl 3 ,600MHz)7.67-7.54(m,3H),7.40-7.39(m,3H),6.75(d,J=16.2Hz,1H),2.67(t,J=7.8Hz,2H),1.69-1.64(m ,2H),1.42-1.36(m,2H),0.95(t,J=7.2Hz,3H);

[0037] 13 C-NMR (CDCl 3 ,150MHz)200.6,142.3,134.6,130.3,128.9,128.2,126.3,40.7,26.5,22.4,13.9;

[0038] ESI-HRMS calculated value C 13 h 16 ONa([M+Na] + ) 211.1099, measured value 211.1092.

Embodiment 2

[0040] Now take 1-(4-methylphenyl)-2-hepten-1-alcohol as an example to prepare (E)-1-(4-methylphenyl)-1-hepten-3-one The method is implemented by the following steps:

[0041] Dissolve 1-(4-methylphenyl)-2-hepten-1-ol (202 mg, 1 mmol) in 4 mL of chlorobenzene, add Yb 3+ - Montmorillonite (100mg) and n-propanol (5mmol, 0.38mL), stirred and heated, reacted at 90°C for 8 hours, filtered to remove Yb 3+ - Montmorillonite, concentrated filtrate, the concentrate was separated by column chromatography to obtain 176 mg of product (E)-1-(4-methylphenyl)-1-hepten-3-one, with a yield of 87%;

[0042] The reaction equation is

[0043]

[0044] 1 H-NMR (CDCl 3 ,600MHz)7.53(d,J=16.2Hz,1H),7.44(d,J=8.4Hz,2H),7.19(d,J=8.4Hz,2H),6.70(d,J=16.2Hz,1H) ,2.65(t,J=7.8Hz,2H),2.37(s,3H),1.69-1.63(m,2H),1.41-1.35(m,2H),0.94(t,J=7.8Hz,3H);

[0045] 13 C-NMR (CDCl 3 ,150MHz)200.7,142.4,140.8,131.9,129.7,128.3,125.4,40.6,26.6,22.5,21.5,13.9;

[0046] ESI-HRMS calculated value C 14 h 18 ONa([...

Embodiment 3

[0048] Now take 1-(2-methylphenyl)-2-hepten-1-ol as an example to prepare (E)-1-(2-methylphenyl)-1-hepten-3-one The method is implemented by the following steps:

[0049] Dissolve 1-(2-methylphenyl)-2-hepten-1-ol (202 mg, 1 mmol) in 2 mL of p-dichlorobenzene, add Fe 3+ - Montmorillonite (100mg) and n-propanol (5mmol, 0.38mL), stirred and heated, reacted at 80°C for 24 hours, filtered to remove Fe 3+ - Montmorillonite, concentrated filtrate, the concentrate was separated by column chromatography to obtain 182 mg of product (E)-1-(2-methylphenyl)-1-hepten-3-one, with a yield of 90%;

[0050] The reaction equation is

[0051]

[0052] 1 HNMR (300MHz, CDCl 3 )7.86(d, J=16.0Hz, 1H), 7.58(d, J=7.0Hz, 1H), 7.29-7.19(m, 3H), 6.67(d, J=16.0Hz, 1H), 2.66(t, J=7.2Hz, 2H), 2.45(s, 3H), 1.73-1.63(m, 2H), 1.45-1.33(m, 2H), 0.95(t, J=7.4Hz, 3H);

[0053] 13 CNMR (75MHz, CDCl 3 ) 200.9, 140.0, 138.2, 133.7, 131.0, 130.3, 127.4, 126.6, 126.5, 41.2, 26.7, 22.7, 20.0, 14.1;

[0054] ...

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Abstract

The invention relates to a preparation method of an alpha-beta-unsaturated carbonyl compound, in particular to a method in which the alpha-beta-unsaturated carbonyl compound is prepared from substitute propargyl alcohol in a mode that positive ion modified imvite serves as a catalyst, the substitute propargyl alcohol serves as the raw material, and Meyer-Schuster rearrangement is utilized. According to the method, the substrate is wide in application range, the catalyst is cheap, easy to manufacture, stable, free of pollution to the environment and capable of being recycled, the reaction yield is high, stereoselectivity is good, and an E-type product can be obtained in a singular mode.

Description

technical field [0001] The present invention relates to a kind of synthesis method of α, β-unsaturated carbonyl compound, especially to a kind of catalyzed montmorillonite with cationic modification, lower saturated alcohol as additive, utilizes Meyer-Shuster rearrangement to prepare α by substituting propargyl alcohol , Preparation method of β-unsaturated carbonyl compound. technical background [0002] α,β-Unsaturated carbonyl compounds are important building blocks in organic synthesis and are widely used in the synthesis of natural products, functional materials, and pharmaceutical molecules. At present, the methods for preparing such compounds include Aldol condensation, Wittig reaction, Hornor-Wadsworth-Emmons reaction, Meyer-Schuster rearrangement and so on. Compared with the Aldol condensation method with many reaction steps and low yield, and the Wittig reaction and Hornor-Wadsworth-Emmon reaction that will simultaneously produce a large amount of organic phosphoru...

Claims

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Application Information

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IPC IPC(8): C07C45/51C07C49/217C07C49/807C07C49/235C07C47/232C07C49/796C07C49/223C07C67/333C07C69/618C07C49/813C07C49/84C07C253/30C07C255/56B01J29/89
CPCC07C45/51B01J29/89B01J2229/18C07B2200/07C07C67/333C07C253/30
Inventor 张琦唐莉苏朵朵韩英蕾李平卢欢欢唐秋萍柴永海
Owner SHAANXI NORMAL UNIV
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