5878-19-3Relevant articles and documents
Bifunctional Catalysis of the Dedeuteration of Methoxyacetone-1,1,3,3,3-d5
Hine, Jack,Sinha, Ashoke
, p. 2186 - 2190 (1984)
The dedeuteration of methoxyacetone-1,1,3,3,3-d5 is subject to bifunctional catalysis by 3-(dimethylamino)-propylamine (3DP) and (1R,2S,3R,4R)-3-((dimethylamino)methyl)-1,7,7-trimethyl-2-norbornamine (DTN).These catalysts act by using their primary amino groups to transform the ketone to an iminium ion and their tertiary amino groups to transfer a deuteron internally, changing the iminium ion to an enamine.Although analogous monofunctional bases favor exchange at the methyl position relative to exchange at the methylene position by factors up to 4-fold, bifunctional catalysis by the diamines used favors the methyl group by 11- to 15-fold.Exchange at the methylene group in the presence of DTN was strongly stereoselective.The pro-S deuteron was removed 12-20 times as rapidly as the pro-R deuteron.This is the result of the steric effect of the methoxy substituent.
Hine et al.
, p. 2664,2665,2668 (1967)
Regio- and chemoselective rearrangement of terminal epoxides into methyl alkyl and aryl ketones
Tian, Yingying,Jürgens, Eva,Kunz, Doris
supporting information, p. 11340 - 11343 (2018/10/31)
The development of the highly active pincer-type rhodium catalyst 2 for the nucleophilic Meinwald rearrangement of functionalised terminal epoxides into methyl ketones under mild conditions is presented. An excellent regio- and chemoselectivity is obtained for the first time for aryl oxiranes.
Method of synthesizing methoxyacetone through catalytic oxidation
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Paragraph 0021-0025; 0027; 0030; 0033; 0036; 0039, (2017/12/29)
The invention discloses a method of synthesizing methoxyacetone through catalytic oxidation. The method comprises the steps of mixing 1-methoxyl-2-propanol with sodium tungstate, tungstic acid and acetic acid, and raising temperature to 80-100 DEG C; adding hydrogen peroxide dropwise into the mixture, so as to obtain a reaction solution; naturally cooling the reaction solution to room temperature, and filtering and separating to obtain a filter cake and a filtrate; regulating pH of the filtrate to 6-7, transferring the filtrate into a rectifying tower and heating and rectifying, separating and purifying in a rectifying kettle to obtain a product methoxyacetone and residual liquid in the rectifying kettle; washing and drying the obtained filter cake to obtain tungstic acid; and mixing the residual liquid in the rectifying kettle and liquid caustic soda, raising temperature to dissolve and keeping warm, adding ethanol crystal, separating, and stoving to obtain the sodium tungstate. The catalyst is sodium tungstate that is low-cost, is easy to recycle, and causes low loss compared with other precious metal catalysts; in production, heavy metal contamination is prevented, fewer three wastes are generated, so that the method is environmentally friendly; and the conversion rate of 1-methoxyl-2-propanol reaches 93%, so that the method is suitable for industrial production.
