A light-induced one-pot method for synthesizing olefinic compounds

A synthesis method and technology for aldehyde compounds, which are applied in the field of light-induced one-pot synthesis of olefin compounds, can solve the problems of hindering the synthesis of functional molecules, limiting the tolerance of functional groups, and inapplicability.

Active Publication Date: 2020-06-19
TSINGHUA UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

These reaction conditions greatly limit the functional group tolerance of the Wittig reaction, which greatly hinders the synthesis of functional molecules
At the same time, the Wittig reaction cannot be applied to reactions involving formaldehyde and aldehyde aqueous solution, which greatly limits the application of some aldehydes containing special functional groups, such as trifluoroacetaldehyde, to prepare olefins containing specific functional groups through the Wittig reaction.

Method used

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  • A light-induced one-pot method for synthesizing olefinic compounds
  • A light-induced one-pot method for synthesizing olefinic compounds
  • A light-induced one-pot method for synthesizing olefinic compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050]

[0051] Add 163.2 mg K to a Schlenk test tube equipped with a magnetic stir bar 2 CO 3 (1.5:1 molar ratio to benzyl chloride), 314.4mg triphenylphosphine (1.5:1 molar ratio to benzyl chloride), 3.8mg Ru(bpy) 3 Cl 2 -6H 2 O (the molar ratio of benzyl chloride to benzyl chloride is 0.005:1), 60mg paraformaldehyde, 10mL acetonitrile, 119μL benzyl bromide or 115μL benzyl chloride, argon blowing for 5 minutes, under visible light, normal temperature, the reaction time is respectively After 4h and 8h, the product was separated and purified by petroleum ether to obtain 70 mg and 62.4 mg of styrene (Formula 1), with yields of 67% and 60%, respectively.

[0052] Styrene: 1 H NMR (CDCl 3 ,400MHz)δ7.41(d,J=6.87Hz,2H),7.32(t,J=6.87Hz,2H),7.24(t,J=6.87Hz,1H),6.72(dd,J 1 =17.40Hz,J 2 =10.99Hz,1H),5.75(d,J=18.78Hz,1H),5.24(d,J=10.99Hz,1H). 13 C NMR (CDCl 3 ,100MHz)δ137.7,137.0,128.6,127.9,126.3,113.9.EI-MS:M + m / z 104.

Embodiment 2

[0054]

[0055] Add 163.2 mg K to a Schlenk test tube equipped with a magnetic stir bar 2 CO3 (1.5:1 molar ratio to 4-methylbenzyl bromide), 314.4mg triphenylphosphine (1.5:1 molar ratio to 4-methylbenzyl bromide), 3.8mg Ru(bpy) 3 Cl 2 -6H 2 O (molar ratio to 4-methylbenzyl bromide is 0.005:1), 60mg paraformaldehyde, 10mL acetonitrile, 185mg 4-methylbenzyl bromide, argon blowing for 5 minutes, under visible light, normal temperature, reaction time After 4 hours, the product was separated and purified by petroleum ether to obtain 90 mg of 4-methylstyrene (Formula 2), with a yield of 76%.

[0056] 4-Methylstyrene: 1 H NMR (CDCl 3 ,400MHz)δ7.33(d,J=8.24Hz,2H),7.16(d,J=7.79Hz,2H),6.72(dd,J 1 =17.40Hz,J 2 =10.99Hz,1H),5.72(d,J=17.40Hz,1H),5.21(d,J=10.99Hz,1H),2.37(s,3H). 13 C NMR (CDCl 3 ,100MHz)δ137.7,136.8,135.0,129.3,126.3,112.9,21.3.EI-MS:M + m / z 118.

Embodiment 3

[0058]

[0059] Add 163.2 mg K to a Schlenk test tube equipped with a magnetic stir bar 2 CO 3 (The molar ratio to p-bromobenzyl bromide is 1.5:1), 314.4mg triphenylphosphine (the molar ratio to p-bromobenzyl bromide is 1.5:1), 3.8mg Ru(bpy) 3 Cl 2 -6H 2 O (the molar ratio to p-bromobenzyl bromide is 0.005:1), 60mg of paraformaldehyde, 10mL of acetonitrile, 248mg of 4-bromobenzyl bromide, bubbling with argon for 5 minutes, under visible light, at room temperature, the reaction time is 4h, the product after Petroleum ether was separated and purified to obtain 164 mg of 4-bromostyrene (Formula 3) with a yield of 93%.

[0060] 4-Bromostyrene: 1H NMR (CDCl 3 ,400MHz)δ7.43(d,J=8.70Hz,2H),7.26(d,J=8.70Hz,2H),6.64(dd,J 1 =17.63Hz,J 2 =10.99Hz,1H),5.73(d,J=17.40Hz,1H),5.27(d,J=10.99Hz,1H).13C NMR(CDCl3,100MHz)δ136.6,135.9,131.7,127.9,121.7,114.7. EI-MS: M+m / z 182.

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Abstract

The invention discloses a method for synthesizing an olefin compound by a photo-induced one-pot process. The method comprises the following step of subjecting a halohydrocarbon and an aldehyde compound to a reaction under the condition of irradiation in an inert atmosphere by taking alkali metal carbonate as a base, taking an organic phosphine compound as an adjuvant and taking a photosensitizer as a catalyst, thereby obtaining the olefin compound. According to the method disclosed by the invention, the olefin compound is produced from the halohydrocarbon and the aldehyde compound in a high-yield manner under the condition of irradiation in the inert atmosphere under normal-temperature reaction conditions by taking acetonitrile, DMF (N,N-dimethylformamide) or DMA (N,N-dimethylacetamide) asa solvent, taking an organic phosphine reagent as a reaction adjuvant, taking the alkali metal carbonate as the base and taking the photosensitizer as the catalyst. Compared with the conventional olefin synthesis methods, the method disclosed by the invention has the obvious advantages that the reaction raw materials are readily available, the tolerance to a variety of functional groups on halohydrocarbons and aldehydes is high, the yield is high, the separation and purification of a product are simple and convenient, and the like.

Description

technical field [0001] The invention relates to a photoinduced one-pot method for synthesizing olefin compounds. Background technique [0002] The synthesis of carbon-carbon double bonds (C=C) has always been a very important reaction in organic chemistry. In addition to direct elimination reactions, there are four reaction pathways that can prepare olefins containing carbon-carbon double bonds: Wittig reaction (Wittig, G.&Geissler,G.Course of reactions of pentaphenylphosphorus and certain derivatives.Liebigs Ann.Chem.580,44-57(1953).), Peterson reaction (Peterson,D.J.Acarbonyl olefination reaction using silyl-substituted organometallic compounds.J.Org.Chem .33,780-784(1968).), Julia-Lythgoe olefin synthesis reaction (Julia,M.&Paris,J.-M.Syntheses using sulfones.5.method for general synthesis of doubles.Tetrahedron Lett.14,4833-4836(1973 )) and olefin metathesis reactions (Nicolaou, K.C., Bulger, P.G. & Sarlah, D. Metathesis reactions in total synthesis. Angew. Chem., Int. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C1/26C07C15/46C07C17/263C07C25/28C07C253/30C07C255/50C07D213/16C07D213/127C07C15/44C07C41/30C07C43/215C07C231/12C07C233/09C07C22/08C07C25/24C07C43/225C07C15/52C07C201/12C07C205/06C07D333/08C07C67/343C07C69/618C07C13/547
CPCC07C1/26C07C17/263C07C41/30C07C67/343C07C201/12C07C231/12C07C253/30C07C2531/22C07D213/127C07D213/16C07D333/08C07C15/46C07C25/28C07C255/50C07C15/44C07C43/215C07C233/09C07C22/08C07C25/24C07C43/225C07C15/52C07C205/06C07C69/618C07C13/547
Inventor 付华蒋敏杨海军
Owner TSINGHUA UNIV
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