3-Hydroxy-alkylamines

Tetrahydro-l,3-oxazines are formed by the addition of CH2O to primary or secondary 3-hydroxy-alkylamines followed by intramolecular elimination of water, i.e. in analogy to the formation of 1,3-oxazolidines (see Section 3.3.8). Accordingly they behave similar, but do not present advantages. Due to their higher molecular weight they release a lower amount (%) of formaldehyde compared with the corresponding 1,3-oxazolidines. Tetrahydro-l,3-oxazines therefore have not much practical importance as preservatives for functional fluids. 

N-Tosylated P-hydroxy alkylamines (which can be easily hydrolyzed to P-hydroxyamines" ) can be prepared " by treatment of alkenes with the trihydrate of Chloramine-T and a catalytic amount of OSO4. In some cases yields can be improved by the use of phase-transfer catalysis." The reaction has been carried out enantioselectively." In another procedure, certain P-hydroxy secondary alkylamines can be prepared by treatment of alkenes with the osmium compounds... 

OxazoUdines — reaction products of 2-hydroxy-alkylamines and formaldehyde... 

After the addition of 1 M CH2O to primary or secondary 2-hydroxy-alkylamines, 1,3-oxazolidines are formed by intramolecular elimination of water (1 M) if at least 1-5 M CH2O are added to a primary 2-hydroxy-alkylamine dioxazolidinyl methanes can be synthesized by the elimination of 3 mol of water intra- and inter-molecularly according to the reaction pattern in Fig. 27. 

Primary 2-hydroxy-alkylamines react with formaldehyde, as is demonstrated in Figure 13, at first to the corresponding N-hydroxymethyl compound which under the separation of water forms the N-methylene compound as an intermediate the latter cyclisizes to 1,3-oxazolidine, or trimerizes exothermically to 1,3,5-hexahydrotriazine. As the 1,3-oxazolidine thus formed disposes of a N-H group, it can react with additional formaldehyde to the corresponding dioxazolidinylmethane. 

Secondary 2-hydroxy-alkylamines react with formaldehyde to 1,3-oxazolidines, too, but constitutionally not to dioxazolidinylmethanes, or 1,3,5-hexahydro-triazines. 

Hydroxymethyl)amino]alkanols result from the addition of formaldehyde to 2-hydroxy-alkylamines. Such compounds are the intermediates in the formation of 1,3-oxazolidines (e.g. 3.3.10.) or hexahydro-s-triazines (e.g. 3.3.18.) see Figures 13 and 10. 

Alkylamination of naphthazarin copper complex (37)22 gives predominantly a mixture of 2(or 3),5-bis(alkylamino)-8-hydroxy-l,4-naphthoquinone (38) and 2,6-bis(alkylamino)-4,8-dihydroxy-l, 5-naphthoquinone... 

O-Alkylation of 4-hydroxy-3-morpholino-l,2,5-thiadiazole 132 has been achieved with the chiral cyclic chloro-methyl sulfite 133 which subsequently suffers ring opening on treatment with simple alcohols <2001RCB436> or alkylamines <2002RJ0213> to afford the timolol analogues 134 with very little racemization (Scheme 20). This indicated an almost exclusive attack of the oxy anion on the exocyclic carbon atom and is a significant improvement on the previous oxirane method, which suffers from racemization. An alternative biocatalytic asymmetric synthesis of (A)- and (R)-timolol has also appeared <2004S1625>. 

Kinetic parameters k, often also and AS, occasionally AV ) for formation and dissociation of several pentacyanoferrate(II) complexes [Fe(CN)5L]" have been established. Ligands L include several S- and A-donor heterocycles,4-methyl- and 4-amino-pyridines, a series of alkylamines, 3- and 4-hydroxy- and 3- and 4-methoxy-pyridines, several amino acids, nicotinamide, " 4-pyridine aldoxime, 3-Me and 3-Ph sydnones, several bis-pyridine ligands,neutral, protonated, and methylated 4,4 -bipyridyl, 1,2-bis(4-pyridyl)ethane and traTO-l,2-bis0-pyridyl)ethene, pyrazine- 4,4 -bipyridyl- and bis(4-pyridyl)ethyne-pentaammine-cobalt(III), edta-ruthenium(III), and pentaammineruthenium-(II)and-(III) complexes of... 

Although electrochemical oxidation of Al-cyclohexyl-Al-hydroxylamine in the presence of pyridine afforded the corresponding dimeric nitroso compound with a low yield, A-hydroxy t-alkylamines were transformed into the corresponding nitroso compounds (equation 8) . Similarly, A-phenylhydroxylamine was transformed into nitrosobenzene under similar reaction conditions. ... 

JAP624149) and a wide variety of l-lV-alkylperhydro-l,7-naphthyridines (207) have been obtained by reaction of the ether (208) with various alkylamines (66KGS427). A convenient synthesis of 5-hydroxy-2-oxo-l,2,3,4-tetrahydro-l,7-naphthyridine (211) starts from the 3-substituted amino isonicotinaldehyde (209) which undergoes a Wittig reaction followed by reduction to give (210), a compound that cyclizes readily in acid solution to (211) (82CPB1257). 

An Stelle der Hydroxy-Derivate lassen sich auch die entsprechenden Alkoxy- oder Alkylamin-Derivate einsetzen, statt Essigsaure auch andere Carbonsauren, aber auch Saureanhydride bzw. Ansolvosauren wie C02, S02, CS2 reagieren mit Aminoderivaten unter Bildung von Amidosauren ... 

Sulfinic acids and sulfoxides are not particularly common, being readily oxidized to the sulfonic acids and sulfones, respectively. Sulfonic acids have high melting points and probably exist as zwitterions. They are amphoteric, but mainly display the characteristics of weak acids. The sulfonic acid group activates an adjacent halogen to nucleophilic displacement, and may itself be displaced, e.g. reaction of alkylamines with benzimidazole-2-sulfonic acid. Imidazolesulfonic acids resist esterification and acid chloride formation, and are only hydrolyzed by concentrated hydrochloric acid at 170 °C the 2-isomers are more resistant than the 4- or 5-isomers. Aqueous alkali converts the free acids into hydroxy derivatives. Sulfonyl chlorides are accessible via the thiols (Section 4.07.3.6.1) which react with ammonia to form sulfonamides, or are reduced by tin(II) chloride to thiols (77JHC889). 

Dieckmann cyclization of fe(2-methoxycarbonylethyl)alkylamines under the action of sodium methoxide gave sodium salts of 4-hydroxy-3-met-... 

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