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Nucleophilic addition reaction method for scandium catalyzed mercaptan to o-quinone methides

A technology of methylene quinone and scandium catalyzing mercaptans, which is applied in the preparation of sulfides and organic chemistry, can solve the problems of cumbersome post-processing operations and unsuitable preparation of compounds, and achieve simple raw materials and reagents, easy separation and purification, The effect of high reaction yield

Active Publication Date: 2018-12-28
山东济清科技服务有限公司
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Problems solved by technology

The reaction research of o-methylene quinone has a long history, and the Michael addition reaction based on P, S and N heteroatoms is relatively mature, but most of the reaction methods still need to use acid-base catalysts, such The reaction method is not suitable for the preparation of compounds containing acid-base sensitive functional groups, and the system needs to be neutralized to neutral after the reaction, and the post-treatment operation is cumbersome

Method used

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  • Nucleophilic addition reaction method for scandium catalyzed mercaptan to o-quinone methides
  • Nucleophilic addition reaction method for scandium catalyzed mercaptan to o-quinone methides
  • Nucleophilic addition reaction method for scandium catalyzed mercaptan to o-quinone methides

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Experimental program
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Effect test

Embodiment 1

[0026]

[0027] In a 100 mL round bottom flask, add 2.00 g (10 mmol) of compound I-1, 1.24 g (20 mmol) of compound II-1, 0.49 g (1 mmol) of solid scandium trifluoromethanesulfonate Sc(OTf) 3 , and finally 20 mL of dry 1,2-dichloroethane was added, and the resulting mixture was stirred and reacted at 30° C. for 10 hours. After the reaction mixture was cooled to room temperature, it was poured into ice water, extracted with 50mL×3 methylene chloride, and the extracted organic phases were combined, washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and remove the solvent to obtain the crude product, which is separated by column chromatography to obtain the pure product of compound III-1. Oily liquid, 2.17g, yield 92%. 1 H NMR (400MHz, CDCl 3 )δ: 7.40 (d, J = 7.4Hz, 2H), 7.32–7.16 (m, 5H), 7.05 (dd, J = 7.6Hz, 1.2Hz, 1H), 6.91 (dd, J = 8.0Hz, 0.7Hz ,1H),6.88–6.82(m,1H),5.39(s,1H),2.49–2.43(m,2H),1.23(t,J=7.4Hz,3H); 13 C NMR (CDCl 3 ,100MHz)δ:155.15,139...

Embodiment 2

[0029]

[0030] In the round bottom flask of 100mL, add 2.00g (10mmol) compound I-1, 1.52g (20mmol) compound II-2, 0.98g (2mmol) solid Sc (OTf) 3 , and finally 25 mL of dry DMF was added, and the resulting mixture was stirred at 40° C. for 3 hours until the reaction was complete. The reaction mixture was cooled to room temperature, poured into water, stirred, extracted with 50mL×3 dichloromethane, combined and extracted organic phases, washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and remove the solvent to obtain the crude product, which is separated by column chromatography to obtain the pure product of compound III-2. Oily liquid, 2.32g, yield 90%. 1 H NMR (400MHz, CDCl 3 )δ7.40(d, J=7.4Hz, 2H), 7.34–7.29(m, 2H), 7.21(ddd, J=15.4Hz, 10.6Hz, 4.4Hz, 2H), 7.03(dd, J=7.6Hz ,1.3Hz,1H),6.95–6.89(m,1H),6.84(td,J=7.6Hz,1.0Hz,1H),5.35(s,1H),2.48–2.39(m,2H),1.61(dd ,J=14.6Hz,7.3Hz,2H),0.95(t,J=7.4Hz,3H); 13 C NMR (CDCl 3 ,100MHz)δ:155.22,139.30,130.1...

Embodiment 3

[0032]

[0033] In the round bottom flask of 100mL, add 2.00g (10mmol) compound I-1, 1.35g (15mmol) compound II-3, 0.12g (0.5mmol) solid Sc(NO 3 ) 3, and finally 50 mL of dry DMSO was added, and the resulting mixture was stirred vigorously at 50 °C for 5 h. After the reaction mixture was cooled to room temperature, it was poured into water, stirred, extracted with 50mL×3 dichloromethane, combined and extracted organic phases were washed once with saturated brine, anhydrous Na 2 SO 4 Dry, concentrate and evaporate the solvent to obtain the crude product, and purify by column chromatography to obtain the pure product of compound III-3. Oily liquid, 2.37g, yield 87%. 1 H NMR (400MHz, CDCl 3 )δ: 7.40 (d, J = 7.4Hz, 2H), 7.31 (dd, J = 13.8Hz, 6.6Hz, 3H), 7.21 (ddd, J = 11.3Hz, 8.7Hz, 4.4Hz, 2H), 7.03 ( dd,J=7.6Hz,1.3Hz,1H),6.92(dd,J=8.0,0.6Hz,1H),6.87–6.80(m,1H),5.31(s,1H),2.35(qd,J=12.5 Hz,6.8Hz,2H),1.83(dt,J=13.4Hz,6.7Hz,1H),0.95(dd,J=8.0Hz,6.8Hz,6H); 13 C NMR (CDCl 3 ...

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Abstract

The invention relates to a nucleophilic addition reaction method for scandium catalyzed mercaptan to o-quinone methides. The method comprises the following steps: dissolving 2-(hydroxyl(phenyl)methyl)phenolic compounds and sulfur alcohol compounds into a solvent, adding a Sc(III) catalyst, stirring and reacting at a temperature of 30-70 DEG C for 5-10 hours; extracting the reacted reaction solution, washing and drying the organic layer, removing the solvent, performing silica gel column chromatography on the residues, thereby obtaining the product. According to the method, a trivalent scandium catalyst is utilized, the method is mild in synthesis condition, small in limitation of replace types of neutral reactions and functional groups and high in yield, and the high-efficiency and environmental-friendly thia-michael addition reaction is realized.

Description

technical field [0001] The invention relates to a thia-Michael addition reaction, in particular to a Sc(III) (scandium)-catalyzed nucleophilic addition reaction method of mercaptan to o-methylenebenzoquinone, which belongs to the technical field of organic synthesis. Background technique [0002] O-methylenebenzoquinone compounds are a class of very active and important intermediates, which are widely used in natural product and medicinal chemistry. Because o-methylene quinone compounds are widely used, the research on their preparation methods has always been the focus of attention of organic synthesis experts. Now there are many methods to prepare such compounds: such as pyrolysis, photochemical reaction, acidic, alkaline conditions, etc., The reaction conditions are harsh. The reaction types of o-methylenebenzoquinones are mainly divided into three categories: nucleophilic addition reactions, cycloaddition reactions and 6π electrocyclization reactions. The reaction rese...

Claims

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Application Information

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IPC IPC(8): C07C319/14C07C323/16
CPCC07C319/14C07C2601/08C07C323/16
Inventor 张硕彭丹赵宁于一涛李冰王峰牟秋红李金辉张方志
Owner 山东济清科技服务有限公司
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