1118-71-4Relevant articles and documents
Synthesis of Sterically Hindered β-Diketones via Condensation of Acid Chlorides with Enolates
Crossman, Aaron S.,Larson, Alec T.,Shi, Jake X.,Krajewski, Sebastian M.,Akturk, Eser S.,Marshak, Michael P.
, p. 7434 - 7442 (2019)
Bulky β-diketones have rarely exceeded dipivaloylmethane (DPM) in steric demand, largely due to synthetic limitations of the Claisen condensation. This work demonstrates hindered acid chlorides to be selective electrophiles in noncoordinating solvents for condensations with enolates. An improved synthesis of DPM is described (90% yield), and crowded β-diketones featuring bulky o-biphenyl or m-terphenyl fragments were prepared in good to excellent yields. These compounds are anticipated to have a steric profile far greater than that of DPM. General reaction conditions and mechanistic considerations are included.
Kopecky et al.
, p. 1036 (1962)
AUTOMATIC ASSEMBLY OF SKELETON STRUCTURES. 3. STEREOSELECTIVE SYNTHESIS, STEREOCHEMISTRY, AND CYCLIZATION OF d,l-α,α'-DIOXY-α,α'-DI-tert-BUTYLGLUTARIC ACID
Vystorop, I. V.,El'natanov, Yu. N.,Kostyanovskii, R. G.
, p. 1227 - 1234 (1992)
Stereoselective synthesis of d,l-α,α'-dioxy-α,α'-di-tert-butylglutaric acid hydroxyiminolactonitrile (3) was conducted by the reaction of dipivaloylmethane with HCN in ether.The corresponding hydroxylacetonitrile (4) and amide (5), acid (6), and its ester (7), from which dilactone (8) was synthesized with preparative yields, were obtained from 3.Benzyl amide (9) was obtained by the reaction of 8 with BnNH2.The iminolactone structure 3 of dipivaloylmethane bis-cyanohydrin, the cis-pseudo-a orientation of the functional substituents in 3-7 and 9, and the structureof the dilactone 8 were confirmed by the 1H, 13C NMR, IR and mass spectra.Keywords: stereoselective synthesis, stereochemistry, cyclization, γ-lactone, 1H and 13C NMR, mass spectra.
Method for synthesizing 1, 3-dicarbonyl compound based on terminal alkyne and acyl halide by one-pot process
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Paragraph 0069-0074; 0135-0137, (2020/07/21)
The invention belongs to the technical field of catalytic synthesis, and discloses a method for synthesizing a 1, 3-dicarbonyl compound by a one-pot process, and the method comprises the following steps: by using simple palladium and copper salts as catalysts, reacting terminal alkyne with acyl halide at 0-80 DEG C for 0.5-12 hours under the action of trifluoromethanesulfonic acid to obtain the 1,3-dicarbonyl compound, wherein the molar ratio of the terminal alkyne to the acyl halide to the palladium salt to the copper salt to the trifluoromethanesulfonic acid is 1 to (1 to 2) to (0.00001 to0.10) to (0.00001 to 0.10) to (0.00004 to 0.40); the catalysts used in the method are common the commercialized palladium salt and copper salt, reagents used in the reaction are commercialized reagents, in addition, the raw materials are cheap and easy to obtain, functional group tolerance is good, reaction conditions are mild, operation is easy and convenient, and atom economy is high.
Synthesis method of 2,2,6,6-tetramethyl-3,5-heptadione
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Paragraph 0052-0055, (2017/08/27)
The invention discloses a synthesis method of 2,2,6,6-tetramethyl-3,5-heptadione. The synthesis method comprises the following steps: a, material feeding: mixing methyl trimethylacetate, alkali and a solvent, and uniformly stirring for 0.5 to 3 hours to obtain a mixed solution; b, reaction: continuously stirring the mixed solution in the step a under a heating condition at the temperature of 20 to 60 DEG C, slowly dripping tert-butyl methyl ketone into the mixed solution, and generating reaction at normal pressure for 8 to 48 hours to obtain reaction liquid containing a product; c, purification: adding water into the reaction liquid in the step b, uniformly stirring, and performing purification. Due to the mode, the synthesis method disclosed by the invention is easy to operate, low in cost and favorable for realizing industrialization, and can meet the technological requirement on green chemistry.