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Synthesis method of imide substituted bridge ring compound

A synthetic method and imide-based technology, applied in the direction of organic chemistry, can solve the problems of low yield and long reaction time, and achieve the effects of lower reaction temperature, simple operation, and favorable industrial production

Inactive Publication Date: 2006-11-22
ZHEJIANG UNIV OF TECH
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  • Application Information

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Problems solved by technology

The first is to synthesize a series of imide-substituted cycloaddition products through the Diels-Alder reaction of imido-substituted α, β-unsaturated ketones and cyclopentadiene in dichloromethane. The method has disadvantages such as low yield and long reaction time
The second is to synthesize a series of imide-substituted cycloaddition products through the Diels-Alder reaction of imide-substituted α, β-unsaturated ketones and five-membered ring dienes in ionic liquids. Although the yield has increased, the reaction time is too long

Method used

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  • Synthesis method of imide substituted bridge ring compound
  • Synthesis method of imide substituted bridge ring compound
  • Synthesis method of imide substituted bridge ring compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1 Diels-Alder reaction of 1-butyrolactam-3-phenylpropenone and cyclopentadiene

[0024] Add 5 mL of dichloromethane and 0.22 g (1 mmol) of 1-butyrolactam-3-phenylpropenone into a 50 mL one-necked flask, then add 0.15 g (0.5 mmol) of zinc iodide and 0.5 mL (5 mmol) of cyclopentanediene ene, placed in an ultrasonic water tank, subjected to ultrasonic radiation (40KHz, 50W) for 30min, added 20mL of saturated sodium bicarbonate solution, extracted with dichloromethane (3×5mL), washed twice with water, dried, concentrated, and subjected to column chromatography (petroleum Ether: ethyl acetate = 9: 1 V / V) to obtain 0.2 g of white needle-like crystals with a melting point of 75-77° C. and a yield of 71%. IR: ν=2989, 1730, 1686, 1458, 1346, 1328, 1286, 1247, 1219, 1020, 793cm -1 . 1 H NMR (400MHz, CDCl 3 ): δ=1.55(m, 1H, H7), 1.96(m, 1H, H7'), 2.02(m, 2H, H17), 2.58(m, 2H, H16), 2.98(s, 1H, H1), 3.38(m, 2H, H16), 3.77(m, 2H, H18), 4.20(dd, J=3.4, 4.9Hz 1H, H5), 5.90...

Embodiment 2

[0025] Example 2 Diels-Alder reaction of 1-succinimide-2-butenone and cyclopentadiene

[0026] Add 5mL of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.17 grams (1mmol) of 1-succinimidyl-2-butenone into a 50mL one-necked flask, then add 0.15 grams (0.5mmol ) zinc iodide and 0.5mL (5mmol) cyclopentadiene, placed in an ultrasonic water tank, subjected to ultrasonic radiation (40KHz, 50W) for 25min, extracted with toluene (3×5mL), washed twice with water, dried, concentrated, and passed through the column layer Analysis (petroleum ether: ethyl acetate = 2:1 V / V) gave 0.22 g of white needle-like crystals with a melting point of 88-89° C. and a yield of 93.3%. IR: ν=2975, 2872, 1795, 1746, 1709, 1429, 1371, 1317, 1253, 1183cm -1 . 1 H NMR (400MHz, CDCl 3 ): δ=1.18 (d, J=7.2, 3H, Me-6), 1.46 (dd, J=9, 1.6Hz, 1H, H-7 a ), 1.63 (d, J=8.8, 1H, H-7 b ), 2.05(m, 1H, H-1), 2.54(s, 1H, H-6), 2.8(s, 4H, H-11, H-12), 3.07(s, 1H, H-4), 3.24(dd, J=3.6, 4Hz, 1H, H-5), 5.91(dd, J=2.6...

Embodiment 3

[0027] Example 3 Diels-Alder reaction of 1-succinimide-2-butenone and cyclopentadiene

[0028] In a nitrogen stream, 0.4 g of dried activated 4A molecular sieve powder and optically active (2R, 3R)-(-)-1,1,4,4-tetrakis-(1-naphthyl)-2,3-( 0.15 g (0.22 mmol) of acetonide)-1,4-butanediol was placed in a 25 mL reactor and sealed. Fill the reaction system with nitrogen to make the reaction system anaerobic and absolutely dry, add 3mL dichloromethane with a syringe, mix and stir thoroughly, and then add 0.2mL TiCl 2 (OPr i ) 2 Add the toluene solution (0.87mol / L) into the reaction system, stir at room temperature for 1 hour, then lower the temperature to -10°C, and dissolve 0.17 g (1 mmol) of 1-succinimide-2-butenone in 4 mL Dichloromethane was first added to the reaction system, and after stirring for a few minutes, 1mL (10mmol) of cyclopentadiene was added, placed in an ultrasonic water tank, subjected to ultrasonic radiation (40KHz, 50W) for 30min, and 20mL of saturated sodium...

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Abstract

This invention relates to a method for synthesizing imide substituted endocyclic compound, comprising: Lewis acid as catalyst, the formula(I) indicated acid imide group substituted alpha-beta-unsaturated ketone and formula(II) indicated Five- membered cyclic dienerite conduct Diels-Alder reaction in the organic solvent at -20-150Deg C under ultrasonic radiation to produce the product. This invention, by using the ultrasonic radiation, accelerates the reaction and decreases the reaction time, having benefits of simple operation, low reaction temperature, energy saving, improved product yield which is good for industrial production. Besides, the ionic liquid catalytic system can be repeated used, which can both decrease the cost and the environmental pollution caused by waste water.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing a bridged ring compound substituted with an imide group. (2) Background technology [0002] Compounds containing imide-substituted bridging rings have certain biological and physiological activities, and are important intermediates of pesticides and medicines. In addition, such substances also have broad application prospects in the synthesis of chiral drugs and natural products. [0003] The inventors of the present invention have previously reported two methods for synthesizing imido-substituted ring-forming compounds. The first is to synthesize a series of imide-substituted cycloaddition products through the Diels-Alder reaction of imido-substituted α, β-unsaturated ketones and cyclopentadiene in dichloromethane. The method has disadvantages such as low yield and long reaction time. The second is to synthesize a series of imide-substituted cycloaddition products through the Diels-Alder reacti...

Claims

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Application Information

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IPC IPC(8): C07D207/27C07D487/04C07D493/04C07D495/04
Inventor 裴文孙莉余长泉
Owner ZHEJIANG UNIV OF TECH
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