Preparation method of alpha-acyloxy ether

A technology of acyloxyether and alkyl, applied in the field of organic synthesis, can solve problems such as cumbersome steps, and achieve the effects of avoiding metal pollution, reducing pollution, and high compatibility

Inactive Publication Date: 2011-04-13
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The method is cumbersome and needs to be carried out under anhydrous conditions

Method used

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  • Preparation method of alpha-acyloxy ether
  • Preparation method of alpha-acyloxy ether
  • Preparation method of alpha-acyloxy ether

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023]

[0024] Load KI (0.1mmol) successively in the reaction bottle, compound a 1 (0.5 mmol), compound b 1 (2 mL), TBHP (2.2 equiv). Then the system was stirred in the air at 100°C for about 2 hours, then a saturated sodium sulfite solution was added to quench the reaction, extracted with ethyl acetate (2mL×3), then adsorbed with 100-200 mesh silica gel, and then passed through a 300-400 mesh The product c was obtained by elution of silica gel column 1 , the yield was 97%. 1 H NMR (CDCl 3 , 400MHz): δ3.66-3.70(m, 1H), 3.82-3.84(m, 2H), 3.89-3.90(m, 2H), 4.21-4.24(m, 1H), 6.10(t, J=2.0Hz , 1H), 7.44-7.48(m, 2H), 7.57-7.61(m, 1H), 8.12-8.14(m, 2H); 13 C NMR (CDCl 3 , 100MHz): 61.6, 66.0, 67.7, 89.7, 128.3, 129.6, 129.7, 133.3, 165.1; ESI-MS (C 11 h 12 o 4 Na): 231; IR (KBr, cm -1 ): 1726. The above detection data confirmed that the target product was obtained.

Embodiment 2

[0026]

[0027] The reaction bottle is filled with I 2 (0.1 mmol), compound a 2 (0.5 mmol), compound b 1 (2 mL), hydrogen peroxide (2.2 equivalents). After stirring for about 8 hours at 80°C in air, add saturated sodium sulfite solution to quench the reaction, extract with ethyl acetate (2mL×3), then absorb with 100-200 mesh silica gel, and then pass through a 300-400 mesh silica gel column. Washed product c 2 , the yield was 97%. 1 H NMR (CDCl 3 , 400MHz): δ3.68-3.72(m, 1H), 3.82-3.95(m, 4H), 4.23-4.29(m, 1H), 6.11(t, J=1.8Hz, 1H), 7.16-7.20(m , 1H), 7.41-7.45(m, 1H), 7.92-7.95(m, 1H), 8.01-8.04(m, 1H); 13 C NMR (CDCl 3 , 100MHz): δ61.6, 65.8, 67.4, 90.4, 94.1, 127.8, 131.2, 132.9, 134.0, 141.3, 164.7; ESI-HRMS: calcd.for C 11 h 11 NaIO 4 , 356.9600; found, 356.9592; IR (KBr, cm -1 ): .1699. The above detection data confirmed that the target product was obtained.

Embodiment 3

[0029]

[0030] Fill the reaction bottle with Bu 4 NI (0.1 mmol), compound a 3 (0.5 mmol), compound b 1 (2 mL), TBHP (2.2 equiv). Then the system was stirred in the air at 50°C for about 18 hours, then a saturated sodium sulfite solution was added to quench the reaction, extracted with ethyl acetate (2mL×3), then adsorbed with 100-200 mesh silica gel, and then passed through a 300-400 mesh The product c3 was obtained by elution on a silica gel column with a yield of 71%. 1 HNMR (CDCl 3 , 400MHz): δ2.37(s, 6H), 3.67-3.70(m, 1H), 3.78-3.82(m, 2H), 3.87-3.88(m, 2H), 4.11-4.21(m, 1H), 6.13 (t, J=2.0Hz, 1H), 7.04-7.05(m, 2H), 7.19-7.22(m, 1H); 13 C NMR (CDCl 3, 100MHz): δ19.6, 61.7, 65.9, 67.6, 89.9, 127.5, 129.4, 133.1, 134.8, 168.6; ESI-MS (C 13 h 16 NaO 4 ): 259; IR (KBr, cm -1 ): 1733. The above detection data confirmed that the target product was obtained.

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Abstract

The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of alpha-acyloxy ether. The method comprises the following steps: (1) configuring a reaction system, wherein the reaction system comprises reaction substrates carboxylic acid, ether, a catalyst and an oxidant; the formula of the carboxylic acid is shown in the specification, wherein R is selected from one of aryl of C6-C12, alkyl of C1-C15, alkenyl of C2-C8 or unsubstituted five / six-membered heterocyclic radical, the ether is selected from one of unsubstituted saturated open-chain ether or cyclic ether, the catalyst is selected from one of potassium iodide, iodine, amine tetrabutylammonium iodide, benzyl trimethyl ammonium iodide or sodium iodide, and the oxidant is tert-butyl hydroper oxide or hydrogen peroxide; and (2) mixing the above reaction system at a temperature ranging from room temperature to 100 DEG C for 2-24hours, thus obtaining the alpha-acyloxy ether. The method is green and moderate, and has high selectivity and wide application.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing α-acyloxy ethers, in particular to a method for catalyzing the oxidation of ortho C-H bonds in ethers by using iodine-containing compounds as catalysts and tert-butanol peroxide or hydrogen peroxide as oxidants The method of reacting with carboxylic acid to obtain α-acyloxyether. Background technique [0002] α-Acyloxy ethers are a very important class of organic compounds, which can be used not only as structural units of various physiologically active natural products, but also widely used in the synthesis of other heterocyclic compounds. [0003] At present, the preparation methods of α-acyloxy ethers mainly contain the following types: [0004] 1. The addition of carboxylic acid to alkenyl ether, the disadvantage of this method is mainly to use expensive alkenyl ether. See references for details: (1) Croxallf, W.J.; Glavis, J.; Neher, H.T....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/00C07D319/12C07D405/12C07D409/12C07D407/12C07D309/12C07C69/78C07C67/24C07D307/20C07C69/75
Inventor 陆新华陈龙刘召军时二波陈书林魏伟徐元李宏万小兵
Owner SUZHOU UNIV
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