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Method of synthesizing 3-carbomethoxy-2-halogen-1,3(Z)-conjugated diolefin

A technology of conjugated dienes and methyl esters, applied in chemical instruments and methods, preparation of organic compounds, preparation of carboxylic acid esters, etc., can solve the problems of requiring noble metals and low stereoselectivity of reactions, and achieve high stereoselectivity Effect

Inactive Publication Date: 2007-10-17
ZHEJIANG UNIV
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  • Abstract
  • Description
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Problems solved by technology

The reaction stereoselectivity of the synthesis method of 1,3-conjugated diene reported in the previous literature is not high or requires the participation of noble metals

Method used

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  • Method of synthesizing 3-carbomethoxy-2-halogen-1,3(Z)-conjugated diolefin
  • Method of synthesizing 3-carbomethoxy-2-halogen-1,3(Z)-conjugated diolefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Add NaI (151.1mg, 1.0mmol), 3-methylester-1,2-hexadien-4-ol (77.0mg, 0.49mmol) and trifluoroacetic acid (1mL) at room temperature, and then reflux at eighty degrees The reaction was complete in 1 hour, cooled to room temperature, quenched with 10 mL of water, neutralized with sodium bicarbonate until almost no bubbles, extracted with ether (3×25 mL), saturated with Na 2 S 2 o 3 The aqueous solution and saturated brine were washed once respectively, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to flash column chromatography to obtain 65.4 mg of the product with a yield of 50%. The product is a colorless liquid.

[0021] 1 H NMR (300MHz, CDCl 3 )δ6.75(t, J=7.8Hz, 1H), 6.08(d, J=1.1Hz, 1H), 6.03(d, J=1.1Hz, 1H), 3.77(s, 3H), 2.29-2.18( m, 2H), 1.06(t, J=7.7Hz, 3H);

[0022] 13 C NMR (75MHz, CDCl 3 ): δ165.3, 146.6, 135.7, 131.2, 96.3, 52.1, 22.8, 12.3;

[0023] MS (m / z): 267 (M + +1, 100);

[0024] IR (neat, cm -1 ): 2962, 1722, 16...

Embodiment 2

[0027] According to the method described in Example 1, the difference is that the substrate and reagent used are: LiBr H 2 O (105.0mg, 1.0mmol), 3-methylester-1,2-hexadien-4-ol (77.1mg, 0.49mmol) and trifluoroacetic acid (1mL), the product was 60.2mg, the yield was 56% . The product is a colorless liquid.

[0028] 1 H NMR (400MHz, CDCl 3 )δ6.88(t, J=7.8Hz, 1H), 5.84(d, J=2.0Hz, 1H), 5.66(d, J=2.0Hz, 1H), 3.79(s, 3H), 2.32-2.26( m, 2H), 1.07(t, J=7.6Hz, 3H); 13 C NMR (100-MHz, CDCl 3 ): δ165.5, 148.5, 132.9, 122.6, 122.3, 52.2, 22.9, 12.8; MS (m / z): 220 (M + (81Br), 8.22), 218 (M + ( 79 Br), 8.32), 139 (100); IR (neat, cm -1 ): 2971, 2952, 1724, 1645, 1615, 1267, 1245. HRMS calcd for C 8 h 11 BrNaO 2 (M + +Na): 242.9822 ( 81 Br), 240.9835 (79Br), Found: 242.9811 ( 81 Br), 240.9833 ( 79 Br).

Embodiment 3

[0030] According to the method described in Example 1, the difference is that the substrate and reagent used are: LiCl H 2 O (122.1mg, 2.02mmol), 3-methylester-1,2-hexadien-4-ol (78.8mg, 0.51mmol) and trifluoroacetic acid (1mL) yielded 35.5mg of the product, yield 40% . The product is a colorless liquid.

[0031] 1 H NMR (400MHz, CDCl 3 )δ6.94(t, J=7.8Hz, 1H), 5.62(d, J=1.2Hz, 1H), 5.26(d, J=1.2Hz, 1H), 3.79(s, 3H), 2.36-2.27( m, 2H), 1.07(t, J=7.6Hz, 3H); 13 C NMR (100MHz, CDCl 3 ): δ165.6, 149.1, 133.0, 131.4, 118.3, 52.2, 23.0, 13.0; MS (m / z): 176 (M + ( 37 Cl), 3.72), 174 (M + (35Cl), 11.67), 139(100); IR (neat, cm-1): 2971, 2955, 1725, 1644, 1619, 1246. HRMS calcd for C 8 h 11 ClO 2 (M + ): 174.0448 ( 35 Cl), Found: 174.0448 ( 35 Cl).

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Abstract

The invention relates to a 3-methyl ester-2-halogen-1,3( Z )-conjugated diene and synthetic method thereof, in which a series of 3-methyl ester-2-halogen-1,3( Z )-conjugated diene compounds is generated through addition-elimination reaction of haloid salt with 3-methyl ester-1,2-allenes-4-alcohol under trifluoroacetic acid or acetic acid counterflow condition. The method is characterized in that it operated simply, its raw material and reagent is obtained easily, it has high stereoselectivity, it is able to induct a plurality of substituent, its products are readily separated and purified simultaneously and it is suitable for synthesizing various substituted 3-methyl ester -2-halogen -1,3( Z )-conjugated diene.

Description

technical field [0001] The present invention relates to a method for synthesizing 3-methyl ester-2-halogen-1,3(Z)-conjugated diene with high stereoselectivity, that is, through halogen salt and 3-methyl ester-1,2-alkene Synthesis of 3-methylester-2-halogen-1,3(Z)-conjugated dienes by addition-elimination reaction of -4-alcohols. 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 synthesis methods of 1,3-conjugated dienes reported in previous literatures have low stereoselectivity or require the participation of noble metals. [0003] Therefore, the effective and convenient synthesis of 1,3-conjugated dienes with high stereoselectivity without the need for noble metals will be a gr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/65C07C67/333
Inventor 麻生明邓友前金鑫
Owner ZHEJIANG UNIV
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