Propionic hydrolysis

The formation of acyloins (a-hydroxyketones of the general formula RCH(OH)COR, where R is an aliphatic residue) proceeds best by reaction between finely-divided sodium (2 atoms) and esters of aliphatic acids (1 mol) in anhydrous ether or in anhydrous benzene with exclusion of oxygen salts of enediols are produced, which are converted by hydrolysis into acyloins. The yield of acetoin from ethyl acetate is low (ca. 23 per cent, in ether) owing to the accompanying acetoacetic ester condensation the latter reaction is favoured when the ester is used as the solvent. Ethyl propionate and ethyl ji-butyrate give yields of 52 per cent, of propionoin and 72 per cent, of butyroin respectively in ether. 

The three thiazoleacetic acids and higher homologs such as the derivatives of propionic acid have been synthesized (5), They are usually prepared by the Hantzsch s method, either as the free acid or as the ester from which the free acid is obtained by hydrolysis (49, 73). 

Other possible chemical synthesis routes for lactic acid include base-cataly2ed degradation of sugars oxidation of propylene glycol reaction of acetaldehyde, carbon monoxide, and water at elevated temperatures and pressures hydrolysis of chloropropionic acid (prepared by chlorination of propionic acid) nitric acid oxidation of propylene etc. None of these routes has led to a technically and economically viable process (6). 

The nitroparaffins have been utilized for many appHcations (114). Some of these uses have been discontinued because of economic and environmental considerations. For instance, significant quantities of 1-nitropropane once were used for the production of hydroxylammonium sulfate and propionic acid by hydrolysis. The need to dispose of an acid waste stream from this process made it uneconomical, so it was discontinued. 

Desalination membranes with improved, rigid, and stable surfaces have been prepared from cellulose acetate propionate (170). These films are generally more resistant to hydrolysis than those from cellulose acetate. 

Propionic acid [79-09-4] M 74.1, b 141 , d 0.992, n 1.3865, n25 1.3843, pK 5-6.8 (Ho scale, aq H2SO4), pK2 4.88. Dried with Na2S04 or by fractional distn, then redistd after refluxing with a few crystals of KMn04. An alternative purification uses the conversion to the ethyl ester, fractional distn and hydrolysis. [Bradbury J Am Chem Soc 74 2709 1952.] Propionic acid can also be heated for 0.5h with an amount of benzoic anhydride equivalent to the amount of water present (in the presence of Cr03 as catalyst), followed by fractional distn. [Cham and Israel 7 C/iem 5oc 96 I960.]... 

The successful labeling of the elusive 14a-position in cholestane represents a very important application of this reaction.It is known that hydroboration of the double bond in 5of-cholest-14-ene (174) occurs on the a-side. Consequently, by using deuteriodiborane (generated by the reaction of boron trifluoride etherate with lithium aluminum deuteride) and then propionic acid for hydrolysis of the alkylborane intermediate, 14a-d,-5a-cholestane (175) is obtained in 90% isotopic purity. This method also provides a facile route to the C-15 labeled analog (176) when the alkylborane derived from 5a-cholest-14-ene is hydrolyzed with propionic acid-OD. ... 

Similar treatment of (25R)-5a-spirost-14-ene with deuteriodiborane and subsequent hydrolysis with propionic acid lead to 14jS-di-(25R)-spirostane in 79% isotopic purity. ... 

Oil-soluble derivatives of testosterone itself predate those of its 19-nor congener these agents too are used to administer depot injections so as to provide in effect long-term blood levels of drug. Thus, acylation of testosterone with propionyl chloride in the presence of pyridine yields testosterone propionate (76a)acylation by means of decanoic anhydride yields testosterone decanoate (76b).Finally, reaction of 75 with 3-cyclopentylpropionyl chloride affords testosterone cypionate (76c)This last undergoes hydrolysis unusually slowly because of the presence of two substituents at the 5 position (see Newman s Rule of 6). ... 

Phenyl-propionitrile, CgHj. CH.2. CH2. CN, is present in nssturtium oil. It is a powerfully smelling oil, boiling at 261°. On hydrolysis by alcoholic potash it yields phenyl-propionic acid, melting at 47°. 

Table 5 Specific Rate Constant kr x 10 min ) of the Resin Catalyzed Hydrolysis of Ethyl Propionate in Aqueous Solvents at 25°C...

Acetylated polysaccharides form part of the structure of wood, the acetyl radical constituting some 2-5Vo by weight of the dry wood. Hydrolysis to free acetic acid occurs in the presence of moisture at a rate varying from one species to another a wood of lower acetyl content can liberate acetic acid much faster under given conditions than another wood of higher content Small quantities of formic, propionic and butyric acids are also formed but their effects can be neglected in comparison with those of acetic acid. There is a broad, but only a broad, correlation between the corrosivity of a wood and its acidity. The chemistry of acetyl linkage in wood and of its hydrolysis has been examined in some detail. ... 

C. Hydrolysis of Ethyl a, fi-Dicyano- -phenyl Propionate — The product thus obtained is hydrolyzed by boiling under a reflux condenser for four hours with 80 cc. of concentrated hydrochloric acid (sp. gr. 1.19). The substance goes into solution and this clear solution, on cooling, deposits phenylsuccinic acid in small crystals which are nearly colorless. These are filtered off, washed with cold water and dried. The yield of product melting at 164-166° is 17.6-18.4 g. (91-95 per cent of the theoretical amount based on the weight of ester used) (Notes 1 and 2). 

To set the stage for the crucial aza-Robinson annulation, a reaction in which the nucleophilic character of the newly introduced thiolactam function is expected to play an important role, it is necessary to manipulate the methyl propionate side chain in 19. To this end, alkaline hydrolysis of the methyl ester in 19, followed by treatment of the resulting carboxylic acid with isobutyl chlorofor-mate, provides a mixed anhydride. The latter substance is a reactive acylating agent that combines smoothly with diazomethane to give diazo ketone 12 (77 % overall yield from 19). 

Enzyme-mediated hydrolysis of some racemic co-arenesulfinylalkanoic methyl esters, ArSO(CH2) COOMe, using Corynebacterium equi has led to a kinetic resolution in which the unreacted sulfinyl esters are enriched in one enantiomer at the sulfoxide center49. The enantiomeric purity of unreacted sulfinyl acetates and propionate ranges from 90 to 97%. 

In contrast to oxoesters, the a-protons of thioesters are sufficiently acidic to permit continuous racemization of the substrate by base-catalyzed deprotonation at the a-carbon. Drueckhammer et al. first demonstrated the feasibility of this approach by performing DKR of a propionate thioester bearing a phenylthiogroup, which also contributes to the acidity of the a-proton (Figure 4.14) [39a]. The enzymatic hydrolysis of the thioester was coupled with a racemization catalyzed by trioctylamine. Owing to the insolubility of the substrate and base in water, they employed a biphasic system (toluene/H2O). Using P. cepacia (Amano PS-30) as the enzyme and a catalytic amount of trioctylamine, they obtained a quantitative yield of the corresponding... 

Similar aggressive reaction conditions characterize the hydrolysis of acid chlorides, in particular when using short-chain alkyl-substituted acid chlorides such as propionic acid chloride. This fast reaction serves well as a model reaction for micro channel processing, especially for IR monitoring owing to the strong changes in the carbonyl peak absorption by reaction [21]. 

The metabolism of carfentrazone-ethyl in animals and plants is similar. The major plant metabolites are carfentrazone-chloropropionic acid (C-CI-PAc), 3-desmethylcarfentrazone-chloropropionic acid (DM-C-CI-PAc), and 3-hydroxymethylcarfentrazone-chloropropionic acid (HM-C-CI-PAc). The major animal metabolites are carfentrazone-chloropropionic acid (C-CI-PAc) and carfentrazone-propionic acid (C-PAc). The tolerance expression for livestock and plant commodities is carfentrazone-ethyl plus the ester hydrolysis product, C-CI-PAc. 

Reactions of 2,3-dioxo-l,2,3,5,6,7-hexahydropyrido[l,2,3-carboxylic acids and the homologous acetic and propionic acids, prepared by basic hydrolysis of the corresponding ester, with amines, 28% NH4OH, and hydroxylamine derivatives in the presence of l-ethyl-3-[3-(dimethylamino)propyl]carbodiimide and hydroxybenztria-zole <1995BML1527>, 1995BML1533>, and in the presence of NEt3 and A, A -bis(2-oxo-3-oxazolidinyl)phosphinic... 

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