3- Amino-l-methoxy

Amino-l-methoxy-cyclohexan 12,2 g (0,1 Mol) 3-Methoxy-anilin werden in 30 ml tert.-Butanol gelost und mit 0,2 g Lithium-dotiertem Rhodium(III)-oxid (s. u.) bei 80°/80-l 00 bar in einem 2(J0-m/-Autokiaven hy-driert. Danach wird destillativ aufgearbeitet Ausbeute 12,15 g (95% d.Th.). 

Amino-l-hexyloxy- 134 3-Amino-l-methoxy- 134 2-Amino-2-mcthyl- 396 2-Amino-l-nitro- 491, 493... 

Reisch et al. (93JHC981) described two different methods for the synthesis of 4-azaacronycine 71. One method involves the fusion of 1,3-dihydroxy-10-methyl-9(10//)-acridone 69 with 3-amino-3-methylbut-l-yne in the presence of CuCb in a closed ampule, followed by methylation (Scheme 13). The second method involves the A-alkylation of 3-amino-l-methoxy-lO-methyl-9(107/)-acridone 70 with 3-chloro-3-methylbut-l-yne, followed by in situ cyclization (Scheme 13). 

Amino-l -isopropylamino-2,2-dimethyl- 379 2-Amino-l-(4-methoxy-3,5-dimethyl-phenyl)- gQ... 

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... 

C8H18N204 L-3-Amino-l,3,6-trideoxy-l-methoxy-6-(methylamino)-c/iiro-inositol (fortamine) (FRTMNE)51... 

Amino-ethyl)-3-hydroxy-l-methoxy-cyclohexen wird schon in der Kalte durch 20%ige Schwefelsaure unter Hydrolyse der Methoxy-Gruppe zu 7-Oxo-2-aza-bicyclo [3.3. l]nonan cyclisiert3. 

Typical primary amines which undergo such nitrosation are m-toluidine, p-xylidine, m-anisidine, 2-amino-4-methoxytoluene, 3-amino-4-methoxy-toluene, m-aminophenol, a-naphthylamine, l-naphthylamine-2-, -6-, -7-, and -8-monosulfonic acids, and l-naphthylamine-4-monosulfonic acid (which reacts with displacement of the sulfonic acid group). The secondary amines derived from these primary amines also can be nitrosated directly (i.e., without the intermediate formation of an JV-nitroso compound which needs to be subjected to the Fischer-Hepp rearrangement). The entering nitroso group appears to substitute exclusively in the para position. 

H NMR spectra of 117/-pyrido[2,l-b]quinazolin-l 1 -one (27) and its 2-amino, 3-amino, 2-methoxy, 8-nitro, 9-methyl, and 3-chloro derivatives were measured using DMSO-d6 (83MI3). 

A number of 1,2,4-triazines such as the parent compound, the 3-methylthio, 3-methoxy and 3-amino-6-bromo derivatives add ammonia in liquid ammonia at -44 °C to the N(4) —C(5) bond to give adducts of type (lOl), as was shown by XH and 13CNMR spectroscopy. No reaction was observed with 3-methoxy-l,2,4-triazine 1-oxide (71), other 3-amino-l,2,4-triazines, or compounds with a substituent in the 5-position. As was shown using lsN-enriched ammonia, an equilibrium between the covalent addition products (101) and the open-chain isomers (102) does not occur (78RTC273). 

Oxidation of 3-methoxy- or 3-phenoxy-1,2,4-triazines (228) with perbenzoic acid converted them into the appropriate 1-oxides (229) (71JOC787). Peracid treatment of 1,2,4-triazin-3-ones with an unsubstituted 5-position (84 R5 = H) gave l,2,4-triazine-3,5-diones (182) (69JHC403), while 5-substituted l,2,4-triazin-3-ones (84) afforded the appropriate 1-oxides (230) (66JOC3914). 3-Amino-l,2,4-triazines with an unsubstituted (86a) or a monosubstituted amino group (86b) were oxidized by peracids to give the 2-oxides (231), while the 3-dialkylamino compounds (86c) afforded the 1-oxides (232) (77JOC546). 

However for the formation of optically active a-alkyl aldehydes, the imine or hydrazone routes have proved of considerable value.122 In the preparative example123 the aldehydes propanal and octanal are converted with (S)-( — )-2-amino-l-methoxy-3-phenylpropane (14) into the imines (15) and (16) respectively. Treatment with lithium diisopropylamide then yields the corresponding lithioenamines [only the (fs)-isomers are formulated, since the (Z)-isomers would be less stable]. These intermediates have a topography which determines the subsequent direction of attack by the alkyl halide (see also Section 5.11.7, p. 688). In the formulation below, this stereoselection is from above the plane of the paper and leads to the (/ )- and (S)-2-methyloctanals respectively. 

Butan 2-Amino-l-methoxy-3-methyl-E21f., 5787 (OH - OCH3)... 

Methylation of 2-amino-3-hydroxypyrazine (62) with methyl iodide and sodium methoxide afforded 3-amino-l-methyl-2-oxo-1,2-dihydropyrazine (63), and when an excess of methyl iodide was used, a mixture of compound (63) and its methio-dide (64) was isolated. Reaction with dimethyl sulfate and alkaU gave compound (63) and l,4-dimethyl-2,3-dioxo-l,2,3,4-tetrahydropyrazine (66) the latter was presumed to be formed by hydrolysis of an intermediate quaternary salt since it was also obtained by treatment of the methiodide (64) with aqueous sodium hydroxide. Reaction of 2-amino-3-hydroxypyrazine with ethereal diazomethane produced a mixture of N- and 0-methyl derivatives, (63) and 2-amino-3-methoxy-pyrazine (65). With methyl toluene-p-sulfonate the quaternary salt 2-amino-3-hydroxy-1-methylpyrazinium toluenesulfonate (67) was obtained on alkaline hydrolysis it gave 3-hydroxy-l-methyl-2-oxo-l,2-dihydropyrazine (68) (832). Pulcherriminic acid with diazomethane gave a dimethyl derivative (99). 

Dipole moments (D) of some aminopyrazines have been determined as follows 2-amino-6-methoxy (3.08, benzene 3.42, dioxane) 2-amino-5-bromo-3-methoxy (2.94, benzene) 2-amino-3-chloro (1.86, benzene 2.26, dioxane) 2-amino-5-bromo-3-mercapto (2.22, dioxane) and 3-amino/l-oxide (3.43, dioxane) (749). 

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