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Fluorine-containing heterocyclic compound and preparation method thereof

A compound and substrate technology, applied in the field of preparation of 2-oxazolinone compounds, to achieve the effect of mild reaction conditions

Active Publication Date: 2016-12-14
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although many methods for the synthesis of 2-oxazolinones have been reported, there is no method for synthesizing trifluoromethyl-containing 2-oxazolinones from cheap, easy-to-get and easy-to-handle raw materials

Method used

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  • Fluorine-containing heterocyclic compound and preparation method thereof
  • Fluorine-containing heterocyclic compound and preparation method thereof
  • Fluorine-containing heterocyclic compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0088] Example 1 3-benzyl-5-phenyl-5-(2,2,2-trifluoroethyl)-2-oxazolinone (3-benzyl-5-phenyl-5-(2,2, 2-trifluoroethyl) oxazolidin-2-one) (hereinafter referred to as compound 2a) preparation

[0089]

[0090] Table 1: Optimal selection of reaction conditions

[0091]

[0092]

[0093] [a]: The yield listed in the table is the GC yield using n-dodecane as the internal standard, and the separation yield is in brackets; [b]: the amount of alkali is 0.6mmol; [c]: 25 degrees Celsius; [d ]: use the first generation of Togni reagent; [e]: use Umemoto reagent; N.D. = not detected; [f]: 80 degrees Celsius; [g] 0.1atm; [h] 20atm.

[0094] According to the conditions shown in Table 1, compound 2a was prepared with 1a as the substrate. The specific operation was as follows: 0.04mmol catalyst and 0.44mmol second-generation Tognis reagent (139mg) were added to a 25mL Schlenk tube with a magnet, and the above operations were carried out in a glove box. completed, then take the reac...

Embodiment 2 to Embodiment 32

[0097] Example 2 to Example 32 Preparation of 2-oxazolinone compounds 2aa, 2ab, 2ac, 2ad, 2ae, 2af, 2b-2z

[0098] Explanation: 2-oxazolone compound 2aa means that the compound is prepared from substrate 1aa, and the naming rules of other 2-oxazolone compounds are the same.

[0099] Prepare 2-oxazolinone compounds 2aa, 2ab, 2ac, 2ad, 2ae, 2af, 2b-2z according to the conditions shown in Table 2 and Table 3. The specific operations are as follows: add 0.04mmol tetraethylcyanide copper hexafluorophosphate (14.9mg), 0.44mmol second-generation Tognis reagent (139mg), 0.40mmol allylamine derivative (if the substrate is solid), the above operations are completed in the glove box, and then The reaction tube was taken out of the glove box, and the 2 Gas replacement three times, followed by CO 2 Add 0.40mmol allylamine derivative (if the substrate is a liquid), 4mL anhydrous acetonitrile, 0.80mmol (120μL) 1,8-diazabicyclo[5.4.0]undec-7- ene (DBU). Then, at one atmosphere of CO 2 Ti...

Embodiment 33 to Embodiment 35

[0250] Application of Example 33 to Example 35 Compound 2a

[0251]

[0252] Compounds 3, 4 and 5 were obtained in high yields from compound 2a. The specific preparation method is as follows.

[0253] N-Benzyl-N-(4,4,4,-trifluoro-2-hydroxy-2-phenylbutyl)-3-enbutyramide (compound 3)

[0254] N-benzyl-N-(4,4,4-trifluoro-2-hydroxy-2-phenylbutyl)but-3-enamide

[0255]

[0256] To a solution of 0.2 mmol (67 mg, 1.0 equiv) of compound 2a in THF (1 mL) was added dropwise 0.6 mmol (3.0 equiv) of allylmagnesium bromide at -78°C. After maintaining the reaction at the above temperature for 3 hours, add 1 mL of saturated ammonium chloride solution, and when the reaction system rises to room temperature, extract 3 times with diethyl ether (3×5 mL), then spin dry, and perform column chromatography (PE:EA= 5:1) separation and purification to obtain the target compound 3 (72 mg) as a colorless oily liquid with a yield of 96%.

[0257] R f (pentane / EtOAc 5:1) = 0.5; 1 H NMR (400MHz...

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Abstract

The invention relates to a method for preparing a 2-oxazolinone compound containing a trifluoromethyl group from an allyl amine compound in virtue of carbon dioxide. Specifically, the allyl amine compound as shown in a formula 1 which is described in the specification reacts with CO2 in a solvent in the presence of a copper catalyst, alkali and a trifluoromethylation reagent so as to prepare the 2-oxazolinone compound as shown in a formula 2 which is described in the specification. In the formula 2, R<1>, R<2>, R<4> and R<5> are independently selected from a group consisting of H, halogen, a cyano group, an alkyl group, a carbonyl group, an ester group, an aryl group, a heteroaryl group and the like, R4 or R5 can optionally form a ring with R1, and the alkyl group, the carbonyl group, the ester group, the aryl group and the heteroaryl group can be optionally substituted by halogen, the alkyl group or the like; and R3 is H, halogen, an alkyl group, an aryl group, or the like.

Description

technical field [0001] The invention relates to the synthesis of fluorine-containing heterocyclic compounds, in particular to a method utilizing CO 2 A preparation method for preparing trifluoromethyl-containing 2-oxazolinone compounds from allylamine compounds. Background technique [0002] As we all know, CO 2 The greenhouse effect has caused many adverse effects on the global environment, how to reduce CO 2 Effective utilization is an urgent problem to be solved. It is a very effective way to achieve its efficient utilization through chemical conversion, and this way can also provide the possibility to solve resource problems. In organic synthesis, CO 2 It can be used as a cheap, easy-to-obtain, safe, non-toxic, and reusable C1 synthon, and has broad application prospects. But so far, the chemical means that can efficiently utilize carbon dioxide are very limited, which is inseparable from its thermodynamic stability and kinetic inertia. [0003] Due to CO 2 The th...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D263/20C07D263/24C07D263/62C07D263/52C07D413/04C07C231/10C07C233/20C07C213/00C07B53/00C07C215/30C07C209/62C07C211/29
CPCC07B53/00C07B2200/07C07B2200/09C07C209/62C07C213/00C07C231/10C07D263/20C07D263/24C07D263/52C07D263/62C07D413/04C07C233/20C07C215/30C07C211/29
Inventor 余达刚叶剑衡颜思顺周文俊宋磊鞠涛殷珠宝张振李静
Owner SICHUAN UNIV
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