3- Amino-5- -2-methoxycarbonyl

The CO-stretching frequencies (in cm" ) of a typical ester, ketone, and aldehyde are, respectively, exemplified by 4-amino-5-methoxycarbonyl-2-methyl- 1700s and 1145s [73JCS(P1)1629], 5-acetyl-4-amino-3-methyl-(1638s [77JCS(P1)1819], and 4-amino-5-formyl-3-methyl- (1650s... 

Among conversions of the amino to the azido group, 4-amino-2-phenyl-5-phenylazotriazole, treated in turn with hydrochloric acid, sodium nitrite, and sodium azide, produced 4-azido-2-phenyl-5-phenylazotriazole (0°C, 30 min, 76%) (70BCJ3587) 4-amino-5-methoxycarbonyl-3-phenyltriazole, similarly treated, gave the 4-azido analog (82%) (83BSB913). 

Amino-5-methoxycarbonyl-2-[4-(2-mcthoxy-phcnyl)-pipcrazinoj- 152 2-Amino-4-(methoxycarbonyl-methyl)-aus ThiobarnstolT/4-Cbloi -3-oxo-butansaure-mcthylcstcr 48 4-Amino-5-methoxycarbonyl-2-(l-oxo-thiolan-l-ylidenamino)- 152 2-Amino-4-mcthoxycarbonyl-5-phenyl- 64 2-Amino-4-(3-methoxycarbonyl-propyl)- 206 4-Amino-5-mcthoxycarbonyl-2-(2-thicnyl)- 152 2-Amino-5-(methoxy-methyl)- 129 2-Amino-4-(4-methoxy-phenyl)- 90, 223 2-Amino-4-[2-(4-methoxy-phenyl)-ethenyl]- 94 2-Ainino-5-(4-methoxy-phenyl)-4-methyl- 108... 

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... 

Finally, some results obtained from indazoles substituted in the carbocycle are of interest, even though in these cases the reaction does not involve the heterocyclic moiety (Section 4.04.2.3.2(ii)). For example, pyrazolo[3,4-/]- (566) and pyrazolo[4,3-/]-quinolines (567) have been obtained from aminoindazoles by the Skraup synthesis (76JHC899). Diethylethoxy-methylenemalonate can also be used to give (566 R = C02Et, R = OH) (77JHC1175). Pyrazolo-[4,3-/]- and -[4,3-g]-quinazolones (568) and (569) have been obtained from the reaction of formamide with 5-amino-4-methoxycarbonyl- and 6-amino-5-carboxyindazole, respectively (81CB1624). 

Pyrazine, 2-amino-5-(3-indoloyl)-synthesis, 3, 180, 181 Pyrazine, 2-amino-3-methoxycarbonyl-chlorination, 3, 163... 

W-(Methoxycarbonyl)triphenylphosphine imide reacts with methyl trifluoro-pyruvate to form methyl A -methoxycarbonyl 2 immo-3,3,3 trifluoropropionate m 95% yield This convenient building block easily adds nucleophiles such as Gngnard reagents without competing side reactions at the ester group to form trifluoromethylated amino acids [J.S] (equation 31)... 

Sodium N-(1-methoxycarbonyl-1 -propen-2-yl)-D(-)-0 -amino-(4-hydroxyphenyl)acetate Ethyl chlorocarbonate... 

The synthesis of the E-ring intermediate 20 commences with the methyl ester of enantiomerically pure L-serine hydrochloride (22) (see Scheme 9). The primary amino group of 22 can be alkylated in a straightforward manner by treatment with acetaldehyde, followed by reduction of the intermediate imine with sodium borohydride (see 22 —> 51). The primary hydroxyl and secondary amino groups in 51 are affixed to adjacent carbon atoms. By virtue of this close spatial relationship, it seemed reasonable to expect that the simultaneous protection of these two functions in the form of an oxazolidi-none ring could be achieved. Indeed, treatment of 51 with l,l -car-bonyldiimidazole in refluxing acetonitrile, followed by partial reduction of the methoxycarbonyl function with one equivalent of Dibal-H provides oxazolidinone aldehyde 52. 

Method B 2-Amino-4-tolyl 2-(methoxycarbonyl)phenyl sulfide (273 g, 1 mol) was heated at 215-230JC for 1 h under N2 and MeOII was allowed to distill off. The mixture was heated at this temperature under vacuum for a further 30 min, cooled to 100°C, diluted with EtOH (400 mL) and refluxed for 1 h. The mixture was cooled and the solid product was collected and recrystallized (EtOH, 400 mL), giving colorless crystals yield 217 g (90%) mp 288 -290 C. 

Dimethyl l- l,2-Bis(methoxycarbonyl)vinyl amino -2-(methylsulfanyl)-4-phenyl-l//-l,3-diazepine-5,6-di-carboxylate (2) Single Procedure 154... 

Allylic oxidation, 25 Aluminum chloride, 28 Amine, dnsopropyl- [2-Propanamine, Af-(l-methylethyl)-], 36 Ammonium, (methoxycarbonylsulfamoyl)-tnethyl-, hydroxide [Ethanaminium, W.W-diethyl-A-t [ (methoxycarbonyl)-amino] sulfonyl] -, hydroxide, inner salt], 41... 

The extranuclear C-nitrosoquinoxalines are typified by 3-(a-methoxycarbonyl-a-nitrosomethyl)-2(l/i)-quinoxalmone (66), made by nitrosation of 3-(methoxy-carbonylmethyl)-2(l/f)-quinoxalmone (65) [AcOH, CI3CO2H, C5H11ONO, 20°C, 3 h 91% spectra suggest that the hydroxyimino tautomer (67) may predominate] and was subsequently reduced to afford 3-(a-amino-a-methoxycarbonylmethyl)-2(l//)-quinoxafinone (68) (PtOa, H2, 1 atm, THF, EtOH, 20°C, 4 h 59%) also by 3-[a-(4-amino-5-methyl-4//-l,2,4-triazol-3-yl)-a-nitrosomethyl]-2(l//)-quinoxa-linone (69, R = NO), prepared by nitrosation of 3-(4-amino-5-methyl-4//-1,2,4-triazol-3-ylmethyl)-2(177)-quinoxalinone (69, R = H) [NaN02 ( 1.25 equiv), AcOH, H2O, no further details 79%]." ... 

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... 

C15H21NO5) see Gusperimus trihydrochloride 4-[hydroxy[5-[[(phenylmethoxy)carhonyl]amino]pen-tyl]amino]-4-oxobutanoic acid (C,7H24N20ft 106410-46-2) see Deferoxamine D-a-(4-hydroxyphenyl)-tx-(2-methoxycarbonyl-l-methyl-cthenylamino)acetic acid anhydride with monoethyl carbonate... 

Perhydropyrido[l,2- ]pyrazin-l-one was prepared in the reaction of methyl pipecolinate and ethylene imine in boiling EtOH <19951JSP5461047>. Cyclocondensation of ethyl 2-amino-2-(2-pyridyl)acetate with DMAD, followed by treatment of reaction mixture with NaOMe, gave the 2-(l-methoxycarbonyl)-4-oxo-47/-pyrido[l,2- ]pyrazin-3-yl)acetate <1996JHC639>. 

Amino-3-(methoxycarbonyl)pyrazine 89 is a versatile reagent for the cyclocondensation reactions leading to heterocondensed pteridines 90-93 (Scheme 6) <2001JHC1173>. 

Frejd and co-workers utilized a different tactic for aniline cyclization by first employing a Heck-Jeffery protocol under solvent-free conditions to prepare o-amino dehydrophenylalanine derivatives from o-aminoaryl iodides with the former undergoing a spontaneous la cyclization-elimination sequence to afford 2-methoxycarbonyl indoles <06S1183>. Dimethyl(methylthio)sulfonium trifluoromethanesulfonate (DMTST) was used by the Okuma group to promote the cyclization of o-vinyl-A-p-toluenesulfonylanilide to N-tosylindole <06CL1122>. 

Similarly, chiral nitrones (61a—c) and (62a—c) were obtained from the corresponding a-amino aldehydes (209, 210), nitrones (63a,b) from p-amino-a-hydroxy aldehydes (211), and chiral nitrones (64) and (65) from IV-fluorenyl-methoxycarbonyl (/V-Fmoc) amino acids and /V-Fmoc-dipeptides (Fig. 2.6) (212). 

Dimethyl allene-l,3-dicarboxylate 476 can react with a variety of nucleophiles with an N=C-NH2 substructure to afford monocyclic or bicyclic compounds 501. In this reaction the iminyl nitrogen first attacks the center carbon atom of the allene moiety to afford 3-amino-4-(methoxycarbonyl)-2-butenoate, in which the other nitrogen atom and the conjugated carboxylate undergo an aminolysis reaction to afford the cyclic product [226],... 

Zhang Y, Adachi M, Zhao X, Kawamura R, Imai K (2004) Histone deacetylase inhibitors FK228, N-(2-aminophenyl)-4-[N-(pyridin-3-yl-methoxycarbonyl)amino-methyl]benzamide and m-carboxycinnamic acid bis-hydroxamide augment radiation-induced cell death in gastrointestinal adenocarcinoma cells. Int J Cancer 110 301—308... 

---