N-Butyl phenyl ketone

N-tert-Buty1oxycarbonyl-4-d1phenylphosphino-2-d1phenylphosphino-methylpyrroUdlne, (2S,4S).-, 63, 18 t-Butyl phenyl ketone (yanohydrin, 60, 17 2-Butyne [503-17-3], 61, 62... 

Borohydride reduction of ketones. The reduction of ketones to alcohols by sodium borohydride in benzene-water has been reported to be catalyzed by this salt (6, 249). However, no asymmetric induction was noted in the case of 2-octanone, 1-phenyl-1-propanone, or acetophenone. More recently, asymmetric induction has been observed with more hindered ketones. The maximum was observed with r-butyl phenyl ketone when an enantiomeric excess of 14% of the (R)-alcohol could be obtained. The enantiomeric excess is only 3.6% in the reduction of isopropyl phenyl ketone. No asymmetric induction was observed when ( —)(R)-N,N-dimethyl-N-dodecylamphetaminium bromide was used as catalyst. The structure of the chiral catalyst is evidently important. ... 

The situation is similar with cyclic boronates, which are prepared by the following procedure. Steroid (10 pmol) and the respective substituted boric acid (10 jumol) are dissolved in ethyl acetate (1 ml) and the mixture is allowed to stand for 5 min at room temperature. Under these conditions, 17,20-diols, 20,21-diols and 17,20,21-triols are converted completely into boronates. Cyclic boronate was mainly produced from 17,21-dihydroxy-20-ketone, but side-products also appeared, the formation of which could be suppressed by adding a 10% excess of the reagent [387—389]. Different substituents on the boron atom, such as methyl, n-butyl, tert.-butyl, cyclohexyl and phenyl, are interesting from the viewpoint of GC—MS application. They are further suitable for converting isolated hydroxyl groups into TMS or acetyl derivatives. 

PB PBI PBMA PBO PBT(H) PBTP PC PCHMA PCTFE PDAP PDMS PE PEHD PELD PEMD PEC PEEK PEG PEI PEK PEN PEO PES PET PF PI PIB PMA PMMA PMI PMP POB POM PP PPE PPP PPPE PPQ PPS PPSU PS PSU PTFE PTMT PU PUR Poly(n.butylene) Poly(benzimidazole) Poly(n.butyl methacrylate) Poly(benzoxazole) Poly(benzthiazole) Poly(butylene glycol terephthalate) Polycarbonate Poly(cyclohexyl methacrylate) Poly(chloro-trifluoro ethylene) Poly(diallyl phthalate) Poly(dimethyl siloxane) Polyethylene High density polyethylene Low density polyethylene Medium density polyethylene Chlorinated polyethylene Poly-ether-ether ketone poly(ethylene glycol) Poly-ether-imide Poly-ether ketone Poly(ethylene-2,6-naphthalene dicarboxylate) Poly(ethylene oxide) Poly-ether sulfone Poly(ethylene terephthalate) Phenol formaldehyde resin Polyimide Polyisobutylene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(methacryl imide) Poly(methylpentene) Poly(hydroxy-benzoate) Polyoxymethylene = polyacetal = polyformaldehyde Polypropylene Poly (2,6-dimethyl-l,4-phenylene ether) = Poly(phenylene oxide) Polyp araphenylene Poly(2,6-diphenyl-l,4-phenylene ether) Poly(phenyl quinoxaline) Polyphenylene sulfide, polysulfide Polyphenylene sulfone Polystyrene Polysulfone Poly(tetrafluoroethylene) Poly(tetramethylene terephthalate) Polyurethane Polyurethane rubber... 

Alkylahn of ketones. Ketones are readily alkylated in the z-position on reaction with alkyl halides in the presence of 50% aqueous sodium hydroxide and catalytic amounts of bcnzyltricthylammonium chloride. The catalytic effect of the salt if particularly marked in the case of weakly active alkyl halides. Thus the reaction o phenylacctone with n-butyl bromide in the ab.sence of catalyst gives 3-phenyl-2-heptanonc in 5% yield the yield is 90% in the presence of Ihe catalyst. Highest yields are obtained with ketones bearing an aromatic substituent at the Z-CH2 group. 

Moreover, the formation of enoxy-silanes via silylation of ketones ) by means of N-methyl-N-TMS-acetamide (7 72) in presence of sodium trimethylsilanolate (7 72) was reported in 1969 and since then, the use of silylating reagents in presence of a catalyst has found wide appreciation and growing utilization as shown in recent pa-pers 2 ) (Scheme 27). Diacetyl (181) can be converted by trifluoromethylsul-fonic acid-TMS-ester (182) into 2,3-bis(trimethylsiloxy)-l,3-butadiene (782) ) (for the application of 782 to nitriles, see )). Propiophenone (184) gives by treatment with ethyl TMS acetate (785)/tetrakis(n-butyl)amine fluoride l-trimethylsiloxy-2-methyl-styrene (786) ), Cyclohexanone reacts with the combination dimethyl-TMS-amine (787)/p-toluenesulfonic acid to 1-trimethylsiloxy-l-cyclohexene (788) ). Similarly, acetylacetone plus phenyl-triethylsilyl-sulfide (789) afford 2-triethylsiloxy-2-pentene-4-one (790) ). 

Triethylamine Diethylomine Methyl tert-Butyl Ketone n-Octane Phenyl Acetate Benzene... 

Syn 3-(Ethylthiomethyl)-4-hydroxy-6-phenyl-2-hexanone (3) and (4).3 To ethane thiol (10 mg, 0.17 mmol) in THF (2 mL) was added 1.54 M n-butyl-lithium in hexane (0.11 mL) at 0°C under Ar. Stannous triflate (69.0 mg, 0.17 mmol) was added and after 20 min the mixture was cooled to 45°C. Methyl vinyl ketone 1 (118 mg, 1.98 mmol) in THF (1.5 mL) was added followed by 3-phenylpropanal 3 (350 mg, 2.61 mmol) in THF (1.5 mL). After 12 h aq. citric acid was added and the organic material extracted with CH2CI2. The residue after evaporation was dissolved in MeOH and treated with citric acid. After 30 min stirring, the mixture was quenched with pH 7 phosphate buffer, extracted with CH2CI2, the solvent evaporated and the residue chromatographed to afford 336 mg of 3 and 4 (75%), symanti = 90 10. 

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