7-Ethyl-7-methyl-5-nitro

Amin (l-Chlor-ethyl)-methyl-nitro-E16a, 1172 (N-Chloralkylier.)... 

Ethyl-methyl-nitro- XI/2, 111 Isopropyl-nitro- E16a, 1149 (NH - N-N02)... 

Amin (2-Cyan-ethyl)-methyl-nitro-E16a, 1169 (NH - N —CH3) Essigsaure Azido- -ethylester X/3, 796 (Cl/N3-Austausch) XI/2, 353 (X/Nj-Austausch)... 

Tile same methodology as mentioned for the preparation of (9) was applied for the synthesis of 8-nitro-l,6-naphthyridines. Heating diethyl N- 3-nitropyridin-4-yl)aminomethylenemalonate (12) in diphenyl ether yields ethyl 8-nitro-l,6-naphthyridin-4(lH)-one 3-carboxylate (13) (63JCS4237, 30%) and acid treatment of 4-( y, y-diethoxypropylamino)-5-nitro-2-(/3,/3 -trifluoroethoxy)-pyridine (14) gives in a similar way 8-nitro-5-(/3, /3-triflu-oroethoxy)-l,2-dihydro-l,6-naphthyridine (15, 76%). Subsequent oxidation with chloranil, acid hydrolysis, and methylation with methyl iodide gives 8-nitro-6-methyl-l,6-naphthyridin-5(6H)-one (16,63%) (81JHC941). 

MethyU2-Nitro-l-Propanol (2-Nitro-2-methyl-1 -propanol, /J-Nitroisobutylalcohol). (CH3)2.C(N02).CH20H, mw 119.12, N 11.76%, OB to C02 —127.60%, needles or plates from methanol, mp 90—91°, bp 94.5—95.5° at. 10mm. Easily sol in ethyl methyl ales, eth and w (350p in lOOp at 20°). May be prepd by treating 2-nitropropane with formaldehyde in the presence of an alkaline catalyst, such as K bicarbonate (Refs 1, 2, 3 4). On nitration, it yields an expl, 2-Methyl-2-Nitro-l-Propanol Nitrate (see below)... 

Ethyl-l-methyl-2(17T)-quinoxalinone 4-oxide Ethyl 3-morpholino-2-quinoxalinecarboxylate Ethyl 6-nitro-2-quinoxalinecarboxylate... 

Nizatidine Nizatidine is N-[2-[[[2-[(dimethylamino)methyl]-4-thiazolyl]methyl] thio] ethyl]-2-nitro-l,l-ethenediamine (16.2.15). According to its chemical structure, nizatidine is somewhat of a hybrid structure of ranitidine and famotidine, in which a side chain of ranitidine and carrying heterocycle, 2-aminothiazol, are used. Likewise, its synthesis also is a specific combination of pathways used for making both prototype drugs. 2-(Dimethyl-aminomethyl)-4-hydroxymethylthiazol serves as the initial compound, from which the desired nizatidine (16.2.15) is synthesized by subsequent reaction with 2-mercaptoethy-lamine hydrochloride and then with iV-methyl-l-methythio-2-nitroethenamine [71,72]. 

Die basenkatalysierte Umsetzung kann auch in Nitrobenzol mil Pyridin als Katalysator [Her-stellung von mehreren 1-(3-Aryloxy-2-hydroxy-propyl)-2-methyl-4-nitro-imidazo-len 38-58%]87t, ohne Losungsmittel mit Kaliumcarbonat als Katalysator [l-(3-ChIor-2-hydroxy-propyl)-2-methyl-4-nitro-imidazol 60%]872 oder in Ethanol mit Natriumhydroxid als Katalysator [l-(2-Hydroxy-ethyl)-2-methyl-4-nitro-imidazol 100%]873 durchgefuhrt we.r-den. Statt Oxiran kann auch 2-Oxo-l,3-dioxolan eingesetzt werden. Dabei entstehen ohne Katalysator bei 160° die 1,4-Regioisomeren [z. B. 2,5-Dimethyl-l-(2-hydroxy-ethyl)-4-nitro-imidazol 60%]874... 

Unter Basenkatalyse ist die 1,4-regioselektive Umsetzung mit Michael-Akzeptoren moglich. So fuhrt die basenkatalysierte Addition von 4(5)-Nitro-imidazol an Acrylnitril in 86% Ausbeute zu l-(2-Cyan-ethyl)-4-nitro-imidazols53. 1-(2-Cyan-ethyl)-5-nitro-imidazole konnen durch Umsetzung von 4(5)-Nitro-imidazolen mit 4-Methyl-benzolsulfonsaure-(2-cyan-ethyl-ester) hergestellt werden873. 

So wird aus 5-Chlor-937, 5-Brom-905 oder 5-Iod-l-methyl-4-nitro-imidazol905 durch Umsetzung mit Kaliumcyanid in Ethanol oder Dimethylformamid in Ausbeuten von 85, 68 bzw. 61% 5-Cyan-l-methyl-4-nitro-imidazol erhalten. Auch 5-Brom-l,2-dimethyl-4-nitro-938, 5-ChIor-l-ethyl-4-nitro-2-propyI-939 und l-Butyl-5-chlor-2-methyl-4-nitro-939 liefern 5-Cyan- 1,2-di-methyl-4-nitro-, 5-Cyan-l-ethyl-4-nitro-2-propyl- (81%) bzw. l-Butyl-5-cyan-2-methyl-4-nitro-imidazol (67%). 

Lithium-2-propan-nitronat reagiert mit 4-(l-Azido-l-methyl-ethyl)-l-nitro-benzol in Ge-genwart von Phosphorsaure-bis-[dimethylamid] zu 4-Nitro-l-(2-nitro-l,1,2-trimethyl-pro-pyl)-benzol (92 %)2 l0. 

Die selektive Nitrierung von Oxidations-anfalligen Hydroxy-arenen, z. B. 1-Hydroxy-naphthalinen, wird bevorzugt mit 3-Methyl- bzw. 3-Ethyl-3-nitro-6-oxo-tetrabrom-1,4-cyclohexadien in Diethylether bei 20° durchgefuhrt1,2 ... 

Diethyl-(4-methoxy-methyl-anilino)- E2, 296 Diethyl-(N-methyl-anilino)- E2, 295, 296 Diethyl-phenoxy- El, 2SI Diethyl-phenyl- -phenylimid XU/1, 177 Difluor-difluormethyl- E2, 836, 854 Difluor-(fluorsulfonyl-methyl)- E2, 857 Difluor-methyl- E2, 836, 854 Difluor-phenyl- E2, 854 Difhior-trifluormethyl- E2, 905 Difluor-triphenyl- E2, 881 Diisopropyloxy-hexyl- El, 135 Diisopropyloxy-methyl- E2, 200, 480 Diisopropyloxy-phenyl- E2. 134, 135, 207 Diisopropyloxy-propyl- E2, 200 Dimcthoxy-methyl- E2, 480 Dimethoxy-phenyl- E2, 204ff, 207, 393, 856, 864 Dimethylamino-diphenyl- E2, 18, 227 Dimethylamino-ethinyl- E2, 230 Dimethylamino-fluor-trifluormethyl- E2, 435 (4-Dimethylamino-phenyl)-diphcnyl- E2, 108 (4-Dimcthylamino-phenyl)-diphcnyl- -(2-nitro-phenylthioimid) E2, 108 Dimethylamino-l-propinyl- E2, 230 (l,l-Dimethyl-butyloxy)-ethyl-methyl- E2, 20, Dimethyl-(diphenylmethylen-amino)- E2, 106 Dimethyl-fluor- E2, 161 Dimethyl-phenyl- E2, 99, 103 Dimethyl-phenyl- -(2-aminocarbonyl-hydrazinocar-bonylimid) E2, 113... 

N-Ethyl-N-nitro-3,6-di methyl-2,4-dinitro-aniline [Ethyl-(dinitrodimethylphenyl)nitramine], (CH8)2CaH(N02)2.N(N02).C2HB mw 284.23,... 

Benzyl-methyl-nitro- E16a, 1155 f. (N-Nitrier.), 1161 (NH -v N-CH3) Methyl-(4-methyl-phenyl)-nitro-E16a, 1175 (N-Nitrier.) Nitro-(l-phenyl-ethyl)- XI/2, 105 Anilin... 

Ethyl-6-nitro- E8a, 1087 (4-N02-Ar-N3 + H5C2-COOH) 5-Methyl-2-nitromethyl- E8a, 1077 (2-NH2 —4-CHj—Ar —OH + 02N-CH = CC12)... 

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