Ethyl 2-methylbenzoate

The mixture of 7.9 g of ethyl a-(4-aminophenyl)propionate and 8.3 g of ethyl 2-chloro-methylbenzoate is refluxed under nitrogen for one hour. The residue is recrystallized from hexane, to yield the ethyl a-[4-(1-oxo-isoindolino)-phenyl]-propionate of the formula... 

B. Ethyl l-Amino-S-methylbenzoate. A 1-1., three-nocked, round-bottomed flask equipped with a mechanical stirrer, a condenser, and a nitrogen-inlet tube is charged with 11.25 g. (0.050 mole) of ethyl 4-amino-3-(methylthiomethyl)benzoate, 300 ml. of absolute ethanol, and 17 teaspoons (ca. 50 g.) of W-2 Raney nickel (Note 7). The reaction mixture is stirred at 25° for one hour, then stirring is discontinued, and the ethanolic solution is decanted from the catalyst (Note 8). The catalyst is then washed with one 300-ml. portion of absolute ethanol and one 500-ml. portion of dichloromethane, the solvent being removed... 

Ethyl 4-amino-3-methylbenzoate has been reported previously.7... 

These authors also reported that /V-acyloxy-/V-alkoxyamides did not undergo methanolysis under the same conditions but treatment of /V-acctoxy-/V-ethoxybenz-amide 25a in more forcing conditions with NaOMe in DME afforded a mixture of ethyl and methylbenzoate, 97 and 98 (Scheme 20). They attributed the formation of the former to a HERON reaction and methyl benzoate to the direct attack of methoxide at the amide carbonyl. 

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... 

Table 19a 13C-19F Coupling Constants" in Ethyl 6-Cyano-4,5,7-trifluoro-2-methylbenzo[6]furan-3-carboxylate...

When chroman is heated on alumina at 250-350 °C, 2-methyl-2,3-dihydrobenzo[6]furan is formed, the amount of product increasing with temperature. At the higher end of this temperature range, 2-methyl-, 2-ethyl- and 2-propyl-phenols are formed (71MI22302). At 300-400 °C in the presence of activated carbon, some 2-methylbenzo[Z>]furan (589) is also produced (75CHE278). 

Although other condensation reactions with 4-aminopyridine are reported to fail, they have in most cases succeeded with 4-aminoquinoline.59 Dey and Joullie87 have prepared a series of trifluoro-methylbenzo[A]-l,6-naphthyridines by condensing ethyl trifluoro-methylacetoacetate with 4-aminoquinaldine. 

Carbonation of the lithium derivative of 2-methoxybenzo[6]thio-phene affords the corresponding 3-carboxylic acid.183 2-Methylbenzo-[6]thiophene-3-carboxylic acid has been obtained (45%) by carbonation of 2-benzo[6]thienylmethylmagnesium chloride (Section VI,D, 4).528 re-Butyllithium reacts selectively with the bromine atom in 3-bromo-2-fluorobenzo[b]thiophene to give a product, which on carbonation affords 2-fluorobenzo[6]thiophene-3-carboxylic acid.482 Benzo[6]thiophene-7-carboxylic acid is obtained by reduction of the corresponding thioindoxyl with amalgamated zinc and acetic acid.315 Benzo[6]thiophene-3-carboxylic acid and its 2-ethyl derivative have been prepared in high yield by treatment of the pyridinium salt of the 3-chloroacetyl derivative with alkali.132... 

First convert 3-methylbenzoic acid to its ethyl ester by Fischer esterification, and then treat the ester with diethylamine to give Deet. 

Fig. 6.3. Alkaline hydrolysis of carboxylic esters according to the mechanism of Figure 6.2 proof of the reversibility of the formation of the tetrahedral intermediate. In the alkaline hydrolysis of ethyl pora-methylbenzoate in H20, for example, the ratio kretlo/kelj is at least 0.13 (but certainly not much more).

The greater acidity of lateral protons means that LDA can usually be used to remove them and hence much more electrophilic directing groups can be used for lateral lithiation than ortholithiation. Ethyl 2-methylbenzoate 427 is deprotonated at -78 °C by LDA but as soon as the product organolithium forms it adds to unreacted starting material to give dimeric products 428.392... 

In the alkaline hydrolysis of ethyl para-methylbenzoate in H20, for example, the ratio relrx/ elirn >S at least 0.13 (but certainly not much more). 

C8H9N02 2-amino-6-methylbenzoic acid 4389-50-8 19.47 1.1446 2 13882 C8H10N2O2 N-ethyl-2-nitroaniline 10112-15-9 25.00 1.1900 1... 

C8H9N02 4-amino-3-methylbenzoic acid 2486-70-6 518.92 45.705 2 13825 1 C8H10CIN 2-(3-chlorophenyl)ethyl amine 13078-79-0 501.03 43.983 2... 

C10H12O2 ethyl 4-methylbenzoate 94-08-6 505 15 44.379 1,2 19630 C10H12O2 4-methyt-2-phenyt-m-dioxolane 2568-25-4 504.61 44.327 2... 

Staggered configurations have also been observed for the tricarbonyl chromium complexes of phenanthrene 294, 295), 9,10-dihydro-phenanthrene 293, 295), anthracene 202), naphthalene 262), and 1-aminonaphthalene 58). The eclipsed configuration has been observed for the tricarbonyl complexes of anisole (57, 229), toluidine 60, 61), methylbenzoate (59), o-methoxyacetylbenzene, o-hydroxyacetylbenzene 101), 2-methoxy-[l-hydroxy-ethyl]benzene (99), and 2-methyl-[l-hydroxy-l-phenylpropyl]benzene (97). It is apparent that the orientation of the chromium tricarbonyl moiety is in many cases controlled by the substituents on the ring to which it is coordinated, and this has been attributed to mesomeric electron repulsion or withdrawal by the substituents 374). 

Potassium tert-butoxide (1 mmol) was added to a premixed mixture of aniline (1 mmol) and methylbenzoate (1 mmol) in a glass test tube which was placed in an alumina bath (neutral alumina 125 g, mesh 150, Aldrich bath 5.7 cm diameter) inside an unmodified household microwave oven and irradiated for the specified time at its full power of 900 W. On completion of the reaction, as determined by TLC (hexane-EtOAc, 4 1, v/v), the reaction mixture was extracted into ethyl acetate. The combined extracts were dried over anhydrous sodium sulfate and the solvent removed under reduced pressure to afford a residue that upon trituration with hexane gave pure product, benzanilide (83%). 

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