Ethoxycarbonylmethyl phenyl

Ethoxycarbonyl-l-mcthyI-ethan)-methyl- -O-cthylester XII/1, 566 Ethoxycarbonylmethyl-phenyl- -O-etbylester aus Ethoxy-phenyl-phosphansulfid, Natrium-ethanolat und Chloressigsaure-etbylcster XII/1, 280... 

Methyl 3-amino-6-bromo-5-ethoxycarbonylmethyl-2-pyrazinecarboxylate Methyl 3-amino-6-bromo-5-methyl-2-pyrazinecarboxylate Methyl 3-amino-6-bromo-5-phenyl-2-pyrazinecarboxylate... 

Ethoxycarbonylmethyl)pyridinium chloride 1 -Trimethylammoniopropion-2-one perchlorate 1 -Phenyl-2-trimethylammonioethan-l -one chloride... 

Japanese workers were the first to use the reactive properties of nitrile compounds to synthesize thiazolo[3,2-a]pyridin-3(2//)-ones (77S839). Ethyl a-cyanocinnamate (88, R = Ph, R = CO Et) reacts with ethyl mer-captoacetate in the presence of triethylamine to give 5-amino-2-benzyli-dene-6,8-bis (ethoxycarbonyl )-7-phenyl-7//-thiazolo [3,2-n]pyridin-3(2//)-one (89, R = R- = Ph, R = R = C02Et), which is also obtained from the reaction of 5-benzylidene-2-ethoxycarbonylmethyl-2-thiazolin-4-one (90a) with ehtyl a-cyanocinnamate (77S839). Reaction of 90a,b with ben-zylidenemalononitrile (88, R- = Ph, R" = CN) and of 90c with ethyl a-cyanocinnamate furnish the respective bicyclic compounds 89 [83ZN(B)781] (Scheme 21). Similar results were also obtained from 88 (R = furan-2-yl-or thiophen-2-yl) (86M105). 

Benzylidene-3-oxo-2,3-dihydro-l-benzotellurophene reacted with hydrogen bromide in glacial acetic acid to produce 2-(2 -phenylethenylcarbonyl)phenyl tellurium bromide. Thienyl ethoxycarbonylmethyl tellurides with a formyl or acetyl group in the orf/to-position to tellurium were also converted to tellurium bromides upon treatment with 48% aqueous hydrobromic acid or glacial acetic acid saturated with hydrogen bromide. Only polymeric materials were obtained from 4-formyl-3-thienyl ethoxycarbonylmethyl tellurium. ... 

Acetylphenyl ethoxycarbonylmethyl tellurium, 2-acetylphenyl phenyl tellurium, and 2-methoxycarbonylphenyl phenyl tellurium lost the alkyl or phenyl groups in refluxing acetic acid containing 30% hydrobromic acid ... 

Attempts to demethylate himbacine with a variety of reagents under several conditions were unsuccessful but dihydrohimbacine was readily converted by cyanogen bromide into the cyanamide (XXVI). This was stable to acid and only slowly hydrolyzed by alkali but catalytic hydrogenation afforded dihydrohimbeline in good yield. By standard methods the following iV-substituted derivatives were prepared ethyl, p-hydroxyethyl (p-nitrobenzoate and trimethylgallate), allyl, m-butyl, ethoxycarbonylmethyl, cyclohexyl, benzyl, /3-phenylethyl, y-phenyl-propyl, and phenylcarbamido. 

The related substrate, 4-methyl-6-oxo-l-phenyl-l,6-dihydro-3,5-pyridazine-dicarbonitrile (154, R = Ph), and a-benzylidenemalononitrile (153) gave 8-amino-3-oxo-2,6-diphenyl-2,3-dihydro-4,7-cinnolinedicarbonitrile (155, R = Ph) [HN(CH2)s, pyridine, reflux, 4h 75%] analogs likewise. Ethyl 5-cyano-1 -o-methoxyphenyl-4-methyl-6-oxo-1,6-dihydro-3-pyridazinecar-boxylate (157) and diethyl 3-oxoglutarate (156) gave ethyl 4-cyano-6-ethoxycarbonylmethyl-8-hydroxy-2-o-methoxyphenyl-2,3-dihydro-7-cinnoU-necarboxylate (158) (AcOH, dioxane, reflux, 8h 79%) one analog... 

The epimeric mixture of 16-ethoxycarbonylmethyl-17-oxo-compounds (45) was prepared from the jS-keto-thiolesters (44) by successive alkylation with bromoacetic ester and treatment with Raney nickel. The epimeric 16-phenyl-selenylandrostenones (46) were prepared via LDA-PhSeCl reaction of the 17-oxo-compound appropriately protected at C-3. Similar reaction of a 20-oxopregnane gave the 21-phenylselenyl derivative (47), and the preparation of the 17a-phenylselenyl analogue involved the reaction of the A -enol acetate... 

A soln. of dimethyl N-(ethoxycarbonylmethyl)iminodithiocarbonate in THF added drop wise to a stirred soln. of K-/cr/-butoxide in the same solvent at -78° under N2, a soln. of phenyl isothiocyanate in the same solvent added slowly after 30 min, stirring continued at —78° for an additional 30 min, the mixture allowed to stand at room temp, for 2 h, then quenched with water 4-ethoxycarbonyl-2-methylthio-5-anilino-thiazole. Y 90%. F.e.s. C. Alvarez-Ibarra et al.. Heterocycles 27, 2177-83 (1988). 

R = H, D) were obtained from the 6-methyl-3-ester derivative and its 6,7,8-deuterio derivative 291 (R = Me, R = COOEt, R -R" = H, D). These derivatives were transformed into 293 (R = H, D) by heating in POCI3. Optically active 291 (R = Me, R = COOEt, R -R = H) afforded optically active 6,7-dihydro-477 294 (R = H), but optically inactive AH-pyrido[l, 2-a]pyrimidine 293 (R = Me, R = COOEt, R = H). Similarly ethyl 9-(A -phenyl-iV-methylamino)-6-methyl-4-oxo-6,7-dihydro-4/7-pyrido[l,2-a] pyrimidine-3-carboxylate gave 9-[iV-(4-formylphenyl)-A -methylamino]-7-dimethylaminomethylene-6-methyl-6,7-dihydro-4-oxo-4/f-pyrido[l,2-u]pyr-imidine-3-carboxylates in a mixture of POCI3 and DMF at lower (20-25 °C) and higher (95 100°C) temperatures, respectively. 9-(Ethoxycarbonyl-methyl)-4-oxo-6,7-dihydro-47/-pyrido[l,2-a]pyrimidine-3-carboxylate 158 (but not 9-ethoxycarbonylmethylene-6,7,8,9-tetrahydro derivative 157) was also transformed into ethyl 9-(ethoxycarbonylmethyl)-7-(l-chloroethyl)-4-oxo-477-pyrido[l, 2-a]pyrimidine-3-carboxylate (99T10221). 

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