Imidazoline derivatives hydrolysis

For generating 3-imidazoline derivatives containing no N-oxide oxygen, 1,2-hydroxylaminoketones were employed, which are formed in the acidic hydrolysis of 1,2-hydroxylaminooximes (Volodarsky and Sevastyanova, 1971), The interaction of 1,2-hydroxylaminoketones with ketones and ammonia under mild conditions (in some cases at 20°C) leads to the formation of l-hydroxy-4-aryl- and l-hydroxy-4-alkyl-2,2,5,5-tetraalkyl-3-imidazolines (12) (Sevastyanova and Volodarsky, 1972 Volodarsky and Sevastyanova, 1973). Compounds 12 are colorless crystalline substances that have lower melting points and are more readily soluble in organic solvents than 3-imidazoline-3-oxides 6. When stored or recrystallized in air, they become partially oxidized to radicals. Oxi-... 

The cyclization of an imidazoline derivative can be followed by observing the disappearance of the bands at 1560 and 1638 cm" and the appearance of the band at 1600 cm" (25). Hydrolysis of the ring structure to produce the amide can be followed by reversing the process. 

Most of the amphopropionate surfactants produced are of the amphodipropionate type, 2 mol of methyl acrylate or sodium acrylate added per mole of imidazoline. Depending on the reaction conditions, 1 mol of acrylate can add to the fatty R group at the alpha carbon. Upon hydrolysis of the imidazoline, the second reacts with the liberated secondary amine to produce the beta alanine derivative. If methyl acrylate is used, the methyl ester of the amphoteric surfactant is formed. An equimolar amount of sodium hydroxide is added to effect saponification to the sodium salt of the surfactant. Methanol is formed as a by-product and it is generally left in the final product as part of the solvent system. 

Like the amphoacetates and amphopropionates above, the amphohydroxypropylsulfonates are derived from hydrolyzed alkyl hydroxyethyl imidazolines. In this, amido-functional alkanolamine hydrolysis product is alkylated with sodium l-chloro-2-hydroxypropane sulfonic acid (see Figure 6.13). These products have good hard water tolerance and have applications including metal cleaning as well as personal cleansing. 

Hydrolysis in aqueous ethanol of 2-methyl imidazolines 561, derived from C2-symmetric diamines and the Pinner salt, leads to mono-protected 1,2-diamines 562. The latter are readily converted into A, A -disubstituted 1,2-diamines (Scheme 131) <2000TL8431>. N-protected A -imidazolines are readily hydrolyzed under milder conditions. Thus peptidyl trifluoromethyl ketones 564 were prepared through hydrolysis of 563 <1996JA8485>. 

Imidazolinium salts are also derived from diethylenetriamine. The diami-doamine that results from the esterification of this molecule is dehydrated into an imidazoline, then quaternized with dimethylsulfate, as shown in Figure 12.4 [51]. The resulting molecule is no longer susceptible to hydrolysis. Despite the low price of the material from which they derive, imidazolinium salts are expensive because of their manufacturing cost. This is due to the costly conditions necessary to convert the diamidoamine into imidazoline [3], Details of the synthesis may be found in Egan [37] or Billenstein and Blaschke [38],... 

On the basis of the previous results. Park, Jew, and co-workers [101] developed in 2009 an efficient synthetic methodology for enantiomerically pure a-alkyl-a,3-diaminopropionic acid. They described the asymmetric PTC alkylation of Af(l)-Boc-2-phenyl-2-imidazoline-4-carboxylic acid /cr/-butyl esters (52) with propargyl, allyl, and substituted benzyl bromides under catalysis with the binaphthalene-derived PTC XXV (Scheme 8.19). Alkylated products were obtained in high yields with excellent enantioselectivities and their acidic hydrolysis furnished corresponding optically active a-alkyl-a,(3-diaminopropionic acids. Another example of PTC alkylation of heterocyclic compounds, namely 1-cyanotetrahydro-(3-carbolines using a binaphthyl-modified V-spiro-type catalyst L, was reported by Maruoka and co-workers [103]. 

SCHEME 1.3 Preparation of amphoacetates, or amphocarboxyglycinates, through the reaction of fatty derivatives with AEEA to produce the imidazoline intermediate, then partial hydrolysis and reaction with SMCA. 

Alkali treatment of 4-dihalomethyl derivatives 65a leads not to aldehyde 83a, but to acid 46. Nitroxyl aldehyde 83a was prepared by acid hydrolysis of 4-iminomethyl-3-imidazoline-3-oxide nitroxide (78). Alkaline hydrolysis of 4-a,a-dichloroethyl nitroxide (65b, X = Cl) leads to ketone 83b (Grigor ev et al, 1979b). 

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