Method for synthesizing 1,3-oxazole-2,4-diketone compounds

A technology of diketones and compounds, which is applied in the field of synthesizing 1,3-oxazole-2,4-diketones, can solve the problems of low yield, high toxicity, low atom economy, etc. Effects of regioselectivity, low toxicity, and high yield

Inactive Publication Date: 2011-04-06
ZHEJIANG UNIV
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Problems solved by technology

[0004] In the past, 1,3-oxazole-2,4-dione compounds were usually directly transformed from other heterocyclic compounds, or α- Hydroxycarboxylates reacted with urea or isocyanate, or α-hydroxyamides reacted with chloroformate or carbonate (ref: Chemical Review, 1958, 58, 63-99; Journal of Medicinal Chemistry, 1991, 34 , 1538-1544; Journal of Medicinal Chemistry, 1994, 37, 322-328; Journal of Medicinal Chemistry, 2002, 45, 1518-1534), the toxicity of isocyanate or methyl chloroformate in the raw material is relatively high, and the atom economy of the reaction Not high, and the general yield is not very high

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  • Method for synthesizing 1,3-oxazole-2,4-diketone compounds

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Experimental program
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Effect test

Embodiment 1

[0022] Potassium carbonate (54.5 mg, 0.39 mmol) was added to the reaction tube, pumped and roasted three times, carbon dioxide gas was introduced, cooled to room temperature, and then added N -Benzyl-3-phenylpropynamide (46.2 mg, 0.20 mmol), and 2 mL dimethyl sulfoxide, stirred, carbon dioxide was introduced into the solution of dimethyl sulfoxide through the catheter, and then the reaction tube was placed at 30 o After stirring in an oil bath of C for 11 hours, take out the carbon dioxide catheter, add 10 mL of water to quench the reaction, extract with ether (15 mL × 3), combine the organic phases, wash with saline once, dry over anhydrous sodium sulfate, and concentrate the solution. Flash column chromatography (petroleum ether / ethyl acetate=20 / 1), obtains solid product ( Z )- N -Benzyl-5-benzoylidene-1,3-oxazole-2,4-dione 34.0 mg, yield 62%, melting point: 158.2-159.2 o C (n-hexane / dichloromethane).

[0023] 1 H NMR (300 MHz, CDCl 3 ) d 7.79-7.70 (m, 2H), 7.50-7.29 (...

Embodiment 2

[0026] By the method described in Example 1, the difference is that the substrate and reagent used are: N -Butyl-3-phenylpropynamide (40.1 mg, 0.20 mmol), potassium carbonate (55.8 mg, 0.40 mmol), the product ( Z )- N -Butyl-5-benzoylidene-1,3-oxazole-2,4-dione 39.0 mg, yield 80%. The product is a solid, melting point: 82.7-83.4 o C (n-hexane / dichloromethane).

[0027] 1 H NMR (300 MHz, CDCl 3 ) d 7.80-7.71 (m, 2H), 7.50-7.36 (m, 3H), 6.76 (s, 1H), 3.65 (t, J = 7.4 Hz, 2H), 1.78-1.62 (m, 2H), 1.46-1.30 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H); 13 C NMR (75 MHz, CDCl 3 ): d 162.4, 152.3, 137.5, 131.0, 130.7, 130.4, 129.0, 113.3, 40.0, 29.6, 19.8, 13.5; MS (m / z): 246 (M + +1, 4.12), 245 (M + , 25.65), 118 (100); IR (KBr, cm -1 ): 1816, 1721, 1666, 1495, 1449, 1413, 1354, 1315, 1264, 1236, 1187, 1082, 1006; Anal. Calcd. for C 14 h 15 NO 3 : C 68.56, H 6.16, N 5.71; Found: C 68.88, H 6.40, N 5.72.

[0028]

Embodiment 3

[0030] By the method described in Example 1, the difference is that the substrate and reagent used are: N -Ethyl-3-phenylpropynamide (34.2 mg, 0.20 mmol), potassium carbonate (55.4 mg, 0.40 mmol), the product ( Z )- N -Ethyl-5-benzoylidene-1,3-oxazole-2,4-dione 28.4 mg, yield 66%. The product is a solid, melting point: 123.6-124.3 o C (n-hexane / dichloromethane).

[0031] 1 H NMR (300 MHz, CDCl 3 ) d 7.85-7.68 (m, 2H), 7.52-7.35 (m, 3H), 6.75 (s, 1H), 3.71 (q, J = 7.2 Hz, 2H), 1.32 (t, J = 7.2 Hz, 3H); 13 C NMR (75 MHz, CDCl 3 ): d 162.1, 152.0, 137.5, 131.0, 130.7, 130.4, 129.0, 113.2, 35.3, 13.0; MS (m / z): 218 (M + +1, 5.78), 217 (M +, 43.70), 118 (100); IR (KBr, cm -1 ): 1813, 1735, 1682, 1496, 1452, 1441, 1415, 1372, 1347, 1320, 1246, 1211, 1169, 1115, 1080, 1045; Anal. Calcd. for C 12 h 11 NO 3 : C 66.35, H 5.10, N 6.45; Found: C 66.31, H 5.33, N 6.46.

[0032]

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Abstract

The invention discloses a method for synthesizing 1,3-oxazole-2,4-diketone compounds. 3-aryl-2-alkyneamide reacts with carbon dioxide under the action of potassium carbonate or cesium carbonate so as to generate a 1,3-oxazole-2,4-diketone compound. The method is easy to operate, raw materials and reagents are readily available and the reaction has high regioselectivity; the product is easy to separate and purify and has low toxicity, high yield and readily available raw materials; and the method is suitable for synthesizing various substituted 1,3-oxazole-2,4-diketone compounds.

Description

technical field [0001] The invention relates to a method for synthesizing 1,3-oxazole-2,4-dione compounds, that is, through the reaction of 3-aryl-2-alkyne amides and carbon dioxide, highly regioselective synthesis of 1,3-oxazole Azole-2,4-dione compounds. [0002] Background technique [0003] 1,3-oxazole-2,4-dione compounds are one of the most important intermediates in organic synthesis and one of the most common structural units in natural products. They have a variety of important physiological activities and are widely used in biotechnology. fields, medicine and pesticides have huge development and utilization value. [0004] In the past, 1,3-oxazole-2,4-dione compounds were generally directly converted from other heterocyclic compounds, or obtained by the reaction of α-hydroxy carboxylate with urea or isocyanate, or α- Reaction of hydroxyamides with chloroformates or carbonates (references: Chemical Review, 1958, 58, 63-99; Journal of Medicinal Chemistry, 1991,...

Claims

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Application Information

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IPC IPC(8): C07D263/44C07D413/06
Inventor 麻生明傅春玲陈国飞
Owner ZHEJIANG UNIV
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