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A kind of preparation method of multi-substituted cyclic amidine

A polysubstituted, cyclic amidine technology, applied in the direction of organic chemistry, can solve the problems of severe reaction conditions, narrow substrate range, use of dangerous reagents, etc., and achieves the effect of simple operation, difficult preparation, and high stereo control.

Active Publication Date: 2016-04-13
山东雪地铝业科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] These methods have certain limitations, such as severe reaction conditions, use of dangerous reagents, and narrow substrate range.

Method used

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  • A kind of preparation method of multi-substituted cyclic amidine
  • A kind of preparation method of multi-substituted cyclic amidine
  • A kind of preparation method of multi-substituted cyclic amidine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Under nitrogen protection, 1.0 mmol of allylamine alkyne 9a (R = p-methoxyphenyl, R' = H, R" = H, n = 0), 1.0 mmol of p-toluenesulfonyl alkene Nitrogen and 5.0 moles of diisopropylethylamine are mixed in 5 ml of toluene, and 0.05 moles of copper 2-thiazole formate are added at 30 degrees, and the mixture is evenly mixed. After 24 hours, 2 ml of saturated ammonium chloride solution is added, and the stirring is continued. After 5 hours, wash with 5 ml of water and 5 ml of saturated brine successively, separate the organic phase and dry it with anhydrous sodium sulfate, filter and remove the organic solvent, add 1 g of 200 mesh silica gel and 6 ml of dichloromethane, mix well, and carefully distill out Solvent, put the remaining silica gel on a silica gel column, elute with ethyl acetate / petroleum ether, collect fractions, and obtain 93% cyclic amidine 10a. 10a: Yellow oil, 94%; 1 HNMR (400MHz, CDCl 3 )δ7.69(d, J=8.2Hz, 2H), 7.22(d, J=9.1Hz, 2H), 7.13(d, J=8.1Hz, 2H), ...

Embodiment 2

[0034] Under nitrogen protection, 1.0 mmol of allylamine alkyne 9b (R = benzyl, R' = phenyl, R" = hydrogen, n = 1), 1.0 mmol of p-toluenesulfonyl azide, 5.0 Mix moles of diisopropylethylamine in 5 ml of toluene, add 0.05 moles of copper 2-thiazole carboxylate at -20°C, stir and mix evenly, after 24 hours, add 2 ml of saturated ammonium chloride solution, and continue stirring for 5 hours , washed successively with 5 milliliters of water and 5 milliliters of saturated saline, separated the organic phase and dried it with anhydrous sodium sulfate, filtered and removed the organic solvent, added 1 gram of 200-mesh silica gel and 6 milliliters of dichloromethane and mixed evenly, carefully distilled off the solvent, The remaining silica gel was applied to a silica gel column, eluted with ethyl acetate / petroleum ether, and the fractions were collected to obtain 91% cyclic amidine 10b.

[0035] 10b: Yellow oil, 93%; 1 HNMR (400MHz, CDCl 3 )δ7.66(d, J=8.2Hz, 2H), 7.55(d, J=7.3Hz,...

Embodiment 3

[0037] Under nitrogen protection, 1.0 mmol of allylamine alkyne 9c (R = n-hexyl, R' = phenyl, R" = hydrogen, n = 0), 1.2 mmol of p-toluenesulfonyl azide, 5.0 One mole of diisopropylethylamine was mixed in 5 milliliters of tetrahydrofuran, and 0.05 moles of copper 2-thiazole formate was added at 60°C, stirred and mixed evenly. After 24 hours, 2 milliliters of saturated ammonium chloride solution was added, and the stirring was continued for 5 hours. Wash with 5 ml of water and 5 ml of saturated brine successively, separate the organic phase and dry it with anhydrous sodium sulfate, remove the organic solvent after filtration, add 1 g of 200 mesh silica gel and 6 ml of dichloromethane and mix well, carefully distill off the solvent, and the remaining Put the silica gel on a silica gel column, elute with ethyl acetate / petroleum ether, collect fractions to obtain 95% cyclic amidine 10c. 10c: Yellow oil, 86%; 1 HNMR (400MHz, CDCl 3 )δ7.80(d,J=8.0Hz,2H),7.22(d,J=7.9Hz,2H),5.80-5....

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Abstract

The invention discloses a preparation method of multi-substituted cyclic amidine, belonging to the technical fields of chemical pharmacy and fine chemical engineering preparation. The preparation of the multi-substituted cyclic amidine is realized, namely, the preparation of multi-substituted alpha-allyl cyclic amidine is realized, the multi-substituted cyclic amidine is efficiently produced at high selectivity by using the reaction of azide and alkyne through metal catalysis and a cyclic rearrangement reaction, and a relative configuration of a product can be effectively controlled. The invention provides a new technical route for efficiently preparing a functionalized cyclic amidine derivative, and is widely applied in the fields of chemical pharmacy and fine chemical engineering.

Description

technical field [0001] The present invention relates to the preparation of multi-substituted cyclic amidines, that is, the preparation of multi-substituted α-allyl cyclic amidines, especially the metal-catalyzed cyclization rearrangement reaction, which can efficiently generate multi-substituted cyclic amidines, and can effectively control the product relative configuration. The invention provides a new technical route for efficiently preparing functionalized cyclic amidine derivatives, and has wide application in the fields of chemical pharmacy and fine chemical industry. Background technique [0002] Amidines are an important class of organic compounds. The amidine functional group has special chemical and biological activities, exists in many natural products and drug molecules, and is also used in functional materials. Cyclic amidines have unique properties and potential uses due to their unique structures. At present, the preparation method of this class of compounds ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D207/22C07D211/72
CPCC07D207/22C07D211/72
Inventor 徐华栋贾志宏徐科沈美华
Owner 山东雪地铝业科技有限公司
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