3719-53-7

Upstream product

• 822-87-7 2-Chlorocyclohexanone 
• 121-45-9 phosphorous acid trimethyl ester 
• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 14839-64-6 (2-oxocyclohexyl)mercury chloride 
• 108-94-1 cyclohexanone 

Downstream Products

• 512-56-1 trimethyl phosphite 
• 108-94-1 cyclohexanone 
• 34006-71-8 Dimethyl-2-oxo-cyclohexyl-phosphat 
• 84960-03-2 dicyclohexylammonium 1-cyclohex-1-enyl phosphate 

Relevant academic research and scientific papers

Radical and Ionic Reactions of (Benzoylmethyl)mercurials

Photolysis of PhCOCH2HgCl or (PhCOCH2)2Hg yields benzoylmethyl radicals which can be trapped by anions such as Me2C=NO2-, RC(CO2Et)2-, RC(O-)=CH2 or by other electron-rich systems such as (RO)3P, N-methylpyrrole, enamines, or norbornene.Electron transfer from the adduct radicals to the mercurials yields PhCOCH2A from the anions A-, PhCOCH2P(O)(OR)2 from P(OR)3, and the phenacyl derivative from N-methylpyrrole or enamines.Easily oxidized anions such as PhCOCPh2- or PhC(CH3)=NO2- react with PhCOCH2* by electron transfer to yield the dimer derived from the anion.Addition of PhCOCH2* to norbornene yields a substituted 3-benzoylpropyl radical which cyclizes at the ortho position of the benzoyl group to give the α-tetralone derivative.

Enol Phosphates from the Action of Monomeric Metaphosphate Ion on Ketones

Prior research from this laboratory had demonstrated that monomeric metaphosphate ion, generated by fragmentation from β-bromophosphonate dianions, reacts with acetophenone in the presence of excess base to give a modest yield of 1-phenylvinyl phosphate.This paper expands on that finding; it presents studies of the effects of concentration of reagents, of solvents, and of variation in amine structure (i.e., of the base) on the reaction.These studies lead to experimental conditions where the yield of the enol phosphate of acetophenone, based on the β-bromophosphonic acid used, exceeds 80percent.Several other ketones can be similarly converted to their enol phosphates, although in inferior yield.

Reaction of 2-Chlorooxiranes with Phosphites and Phosphanes: A New Route to β-Carbonylphosphonic Esters and -phosphonium Salts

Reaction of alkylsubstituted 2-chlorooxiranes 6 with trialkyl phosphites 11 gives β-carbonylphosphonic diesters (12a, b, 15a, b, 20a, 21a), free of isomeric enol phosphates or α,β-epoxyphosphonates. 2-Chloro-2-(chloromethyl)oxirane (6c) undergoes with 11 an Arbusov reaction followed by a Perkow reaction ( -> 18 -> 17).The limitation of the method is probed with sterically crowded substituents in 3-position of 6. 6b yields with triphenylphosphane a β-ketophosphonium salt (23), which can be converted to a keto-ylide (24).