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Process for isomerizing and converting (Z)-olefins to (E)-olefins

A technology for isomerization of olefins and olefins, applied in the field of isomerization of -olefins into -olefins, can solve the problems of low catalytic efficiency, small scope of substrate application, large amount of catalyst, etc., and achieve simple reaction process and post-treatment operation , High industrial application prospect and value, high stereoselective effect

Pending Publication Date: 2020-03-13
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] In summary, the problems in the prior art are: 1. The catalytic efficiency is low, and the consumption of the catalyst is large (5-10mol%); 2. The catalyst is a noble metal catalyst, which is expensive and not environmentally friendly; 3. The scope of application of the substrate is small or An equivalent amount of additional reagent is required;

Method used

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  • Process for isomerizing and converting (Z)-olefins to (E)-olefins
  • Process for isomerizing and converting (Z)-olefins to (E)-olefins
  • Process for isomerizing and converting (Z)-olefins to (E)-olefins

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Example 1: Cobalt-catalyzed isomerization of Z-type olefins into E-type olefins

[0049]

[0050] Operation steps: Add CoCl to a dry reaction test tube at 25°C 2 (0.01mmol), PNP or PAO ligand (0.01mmol), E / Z-mixed alkenes (10mmol), toluene (1mL), injected into sodium triethylborohydride (0.03mmol), then stirred at room temperature for 10 minutes The product was separated by column chromatography.

[0051] Product 1: (E)-Anisene.

[0052]

[0053] Colorless oily liquid, yield 98%, E / Z>99 / 1. 1 H NMR: (400.0MHz, CDCl 3 )δ7.28-7.21(J=6.8,2.2Hz,2H),6.83(dd,J=6.8,2.2Hz,2H),6.34(dq,J=16.0,1.6Hz,1H),6.15-6.03(m ,1H),3.79(s,3H),1.85(dd,J=6.6,1.6Hz,3H).

[0054] Product 2: (E)-Methylisoeugenol.

[0055]

[0056] Colorless oily liquid, yield>99%, E / Z>99 / 1. 1 H NMR: (400.0MHz, CDCl 3 )δ7.30(d, J=8.4Hz, 1H), 6.62(dq, J=16.0, 1.8Hz, 1H), 6.50-6.40(m, 2H), 6.16-6.04(m, 1H), 3.82(s ,3H),3.80(s,3H),1.87(dd,J=6.8,1.8Hz,3H).

[0057] Product 3: (E)-Methyleugenol.

[00...

Embodiment 2

[0120] Example 2: Comparison of regioselective hydrosilation reactions of E / Z mixed olefins and E-olefins

[0121]

[0122] Reaction operation: at 25°C, add [Fe] (0.05mmol), olefin (1mmol), phenylsilane (PhSiH 3) (1.2mmol), tetrahydrofuran (THF) (1mL), injected into ethylmagnesium bromide (EtMgBr) (0.11mmol), then stirred at room temperature for 24 hours and separated by column chromatography to obtain the product.

[0123] Reaction 1 uses E / Z mixed β-methylstyrene as raw material, and the product is a mixture of branched and terminal hydrosilylation products in a ratio of 1.1:1; Reaction 2 uses E-β-methylstyrene as raw material, and the product It is a branched chain hydrosilation product.

[0124] Product 24: phenyl(1-phenylpropyl)silane

[0125]

[0126] Colorless liquid, yield 95%. 1 H NMR (400MHz, CDCl 3 )δ7.44-7.33(m,3H),7.35-7.21(m,4H),7.14(t,J=7.3Hz,1H),7.07(d,J=7.3Hz,2H),4.37-4.24(m ,2H),2.43-2.33(m,1H,),1.99-1.77(m,2H),0.93(t,J=7.2Hz,3H); 13 C NMR (101MHz...

Embodiment 3

[0130] Example 3: Comparison of diastereoselective sulfur-amidation reactions of E / Z mixed olefins and E-olefins

[0131]

[0132] Reaction operation: at 25°C, add olefin (1mmol), p-methylthiophenol (1.5mmol), acetonitrile (CH 3 CN) (2mL), iodine (I 2 ) (0.3mmol) and dimethyl sulfoxide (DMSO) (1.5mmol), then warmed up to 80°C and stirred for 24 hours, and then separated by column chromatography to obtain the product.

[0133] Reaction 1 uses E / Z mixed β-methylstyrene as raw material, and the diastereoselectivity of the sulfur-amidated product is 3:1; Reaction 2 uses E-β-methylstyrene as raw material, sulfur- The diastereoselectivity of the amidation product is greater than 20:1, product 27: N-1-phenyl-2-(p-tolylthio)propyl)acetamide

[0134]

[0135] Yellow solid, yield 78%. 1 H NMR (CDCl 3 ,500MHz):δ7.37-7.31(m,4H),7.32-7.28(m,3H),7.15(d,J=7.1Hz,2H),6.23(d,J=6.2Hz,1H),5.14( dd,J 1 =4.4Hz,J 2 =6.3Hz,1H),3.67-3.57(m,1H),2.35(s,3H),2.02(s,3H),1.20(d,J=6.3Hz,3H); 13...

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Abstract

The invention belongs to the technical field of metal catalytic synthesis, and discloses a method for isomerizing and converting (Z)-olefins into (E)-olefins. The (E)-olefins are prepared through a reaction at -30-80 DEG C for 0.5-48 h by using a combination of CoX2 and a PNP or PAO ligand as a catalyst in the presence of an activating reagent; and a molar ratio of the (Z)-olefins to the CoX2 to the PNP or PAO ligand to the activating reagent is 1:(0.00001-0.10):(0.00001-0.10):(0.00003-0.30). The catalyst used in the invention is the combination of the cheap metal cobalt salt and the simple and easily available ligand, no other toxic transition metal (such as ruthenium, rhodium and palladium) salt is added in the reaction, and the method also has the advantages of cheap and easily available raw material, good functional group tolerance, mild reaction conditions, simplicity in operation, and e atom economy of 100%.

Description

technical field [0001] The invention belongs to the technical field of metal catalytic synthesis, in particular to a method for isomerizing (Z)-alkenes into (E)-alkenes. Background technique [0002] At present, the closest prior art: olefins are a kind of common organic compounds with relatively stable chemical properties. At the same time, due to the existence of double bonds, olefins are easy to undergo derivatization reactions to obtain high value-added products. Alkenes can be obtained in large quantities through petroleum cracking industry, and can also be prepared in the laboratory through classic reactions such as Wittig reaction, Julia reaction, alkyne reduction and olefin metathesis. However, the 1,2-disubstituted olefins prepared by these methods are usually a mixture of E and Z olefins, and it is difficult to obtain pure (E)- or (Z)-alkenes through separation. However, the E configuration and the Z configuration of the same olefin have the same molecular composi...

Claims

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Application Information

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IPC IPC(8): C07B35/08C07C5/22C07C15/44C07C15/58C07C15/52C07C17/358C07C25/24C07C22/08C07C41/32C07C43/215C07C209/68C07C211/45C07C319/18C07C323/41C07D213/127C07D213/16C07D301/12C07D303/04C07D333/08C07F7/08B01J31/24
CPCB01J31/189B01J2531/845C07B35/08C07B2200/09C07C5/2253C07C17/358C07C41/32C07C209/68C07C319/18C07D213/127C07D213/16C07D301/12C07D303/04C07D333/08C07F7/0829C07C43/215C07C15/44C07C25/24C07C22/08C07C15/58C07C211/45C07C15/52C07C323/41
Inventor 陈建辉刘红梅蔡成丁洋浩刘波盛夏远志
Owner WENZHOU UNIVERSITY
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