5-Methoxycarbonyl-2-nitro

Die Umsetzung von verschiedenen elektronenreichen Alkenen mit Diazo-nitro-essigsaure-methylester in Gegenwart katalytischer Mengen Rhodium(II)-acetat liefert Gemische aus substituierten 1 -Methoxycarbonyl-1 -nitro-cyclopropanen und N-substituierten Acethydroxamsauren1-2 z. B. ... 

The effect of substituents on the reactivity of heterocyclic nuclei is broadly similar to that on benzene. Thus mem-directing groups such as methoxycarbonyl and nitro are deactivating. The effects of strongly activating groups such as amino and hydroxy are difficult to assess since simple amino compounds are unstable and hydroxy compounds exist in an alternative tautomeric form. Comparison of the rates of formylation and trifiuoroacetylation of the parent heterocycle and its 2-methyl derivative indicate the following order of sensitivity to substituent effects furan > tellurophene > selenophene = thiophene... 

Dimethyl-2-phenyl- 365 6-Nitro-3-oxo-2-methoxycarbonyl- 568 6-Nitro-3-oxo-2-methoxycarbonyl- -1-oxid 568... 

Amino-7-methoxy-2-methoxycarbonyl-3-phenyl-5,8-quinoxalinequinone 6-Amino-7-methoxy-l-methyl-2-oxo-3-phenyl-1,2-dihydro-5,8-quinoxalinequinone 3-Amino-6-methoxy-8-nitro-2-quinoxalinecarbo-nitrile 1,4-dioxide... 

Bicychc pyrazinones foimd in several natural products were synthesized via Michael addition of heterocyclic amines to nitro olefin followed by reduction/cyclization of the nitro group of the adduct [20] (Scheme 5). Further elaboration of the C-6 methoxycarbonyl group in pyrazinone to the n-propyl guanidine group could result in the synthesis of indoloperamine. 

Alkylation of ll-mercaptopyrido[l,2-h]cinnolin-6-ium hydroxide inner salts (e.g., 41) with ethyl bromoacetate gave ll-(ethoxycarbonylmethyl(thio derivatives 64 (R = H), which could be hydrolyzed to the ll-(carboxy-methyl)thio derivative or back to the starting compound 41 (74JHC125). Hydrolysis of the ll-bis(methoxycarbonyl)methylene 66 (R = H), and 2-cyano derivatives of 17 (R = H) in boiling HCl afforded 11-methyl and 2-carboxylic acid derivatives, respectively (74JHC125). The 2-nitro derivative of 17 (R = H) was reduced to the 2-amino derivative over Pd/C with NaBH4 in aqueous methanol, and the 2-amino group was acylated with acetic anhydride at 100°C. 

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-... 

Benzofurazane sind auch durch thermische Zersetzung ( 255°) von 2-(Methoxycarbonyl-ami-no)-l-nitro-benzolen zuganglich47. 

Die Reaktion kann auch einen umgekehrten Verlauf nehmen (s. S. 790). 4-Carboxy-benzofurazan-l-oxid (R = OH) sowie 4-Methoxycarbonyl- (R = OCH3) bzw. 4-Ami-nocarbonyl-benzofurazan-l-oxid (R = NH2) lagern sich offensichtlich nicht in die zu erwarten-den 3-substituierten 7-Nitro-2,l-benzoxazole um274 moglicherweise sind in diesen Fallen die Benzofurazan-1-oxide thermodynamisch stabiler. 

Die Umsetzung von l-Methoxycarbonyl-3-nitro-10-oxo-pentacyclo[5.3.0.02 5.03,9.04,8]decan mit N-Brom-succinimid (NBS) in waBr. 1,4-Dioxan-Losung und anschlicBende Ozonolyse liefert 3,I0-Dinitro-l-metho-xycarbonyl-pentacyclo[5.3.0.O1. 0A,li decan (16%)2. 

Die C-Hetarylierung1,2 von Nitro-alkanen gelingt in hohen Ausbeuten mit substituierten 5-Acetyl-2-nitro- und 5-Methoxycarbonyl-2-nitro-furan unter Denitrierung am Furan-System in Kalium-tert.-butanolat/Phosphorsaure-tris-[dimethylamid]1 ... 

Methyl-4-nitro-butanal 2- (6-Methoxycarbonyl-hexyl)-3-nitromethyl-1-oxo-cyclopentan 4-Hydroxy-2- (6-meth-oxycarbonyl-hexyl)-3-nitromethyl-l-oxo-cyclopentan... 

In Gegenwart von sek. Aminen (z. B. + -tp-Ephedrinen) reagiert 3-Methoxycarbonyl-1-oxo-1,3-dihydro-2-benzofuran mit 2-Nitro-1-phenyl-ethen zu l-Methoxycarbonyl-l-(2-ni-tro-l-phenyl-ethyl)-3-oxo-l, 3-dihydro-2-benzofuran ( 100%) ... 

COOCHa O-Q Benzol, Pyrrogalol 0 25 -78 4 5-exo-Methoxycarbonyl-6-endo-nitro-1 -(2-tetra-hydropyranyloxy) -bi-cyclo[2.2.2 oct-2-en 82 85-97 2... 

H (fj j>-C00CH3 O-CO-CF, NaNOj/ CuSO DMF 2-Methoxycarbonyl-4-nitro-2,3-dihydro-indol 54 186- 187 3... 

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