Method for synthesizing Beta-bromo-Beta, Gamma-unsaturated olefin ketone

An unsaturated, enone-based technology, applied in the field of synthesis of β-bromo-β, to achieve a highly regioselective effect

Inactive Publication Date: 2009-09-02
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

One of the β-bromo-β, γ-unsaturated enones has rarely been reported in the past

Method used

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  • Method for synthesizing Beta-bromo-Beta, Gamma-unsaturated olefin ketone
  • Method for synthesizing Beta-bromo-Beta, Gamma-unsaturated olefin ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Add 1-propadienylcyclohexanol (41.3mg, 0.30mmol) and water (4.0mL) successively at room temperature, then add N-bromosuccinimide (54.8mg, 0.31mmol), and react for 2 hours Add 1mL of saturated sodium thiosulfate solution to quench, extract with ether (3×10mL), wash once with 10mL of saturated saline, dry over anhydrous sodium sulfate, filter and concentrate, perform flash column chromatography (the column is rinsed with 10 drops of acetic acid in advance) washing), to obtain 37.8mg of product, the yield was 58%. The product is a colorless liquid.

[0018] 1 HNMR (300MHz, CDCl 3 )δ 5.70(d, J=1.8Hz, 1H), 5.58(d, J=1.8Hz, 1H), 3.45(dd, J 1 =10.8Hz,J 2 =3.3Hz, 1H), 2.71-2.50(m, 2H), 2.09-1.73(m, 5H), 1.62-1.28(m, 3H); 13 C NMR (75MHz, CDCl 3 )δ 210.9, 131.6, 118.7, 62.2, 43.4, 30.8, 29.6, 28.3, 24.6; IR (neat) v (cm -1 ) 2931, 2856, 1709, 1625, 1454, 1322, 1231, 1146; MS (70eV, EI) m / z (%): 218 (M + ( 81 Br), 26.3), 216 (M + ( 79 Br), 26.6), 67(100); HRMS calcd fo...

Embodiment 2

[0020] Add acetonitrile (4.0mL), 1-propadienyl cyclopentanol (37.8mg, 0.30mmol) and water (0.27mL) successively at room temperature, and then add N-bromosuccinimide (54.2mg, 0.30mmol ), add 1mL saturated sodium thiosulfate solution to quench after reacting for 2 hours, extract with ether (3×10mL), wash once with saturated brine 10mL, dry over anhydrous sodium sulfate, filter and concentrate, flash column chromatography (chromatographic column Rinse with 10 drops of acetic acid in advance) to obtain 33.1 mg of the product with a yield of 53%. The product is a colorless liquid.

[0021] 1 H NMR (300MHz, CDCl 3 )δ 5.69-5.64 (m, 2H), 3.34 (dd, J 1 =11.7Hz,J 2 =5.4Hz, 1H), 2.54-2.43(m, 1H), 2.40-2.27(m, 1H), 2.25-2.13(m, 1H), 2.11-1.88(m, 3H), 1.82-1.62(m, 2H ); 13 C NMR (75MHz, CDCl 3 )δ 207.3, 130.5, 119.4, 60.5, 41.9, 33.2, 27.2, 24.3; IR (neat) v (cm -1 ) 2940, 2865, 1716, 1630, 1449, 1425, 1297, 1204, 1129, 1069; MS (70eV, EI) m / z (%): 204 (M + ( 81 Br), 30.4), 202 (...

Embodiment 3

[0023] According to the method described in Example 1, the difference is that the substrates and reagents used are: 1-propadienyl cycloheptanol (45.4 mg, 0.30 mmol) and N-bromosuccinimide (53.5 mg, 0.30 mmol), reacted for 2 hours to obtain 42.7 mg of product, and the yield was 62%. The product is a colorless liquid.

[0024] 1 HNMR (300MHz, CDCl 3 )δ 5.77(dd, J 1 =2.4Hz,J 2 =1.2Hz, 1H), 5.61(d, J=2.4Hz, 1H), 3.67(dd, J 1 =10.2Hz,J 2 =4.2Hz, 1H), 2.57(ddd, J 1 =14.1Hz,J 2 =12.2Hz,J 3 =3.9Hz, 1H), 2.45(ddd, J 1 =14.1Hz,J 2 =6.0Hz,J 3 =3.9Hz, 1H), 2.07-1.80(m, 4H), 1.80-1.57(m, 2H), 1.53-1.21(m, 4H); 13 C NMR (75MHz, CDCl 3 )δ 214.2, 130.6, 118.1, 59.7, 42.7, 32.1, 27.4, 25.1, 24.6, 24.4; IR (neat) v (cm -1 ) 2930, 2857, 1712, 1633, 1619, 1465, 1446, 1411, 1357, 1326, 1309, 1234, 1190, 1160, 1126, 1103, 1078, 1061; MS (70eV, EI) m / z (%): 232(M + ( 81 Br), 8.96), 230 (M + ( 79 Br), 9.52), 151 (M + -Br, 79.2), 81(100); HRMS calcd for C 10 h 15 o 79 Br(M + ):...

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Abstract

The invention relates to a method for synthesizing the Beta-bromo-Beta, Gamma-unsaturated olefin ketone. A series of Beta-bromo-Beta, Gamma-unsaturated olefin ketone compounds containing a plurality of substitutional groups are obtained by electrophilic addition and 1, 2-shift reaction through NBS and 2, 3-allenes trisubstituted carbinol in a water phase under the room temperature. The method is simple to operate and easy to obtain raw materials and reagent; the reaction is carried out in the water phase without environment pollution; the reaction can simultaneously introduce a plurality of substitutional groups and is suitable for synthesizing various substitutional Beta-bromo-Beta, Gamma-unsaturated olefin ketones.

Description

technical field [0001] The present invention relates to a method for synthesizing β-bromo-β, γ-unsaturated ketene, namely through the electrophilic addition of N-bromosuccinimide and 2,3-alkenyl tertiary alcohol in water phase Synthesis and 1,2-transfer reaction, highly regioselective synthesis of β-bromo-β, γ-unsaturated enone. Background technique [0002] β, γ-unsaturated enone is one of the 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. Huge development and utilization value. One of them, β-bromo-β, γ-unsaturated enones, has rarely been reported in previous literatures. Contents of the invention [0003] The object of the present invention is to provide a method for synthesizing β-bromo-β, γ-unsaturated enones with high regioselectivity. [0004] The present invention synthesizes β-bromo-β...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/29C07C45/63C07C45/67C07C49/687C07C49/227C07C49/235C07C49/255
Inventor 李晶余亦华傅春玲麻生明
Owner ZHEJIANG UNIV
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