Method for preparing 1,4-dicarbonyl derivative

A technology of derivatives and dicarbonyl, applied in the field of preparation of organic compounds, can solve the problems of narrow use range of substrates, narrow range of applicable substrates, harsh reaction conditions, etc., to avoid the use of precious metal catalysts, easy to obtain, and short reaction time short effect

Active Publication Date: 2013-12-25
安徽(淮北)新型煤化工合成材料基地管理委员会科技服务中心
View PDF2 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, the research group of Charles K. Zercher reported that 1,4-dicarbonyl derivatives were prepared by using 1,3-dicarbonyl and organozinc reagents through a two-step method; however, the reaction conditions of this method are harsh and require an anhydrous and oxygen-free environment (see : Ramona Hilgenkamp; Charles K. Zercher. Org. Lett(ACS). 2001, 3(19), 3037-3040); Aiwen Lei's research group reported that acetophenone derivatives and chlorinated diphenyl Ethyl ketone is used as a reactant, and the synthesis of 1,4-dicarbonyl derivatives is realized through a t

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for preparing 1,4-dicarbonyl derivative
  • Method for preparing 1,4-dicarbonyl derivative
  • Method for preparing 1,4-dicarbonyl derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022]

[0023] Cobalt acetylacetonate (Ⅱ) Co(acac) 2 (0.2 mmol, 51.6 mg), compound 1a (2 mmol, 380 uL), compound 2a (6 mmol, 816 uL), tert-butanol hydroperoxide TBHP (1.1 mL), Et 3 N 8 mL was charged into the reactor; then the system was heated in the air at 100 °C for about 24 hours, quenched with saturated sodium sulfite, extracted with ethyl acetate (40 mL × 3), dried over anhydrous sodium sulfate, and passed a simple The product can be obtained by column chromatography 3a , the yield is 86%.

[0024] 1 H NMR (400 MHz, CDCl 3 ) δ 7.92 (d, J = 8.0 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 4.15 (q, J = 8.0 Hz, 2H), 3.50 – 3.42 (m, 1H), 3.16 – 3.06 (m, 1H), 3.05 – 2.96 (m, 1H), 1.34 (s, 9H), 1.30 – 1.22 (m, 6H); 13 C NMR (100 MHz, DMSO) δ 197.6, 175.1, 156.2, 133.9, 127.8, 125.4, 59.8, 41.3, 34.8, 34.5, 30.7, 16.9, 14.0. HRMS: Anal. 17 h 24 NaO 3 : 299.1623, Found: 299.1630. IR (KBr, cm -1 ): ν 2970, 2907, 2874, 1732, 1689, 1606, 1568, 1406.

Embodiment 2

[0026]

[0027] Cobalt acetylacetonate (Ⅱ) Co(acac) 2 (0.1 mmol, 25.8 mg), compound 1a (2 mmol, 380 uL), compound 2a (6 mmol, 816 uL), tert-butanol hydroperoxide TBHP (1.1 mL), Et 3 N 8 mL was loaded into the reactor; then the system was heated in the air at 100 °C for about 24 hours, quenched with saturated sodium sulfite, extracted with dichloromethane (40 mL × 3), dried over anhydrous sodium sulfate, and passed a simple The product can be obtained by column chromatography 3a , the yield is 75%.

Embodiment 3

[0029]

[0030] Cobalt acetylacetonate (Ⅱ) Co(acac) 2 (0.4 mmol, 103.2 mg), compound 1a (2 mmol, 380 uL), compound 2a (6 mmol, 816 uL), tert-butanol hydroperoxide TBHP (1.1 mL), Et 3 N 8 mL was charged into the reactor; then the system was heated in the air at 100 °C for about 24 hours, quenched with saturated sodium sulfite, extracted with ethyl acetate (40 mL × 3), dried over anhydrous sodium sulfate, and passed a simple The product can be obtained by column chromatography 3a , the yield is 70%.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention discloses a method for preparing a 1,4-dicarbonyl derivative. The method comprises the following step of performing an oxidative coupling reaction on olefins in an organic solvent by taking a styrene derivative and a bromine-containing compound as reactants, a metallic cobalt compound as a catalyst and tertiary butanol hydrogen peroxide as an oxidizing agent, thereby preparing the 1,4-dicarbonyl derivative. The method disclosed by the invention is moderate in reaction condition, and simple in reaction process and aftertreatment because being only performed in the air, so that the 1,4-dicarbonyl derivative can be obtained by performing a simple column chromatography after the reaction is finished. In addition, raw materials for the reaction can be obtained widely, so that the method conforms to the requirement and the direction of the modern environment-friendly chemical development. Thus, the method has an industrial application value.

Description

technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and in particular relates to a catalytic preparation method of 1,4-dicarbonyl derivatives. Background technique [0002] 1,4-dicarbonyl derivatives are a very important structural unit, which widely exist in natural products and drug molecules with physiological and pharmaceutical activities, and are also very important intermediates in organic synthesis, used to synthesize a variety of rings Compounds and five-membered heterocyclic compounds, such as cyclopentenone, furan, pyrrole, thiophene. The synthesis of 1,4-dicarbonyl derivatives has attracted the attention of many researchers. [0003] At present, the methods for preparing 1,4-dicarbonyl derivatives mainly include: the addition of acyl anions to unsaturated carbonyl compounds, the chain extension reaction of 1,3-dicarbonyl, the substitution reaction of α-halogenated compounds to ketones, Oxidative coupling react...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
IPC IPC(8): C07B41/06C07C67/343C07C69/738C07C271/28C07C269/06C07C255/57C07C255/40C07C253/30C07D213/55C07D333/28C07D307/33C07C49/792C07C49/76C07C49/784C07C45/27C07D211/74C07C235/78C07C231/12C07D295/182
Inventor 万小兵张凤杜鹏姜捷文姜秋石刘春梅
Owner 安徽(淮北)新型煤化工合成材料基地管理委员会科技服务中心
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap