Butanone 3,3-diphenyl

The addition of phenyllithium to 3-hydroxy-l,3-diphenyl-1-butanone (4. R1 = R3 = C6HS R2 = H) leads to the predominant formation of either one or the other diastereomer, depending on the reaction temperature146. Thus, for this type of addition reaction there are at least two competing mechanisms which have quite different activation entropies147. 

In the reaction of 2-cyclohexenone and of 4-phenylbut-3-en-2-one with chiral organocuprates of type (205), optical yields of only 5% and 15%, respectively, were obtained201 . Methylation of l,3-diphenyl-2-propene-l-one with (205) (R = CH3) produced (S)-l,3-diphenyl- 1-butanone in 68% enantiomeric excess 202>. 

Acetone, methyl ethyl ketone (2-butanone) and methyl isobutyl ketone (4-methyl-pentan-2-one) (6.8 mmol/kg bw for 3 days) increased the hepatotoxicity of carbon tetrachloride to Sprague-Dawley rats (Raymond Plaa, 1995a) this enhancement of toxicity was coincident with increased microsomal aniline hydroxylase activity (Raymond Plaa, 1995b). In addition to the effect on cytochrome P450, acetone, but not the other ketones, increased basal canalicular membrane fluidity, as measured by fluorescence polarization of 1,6-diphenyl-1,3,5 -hexatriene or 1 - [4-(trimethylammoniumphenyl)-6-phenyl] -1,3,5 -hexa-triene (Raymond Plaa, 1996). 

Migration of a benzyl group appears to occur in preference to hydrogen, alkyl, or aryl migration, as with 1,3-diphenyl-2-methyl-1,2- Toxypropane (Eq. 461), which yields 3,4-diphenyl-2-butanone -elusively.1024-102 Of some interest, incidentally, is the report that... 

Dimethyl-1-cyclohexyl-1-trimethylsiloxy-ethene (191) gives by means of methyllithium/ethylbromide in dimethoxyethane (DME) 1-cyclohexyl-2,2-dimethyl-1-butanone (297)133 Dimerizations occur when substances such as 1-trimethylsiloxy-styrene (192) or 1-trimethylsiloxy-l-cyclopentene (195) are treated with silver oxide/ DMSO to afford l,5-diphenyl-2,5-butadione (198) and 2,2 -dicyclopentanonyl (199)l34 respectively. Under the catalytic influence of Cu2+ ions, 192 plus ben-zenesulfonyl chloride yield phenyl-(l-phenyl-l-ethanone-2-yl)sulfone (200)l3 ... 

A mixture of 3.5 grams (0.013 mole) of the above a,a-diphenyl-alpha-(2-piperidyl)methanol, 4 g (0.05 mole) of formaldehyde (37%), and 6 grams (0.1 mole) of formic acid was refluxed for 2 days. The reaction mixture was treated with 1.3 g (0.013 mole) of cone, hydrochloric acid and vacuum distilled on the steam bath. The residue was recrystallized from butanone to give the a,a-diphenyl-alpha-(2-piperidyl)methanol hydrochloride which melted at 228-229°C (dec.). 

Reaction of phenacyl iodide with indium metal gives 3,4-epoxy-1,3-diphenyl-1-butanone which, on treatment with silica gel, gives 2,4-diphenylfuran and 2,4-diphenyl-4-oxobutanal (Scheme 92). Metallic indium as well as indium(i) iodide mediate the aldol condensation between ce-halo ketone and aldehyde.333... 

The radical anion of benzoylcyclopropane cleaves reversibly, but the ring-opened radical anion reacts with the substrate to dimers or trimers, whereas the radical anion of 2-phenyl benzoylcyclopropane cleaves irreversibly with foiTnation, after further uptake of one electron, of 1,4-diphenyl-1-butanone [6]. 

Reaction of cis- and tra i-l,3-diphenyl-2,3-epoxy-4-bromo-l-butanones with triethyl phosphite at 120°C goes to completion to give diethyl cis- or tra i-l,3-diphenyl-4-oxo-2,3-epoxybutylphospho-nates as the only isolated products in high yields." Several preparations of 4-oxoaIkylphosphonates are based on the use of masked ketones. For example, the Michaelis-Arbuzov reaction of 5-chloro-2-pentanone ethylene ketal with triethyl phosphite followed by unmasking of the latent carbonyl group gives diethyl 4-oxopentylphosphonate in modest yield (38%)." ° ... 

Acrylophenone 7.2 To a solution of LDA under N2 in THF was added 1,4-diphenyl-1-butanone. After 10 min stirring, 2 was added dropwise at -78°C. To the solution at 0°C, H202 was added and the reaction mixture was stirred for 30 min at 20-25°C. Usual work up and chromatography afforded 7 in 85% yield. 

Simple diols have been subjected to the pinacol rearrangement in the presence of Amberlyst 15, a polystyrene sulfonic resin with a high concentration of acidic centers. When excess catalyst is used (g catalyst/g diol = 1.25) pinacol gives 3,3-dimethyl-2-butanone in near quantitative yield (batch reactor, 373 K, 2 h) [33]. Of the two isomeric ketones 3,3-diphenyl-2-butanone (10), formed with phenyl migration, is the sole product when 2,3-diphenyl-2,3-butanediol (9) is reacted (Scheme 6). This feature is very similar to that observed under homogeneous conditions in the presence of sulfuric acid [2]. An arylsulfonic silica catalyst prepared by grafting and sulfonation proved to be less selective [33]. 

Methyl-l,l-diphenyl-1,2-propanediol (50 g) is added with stirring to concentrated sulfuric acid (300 ml) at 5°. The mixture is left at room temperature for 2 h, then poured on ice and diluted with water (to 3 1) the precipitated 3,3-diphenyl-2-butanone is distilled in a vacuum, then having b.p. 101-103°/0.3 mm and m.p. 40-41° (38 g). 

Bond, D.R. Caira, M.R. Harvey. G.A. Nassimbeni. L.R. Complexation with diol host compounds. 5. Structures and thermal analysis of inclusion compounds of rra i-9.10-dihydroxy-9.10-diphenyl-9.10-dihydroanthracene with 2-butanone. 4-vinylpyridine, 4-methylpyridine and 2-methyl-pyridine. Acta Crystallogr. 1990. B46. 771-780. 

The rearrangement is frequently observed when geminal diols react with acid. The structure of the products from unsymmetrical diols can be predicted on the basis of ease of carbocation formation. For example, l,l-diphenyl-2-methyl-l,l-propanediol rearranges to 3,3-diphenyl-2-butanone because the diarylcarbinol is most readily ionized. Synthetically useful examples of this type of rearrangement are discussed in Section 10.1.2 of Part B. 

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