2-phenyl-propiophenone

In addition to phenylacetonitrile and fluorene, various active methylene compounds such as indene, propiophenone, phenyl propionate, benzyl phenylacetate afforded the corresponding carboxylated products by the carboxylation reaction with La(0 Pr)3-Ph-N=C=0-C02 system. Of fundamental and practical importance is that S-benzyl thiopropionate was effectively carboxylated into a thioester of 2-methylmalonate in a good yield, since this reaction is related to the biological carboxylation of propionyl coenzyme A with a biotin enzyme. Other thioesters were also carboxylated similarly, where successful examples were thioesters of phenylacetic, acetic, and isovaleric acids carrying active methylene and methyne groups, respectively. 

The 4-arylthiazoles are obtained from phenacylbromide and its substituted derivatives (in 40 to 87% yields) (264, 335, 646), and 4-phenyl-5-methylthiazole (129, 641) and 4,5-diphenylthiazole (519) from -bromo-propiophenone and desylchloride, respectively. 

Propiophenone. Propiophenone [93-55-0] (ethyl phenyl ketone) is a colorless Hquid with a flowery odor. It can be prepared by the Friedel-Crafts reaction of benzene and propionyl chloride in the presence of aluminum chloride (346), or by the catalytic reaction of benzoic acid and propionic acid in the presence of water (347). Propiophenone is commercially available (348), and is sold in Japan at 2700 Y/kg (349). It is used in the production of ephedrine, as a fragrance enhancer, and as a polymerization sensitizer. 

The reaction of a dibromochalcone with hydroxylamine hydrochloride in pyridine gave three products with the expected 2-isoxazoline product as the predominate compound. A ring bromination product and an isoxazole were also isolated (70UC796). The reaction of hydroxylamine with /S-thiosulfates of propiophenone at reflux produced 3-phenyl-2-isoxazo-line (455). At room temperature a bis-Michael product (456) was produced. The reaction with N -phenylhydroxylamine yielded a mono-Michael type product (457) (74CPB1990). 

Phenyl-2-butanol has a methyl group, an ethyl group, and a phenyl group (—Cgl ) attached to the alcohol carbon atom. Thus, the possibilities arc addition of ethylmagnesium bromide to acetophenone, addition of methylmagnesium bromide to propiophenone, and addition of phenylmagnesimn bromide to 2-butanone. 

Hydroxy-propiophenon wird in 10%-iger Natronlauge an Zinn-beschichteter Kup-fer-Kathode zu 3,4-Bis- 4-hydroxy-phenyl]-hexandiol-(3,4) (96% d.Th.) dimerisiert8 ... 

A recent report indicates that thiophenes (not benzothiophenes) may be formed from alkyl phenyl ketones by treatment with a slight excess of thionyl chloride in the cold.58 Propiophenone, for example, yields 3,4-dibenzoyl-thiophene (47). Adipic acid and related carboxylic acids yield thiophene derivatives upon treatment with thionyl chloride in the presence of pyridine.59... 

Treated with ZnBr2 followed by enamines, phenyl thioethers 829 derived from aryl aldehydes are converted to (l-(phenylthio)alkyl ketones or aldehydes 830 in moderate to good yields (Equation 19). Enamines used in these syntheses are (1) morpholine enamine derived from diethyl ketone, (2) diethylamine enamine of propiophenone, (3) piperidine enamine derived from isovaleraldehyde, and (4) pyrrolidine enamine of cyclohexanone <2000H(53)331>. 

Diethylpropion Diethylpropion, l-phenyl-2-diethylaminopropanon (8.3.6), is synthesized by the bromination of propiophenone into a-bromopropiophenone (8.3.5) and the subsequent substitution of the bromine atom with a diethylamino group [25,26]. 

Biperiden Biperiden, l-(5-norbomen-2-yl)-l-phenyl-3-piperidinopropan-l-ol (10.2.4), is also synthesized according to the method of making trihexyphenidyl, except by reacting 2-(l-piperidino)propiophenone (10.2.1) with 5-norbomen-2-ylmagnesiumbromide [33,34],... 

Phenylpropanolamine Phenylpropanolamine, D,L-erythro-1 -phenyl-2-methylamino-propanol-1 (11.3.7), is synthesized from propiophenone by nitrosation into an isonitroso derivative (11.3.6). Reduction of this by hydrogen in hydrochloric acid while simultaneously using two catalysts, palladium on carbon and platinum on carbon, gives norephedrine (11.3.7) [56-59]. 

S-methyIbutyraldehyde, 3-methylbutanal (c) a-chlorovaleraldehyde, 2-chloropentanal (d) methyl isopropyl ketone, 3-methyl-2-butanone (e) ethyl phenyl ketone, 1-phenyl-1-propanone (propiophenone) (/) methyl vinyl ketone, 3-buten-2-one. The C=0 group has numbering priority over the C=C group. 

The cyclization is therefore a low-yield secondary reaction and not a useful route to 3-phenyl benzofurans. a-Phenoxypropiophenones and a-(3-methoxyphenoxy)acetophenones give fission products only.251 Benzofuryl-Bz-oxyacetophenones yield 5% of furobenzofurans only.255 a-(3-Methoxyphenoxy)propiophenones resist thermal cracking under the same conditions.245... 

Over the zeolites mentioned above, acetophenone and propiophenone are easily and quantitatively produced from the hydration of phenyl acetylene and 1-phenylpropyne in very short periods of time, whatever zeolite is used. This result is in agreement with the special high reactivity of phenyl acetylene and derivatives towards hydration already found in homogeneous catalysis (ref.6). On the other hand, 1-hexyne and 2-hexyne, which are known to be less reactive towards hydration, are converted into the corresponding hexanones in relatively convenient yields. For example, over HM (Si/A1=8), 30% 2-hexanone is produced from 1-hexyne after one hour reaction. 

Deamination of amines often gives rise to hot, short-lived carbocations (Section 5.2, p. 226). Deamination of ( + )-1,1-diphenyl-2-amino-l-propanol specifically labeled with 14C in one of the two phenyl groups (25) gives a-phenyl-propiophenone as product, 88 percent of it inverted and 12 percent retained. All the inverted ketone comes from migration of the 14C-labeled phenyl and all the retained from migration of the unlabeled phenyl group (Equation 6.22).39 This... 

A Ru complex with a chiral oxazolinylferrocenylphosphine (S)-6 (substrate Ru=100 l) with Cu(0S02CF3)2 promoted hydrosilylation of acetophenone using diphenylsilane (2 equivalents) in ether at 0 °C to give (R)-l-phenylethanol in 95% ee and in 59% yield after hydrolysis (Scheme 16) [31]. Propiophenone was reduced with 97% optical yield. This complex was also effective for the hydrosilylation of 2-phenyl-l-pyrroline in toluene at 0 °C to afford the S chiral amine in 88% ee [31].RuCl2[(.R)-TolBINAP][(S)-7] and Ag0S02CF3 catalyzed the hydrosilylation of acetophenone (substrate Ru Ag=100 l 4) with diphenylsilane to give the R product in 82% ee [32,33]. 

The effect of the KOH content of the reaction mixture upon the yield of 3-methyl-2-phenyl-l-vinylpyrrole from propiophenone oxime and acetylene (100°C, 3 hr) is expressed as follows (78ZOR1733)... 

Moreover, the formation of enoxy-silanes via silylation of ketones127 by means of N-methyl-N-TMS-acetamide (1 72) in presence of sodium trimethylsilanolate (173) 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 papers128-132 (Scheme 27). Diacetyl (181) can be converted by trifluoromethylsul-fonic acid-TMS-ester (182) into 2,3-bis(trimethylsiloxy)-l, 3-butadiene (7treatment with ethyl TMS acetate (7 5)/tetrakis(n-butyl)amine fluoride l-trimethylsiloxy-2-methyl-styrene (i<56)130. Cyclohexanone reacts with the combination dimethyl-TMS-amine (18 7)/p-toluenesulfonic acid to 1-trimethylsiloxy-l-cyclohexene (iSS)131. Similarly, acetylacetone plus phenyl-triethylsilyl-sulfide (189) afford 2-triethylsiloxy-2-pentene-4-one (790)132. ... 

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