3- Ethoxycarbonyl-2-methyl-2- pyrrole

Pyrrol 5-Amino-4-cyan-2,3-dimethyl-1 -(ethoxycarbonyl-methyl)- E6a, 638 [H3C-CO-CH(CH3)-OH + H2N-CH2-COOR ... 

Cyciohexene (4R,5R)-5-Methoxycar-bonyl-1 -methyl-4-(2-oxo-1,3-oxazolidinocarbonyl)- E21c, 2670 (En —CO —NR2 4- 1,3-Dien) 2861 (R2N-CO-CH = CH —COOR + 1,3-Dien) Propansaure 2-Methoxy-2-(phen-oxy-acetamino)- -methylester E14a/2, 294 (En-amin/R-OH) Pyridin 2-(Acetoxy-methyl)-6-ethin-yl-5-hydroxy-l -methoxycarbo-nyl-4-methyl-l,2,5,6-tetrahydro-E21b. 1992 [1-COOR-2-C = CH-4-CH3-l,2-H2-py + 02/SnCl2 H2C = C(CH3)- OR] Pyrrol 5-Ethoxycarbonyl-4-(ethoxycarbonyl-methyl)-3-formyl-2-methyl- E3, 453 (CO-SR - CHO)... 

Ethoxycarbonyl-4-ethoxycarbonylmethyl-3-formyl-2-methyl-pyrrol kann nach folgen-den drei Vorschriften erhalten werden ... 

Methode (a) 50 g W-2 Raney-Nickel werden zu 150ml Aceton gegeben und 2 Stdn. unter Riihren undunter RiickfluB gekocht. 3,77 g (0,011 mol) 5-Ethoxycarbonyl-4-ethoxycarboiiylmethyl-3-(ethylthio-carbonyl)-2-methyl-pyrrol in 100 ml Aceton und 50 ml Methanol werden zugegeben und 2 Stdn. unter RiickfluB gekocht. Der Katalysator wird abfiltriert und das Filtrat i. Vak. zur Trockne eingedampft. Der Riickstand wird aus Methanol umkristallisiert Ausbeute 2,16 g (71%) Schmp. 153—154,5°. 

Ludwig. This compound has an empirical formula corresponding to structure (1) and shows the ultraviolet and infrared" absorptions of a pyrrole-3-carboxylic ester. Its acetylation gives a tetra-O-acetyl derivative." Oxidation with lead tetraacetate yields ethyl 5-formyl-2-methyl-pyrrole-3-carboxylate (4), identical with the compound prepared in a different way. Oxidation with potassium permanganate in alkaline solution at low temperature yields 3-(ethoxycarbonyl)-2-methylpyrrole-5-carboxylic acid (7) which can be transformed " into the diethyl ester (8), identical... 

Pyrrolo[l,2-a]azepin-5-one (11), prepared by cyclization of methyl 5-(pyrrol-2-yl)penta-2,4-dienoate (10) with sodium hydride in toluene, in trifluoroacetic acid solution forms the diatropic 5-hydroxypyrrolo[1,2-a]azepinium ion 12.216 6-Methyl-5//-pyrrolo[l,2-tf]azepin-5-one(mp41 -43 C), formed in low yield (20%) by the action of [(ethoxycarbonyl)methylene]triphenylphos-phorane on 4-(pyrrol-2-yl)but-3-en-2-one, behaves similarly. 

Spiro 1 - methylsulfony 1-3//-indoline -3,2 -[3, 5 -di(ethoxycarbonyl)-4 -methyl-2 //-pyrrole] (64) underwent molecular rearrangement with 100% H3PO3,60% H2SO4, or by heating at 200° to 1,3-di(ethoxycarbonyl)-2-methyl-6-methylsulfonyl-4,5-dihydropyrrolo[ 1,2-c]quinazoline (65)... 

The intramolecular cyclization of 10-chloroacetyl-10,lTdihydro-ll-ethoxycarbonyl-5-ethyl-577-pyrrolo[l,2- ][l,2,5]ben-zotriazepine 87 in the presence of sodium hydrogen carbonate results in the formation of ethyl l,2-dihydro-2-oxo-8-methyl-12b-azeto[2,l- /]pyrrole[l,2-4][l,2,5]benzotriazepine-12b-carboxylate 51 (Scheme 17) <1996FES425>. 

Fig. 11 2 (E)-2-[5-(Methoxycarbonyl)-4//-furo[3,2-Z>]pyrrol-2-yl]vinyl -3-methyl-l,3-ben-zothiazolium iodide 82a, 3-benzyl-2 ( )-2-[5-(methoxycarbonyl)-4//-furo[3,2-2>]pyrrol-2-yl] vinyl -l,3-benzothiazolium bromide 82b, 3-benzyl-2 (E)-2-[5-(ethoxycarbonyl)-4-methyl-furo 3.2-h pyrrol-2-yl vinyl)-l,3-benzothiazolium bromide 82c, 3-benzyl-2 ( )-2- 5-(cthoxycar-bonylj-4-bczylfuro[3,2-h]pyrrol-2-yllvinyl (-1,3-benzothiazolium bromide 82d [23]...

Azaindoles are readily acylated on the pyrrole nitrogen by warming on a water bath with acid anhydrides or with acid chlorides in the presence of carbonate or pyridine. Good yields were obtained by this procedure for the following compounds l-acetyl-7-azaindole, 1-benzoyl- and l-benzenesulfonyl-7-azaindole, l-benzoyl-2-methyl-7-azaindole, 1-ethoxycarbonyl- and l-chloroacetyl-7-azaindole, l-acetyl-3-cyano-7-azaindole, 1-benzoyl-4-azindole, and 1-acetyl- and l-benzoyl-2,5-dimethyl-4-azaindole. The only reported failure was with 5-methyl-2-phenyl-4-azaindole, which failed to react with acetic anhydride or benzoyl chloride. 2-Methyl-7-azaindole-3-acetic acid was acylated by treatment of its ierGbutyl ester with sodium hydride in dimethylformamide, followed by p-chlorobenzoyl chloride. ... 

Phenol 6-Hydroxymethyl-4-methyl-2-thiocyanatomethyl- IX, 858 3H-Pyrrol 3-Phenylsulfonyl-4,5-dihydro-Ell, 1254 (C,C-Aufbau) Thiophen 4-Cyan-2-ethoxycarbonyl-5-ethyl-3-hydroxy- E6a, 297 [HS-CH2-COOR + RO-C(C2H 5) = C(CN) - COOR]... 

Carbamidsanre N-(l-Hydroxy-2,2,2-trifluor-ethyl)- -(4-methoxy-benzylester) E14a/2, 60 (R-CHO/RO-CO-NH2) Pyrrol 4-Acetyl-2-ethoxycarbonyl-5-methyl-3-trifluormethyl-E6a, 625 (F3C-CO-CH2-COOR + HN02 2,4-Pentandion/Zn)... 

Pyrrol 2-Ethoxycarbonyl-4-ethyl-5-methyl-3-trifluormethyl- E6a, 625 (4-CO-CHj - 4-C2H5)... 

It was noted that the decomposition of the addition product (196) may proceed simultaneously by two different routes, giving either the expected pyridine derivative (197) or pyrrole derivative (198) as the major product (Scheme 10). Treatment with ethanolic hydrochloric acid gives mainly 197 (formed by cleavage of the C—0 bond of the adduct), while aqueous hydrochloric acid gives mainly 2-acety 1-3,4-bis(ethoxycarbonyl)pyrrole (198), probably by hydrolysis of the C=N bond of adduct 196. Similar results have been obtained with 4-methyl-5-ethoxyoxazole.352... 

In the pyrrole series, in which the presence of the destabilizing amino group is better avoided, it has been shown that the ureide 182 can be made by Curtius rearrangement of the corresponding 3-carboxyazide. This ureide was converted to 7-methylpyrrolo[3,2-d]pyrimidine-2,4-dione (see 14) in good yield when refluxed in methanolic sodium methoxide for 5 min. 5-Methylpyrrolo[2,3-d]pyrimidine-2,4-dione (see 12) was similarly made from 3-ethoxycarbonyl-4-methyl-2-ureidopyrrole.343... 

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