2-ethoxycarbonyl-6-methyl

Die Cyclisierung von 2-Diazo-4-phenyl-3-pentensaure-ethylester ist mit einer van Alphen-Hiittel-Umlagerung des Phenyl-Restes zum N-Atom verbunden es wird 3-Ethoxycarbonyl-5-methyl-1-phenyl-1 H-pyrazol [87% Sdp. 73°/0,03Torr (3,99 Pa)] gebildet1383. 

Ethoxycarbonyl-2-imino-5-methyltetrahydrofuran-3-yl)-l,4(2//,3//)-phtha-lazinedione (124, X = NH) gave 2-(3-ethoxycarbonyl-5-methyl-2-oxotetra-hydrofuran-3-yl)-l,4(2//,3//)-phthalazinedione (124, X = 0) (HCl, H2O, EtOH, reflux, briefly 92%). ... 

The organic layer is then dried, filtered and evaporated. The oily residue is distilled in vacuo, yielding 1,600 parts dl-N-formyI-N-[(ethoxycarbonyl)methyl] -1 -phenylethylamine (boiling point 160°C to 170°Cat 0.8 mm pressure). 30 parts of a sodium dispersion, 50% in paraffin oil are added to 450 parts tetrahydrofuran and the whole is slowly heated to a temperature of 40°C, while stirring. While maintaining this temperature (cooiing on a water bath is necessary) there are added portionwise 30 parts ethanol. 

After the addition is complete, the whole Is cooled on an ice bath and there is added drop-wise a solution of 144 parts dl-N-formyl-N-[(ethoxycarbonyl)methyl] -1-phenylethylamine in 133 parts ethyl formate. After the addition is complete, the mixture is stirred overnight at room temperature. 

EthoxycarbonylaIlylamino)nitrobenzene (53) gave 2-ethoxycarbonyl-methyl-l,2,3,4-tetrahydroquinoxaline (54) (Fe, AcOH, N2, reflux, 30 min ... 

The same substrate (218) and ethyl ethoxalylacetate (Et02CC0CH2C02Et) gave 3-ethoxycarbonylmethyl-2(l//)-quinoxalinone (221, R = H) (EtOH, reflux, 3 h 80% ° likewise but 15 min 64%) the homologous substrate, 3,6-dimetyl-l,2-benzenediamine, and the same synthon gave 3-ethoxycarbonyl-methyl-5,8-dimethyl-2(l//)-quinoxalinone (221, R = Me) (AcOH, reflux, briefly 61%). ... 

Nitroquinoxaline (49) with appropriate carbanions gave 2-(dicyanomethyl)-quinoxaline (48) (95%), 2-[di(ethoxycarbonyl)methyl]quinoxaline (50) (85%), and the like. ... 

Hydrobis(ethoxycarbonyl)methyl Addition - Michael Addition... 

Hirsch A, Lamparth I, Karfunkel HR (1994) Fullerene chemistry in three dimensions isolation of seven regioisomeric bisadducts and chiral trisadducts from C60 and bis(ethoxycarbonyl)methyl ene. Angew. Chem. Int. Ed. Engl. 33 437 138. 

Of interest is also that the rate of liberation of penicillin G from the prodrug was much faster than the breakdown of the former by opening of its /3-lactam ring. Furthermore, no breakdown of the pro-moiety A-(hydroxy-methyl)-A-[(ethoxycarbonyl)methyl]benzamide (8.58) to liberate formaldehyde was detected over the timescale of ester hydrolysis. 

Heating ethyl 5-fluoro-4-[cyano(ethoxycarbonyl)methyl]-2,3-dihydro-l-methyl-7-oxo-l//,7//-pyrido[3,2,l-i7]cinnoline-8-carboxylate (83, R = COOEt) in a mixture of cone. HCl and acetic acid gave the 8-carboxy-4-acetic acid derivative (92EUP470578). The acetic acid group was decarboxylated by heating in boiling ethanol in the presence of NEts to give the 4-methyl derivative. When the 4-[cyano(tert-butoxycarbonyl)methyl]-8-carboxylate 83 (R = COOrBu) was treated with trifluoroacetic acid in methylene chloride at room temperature, the 4-cyanomethyl-8-carboxylate 83 (R = H) was obtained. 

In contrast, when the reaction was conducted using diethyl malonate instead of bromomalonate in the presence of Na2C03 under the HSVM conditions, there was obtained not the cyclopropanated product but a C o derivative having two bis(ethoxycarbonyl)methyl groups at the 1,4-positions 46 in 18% yield (82% based on consumed Cgo) (Scheme 21) [52]. Previously it was reported that... 

Durch Umsetzung von Oxo-phenyl-thioessigsaure-amid mit Glycin-ester und Aldehyden in Ethanol bei 20-40° konnen die entsprechenden l-(Ethoxycarbonyl-methyl)-4-mercap-to-5-phenyl-imidazole hergestellt werden78. 

Substituierte l-(Ethoxycarbonyl-methyl)-4-mercapto-5-phenyl-imidazole allgemeine Arbeitsvorschrift78 ... 

CH2-COOC2H5. .. -4-(4-brom-phenyl)-2-(ethoxycarbonyl-methyl)-. .. 50 236 (Acetonitril) 101... 

Der durch Umsetzung von Bemsteinsiiure-diethylester mit Harnstoff unter Katalayse mit Na-triumethanolat zugangliche N-Acyl-harnstoflf cyclisiert unter Saurekatalayse zu 2,4-Dioxo-5-(ethoxycarbonyl-methyl)-imidazolidin 365. 

HiCiOOC —CH2—Cl KOC2H, ]-( Ethoxycarbonyl-methyl) -2-methyl-4-nitro-... 86 112 855... 

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