Amino alkoxides

Dihydric alcohols give normal or cycHc alkoxides. Amino alcohols react similarly (57) ... 

When 6-amino-3-chloropyridazine 1-oxide is diazotized in 50% sulfuric acid, 6-hydroxy-3-pyridazinediazonium anhydro salt is formed. An azido group at either position in pyridazine A-oxides can readily be replaced with sodium alkoxides. 

There are two main classes here. Firstly, 5-substituted 4(6)-aminopyrimidines, e.g. the 5-ester (227), are reacted with esters in the presence of sodium (63CB1868), or with acetals in the presence of alkoxide (78KGS1549), to give pyrido[2,3-Keto esters give 6-ketones (229) (80USP4215216), whilst use of aminopyrimidine nitriles gives 7-oxo-5-amino derivatives (81USP4245094). 

Azirines react with alcohols in the presence of alkoxides to give alkoxyaziridines (67JA4456). Further treatment with alcohol and alkoxide results in the formation of amino ketone acetals. Alkoxyaziridines are not isolated in general from the acid-catalyzed addition of methanol to azirines. Azirines are also known to react with amines (66JOC1423). Frequently the initially produced adducts undergo subsequent transformations. 

In contrast reaction with aprotic nucleophiles, e.g. alkoxides, LiAlILt and sulfur ylides (Z ), yields amino acid derivatives (341), resulting from sp C—N bond scission. The third possible way of ring opening, namely at the C—C bond, has also been observed in certain cases, i.e. (342) -> (343) (67TL5033). 

Purines, N-alkyl-N-phenyl-synthesis, 5, 576 Purines, alkylthio-hydrolysis, 5, 560 Mannich reaction, 5, 536 Michael addition reactions, 5, 536 Purines, S-alkylthio-hydrolysis, 5, 560 Purines, amino-alkylation, 5, 530, 551 IR spectra, 5, 518 reactions, 5, 551-553 with diazonium ions, 5, 538 reduction, 5, 541 UV spectra, 5, 517 Purines, N-amino-synthesis, 5, 595 Purines, aminohydroxy-hydrogenation, 5, 555 reactions, 5, 555 Purines, aminooxo-reactions, 5, 557 thiation, 5, 557 Purines, bromo-synthesis, 5, 557 Purines, chloro-synthesis, 5, 573 Purines, cyano-reactions, 5, 550 Purines, dialkoxy-rearrangement, 5, 558 Purines, diazoreactions, 5, 96 Purines, dioxo-alkylation, 5, 532 Purines, N-glycosyl-, 5, 536 Purines, halo-N-alkylation, 5, 529 hydrogenolysis, 5, 562 reactions, 5, 561-562, 564 with alkoxides, 5, 563 synthesis, 5, 556 Purines, hydrazino-reactions, 5, 553 Purines, hydroxyamino-reactions, 5, 556 Purines, 8-lithiotrimethylsilyl-nucleosides alkylation, 5, 537 Purines, N-methyl-magnetic circular dichroism, 5, 523 Purines, methylthio-bromination, 5, 559 Purines, nitro-reactions, 5, 550, 551 Purines, oxo-alkylation, 5, 532 amination, 5, 557 dipole moments, 5, 522 H NMR, 5, 512 pJfa, 5, 524 reactions, 5, 556-557 with diazonium ions, 5, 538 reduction, 5, 541 thiation, 5, 557 Purines, oxohydro-IR spectra, 5, 518 Purines, selenoxo-synthesis, 5, 597 Purines, thio-acylation, 5, 559 alkylation, 5, 559 Purines, thioxo-acetylation, 5, 559... 

The reactions of 2- and 4-cyanoquinazolines are similar to those of the chloro compounds. Thus the cyano group can be replaced by alkoxide, phenoxide, substituted amino, and hydrazino groups substitution of the 4-cyano takes place more readily than that of the 2-cyano group.The nitrile substituent can also be hydrolyzed to an alkoxycarbonyl and amide group/ ... 

The indirect deactivation in 2-amino-4-chloroquinoline (187) requires vigorous conditions (potassium hydroxide in hot ethylene glycol, or boiling propanolic propoxide for 16 hr) to displace the chloro group, which is stable to aqueous alkali and to hydriodic acid. The direct deactivation in 5-amino-2-chloro-3-cyano-6-methyl-pyridine (188) prevents reaction with alkoxide ion under conditions which produce smooth reaction of the des-amino analog. 

Factor b above is discussed in Sections II, B, 1 II, B, 4 and II, C. A hydrogen-bonded structure such as 221 can account for the facile reaction of 5-bromouracil or for the unique, so-called hydrolyzability of carboxymethylthio-azines (237). The latter may also react via the intramolecular mechanism indicated in 136. The hydrogen-bonded transition state 238 seems a reasonable explanation of the fact that 3,4,6- and 3,4,5-trichloropyridazines react with glacial acetic acid selectively to give 3-pyridazinones while other nucleophiles (alkoxides, hydrazine, ammonia, or sulfanilamide anion) react at the 4- and 5-positions. In this connection, 4-amino-3,5-dichloro-pyridazine in liquid hydrazine gives (95°, 3hr, 60%yield)the isomer-... 

Substitution of an additional nitrogen atom onto the three-carbon side chain also serves to suppress tranquilizing activity at the expense of antispasmodic activity. Reaction of phenothia zine with epichlorohydrin by means of sodium hydride gives the epoxide 121. It should be noted that, even if initial attack in this reaction is on the epoxide, the alkoxide ion that would result from this nucleophilic addition can readily displace the adjacent chlorine to give the observed product. Opening of the oxirane with dimethylamine proceeds at the terminal position to afford the amino alcohol, 122. The amino alcohol is then converted to the halide (123). A displacement reaction with dimethylamine gives aminopromazine (124). ... 

Alcohol dehydrogenase, 178 Alkaline error, 149 Alkaline phosphatase, 185 Alkanethiols, 46, 123 Alkoxide precursor, 120 Amino acids, 92, 187 Ammonium sensor, 181, 182 Amperometric sensors, 172 Aniline, 35, 39... 

The organotin alkoxides RgSnOR and R2Sn(OR >2 can be prepared by treating the appropriate organotin chlorides with sodium alkoxides, and this procedure has been extended to the preparation of the monoal-kyltin trialkoxides, RSnCOR la (190), which serve as useful reagents for the synthesis of other monoalkyltin derivatives. Alternatively, the trialkoxides can be prepared by alcoholysis of the tris(amino) compounds RSn(NR )3 (191). 

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