Method for catalytically synthesizing 4-chlorotetrahydrofuran compound by using titanocene dichloride as lewis acid and chloride ion source

A technology of chlorinated tetrahydropyran and dichlorotitanocene, which is applied in the field of synthesis of chlorinated tetrahydropyran compounds, can solve the problems of harsh reaction conditions, high toxicity, strong corrosion, etc., and achieve short reaction time , low toxicity, and mild reaction conditions

Active Publication Date: 2018-11-02
SHAANXI NORMAL UNIV +1
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  • Abstract
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Problems solved by technology

[0004] The technical problem to be solved by this invention is to overcome existing 4-chlorinated tetrahydropyrans compound synthetic method to use Lewis acid alone or Due to the defects of strong corrosion, high toxicity and harsh reaction conditions caused by acid, a kind of titanium dichloride is used as a Lewis acid catalyst and a source of chloride ions at the same time, and 3,5-dinitrosalicylic acid is used as a cocatalyst. A method for synthesizing 4-chlorotetrahydropyran compounds by catalyzing Prins cyclization reaction, the method has mild reaction conditions, strong atom economy, safety and high efficiency

Method used

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  • Method for catalytically synthesizing 4-chlorotetrahydrofuran compound by using titanocene dichloride as lewis acid and chloride ion source
  • Method for catalytically synthesizing 4-chlorotetrahydrofuran compound by using titanocene dichloride as lewis acid and chloride ion source
  • Method for catalytically synthesizing 4-chlorotetrahydrofuran compound by using titanocene dichloride as lewis acid and chloride ion source

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] Synthesis of 4-chloro-4-methyl-2-(4-nitrophenyl)-tetrahydropyran with the following structural formula

[0013]

[0014] 0.1511g (1.0mmol) p-nitrobenzaldehyde, 151μL (1.5mmol) 3-methyl-3-buten-1-alcohol, 0.248g (1.2mmol) titanocene dichloride, 0.2281g (1.0mmol) Add 3,5-dinitrosalicylic acid and 3 mL of dry dichloromethane into a Shrek tube, stir and react at room temperature for 5 hours, stop the reaction, and separate by column chromatography to obtain solid 4-chloro-4-methyl-2 -(4-nitrophenyl)-tetrahydropyran, its yield is 88%, and the structural characterization data is: 1 H NMR (600MHz, CDCl 3 )δ8.17(d, J=8.6Hz, 2H), 7.50(d, J=8.6Hz, 2H), 4.87(d, J=10.0Hz, 1H), 4.07(s, 2H), 2.14(d, J=14.2Hz, 1H), 1.90(dd, J=9.3, 4.4Hz, 2H), 1.67(s, 3H), 1.64(dd, J=14.1, 11.2Hz, 1H); 13 C NMR (151MHz, CDCl 3 )δ147.16(s), 64.83-64.70(m), 40.15(s), 33.94(s).

Embodiment 2

[0016] Synthesis of 2-(3-nitrophenyl)-4-chloro-4-methyl-tetrahydropyran with the following structural formula

[0017]

[0018] In this example, the p-nitrobenzaldehyde in Example 1 is replaced with equimolar 3-nitrobenzaldehyde, and other steps are the same as in Example 1 to obtain solid 2-(3-nitrophenyl)-4-chloro -4-Methyltetrahydropyran, its yield is 83%, and the structural characterization data is: 1 H NMR (600MHz, CDCl 3 )δ8.22(s,1H),8.09(dd,J=8.1,1.4Hz,1H),7.65(d,J=7.7Hz,1H),7.49(t,J=7.9Hz,1H),4.86( dd,J=11.1,1.6Hz,1H),4.05(ddd,J=13.5,8.6,4.1Hz,2H),2.16(d,J=14.1Hz,1H),1.90(dd,J=8.2,4.0Hz ,2H),1.68(d,J=3.3Hz,3H); 13 C NMR (151MHz, CDCl 3 )δ144.27(s), 120.83(s), 68.69(s), 63.99(s), 48.23(s).

Embodiment 3

[0020] Synthesis of 4-chloro-4-methyl-2-(3,4-dimethoxyphenyl)-tetrahydropyran with the following structural formula

[0021]

[0022] In this example, the p-nitrobenzaldehyde in Example 1 was replaced with equimolar 3,4-dimethoxybenzaldehyde, and the other steps were the same as in Example 1 to obtain solid 4-chloro-4-methyl-2 -(3,4-dimethoxyphenyl)-tetrahydropyran, the yield is 78%, and the structural characterization data are: 1 H NMR (600MHz, CDCl 3 )δ6.91-6.82(m,3H),4.72(dd,J=11.0,1.7Hz,1H),4.07-4.02(m,2H),3.89(s,3H),3.86(d,J=2.9Hz ,3H),2.10(d,J=14.2Hz,1H),1.90(dd,J=7.5,4.3Hz,2H),1.79-1.74(m,1H),1.68(s,3H); 13 C NMR (151MHz, CDCl 3 )δ147.92(s), 108.31(s), 63.54(s), 54.86(s), 38.96(s), 33.05(s).

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Abstract

The invention discloses a method for catalytically synthesizing a 4-chlorotetrahydrofuran compound by using titanocene dichloride as lewis acid and a chloride ion source. According to the method, by using titanocene dichloride as a lewis acid catalyst and the chloride ion source, and 3,5-dinitrosalicylic acid as a cocatalyst, a homoallylic alcohol compound and aromatic aldehyde undergo Prins cyclization reaction under mild conditions and further a target compound, namely 4-chlorotetrahydrofuran compound is prepared. The method disclosed by the invention has the advantages of simple operation steps, mild conditions, strong atomic economy, wider applicability of a substrate and high yield of the target compound and can be widely used in the preparation of chlorine compounds for oxa, aza andthiane Prins cyclization reactions.

Description

technical field [0001] The invention belongs to the technical field of synthesis of chlorinated tetrahydropyran compounds, and specifically relates to a method that uses titanocene dichloride as a Lewis acid catalyst and a source of chloride ions at the same time, and 3,5-dinitrosalicylic acid as a cocatalyst. A method for synthesizing 4-chlorotetrahydropyran compounds under normal temperature conditions using homoallyl alcohol compounds and aromatic aldehydes as reaction substrates. Background technique [0002] The Prins reaction is a kind of addition reaction between alkenes and carbonyl groups through the intermediate state of oxonium ions. As an effective method to form carbon-carbon bonds, it has gradually attracted the attention of organic chemists. This reaction refers to a condensation reaction of aldehydes or ketones with alkenes or alkynes under acid catalysis. At present, Prins cyclization reactions include direct thermal condensation reactions and catalytic synt...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D309/08
CPCC07D309/08
Inventor 高子伟王芸芸杨明明张伟强简亚军孙华明
Owner SHAANXI NORMAL UNIV
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