High-selectivity synthesis method of alpha,beta-unsaturated iodoketenes and olefine aldehydes

A technology of iodoketene and high selectivity, which is applied in the high selectivity synthesis of α, to achieve the effects of high cis-trans selectivity, convenient preparation and mild conditions

Inactive Publication Date: 2013-04-10
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Controlling the reaction selectivity of two double bonds is the biggest challenge so far

Method used

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  • High-selectivity synthesis method of alpha,beta-unsaturated iodoketenes and olefine aldehydes
  • High-selectivity synthesis method of alpha,beta-unsaturated iodoketenes and olefine aldehydes
  • High-selectivity synthesis method of alpha,beta-unsaturated iodoketenes and olefine aldehydes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Embodiment 1, synthesis ( Z )-4-iodo-5-nonanone-3-ene:

[0026]

[0027] Add 5-phenylsulfinyl-3,4-nonadiene (74.8 mg, 0.3 mmol), chloroform (1 mL), ethanol (30 µL) to the reaction tube. Place the reaction tube in a 40°C oil bath, add iodine (267.2 mg, 1.05 mmol), stir for 5 minutes, then add benzylthiol in chloroform (0.6 M, 0.5 mL). After stirring for 15 minutes, 6 mL of water was added to quench the reaction, and saturated sodium thiosulfate was added dropwise to neutralize excess iodine. Extract with ether (20 mL × 3), wash with saturated sodium chloride, and dry over anhydrous sodium sulfate. Filtration, concentration, flash column chromatography (eluent: petroleum ether ~ petroleum ether / ether = 300 / 1) to obtain the product ( Z )-4-iodo-5-nonanone-3-ene (66.1 mg, 82%): liquid.

[0028] 1 H NMR (300 MHz, CDCl 3 ) δ 6.99 (t, J = 6.9 Hz, 1 H, =CH), 2.83 (t, J = 7.4 Hz, 2 H, COCH 2 ), 2.49-2.37 (m, 2 H, CH 2 ), 1.69-1.56 (m, 2 H, CH 2 ), 1.44-1.23 (...

Embodiment 2

[0029] Embodiment 2, synthesis ( Z )-1-phenyl-3-iodo-4-octanone-2-ene:

[0030] According to the method described in Example 1, the difference is that the substrate used is: 1-phenyl-4-benzenesulfinyl-2,3-octadiene (93.1 mg, 0.3 mmol), 30 μL ethanol, 1 mL Chloroform, iodine (266.6 mg, 1.05 mmol), benzylthiol in chloroform (0.6 M, 0.5 mL) to give ( Z )-3-iodo-1-phenyl-4-octanone-2-ene (63.8 mg, 65%) (eluent: petroleum ether ~ petroleum ether / ether = 300 / 1 ~ petroleum ether / ether = 100 / 1): Liquid.

[0031] 1 H NMR (300 MHz, CDCl 3 ) δ 7.40-7.21 (m, 5 H, ArH), 7.11 (t, J = 6.9 Hz, 1 H, =CH), 3.77 (d, J = 6.6 Hz, 2 H, CH 2 Ar), 2.80 (t, J = 7.5 Hz, 2 H, COCH 2 ), 1.68-1.55 (m, 2 H, CH 2 ), 1.42-1.23 (m, 2 H, CH2 ), 0.90 (t, J = 7.5 Hz, 3 H, CH 3 ); 13 C NMR (75 MHz, CDCl 3 ) δ 194.9, 149.7, 137.1, 128.8, 128.6, 126.9, 113.1, 44.2, 37.5, 26.9, 22.2, 13.8; IR (neat) ν (cm -1 ) 3063, 3027, 2957, 2926, 2867, 1682, 1598, 1495, 1453, 1251, 1145, 1100; MS (...

Embodiment 3

[0032] Embodiment 3, synthesis ( Z )-2-methyl-4-iodo-5-nonanone-3-ene:

[0033]

[0034] According to the method described in Example 1, the difference is that the substrate used is: 1-methyl-5-benzenesulfinyl-3,4-nonadiene (79.1 mg, 0.3 mmol), 30 μL ethanol, 1 mL Chloroform, iodine (267.4 mg, 1.05 mmol), benzylthiol in chloroform (0.6 M, 0.5 mL) to give ( Z )-2-methyl-4-iodo-5-nonanone-3-ene (70.6 mg, 83%, 99.3% purity) (eluent: petroleum ether ~ petroleum ether / ether = 300 / 1): Liquid.

[0035] 1 H NMR (300 MHz, CDCl 3 ) δ 6.74 (d, J = 8.4 Hz, 1 H, =CH), 2.92-2.77 (m, 3 H, COCH 2 + CH), 1.77-1.56 (m, 2 H, CH 2 ), 1.44-1.23 (m, 2 H, CH 2 ), 1.12 (d, J = 6.6 Hz, 6 H, 2 × CH 3 ), 0.92 (t, J = 7.5 Hz, 3 H, CH 3 ); 13 C NMR (75 MHz, CDCl 3 ) δ 195.1, 157.1, 109.6, 37.5, 37.3, 27.0, 22.2, 20.7, 13.8; IR (neat) ν (cm -1 ) 2960, 2931, 2870, 1682, 1602, 1465, 1412, 1382, 1363, 1329, 1267, 1166, 1128, 1086; MS (70 eV, EI) m / z (%) 280 (M + , 0.76), 237 (100); H...

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Abstract

The invention relates to a high-selectivity synthesis method of alpha,beta-unsaturated iodoketenes and olefine aldehydes. Simple and accessible allenic sulfoxide, iodine and benzyl mercaptan used as raw materials are synthesized into various alpha,beta-unsaturated iodoketenes and olefine aldehydes at high selectivity. The allenic sulfoxide can react with the iodine and benzyl mercaptan in a solvent in which the chloroform/ethanol ratio is 50/1 to generate iodoketenes and olefine aldehydes at high selectivity; and C-I bonds in the iodoketenes and olefine aldehydes can be subjected to coupling reaction to efficiently synthesize the alpha,beta-unsaturated olefine aldehydes. The invention has the advantages of simple and accessible raw materials, mild conditions, high operability, favorable substrate universality, and high selectivity for cis or trans reaction, is convenient for preparation, can be used for synthesizing various substituted alpha,beta-unsaturated iodoketenes and olefine aldehydes; and the product is easy to separate and purify.

Description

technical field [0001] The invention relates to a highly selective synthesis α，β - The method of unsaturated iodoketene and alkenal, using simple and easy-to-obtain allene sulfoxide, iodine, and benzyl mercaptan as raw materials, synthesized various types of thiols with high selectivity α,β - Unsaturated iodoketenes, alkenes. [0002] Background technique [0003] α，β - Unsaturated ketene compounds are important skeletons in the field of organic synthesis, especially multi-substituted ketenes, which have important applications in organic synthesis. But so far, there are still few methods for the highly selective synthesis of multi-substituted enones. Allenes have attracted the research interest of scientists due to their biological activities exhibited in natural products and pharmaceuticals. Allenes can exhibit different reactivity from enynes due to the presence of two cumulative double bonds. Controlling the reaction selectivity of two double bonds is the biggest ch...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/51C07C49/227C07C49/235C07C49/23C07C47/24
Inventor 麻生明王敏燕傅春玲
Owner ZHEJIANG UNIV
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