Butyrophenones Alcohol

The initial series of major tranquilizers consists of alkylated derivatives of 4-aryl-4-hydroxypiperidines. Construction of this ring system is accomplished by a set of rather unusual reactions. Condensation of methylstyrenes with formaldehyde and ammonium chloride afford the corresponding hexahydro-1,3-oxazines (119). Heating these oxazines in the presence of acid leads to rearrangement with loss of water to the tetrahydropyridines. Scheme 1 shows a possible reaction pathway for these transformations. Addition of hydrogen bromide affords the expected 4-bromo compound (121). This last is easily displaced by water to lead to the desired alcohol (122) The side chain (123) is obtained by Friedel-Crafts acylation of p-fluorobenzene with 4-chloro-butyryl chloride. Alkylation of the appropriate arylpiperidinol with 123 affords the desired butyrophenone derivative. Thus,... 

A 1,2-amino alcohol, ( + )-(lR,4S)-3-exo-anilino-2-exo-hydroxybornane (103), was synthesized from (-I-)-camphor and converted to its LAH complex (eq. [26]). Reduction of acetophenone, propiophenone, and butyrophenone at low... 

Abramson Aerosol Study of LSD TETRAHYDROCANNABINOLS ETHYL ALCOHOL BUTYROPHENONES VOLUNTEER STATISTICS FOLLOW-UP STUDIES THE NUREMBERG CODE... 

A mixture of 107 g (0.4 mole) of a,a-diphenyl-4-piperidinemethanol, 105 g (0.44 mole) of 4 -tert-butyl-4-chlorobutyrophenone, 70 g (0.7 mole) of potassium bicarbonate, and a small amount of potassium iodide in 600 ml of toluene was refluxed and stirred for 2.5 days then filtered. The filtrate was treated with charcoal, filtered through celite then treated with ethereal HCI. The resulting solid was recrystallized from methanol and isopropyl alcohol to give the 4 -tert-butyl-4-[4-(a-hydroxy-a-phenylbenzyl)piperidinoj-butyrophenone hydrochloride, melting point 234°-235°C. 

The use of enzymes to carry out stereospecific chemical reactions is not new, but it is not always possible to predict if an enzymatic reaction (unlike a purely chemical reaction) will occur, or how stereospecific it will be if it does. Because this experiment is easily carried out, it might be an interesting research project to explore the range of possible ketones that yeast will reduce to chiral alcohols. For example, butyrophenone can be reduced to the corresponding chiral alcohol. For a review, see Sih and Rosazza. The present experiment is based on the work of Seebach, Mori, and Ridley. See also the work of Bucciarelli, et al. ... 

Any change in this order of precedence of functions means a change in the name of a compound and in its location in an index. If alcohols were placed ahead of ketones in this order the name 3-hydroxybutyrophenone, indexed imder B (Butyrophenone, 3-hydroxy-) would become I-benzoyl-2-propanol, indexed under P (2-Propanol, I-benzoyl-). The importance of maintaining the same order of precedence can be readily seen. 

For example, borane reduction of butyrophenone using the polymeric catalyst 24 gave the alcohol in quantitative yield with 97% ee [71 ] (Scheme 15). Since the polymeric catalyst is crosslinked and insoluble in the organic solvent used, this catalyst can be used not only in a batch system, but also in a continuous flow system, in which the ketone is converted into the enantio-enriched alkoxybo-rane by passing it through a column filled with the polymeric catalyst. 

Figure 9.8 Log k vs. log Pow (a) and k vs. log (b) relationships predicted by eqs. 9.23 and 9.24 (solid lines), and experimental values (symbols) for a series of monosubstituted benzenes acetanilide, acetophenone, benzaldehyde, benzene, benzonitrile, benzyl alcohol, benzylamine, bromobenzene, butyrophenone, he phenone, methyl benzoate, methyl phenyl ether, nitrobenzene, propiophenone, toluene, and valerophenone. Molar concentrations of SDS in mobile phase (1,a) 0, (2, ) 0.016, (3,0) 0.05, (4,°) 0.1, and (5) 0.15. Reprinted from Ref 21 with permission of Elsevier.

Hexamethyldisilane can also act as an oxidant in the conversion of benzyl alcohols to carbonyl cort5)ounds. Under alkaline conditions, reaction of a-cyclopropylbenzyl alcohol or 3-methoxybenzyl alcohol with hexamethyldisilane generates (y-trimethylsilyl)butyrophenone or 3-methoxybenzaldehyde, respectively. 

Bromal hydrate, 38 Ji-Butyl alcohol, 37 sec-Butyl alcohol, 37 Butyl alcohol, 37 Butyl chloral hydrate, 38 2,3-Butylene glycol, 38 Butyrophenone, 54... 

---