52776-41-7

Upstream product

• 594-71-8 2-chloro-2-nitro-propane 
• 57204-88-3 propiophenone lithium enolate 
• 50902-98-2 1-phenyl-2,3,3-trimethylcyclopropene 
• 78706-73-7 2,3-dimethyl-3-nitro-1-phenyl-1-butanone 
• 563-80-4 3-methyl-butan-2-one 
• 98-07-7 Benzotrichlorid 
• 61541-58-0 3,3-Bis(methylthio)-2-methyl-1-phenyl-2-propen-1-one 
• 917-54-4 methyllithium 
• 513-35-9 2-methyl-but-2-ene 
• 7646-78-8 tin(IV) chloride 
• 98-88-4 benzoyl chloride 
• 28143-80-8 Trifluoro-methanesulfonic acid 1,2-dimethyl-propenyl ester 
• 455-32-3 benzoyl fluoride 
• 100-52-7 benzaldehyde 

Downstream Products

• 54440-17-4 2,3,3-trimethyl-indan-1-one 
• 82323-79-3 2,3-dimethyl-1-phenyl-2-buten-1-one tosylhydrazone 
• 65103-90-4 1-Methoxy-1-phenyl-2,3-dimethyl-2-buten 
• 33508-02-0 1-phenyl-2,3,3-trimethyl-2,3-dihydro-1H-indene 
• 82323-76-0 5-phenyl-3,3,4-trimethyl-3H-pyrazole 
• 82323-72-6 2,3-dimethyl-1-phenyl-1-diazo-2-butene 
• 50902-98-2 1-phenyl-2,3,3-trimethylcyclopropene 

Relevant academic research and scientific papers

Ni-Catalyzed 1,2-Acyl Migration Reactions Triggered by C-C Bond Activation of Ketones

A Ni-catalyzed 1,2-acyl migration triggered by C-C bond cleavage was developed. The process of 1,2-acyl migration followed by olefin isomerization provides a convenient access to α,β-unsaturated ketones, which are well-known building blocks in organic syn

Method for synthesizing polysubstituted alpha, beta unsaturated ketones

The invention particularly relates to a method for synthesizing polysubstituted alpha, beta unsaturated ketones. The method comprises the following steps: 1, adding Ni(cod), an N-heterocyclic carbene ligand, Cs2CO3 and a beta, gamma unsaturated ketone into a non-polar aprotic organic solvent, and mixing to obtain a mixture; 2, adding the mixture obtained in the step 1 into a dried container, reacting for 10-40 hours at the reaction temperature of 120-180 DEG C, and cooling to room temperature after the reaction is finished, so as to obtain a crude product; 3, purifying. According to the method, cheap Ni(cod) is adopted as a catalyst, carbon-carbon bonds are activated by a transition metal, power is provided for the reaction through isomerization of double bonds, the synthesis methodis simple, the substrates are stable and cheap, the reaction is less limited by the substrate, and the substrates are wide in application range.

Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls

2,3-Dichloropyridine N-oxide, a novel oxygen transfer reagent, allows the conductance of the gold(I)-catalyzed oxidation of alkynes to 1,2-dicarbonyls in the absence of any acid additives and under mild conditions to furnish the target species, including those derivatized by highly acid-sensitive groups. The developed strategy is effective for a wide range of alkyne substrates such as terminal- and internal alkynes, ynamides, alkynyl ethers/thioethers, and even unsubstituted acetylene (40 examples; yields up to 99%). The oxidation was successfully integrated into the trapping of reactive dicarbonyls by one-pot heterocyclization and into the synthesis of six-membered azaheterocycles. This synthetic acid-free route was also successfully applied for the total synthesis of a natural 1,2-diketone.

Enones from Acid Fluorides and Vinyl Triflates by Reductive Nickel Catalysis

A nickel-catalyzed reductive coupling between acid fluorides and vinyl triflates has been described. This method provides an efficient access to various enones and avoids the requirement for acyl or vinyl metallic reagents in the conventional approaches.

Features of the chromatography-mass spectrometric identification of condensation products of the carbonyl compounds

By the example of the condensation products of acetone with the simplest aromatic carbonyl compounds it was shown that the joint interpretation of mass spectrometric and chromatographic data in conjunction with a priori assumptions about the nature of the chemical structure allows the detection of the components of reaction mixtures that were not previously characterized by standard mass spectra or by retention indices on standard stationary phases. A necessary condition for solving such problems is creating a hypothesis about the sample composition that is possible for the expected products of the known organic reactions.

Identification of alkylarene chloromethylation products using gas-chromatographic retention indices

Gas-chromatographic retention indices on standard nonpolar polydimethylsiloxane stationary phases allow identification of products formed by known organic reactions even without using mass-spectrometric data. The efficiency of this approach was demonstrated by the example of identification of previously uncharacterized chloromethyl derivatives of alkylarenes, including structural isomers of compounds containing several chloromethyl groups, directly in reaction mixtures. Chromatographic analysis of such reaction mixtures allows identification of positional isomers of the starting alkylarenes even when they are present simultaneously. The retention indices were determined for the first time for more than 50 alkyl-(chloromethyl)arenes, by-products of chloromethylation, and chloromethyl derivatives of the simplest alkyl phenyl ketones. Nauka/Interperiodica 2007.

Cathodic Addition of Benzylidyne Trichloride to Ketones and Aldehydes

Ketones are converted to homologated enones 7a-g in good yields by cathodic addition of benzylidyne trichloride (1d).As intermediates α-Chlorooxiranes 6 are assumed, which rearrange via α-keto carbenium ions 9 to enones.The intermediacy of 9 is supported by the addition of 1d to norcamphor, where the products indicate equilibrating norbornyl cations as intermediates. α,β-Unsaturated ketones lead depending on steric shielding of the double bond to the cyclopropane 23 as 1,4-adduct or the enone 26 as 1,2-adduct.With aldehydes and 1d, α-chloro or βhydroxy ketones, the conversion products of 2-chlorooxiranes, are obtained.

Coupling of Enolates of Phenones with 2-Chloro-2-nitropropane

Lithium enolates of acetophenone, α-methoxyacetophenone, propiophenone, meta- or para-substituted propiophenones, butyrophenone, isovalerophenone, 1-phenyl-1-hexanone, 1-indanone, 1-tetralone, or 1-benzosuberone react with 2-chloro-2-nitropropane in THF by free radical chain processes to produce ArCOCH(CMe2NO2)R or ArCOC(R)=CMe2 and when R H the product of oxidative dimerization, 2.The enolate anion of deoxybenzoin yields in a free radical chain process only the dimerization product.

Mechanism of Nucleophilic Addition to the Carbonyl Group. Part III. Evidence for the Reactant-like Nature of the Transition State in the LiAlH4 Reduction of Alkyl Aryl Ketones.

A Hammett-type free energy relationship is established for the LiAlH4 reduction of 1-(X-phenyl)-2,3,3-trimethyl-1-butanones (X = H, p-F, m-F, p-Me, m-Me, p-MeO, m-MeO, p-NMe2 and m-NMe2) in Et2O at 30 deg C.A ρ value of 1.77 has been obtained.Rate ratios

THE REACTION OF CARBANIONS WITH 2-SUBSTITUTED -2-NITROPROPANES SUBSTITUTION AND DIMERIZATION OCCURRING BY RADICAL CHAIN PROCESSES INVOLVING ELECTRON TRANSFER

The reaction of mono-enolate anions with O2NCMe2X where X=Cl, NO2, p-MePhSO2 yield coupling (RCOCH(R')(CMe2NO2) and enolate dimerization products (RCOCH(R')CH(R')COR) by free radical chain mechanisms involving bimolecular substitution or electron transfer reactions between the enolate anion and the intermediate nitro alkane radical anion (XCMe2NO2(1-)).