7115-18-6

Upstream product

• 186581-53-3 diazomethane 
• 16859-59-9 3-hydroxy-1(3H)-isobenzofuranone 
• 2852-91-7 (2-carboxyphenyl)acetone 
• 15288-53-6 o-(trimethylsilyl)phenol 
• 1276113-19-9 2-(trimethylsilyl)phenyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate 
• 105-45-3 acetoacetic acid methyl ester 
• 108-22-5 Isopropenyl acetate 
• 134-20-3 2-carbomethoxyaniline 
• 67-56-1 methanol 
• 15868-29-8 1-oxo-1H-isochromene-4-carboxylic acid 
• 342-54-1 2-(methoxycarbonyl)benzenediazonium tetrafluoroborate 
• 73927-93-2 (C₄H₉)3SnOOCC₆H₄I-2 
• 123-54-6 acetylacetone 
• 88-67-5 2-Iodobenzoic acid 

Downstream Products

• 67-56-1 methanol 
• 2852-91-7 (2-carboxyphenyl)acetone 

Relevant academic research and scientific papers

Salicylic Acid-Catalyzed Arylation of Enol Acetates with Anilines

α-Aryl ketones are both structure moieties commonly found in bioactive compounds and versatile synthetic intermediates for the preparation of drug-like molecules. An operationally simple and scalable protocol has been developed to prepare α-aryl ketones from readily available aromatic amines and enol acetates (or silyl enol ethers). This metal-free methodology features the use of salicylic acid as a convenient catalyst to promote the formation of aryl radicals from in-situ generated aryl diazonium salts, without demanding thermal or photochemical activation. The mild reaction conditions used are compatible with anilines substituted with diverse functionalities. Structural elaboration of some prepared α-aryl ketones was accomplished to illustrate their usefulness as building blocks. (Figure presented.).

Identification of ortho-Substituted Benzoic Acid/Ester Derivatives via the Gas-Phase Neighboring Group Participation Effect in (+)-ESI High Resolution Mass Spectrometry

Benzoic acid/ester/amide derivatives are common moieties in pharmaceutical compounds and present a challenge in positional isomer identification by traditional tandem mass spectrometric analysis. A method is presented for exploiting the gas-phase neighbor

Continuous-flow synthesis of trimethylsilylphenyl perfluorosulfonate benzyne precursors

2-(Trimethylsilyl)phenyl perfluorosulfonated aryne precursors may now be accessed using flow chemistry, enabling the fast preparation of pure compounds with no requirement for low temperature lithiation or column chromatography. The process has been adapted to novel nonaflate precursors, utilizing the cheaper and more user-friendly nonaflyl fluoride reagent. The resultant nonaflates are shown to successfully participate in a range of aryne reaction classes.

A practical synthesis of α-aryl methyl ketones via a transition-metal-free Meerwein arylation

We report herein a simple, scalable, transition-metal-free approach to the synthesis of α-aryl methyl ketones from diazonium tetrafluoroborate salts under mild conditions. This methodology uses easily accessible and nontoxic starting material and was applied to the multi-kilogram-scale preparation of 1-(3-bromo-4-methylphenyl)propan-2-one.

Aqueous organotin chemistry: Tin hydride mediated dehalogenation of organohalides and a novel organotin mediated nucleophilic substitution on 2- iodobenzoates in water

This paper describes the dehalogenation of water soluble and water insoluble organohalides in water by tri-n-butyltin hydride (TBTH), preformed TBTH and triphenyltin hydride (TPTH) in water. TBTH in the presence of a radical trap, and Ph4Sn were also found to effect nucleophilic substitution of 2-iodobenzoates in the presence of various nucleophiles.

Reactions of carbonyl compounds in basic solutions. Part 21. The mechanisms of the alkaline hydrolysis of substituted methyl 2-(2-oxopropyl)- and 2-(2-oxo-2-phenylethyl)-benzoates and 2-(2-acetylphenyl)- and 2-(2-benzoylphenyl)-acetates

Rate coefficients have been measured for the alkaline hydrolysis of methyl 2-[2-oxo-2-(3- or 4-substituted phenyl)ethyl]benzoates, 2-[2-(3- or 4-substituted benzoyl)phenyl]acetates,2-(2-oxopropyl) and 2-(1,1-dimethyl-2- oxopropyl)benzoates, 2-(2-acetylphenyl)acetate and 2-(2-acetylphenyl)-2,2- dimethylacetates in 70% (v/v) dioxane-water at 30.0 °C. Those for the six parent esters were also measured at 45.0 and 60.0 °C and the enthalpies and entropies of activation have been evaluated. The relative rates of hydrolysis, activation parameters and substituent effects have been used to demonstrate neighbouring participation by the keto-carbonyl groups in the alkaline hydrolysis of the esters under study. For comparable systems, participation by six-membered ring intermediates appears somewhat less advantageous than five-membered.

Nickel-catalyzed direct electrochemical cross-coupling between aryl halides and activated alkyl halides

The electrochemical reduction of a mixture of aryl halides and activated alkyl halides in DMF in the presence of catalytic amount of NiBr2bipy leads to cross-coupling products in good to high yields. The method applies to the synthesis of α-aryl ketones, α-aryl esters, and allylated compounds from readily available organic halides. Optimization of the process has been obtained by slowly adding the most reactive organic halide (usually the activated alkyl halide) during the electrolysis which is best conducted at 70 °C when aryl bromides are involved.

Aromatic Spiranes XXI [1]: Syntheses of Methyl Substituted Phthalaldehydic Acids and their Ethyl and Methyl Esters as Synthones for Syntheses of Methylated 2,2′-Spirobiindandiones

The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation (NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields.

A novel method of arylation of α-chloroketones

α-Arylated ketones were obtained in moderate to good yields by one-step electroreductive coupling of α-chloroketones and arylhalides in DMF and in the presence of a Al- or Zn-sacrificial anode and a catalytic amount of a nickel complex.

NOVEL OXIDATIVE CLEAVAGE OF CARBON-CARBON BOND IN HYDRAZONES BY OXYGENATION WITH COBALT SCHIFF BASE COMPLEX

Oxygenation of aromatic ketone hydrazones with Co(salen) in methanol resulted unexpectedly in oxidative degradation to give methyl benzoate derivatives.A mechanism involving nucleophilic attack by methanol on a diazo intermediate is discussed.