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Synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone

A technology of acyloxyacylmethyl and synthesis method, applied in the direction of organic chemistry, etc.

Active Publication Date: 2014-12-31
DALIAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far there is no method for the simple synthesis of β-alkoxyacylmethyl-γ-butyrolactone through a one-pot reaction. To the complex process of separation and purification of intermediate compounds

Method used

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  • Synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone
  • Synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone
  • Synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] The following reaction was carried out by method 1 to obtain the product.

[0058] The following reaction was carried out by method 1 to obtain the product.

[0059] Add [CuHPPh 3 ] 6 (4.890 g, 15 mmol CuH), toluene (30 mL), stirred to dissolve, cooled to -30°C, and maintained at this temperature in subsequent reactions. A solution of methyl 4-oxo-4-phenylbutyrate (2.300 g, 12.0 mmol) and methyl 2-butenoate (1.6 mL, 15.1 mmol) in toluene (10 mL) was added dropwise to the above solution, After about 20 min of dripping, the stirring reaction was continued for 0.5 h. Warm to room temperature, stir for 0.5 h, then add 20 mL of saturated NH 4 Cl aqueous solution, and continue stirring for 0.5 h. Stand to separate phases. The aqueous phase (3×10 mL) was extracted with toluene, and the combined organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain γ-phenyl-γ-(1-methyl oxyacyl)p...

Embodiment 2

[0062] The following reaction was carried out by method 2 to obtain the product.

[0063] Vacuumize the dried reaction bottle, inject nitrogen, repeat three times, add [CuHPPh 3 ] 6 (16 mg, 0.049 mmol CuH) and toluene (1 mL), stirred at 25°C for 2 min to make [CuHPPh 3 ] 6 All melted. Add poly(methylhydrogensiloxane) (120 mL, 2.00 mmol SiH) and methyl 4-oxo-4-phenylbutyrate (0.193 g, 1.00 mmol) to the above solution, stir for 2 min and then add acrylic acid A solution of methyl ester (137 mL, 0.152 mmol) in toluene (2 mL). After stirring for 2.0 h, add 2 mL of 1.5 mol / L NH 4 Methanol-water solution (methanol:water = 3:1) of F, stirred for 0.5 h, then stood still for phase separation, the aqueous phase filtrate was extracted with dichloromethane (3×10 mL), and the combined organic phase was washed with saturated brine, After drying over anhydrous sodium sulfate and concentration, the product γ-phenyl-γ-(1-methoxyacyl)ethyl-γ-butyrolactone (0.203 g, yield 82%) was obtaine...

Embodiment 3

[0067] Add CuF (5.0 mg, 0.060 mmol), 1,1'-bis(di-phenylphosphino)ferrocene, (33.2 mg, 0.060 mmol), ethyl acetate to a dry reaction flask under nitrogen atmosphere (3 mL), stirred at 40°C for 30 min. Add diphenylsilane (2.22 mL, 24.0 mmol SiH) to the above solution, stir for 30 min, then add 4-oxo-4-phenylbutyric acid methyl ester (2.30 g, 12 mmol), drop into methyl acrylate Ethyl acetate solution (10 mL) of ester (2.20 mL, 24 mmol) was dropped in about 10 min and stirred for 5 h. Add 30 mL of 1.5 mol / L NH to the reaction mixture 4 Methanol-water solution of F (methanol: water = 3:1), stirred for 0.5 h and allowed to stand for phase separation. The aqueous phase was extracted with ethyl acetate (3 x 30 mL). The combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain the product γ-phenyl-γ-(1-methoxyacyl)ethyl-γ-butyrolactone (1.63 g, yield 55%).

[0068]

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PUM

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Abstract

The invention belongs to the field of chemical technology, and in particular to a synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone. CuH compound as a reducing agent reacts with keto ester, alpha, beta-unsaturated carboxylic ester; keto ester, alpha,beta-unsaturated carboxylic ester, a silicon hydride or boron hydride react with each other with CuH compound as the catalyst; and other copper compound, phosphine ligand, silicon hydride or boron hydride react with each other to generate a catalyst, which directly catalyses silicon hydride or boron hydrogen to react with keto ester, alpha,beta-unsaturated carboxylic ester. The synthesis reaction is carried out through the above three methods. reaction of this three method of The method of the invention uses cascade reaction for synthesis, three steps of reaction are carried out continuously in the same reaction vessel; separation of intermediates is not required, so as to avoid the separation process and the resulting loss; and the method has simple operation, improved reaction efficiency, and good application value.

Description

technical field [0001] The invention belongs to the technical field of chemical industry, and specifically relates to a synthesis method of gamma-alkoxyacylmethyl-gamma-butyrolactone and delta-alkoxyacylmethyl-delta-valerolactone. Background technique [0002] γ-butyrolactone and δ-valerolactone compounds are important organic synthesis intermediates and biologically active substances. from plant endophytes Pestalotiopsis photiniae γ-butyrolactone substances 1 and 2 were isolated from , which had inhibitory effect on breast cancer cell line MDA-MB-231 (Ding, G.; Zheng, Z. H.; Liu, S. C.; Zhang, H.; Guo, L. D.; Che, Y.S. J. Nat. Prod ., 2009, 72 , 942). from lichens Punctelia microsticta (Muell. Arg.) Krog Paraconic acid 3 and its derivatives 4 isolated from the study have anti-inflammatory and anti-tumor activities (Maier, M. S.; Marimon, D. I. G..; Stortz, C. A.; Adler, M. T. J. Nat. Prod . 1999, 62 , 1565; Park, B. K.; Nakagawa, M.; Hirota, A.; Nakayama, M. J. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/33C07D309/30
CPCC07D307/33C07D309/30
Inventor 李争宁王崇年姜岚
Owner DALIAN UNIV
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