Methyl -2-phenylpropanoate

Certain of the monoalkylated ethyl phenylacetates have been further alkylated with alkyl and aralkyl halides to produce the corresponding disubstituted phenylacetic esters.8 Ethyl 2-phenyl-propanoate has been alkylated by methyl iodide to give pure ethyl 2-methyl-2-phenylpropanoate in 81% yield. Similarly, the alkylations of ethyl 2-phenylhexanoate with methyl iodide, w-butyl bromide, and benzyl chloride gave the corresponding pure dialkylated products in 73%, 92%, and 72% yields, respectively. 

Likewise, reaction of the dimethyl acetal 1b gives rise to mixtures of 2-bromopropiophenone (2), methyl 2-phenylpropanoate (3b) and 2-... 

Copper(Il) complexes 18a-f of methyl or ethyl 3-oxobutanoate la, 2-bromo-3 oxobutanoate lb, 2-(anilinocarbonyl)-3-oxobutanoate Ic, 3-oxo-3- rfienylpro-panoate Id, 2-bromo-3-oxo-3-phenylpropanoate le, or 3-aniHno-2-benzoyl-3-oxopropanoate If were reacted with phenylhydrazine hydrochloride and sodium ( )... 

One of the first examples of this type of reaction, using a chiral alcohol as an auxiliary, was the asymmetric synthesis of 2-hydroxy-2-phenylpropanoic acid (atrolactic acid, 3, R1 =C6H5 R3 = CH3) by diastereoselective addition of methyl magnesium iodide to the men-thyl ester of phcnylglyoxylie acid4,5 (Table 22). 

Alkaline hydrolysis of the crude adduct formed with benzaldehyde, followed by treatment with diazomethane and column chromatography, affords methyl (2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoate in 96% ee. Reduction of the crude products formed in the reactions with 2-inethylpropanal and 2,2-dimethylpropanal leads to the corresponding 1,3-diols with >96% ee. In both the hydrolysis and the reduction procedures, the chiral auxiliary reagent, 1,1,2-triphenyl-1,2-ethanediol, can be recovered and reused72. 

Methyl 3-Hydroxy-2-methyl-3-phenylpropanoate Typical Procedurel06a ... 

The aldol addition of deprotonated (3-isopropyl-6-methyl-2-oxo-2-propionyl)-l,3.2-oxazaphos-phorinane 36 to benzaldehyde delivers (2f ,3/ )-3-hydroxy-2-methyl-3-phenylpropanoic acid in 47% ee via the /1-lactone 37, with syn/anti ratio of 94 6106c. 

R = C61I5 methyl 3-(2.2-[Pg.922]

This regioselectivity is practically not influenced by the nature of subsituent R. 3,5-Disubstituted isoxazolines are the sole or main products in [3 + 2] cycloaddition reactions of nitrile oxides with various monosubstituted ethylenes such as allylbenzene (99), methyl acrylate (105), acrylonitrile (105, 168), vinyl acetate (168) and diethyl vinylphosphonate (169). This is also the case for phenyl vinyl selenide (170), though subsequent oxidation—elimination leads to 3-substituted isoxazoles in a one-pot, two-step transformation. 1,1-Disubstituted ethylenes such as 2-methylene-1 -phenyl-1,3-butanedione, 2-methylene-1,3-diphenyl- 1,3-propa-nedione, 2-methylene-3-oxo-3-phenylpropanoates (171), 2-methylene-1,3-dichlo-ropropane, 2-methylenepropane-l,3-diol (172) and l,l-bis(diethoxyphosphoryl) ethylene (173) give the corresponding 3-R-5,5-disubstituted 4,5-dihydrooxazoles. 

In the second example, one carbon atom of the future allene group is contributed by the sulfoxide 72, which is first converted to the ketone 74 by LDA treatment followed by quenching of the resulting carbanion with methyl 3-phenylpropanoate (73). To convert the now complete carbon framework into a central allene unit, the enol triflate of 74, intermediate 75, is produced under the conditions given in the scheme. Ultimate butyllithium treatment of 75 then furnishes the alkylated allene 76 [23],... 

Methyl 2-methylbenzoate Methyl 3-methylbenzoate Methyl 4-methylbenzoate Phenyl acetate Benzyl acetate Methyl phenylacetate Ethyl phenylacetate Methyl 3-phenylpropanoate Ethyl 3-phenylpropanoate Methyl 4-phenylbutanoate Dimethyl phthalate Benzonitrile... 

Experimental Procedure 4.2.2. Preparation of an Indole by Intramolecular C-H Insertion Methyl (2S)-2-(3-Acetyl-2-hydroxy-5-aito-lff-l-indolyl)-3-phenylpropanoate [1083]... 

Immobilisation of an Acetobacter aceti strain in calcium alginate resulted in improvement of the operational stability, substrate tolerance and specific activity of the cells and 23 g phenylacetic acid was produced within 9 days of fed-batch cultivation in an airlift bioreactor [133]. Lyophilised mycelia of Aspergillus oryzae and Rhizopus oryzae have been shown to efficiently catalyse ester formation with phenylacetic acid and phenylpropanoic acid and different short-chain alkanols in organic solvent media owing to their carboxylesterase activities [134, 135] (Scheme 23.8). For instance, in n-heptane with 35 mM acid and 70 mM alcohol, the formation of ethyl acetate and propylphenyl acetate was less effective (60 and 65% conversion yield) than if alcohols with increased chain lengths were used (1-butanol 85%, 3-methyl-l-butanol 86%, 1-pentanol 91%, 1-hexanol 100%). This effect was explained by a higher chemical affinity of the longer-chain alcohols, which are more hydrophobic, to the solvent. 

Synthesis of Amino Acid Ester Isocyanates Methyl (S)-2-lsocyanato-3-phenylpropanoate. 

Methyl (25, 3i )-2-(ferf-Butoxvcarbonylamino)-3-f(methylsulfonyl)oxy]-3-phenylpropanoate (99A) [13°1 To a soln of alcohol 98A (0.94 g, 3.18 mmol) and TEA (0.73 g, 7.18 mmol) at 0°C in CH2C12 was added MsCl (418 mg, 3.65 mmol). The mixture was stirred at 0°C for 45 min, and then quenched with aq dil HC1 and extracted with CH2C12. The organic layer was washed with aq NaHC03, followed by brine, and dried (Na2S04). The solvent was removed under reduced pressure to give the crude mesylate 99A as a foamy white solid that was used in the next step without further purification. 

Methyl (2f ,3f )-3-( Acetylsulfanvl )-2-(fert-butoxycarbonylamino)-3-phenylpropanoate (lOOB) 1 1... 

Methyl (2/ ,3/ )-2-(ferf-Butoxycarbonylamino)-3-f(4-methylbenzyl)sulfanyll-3-phenylpropanoate... 

Na (0.92 g, 40 mmol) was dissolved in EtOH (40 mL). To this soln were added nnri-benzaldoxime 17 (4.84 g, 40 mmol) and methyl (f ,5)-2-bromo-3-phenylpropanoate (18 10.7 g, 44 mmol). The mixture was allowed to stand until it reached pH 7 (2h), at which point it was concentrated to dryness. H20 (30 mL) was added to the residue and the aqueous phase was extracted with CHC13 (40 mL). The organic layer was dried (MgS04) and concentrated to dryness. Nitrone 19 was crystallized (EtOH/Et20) yield 7.58 g (67%) mp 142 °C. 

Finally, the last uncertain case concerns the prevailing isomer arising from hydrocarbalkoxylation of (E)-l-phenyl-l-propene. In this case practically none of the predicted prevailing isomer 2-methyl-3-phenylpropanoate is formed. However, the prevailing ester (55%) is not the other expected isomer (2-benzylpropanoate) but rather the 4-phenylbutanoate which arises from isomerization of either the substrate ((E)-1-phenyl-1-propene to 3-phenyl-l-propene) or the catalyst-substrate complex. 

R,3/ ,45)- and (25,35,4/ )-acids (38). Resolution of ( )-(E)-2,3,4-trimethyl-2-pentenedioic acid gave the two separate isomers. The configuration of each isomer was assigned by correlation with (-)-(/ )-2-phenylpropanoic acid. Then methylation of the (45)-acid (39), followed by cw-hydroxylation, hydrolysis, and separation of the diastereoisomeric acids, yielded the (2/ ,35,45)- (40) and (25,3/ ,45)-isomers (41) of monocrotalic acid (Scheme 10). The stereochemistry... 

Atropine (Atr C17H23N03 MW 289.17 g/mol CAS-No. 51-55-8 8-methyl-8-azabicyclo[3.2.1]octane -3-yl 3-hydroxy-2-phenylpropanoate). 

Dehalogenation of vicinal dibromides by electrogenerated polysulfide ions in DMA provides an indirect method to accomplish the same goal. A series of vicinal dibromides has been examined. These include methyl erj /2ro-2,3-dibromo-3-phenylpropanoate (152),... 

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