2-methoxycarbonylphenyl

On saponification l-(2-methoxycarbonylphenyl)pyrrole yields l-(2-carboxyphenyl)pyrrole, m.p. 106-107°, which on reaction with polyphosphoric acid at 70° is cyclized to 9-keto-9H-pyrrolo-(l,2-a)indole in 28-32% yield. Through the choice of the appropriate amine and acetal components, the substituted l-(2-meth-oxycarbonylphenyl)pyrroles become readily available intermediates in the preparation of a variety of derivatives of the pyrrolo( 1,2-a) indole ring system. 

Although the preparation has been repeated, there have been no other reports of the type of reaction, (described in 1923) in which carbazole in the presence of excess potassium hydroxide and nitrobenzene at only 50°C gave a good yield of 9-(4-nitrophenyl)-carbazole, presumably via an adduct such as 43 subsequently oxidized by excess nitrobenzene and/or air. More recent examples of N-arylation of carbazoles have involved copper catalysis in reaction of aryl halides with carbazoles. Thus, copper bronze and potassium carbonate heated with the carbazole and the appropriate aromatic halide have produced 9-(4-methoxyphenyl)- and 9-(2-tolyl)carbazoles 9-(4-phenylphenyl)carbazole, l,4-di(carbazol-9-yl)benzene, 4,4 -di(carbazol-9-yl)biphenyl, and 9-(2-pyridyl)- and 9-(2-quinolyl)carbazoles 9-[2-(2-phenylphenyl)phenyl]- and 9-[2-(4-methylphenyl)phenyl] carbazoles 9-(3-bromo-6-nitrophenyl)-, 9-[3-(carbazol-9-yl]-, 9-(2-nitrophenyl)-, 9-(4-methyl-2-nitrophenyl)-, 9-(4-methoxycarbonyl)-l-nitro-, and l-nitro-9-(4-tolyl)carbazoles 9-(2-methoxycarbonylphenyl)carbazole 9-[2- 2-... 

Trithioisatoic anhydrides were also cyclized to thiazolo-[2,3-bjquinazolines (255) upon reaction with 2-aminoethanol or l-amino-2-dimethoxyethane (80PHA124 83ZC215). Double ring closures occured when jV-(2-methoxycarbonylphenyl)thiocarbamate reacted with 2-aminothioethanol (82JIC1117) to give 256. Thermal molecular rearrange-... 

Methoxycarbonylphenyl Tellurium Bromide1 7.2 g (20 mmol) of 2-methoxycarbonylphenyl phenyl tellurium are dissolved in 50 ml of glacial acetic acid saturated with hydrogen bromide. This solution is diluted with 50 ml of acetic acid, the mixture is heated under reflux for 24 h, and then cooled to 20° to allow the product to crystallize yield 6.25 g (87%) m.p. 127-128". 

Acetylphenyl cthoxycarbonylmethyl tellurium, 2-acetylphenyl phenyl tellurium, and 2-methoxycarbonylphenyl phenyl tellurium lost the alkyl or phenyl groups in refluxing acetic acid containing 30% hydro bromic acid5-7. 

FVP of l-(2-methoxycarbonylphenyl)pyrrole 19 at925°C (0.001 Torr) gives the unusual 5//-pyrrolo[2,l- 7]isoindol-5-one system 21 (79%) by a novel three-step cascade process involving rate-determining [l,5]-aryl migration. 

Cyano-l-(2-methoxycarbonylphenyl)-2-phenylisourea, on treatment with ammonia in propan-2-ol at room temperature, cyclizes in 84% yield to 2-(cyanoimino)-l,2-dihydroquina-zolin-4(3F/)-one, which can be hydrolyzed in concentrated hydrochloric acid to give 2-amino-quinazolin-4(3//)-one. ... 

Josey, A. D. 1973. l-(2-Methoxycarbonylphenyl)pyrrole. In Organic syntheses, Collective volume 5, ed. H. E. Baumgarten, 716-717. New York John Wiley Sons. 

To a mixture of 2-methoxycarbonylphenyl tosylate (293, 3.04 g, 10 irnnol), phenyl boronie acid (260, 1.83 g, 15 mmol,1.5 eq.) and potassium phosphate (4.25 g, 20 mmol, 2 eq.) in dioxane (20 ml), deggased with argon was added Ni(PCy3)2Cl2 (210 mg, 0.3 mmol, 3 mol%) followed by tricyclohexylphosphine (340 mg, 0.12 mmol, 4 eq. to Ni). The reaction mixture was refluxed under argon for 60 h. Then the solvent was evaporated and the residue was chromatographed on silica gel column (n-hexane / dichloromethane) affording 1.0 g (47%) of pure methyl biphenyl-2-carboxylate (294). 

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