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High-efficiency catalyst for catalyzing amine and carbodiimide to process addition reaction and application

A carbodiimide and addition reaction technology, which is applied in the direction of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, cyanide reaction preparation, etc., can solve the problem of insufficient economy and achieve catalyst volume Less, easy post-processing, cost reduction effect

Inactive Publication Date: 2008-09-17
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2003, the Richeson group in Canada reported that the structural formula is {(Me 2 N)C(NiPr) 2 } 2 Ti=NC 6 f 5 Titanium (J.Am.Chem.Soc.125, 27, 2003 8101) and vanadium imides (F.Montilla, A.Pastor, A.Galindo, J.Organomet.Chem.2004, 689, 993-996 ) can be used as a catalyst to successfully catalyze the addition reaction of primary aromatic amines and carbodiimides to the corresponding guanidines, but secondary amines cannot be used for this reaction
[0006] The above research has achieved many results, but the existing reported rare earth catalysts are all carried out under solvent conditions. With the reported catalyst trimethylsilylamide ytterbium, 1% catalyst dosage is required. At a reaction temperature of 60 ° C, the reaction 4 hours, which is obviously not economical enough

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Embodiment one: Catalyst Sm[N(TMS) 2 ] 2 (THF) 3 Synthesis

[0025] In the reaction flask that has been dehydrated and deoxygenated, add an appropriate amount of SmI with a syringe under the protection of argon. 2 THF solution, then at room temperature, press SmI 2 than NaN(TMS) 2 To a molar ratio of 1:2, add NaN(TMS) by syringe 2 The THF solution was reacted for 6 hours, the solvent THF was removed in vacuo, the residue was extracted with hexane, the precipitate was removed by centrifugation, and the clear liquid was transferred to another crystallization bottle. After concentration, the tube was sealed and placed in a refrigerator (-20°C) to freeze , get Sm[N(TMS) 2 ] 2 (THF) 3 of tan crystals.

Embodiment 2

[0026] Embodiment two: Sm[N(TMS) 2 ] 2 (THF) 3 Catalyzing the reaction of p-fluoroaniline and N,N'-diisopropylcarbodiimide to synthesize guanidine

[0027] In the reaction flask that has been treated with dehydration and deoxygenation, add 0.004 gram of catalyst Sm[N(TMS) under the protection of argon. 2 ] 2 (THF) 3 , and then sequentially added 0.187 milliliters of N, N'-diisopropylcarbodiimide and 0.11 milliliters of p-fluoroaniline with a syringe, the mixture was stirred at room temperature, and the system became solid after 2 minutes of reaction, and then, after another minute of reaction, Terminate the reaction with 0.5ml of water, then extract 3 times with dichloromethane, 10ml each time, the extract is dried over anhydrous sodium sulfate, filtered, and finally the solvent is removed under reduced pressure, and 0.278 grams of the product is obtained by recrystallization with hexane. The rate is 98%.

Embodiment 3

[0028] Embodiment three: Yb[N(TMS) 2 ] 2 (THF) 3 Catalyzing the reaction of p-fluoroaniline and N,N'-diisopropylcarbodiimide to synthesize guanidine

[0029] Preparation of Catalyst Yb[N(TMS) 2 ] 2 (THF) 3 , the steps refer to Example 1, the difference is that the SmI 2 Change to YbI 2 .

[0030] In the reaction flask that has been processed through dehydration and deoxygenation, add 0.005 gram of catalyst Yb[N(TMS) under argon protection 2 ] 2 (THF) 3 , then add 0.23 milliliters (1.5 millimoles) of N, N'-diisopropylcarbodiimide and 0.143 milliliters (1.5 millimoles) of p-fluoroaniline successively with a syringe, and the mixture is stirred at room temperature, and the reaction system becomes Solid, stop the reaction with 0.5 ml of water after one minute, then extract 3 times with dichloromethane, 10 ml each time, dry the extract with anhydrous sodium sulfate, filter, then remove the solvent under reduced pressure, and recrystallize with hexane to obtain the product ...

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Abstract

The invention discloses a complex based on divalent rare earth as center ion, which is represented in a general formula as L 2 LnL', wherein Ln means center ion that is bivalent ion of the rare earth metal, which is selected from one of samarium, europium, and ytterbium in the lanthanides; L and L' mean two ligands, L is selected from one of 2,6-butylated hydroxytoluene, di-trimethyl silylamino, dimethylcyclo-pentadienyl, N,N'-dimethylamino bridged bisphenol; L' is a complex solvent, which is selected from one of tetrahydrofuran and glycol dimethyl ether. The complex has the advantages of being used as a reaction catalyst to additionally synthesize guanidine by the amine and carbodiimide, catalyzing the amine and carbodiimide in an extremely high activity to additionally react at a moderate temperature, having wide adaptability for the reaction substrate, showing the extremely high activity for the amine in aromatic series and the fat, and conducting reaction without the solvent.

Description

technical field [0001] The invention relates to a catalyst for synthesizing guanidine, in particular to a catalyst for preparing guanidine through the addition reaction of amine and carbodiimide. Background technique [0002] Guanidine is a class of compounds with important physiological activity, which widely exists in drugs and natural products as the main skeleton; guanidine derivatives are also widely used as an important auxiliary ligand to stabilize main group metals, transition metals, and Organometallic compounds of rare earth metals. Therefore, the study of its synthesis has important theoretical and practical value. [0003] The commonly used method for synthesizing guanidine is to use an amine and a suitable electrophilic amidine reagent or a reagent that can generate a guanidine structure to react. This method uses the amine to replace the leaving group on the amidine, so the amidine The substituent on nitrogen is the protecting group of carbamate, which is use...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J31/26C07C227/02C07B43/00
Inventor 沈琪杜柱陈晓妞朱雪华
Owner SUZHOU UNIV
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