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A method for synthesizing 3-methoxycarbonyl-2-chloro-1,3(z)-diene

A technology of methoxycarbonyl and diene, which is applied in the field of synthesizing 3-methoxycarbonyl-2-chloro-1, can solve the problems of limited substrate application range, low reaction stereoselectivity, and low yield, and achieve High yield, convenient operation, and good stereoselectivity

Inactive Publication Date: 2012-02-08
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The reaction stereoselectivity of the synthesis method about 1,3-conjugated dienes reported in the literature is not high, and the scope of substrate application is not wide (Ma, S.; Wang, G.Tetrahedron Lett.2002,43,5723) or need The involvement of precious metals (Horvath, A.; J.-E.J.Org.Chem.2001, 66, 8120)
(Deng, Y.; Jin, X.; Ma, S.J.Org.Chem. 2007, 72, 5901) reported the synthesis of 3-methoxycarbonyl-2-chloro-1,3(Z)-diene but the yield Low (26~59%)

Method used

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  • A method for synthesizing 3-methoxycarbonyl-2-chloro-1,3(z)-diene
  • A method for synthesizing 3-methoxycarbonyl-2-chloro-1,3(z)-diene
  • A method for synthesizing 3-methoxycarbonyl-2-chloro-1,3(z)-diene

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] To a solution of oxalyl chloride (152.0 mg, 1.2 mmol) in dichloromethane (2 mL) was slowly added dropwise a solution of dimethyl sulfoxide (187.1 mg, 2.4 mmol) in dichloromethane with stirring at -78°C (2mL), after stirring and reacting for 9 minutes, a dichloromethane solution of 3-methoxycarbonyl-1,2-nonadien-4-ol (81.8mg, 0.4mmol) was added to the above reaction mixture at -78°C ( 2 mL), continued to stir at -78°C for 18 minutes, and reacted at room temperature for 5 hours. Then add 10 mL of water at room temperature, extract with ether (3x25 mL), wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform flash column chromatography to obtain 74.2 mg of the product with a yield of 83%. The product is a colorless liquid.

[0021]

[0022] CH 2 Cl 2 , -78℃, 18min

[0023] then rt, 5h

[0024] 1 H NMR (300MHz, CDCl 3 )δ6.93(t, J=7.8Hz, 1H), 5.59(d, J=1.2Hz, 1H), 5.23(d, J=1.2Hz, 1H), 3.76(s, 3H), 2.28(q, J=7.5Hz, 2H), ...

Embodiment 2

[0026] According to the method described in Example 1, the difference is that the substrates and reagents used are: oxalyl chloride (153.9 mg, 1.2 mmol), dimethyl sulfoxide (187.8 mg, 2.4 mmol), 4-methoxycarbonyl-4, 5-Hexadien-3-ol (65.6mg, 0.4mmol) and dichloromethane (6mL) gave 56.1mg of the product with a yield of 76%. The product is a colorless liquid.

[0027]

[0028] CH 2 Cl 2 , -78℃, 19min

[0029] then rt, 5h

[0030] 1 H NMR (300MHz, CDCl 3 )δ6.92(t, J=7.5Hz, 1H), 5.60(d, J=0.9Hz, 1H), 5.24(d, J=0.9Hz, 1H), 3.77(s, 3H), 2.38-2.22( m, 2H), 1.06(t, J=7.5Hz, 3H).

Embodiment 3

[0032] According to the method described in Example 1, the difference is that the substrates and reagents used are: oxalyl chloride (153.9 mg, 1.2 mmol), dimethyl sulfoxide (187.8 mg, 2.4 mmol), 3-methoxycarbonyl-1, 2-Heptadien-3-ol (70.0mg, 0.4mmol) and dichloromethane (6mL) gave 65.7mg of the product with a yield of 85%. The product is a colorless liquid.

[0033]

[0034] CH 2 Cl 2 , -78℃, 17min

[0035] then rt, 5h

[0036] 1 H NMR (300MHz, CDCl 3 )δ6.94(t, J=7.8Hz, 1H), 5.60(d, J=1.2Hz, 1H), 5.24(d, J=1.2Hz, 1H), 3.77(s, 3H), 2.27(q, J=7.5Hz, 2H), 1.56-1.41(m, 2H), 0.93(t, J=7.5Hz, 3H).

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Abstract

The present invention relates to a method for synthesizing 3-methoxycarbonyl-2-chloro-1,3(Z)-diene with high stereoselectivity: at -78°C, oxalyl chloride reacts with dimethyl sulfoxide to obtain intermediate body; after reacting this intermediate with 2-methoxycarbonyl-2,3-alkenol at -78°C for a certain period of time, continue to stir at room temperature until the reaction is complete to obtain 3-methoxycarbonyl-2-chloro-1, 3(Z)-Dienes. The invention has simple operation, easy access to raw materials and reagents, high stereoselectivity in reaction, easy separation and purification of products, and is suitable for synthesizing 3-methoxycarbonyl-2-chloro-1,3(Z)-diene compounds.

Description

technical field [0001] The present invention relates to a method for synthesizing 3-methoxycarbonyl-2-chloro-1,3(Z)-diene. Background technique [0002] 1,3-conjugated diene is one of the most important intermediates in organic synthesis and one of the most common structural units in natural products. It has a variety of important physiological activities and is widely used in biotechnology, medicine and pesticides. It has great development and utilization value. The reaction stereoselectivity of the synthesis method about 1,3-conjugated dienes reported in the literature is not high, and the scope of substrate application is not wide (Ma, S.; Wang, G.Tetrahedron Lett.2002,43,5723) or need The involvement of precious metals (Horvath, A.; J.-E.J.Org.Chem. 2001, 66, 8120). (Deng, Y.; Jin, X.; Ma, S.J.Org.Chem. 2007, 72, 5901) reported the synthesis of 3-methoxycarbonyl-2-chloro-1,3(Z)-diene but the yield Lower (26-59%). Contents of the invention [0003] The object of t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/307C07C67/327C07C69/65
Inventor 麻生明邓友前金鑫傅春玲
Owner ZHEJIANG UNIV