Hydroxyalkylation carboxylates

Epoxides give p-hydroxyalkyl carboxylates when treated with a carboxylic acid or a carboxylate ion and a suitable catalyst. Tetrahydrofiiran was opened to give O-benzoyl-4-iodo-l-butanol by treatment with benzoyl chloride and SmK. ... 

Although potassium permanganate does not oxidize acetals in aqueous media, with a phase-transfer catalyst under non-aqueous conditions, cyclic acetals are converted into hydroxyalkyl carboxylates [36]. 

Tishchenko reaction. anti-3-Hydroxyalkyl carboxylates are formed in the reaction of P-ketoalcohols with aldehydes. 

The synthetically useful / -keto y-sultones can be prepared by the cycloelimination reactions of (a-carboxyethyl) alkyl alkanesulphonates66, which in turn can be synthesized by reacting alkanesulphonyl chlorides with ethyl a-hydroxyalkyl carboxylates, as illustrated for the synthesis of 5-methyl-l,2-oxathiolan-4-one-2,2-dioxide (20) in equation 49. The ring-closure step involves the generation of a carbanion which is resonance-stabilized by the adjacent sulphonyl group (equation 50). 

Dihydrooxazoles are prepared from y0-amino alcohols (from oxiranes and ammonia, see p 18) and carboxylic acids or carboxylic esters [75]. A -(2-Hydroxyalkyl)carboxylic acid amides can be isolated as intermediates and subsequently subjected to thermal cyclodehydration or to the action of H2SO4, SOCI2 or to other dehydrating agents ... 

Bis(acyloxy)iodo]arenes in the presence of bromide anion in water also oxidize primary and secondary alcohols similarly to the (PhIO) /KBr system [11,12]. The oxidation of primary alcohols using ArI(OAc)2/KBr in water or aqueous methanol affords carboxylic acids or esters [9, 13], while the oxidation of secondary alcohols under similar conditions results in the formation of the respective ketones in excellent yields [14]. Aldehydes can be converted into methyl esters by a similar procedure using PhI(OAc)2/NaBr in an acidic aqueous methanol solution [15]. Likewise, acetals 3 can be converted into the corresponding hydroxyalkyl carboxylic esters 4 by oxidation with PhI(OAc)2/LiBr in water (Scheme 6.3) [16]. 

Chem. Descrip. Hydroxyalkyl carboxylic ester lenic Nature Anionic... 

A perfect transformation of an a2 + b2b into an ab2 polycondensation was first reported by a team of DSM NV [78, 79], Bis(2hydroxypropyl)amine reacts rapidly and almost quantitatively with the amino group, so that a bis(hydroxyalkyl) carboxylic acid is formed (see Formula 10.5). The polyesterification at higher temperatures yields a poly(ester amide), which was commercialized under the trademark Hybrane. Another example of an in situ formation of an ab2 monomer was described by Shu et al. [80]. The reaction of 1,4-diaminobenzene with the monoanhydride of a diphenyl ether tetracarboxylic acid (see Formula 10.5) produces an amino dicarboxylic acid which upon further polycondensation yields a hb poly(amide imide). Polycondensations of 4,3, 5 -trifluorodiphenylsulfone with commercial diphenols were studied by the Fossum group [81, 82]. The para C-F bond id particular reactive and substitution of one meta-position lowers the reactivity of the last C-F group. Therefore, variation of the reactions conditions allows for systematic variation of the DB. 

Carboxylic Amides. Carboxyhc amide nonionic surfactants are condensation products of fatty acids and hydroxyalkyl amines. 

In these compounds the following substituents can be present alkyl,alkenyl,aryl, halogen,sulfonic acid, amino, hydroxyalkyl, acyl, and carboxyl. The cleavages of 5,5 - (109) and 3,5 -diisoxazolyl (111) proceed similarly both isoxazole rings are cleaved in the former (109—> 110). ... 

Substituted allylsilanes are available from the corresponding carboxylic acid esters by treatment with an excess of trimethylsilylmethylmagncsium chloride and cerium(UI) chloride followed by acid catalyzed elimination31. Lactones give rise to 2-([Pg.344]

Aluminum oxide catalyzed addition of ethyl nitroacetate to racemic 2,3-cpoxy aldehydes 7 affords substituted 4,5-dihydroisoxazole 2-oxides through a regio- and stereospecific tandem nitroaldol cyclization process. High diastereoselectivities are observed in the reaction of cis-epoxyaldehydes to yield the ethyl, vi7 -4.5-dihydro-4-hydroxy-5-( I -hydroxyalkyl)-3-isoxazole-carboxylate 2-oxides, with tram configuration at the ring positions, whereas reactions of trans-and 3,3-disubstituted 2,3-epoxyaldehydes proceed with lower selectivities28. 

The reaction fails if the decarboxylation produces a radical that is easily oxidized, such as an a-hydroxyalkyl radical.2 In intermediate cases, such as tert-alkyl or a-alkoxyalkyl radicals,2 the yield based on the parent quinono is usually improved by using an excess of persulfate and carboxylic acid to compensate for the loss of radicals due to oxidation (footnote b, Table I). 

A radical approach to asymmetric aldol synthesis, which is based on the radical addition of a chiral hydroxyalkyl radical equivalent to a nitroalkene, has been reported, as shown in Eq. 4.93.113 The radical precursor is prepared from the corresponding carboxylic add by the Barton reaction,114 which has been used for synthesis of new (3-lactams.115... 

The transformation of lithio derivatives of dibenzothiophene into alkyl, alkenyl, hydroxyalkyl, formyl, acetyl, carboxylic acid, alkyl and arylsilyl, boronic acid, aryl and carbinol derivatives of dibenzothiophene is dealt with in the appropriate sections. In addition, the four mono-tritio derivatives of dibenzothiophene have been prepared from the corresponding lithio derivatives via hydrolysis with tritiated water (Section III, 0,2). ... 

Smith and Liu have successfully prepared an unsymmetrical analog of a Katsui-type salen ligand possessing a hydroxyalkyl group in the 6-position, which facilitated the formation of an ester Hnkage to a polystyrene carboxyl chloride resin (Figure 5.19) derived from Merrifield s resin (chloromethylated polystyrene,... 

Cyclization of 1 -amino-8-(2-hydroxyalkyl)-4-oxoquinoline-3-carboxyl-ates (130) on the action of diethyl azodicarboxylate in the presence of triphenylphosphine afforded 7-oxopyrido[3,2,l-jy]cinnoline-8-carboxylates (131) (92EUP470578). 

The hypothesis ofWindaus and Ullrich48 that imidazole-4(5)-carbox-ylic acid (31) is formed after oxidation of D-glucose to 2-oxomalon-aldehydic acid, 0CH-C0-C02H, needs revision. As the reaction mixture was kept for three years, it is far more probable that a 4(5)-(hydroxyalkyl)imidazole was first formed, and that this was subsequently oxidized by the copper hydroxide in the reaction mixture to imidazole-4(5)-carboxylic acid. 

In contrast to what has been reported (75CB379), 2-(a-hydroxyalkyl)pyri-dinium salts 50 are stable in alkaline solution if no oxidizing agents are present. 2-Acylated compounds (51), however, will hydrolyze instantaneously in alkali and form 52 by elimination of carboxylic acids (65CJC1250 82JHC1549). If oxidation at the 2-a-C position is prevented as in 53, 54 is obtained as might be expected. The alternative oxidation to the 4-pyridone 54 does not occur (75AP637). 

Nitrofuran antibacterials are synthetic compounds that are substitution products of the 5-nitrofuran nucleus, differing in the substituent at position 2. This substituent may be an azomethine group connected with other ring systems, or an alkyl, acyl, hydroxyalkyl, or carboxyl group, free or esterified. All these antibacterials are susceptible to photolysis, particularly by sunlight, and manipulations must be carried out under subdued light. 

No cross ozonide was formed from unsymmetrical alkenes. The authors theorized628 that the carbonyl oxide zwitterionic species formed on wet silica gel immediately adds water followed by rapid decomposition of the intermediate hydroxyalkyl hydroperoxide to carboxylic acid and water. It means that water on silica gel acts as participating solvent. In the absence of adsorbed water, rapid recombination of the adsorbed aldehyde and carbonyl oxide due to a favorable proximity effect gives normal ozonide. The low mobility of adsorbed species on the silica surface accounts for the absence of cross ozonides. 

We have previously reported on the synthesis of a series of mono- and bifunctional poly(DMS) having a variety of reactive end groups, such as silan (Si-H), vinyl, hydroxyalkyl, dimethylamino and carboxyllic acid groups.7 We have also described already on telechelic poly(DMS) having tosylate end group, lb and l b, where the hydrosilation reaction of poly(DMS) having silan end group was performed with allyl alcohol in the presence of Pt/C catalyst, followed by the tosylation reaction with tosyl chloride in the presence of dimethylaminopyridine.9... 

The Reimer-Tiemann reaction is not an effective route to formyl-pyrroles or -indoles (see Section 3.05.1.6) and the oxidation of alkyl and hydroxyalkyl derivatives of the heterocycles and the reduction of carboxylic acid derivatives are discussed in Sections 3.05.2.2 and 3.05.2.4, respectively. 

Carboxylic Amides. Carboxylic amide nonionic surfactants are condensation products of fatty adds and hydroxyalkyl amines. They include diethanolamine condensates, monoalkanolamine condensates, and polyoxyethylene fatty acid amides. 

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