Transesterification, partial

Manufacture. Cyanoacetic acid and cyanoacetates are iadustrially produced by the same route as the malonates starting from a sodium chloroacetate solution via a sodium cyanoacetate solution. Cyanoacetic acid is obtained by acidification of the sodium cyanoacetate solution followed by organic solvent extraction and evaporation. Cyanoacetates are obtained by acidification of the sodium cyanoacetate solution and subsequent esterification with the water formed being distilled off. Other processes reported ia the Hterature iavolve the oxidation of partially oxidized propionittile [107-12-0] (59). Higher esters of cyanoacetic acid are usually made through transesterification of methyl cyanoacetate ia the presence of alumiaiumisopropoxide [555-31-7] as a catalyst (60). 

Although these Boc derivatives underwent methylation with poor selectivity (compared to 3-amino-N-benzoyl butanoates [106] and Z-protected methyl 4-phen-yl-3-aminobutanoate [107]), epimers were succesfully separated by preparative HPLC or by flash chromatography. However, saponification of the methyl ester caused partial epimerization of the a-stereocenter and a two-step (epimerization free) procedure involving titanate-mediated transesterification to the corresponding benzyl esters and hydrogenation was used instead to recover the required Boc-y9 -amino acids in enantiomerically pure form [104, 105]. N-Boc-protected amino acids 19 and 20 for incorporation into water-soluble /9-peptides were pre-... 

The lipases demonstrated very high stability in media partially or totally composed of organic solvent. In such media, the lipases catalyze esterification, transesterification, and resolution of enantiomers [19,45,75,97-100]. Nevertheless, several biphasic systems (organic-aqueous) are used for hydrolysis of lipid and fats [7,34,101]. Kinetic studies in biphase media or in inverted micelles demonstrate that the lipase behavior is different... 

The various tri-, di- and monoorganotin hydroxides and oxides that can be obtained by partial or complete hydrolysis of the corresponding halides or carboxylates often behave as catalysts for reactions such as esterification or transesterification, and it is partly with the aim of obtaining better and more selective catalysts that a lot of work has been carried out on these compounds in the past decade.347... 

Fig. 4 Transesterification of PVAc with methanol (often regarded as saponification) to completely hydrolysed PVA via partially hydrolysed PVAc-co-PVA...

This experimental procedure must be followed carefully to avoid partial decomposition of ethyl a-(hydroxymethyl)acrylate. The reaction is stopped rapidly after the addition of the carbonate solution (5 min) to prevent formation of high molecular weight by-products which result from transesterification and Michael addition, both of which occur in the basic medium. However, about 25% of the product is lost. Addition of diethyl ether during cooling minimizes side reactions. 

Alcohols with electronegative substituents in the a-position (phenol [42] and hydroxyacetonitrile [43]) undergo only partial alcoholysis with ethyl orthoformate. The use of ethyl orthoacetate also allows only partial transesterification to take place [42, 44]. 

Fig. 16. Effect of degree of crosslinking (% DVB) of standard (non-porous) ion exchanger on initial transesterification rate, r° (mol kg-1 h-1), of ethyl acetate with 1-propanol [436]. (1) Liquid phase at 52°C initial composition (mole%), 0.4 ethyl acetate, 0.4 1-propanol, 0.2 dioxan (solvent). (2) Vapour phase at 120°C partial pressure of reactants, 0.5 bar (ester—alcohol ratio 1 1).

Gas-Liquid Chromatography. Gas-liquid chromatography (GLC) affords both a qualitative and, if adequate internal standards are used, a quantitative analysis of the products of lipolysis. It is necessary, however, first to isolate the acids by a suitable method and then to inject them as free acids or as esters. The partial glycerides can be isolated by thin-layer chromatography and can also be determined by GLC of suitable derivatives. The acid(s) remaining in the partial glycerides can be identified readily by GLC following transesterification. Jensen and co-workers have utilized these techniques in their studies of lipase specificity (Jensen et al 1964). 

In continuation of their studies of the resolution of myo-inositol derivatives via their orthoesters with sugar derivatives, Evstigneeva et al. [296] converted the racemic 1,2 3,4-di-O-cyclohexylidene-wyo-inositol (431) by transesterification with the mannose orthoester (425) into a mixture of diastereoisomers (426) formed by esterification of the 5- and 6-positions of (431). One of the four possible isomers was separated by crystallisation and the other three were obtained by preparative TLC. Partial hydrolysis of the resolved isomers gave both enantiomers of 1,2-0-cyclohexylidene-myo-inositol (432). 

An example of a solvent-dependent change in regioselectivity is the lipase-catalysed partial transesterification of the diester derived from 2-octyl-1,4-... 

AO containing various phenolic moieties were prepared by transesterification in the presence of tetraalkyl titanates. Randomly distributed -active moieties are characteristic of 140 (only the hard polyester segment is given) prepared from dimethyl terephthalate, 1,4-butanediol, poly(tetramethylene oxide)diol and dimethyl 5-(3,5-di-tm-butyl-4-hydroxybenzenepropaneamido)isophthalate [181]. The mentioned polymeric AO was used for stabilization of polyether-polyester elastomers. A partial attachement of tetrakis[methylene 3(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate]methane (3) via transesterification reaction was expected in the synthesis of another polyether-polyester elastomer by [182]. A reversible redox polyester was formed from 2,5-bis(2-hydroxyethyl)hydroquinone and dichlorides of aliphatic dicarboxylic acids [137],... 

Kinetic resolution of ferrocene derivatives, mainly alcohols, had an important place during the early stage of stereochemical investigations of ferrocene derivatives. The reaction of (partially) resolved ferrocenylalkyl alcohols and amines with racemic 2-phenylbutyric acid anhydride (Korean s method) was the basis for the configurational assignment before the establishment of structures by X-ray crystallography [41]. There has been some debate on the reliability of the method [62, 63], and additional chirality information seems necessary for certainty. Recently, the kinetic resolution of 1-ferrocenylethanol by transesterification with vinyl acetate, catalyzed by a lipase from PseudomonasJluorescens, led to an enantiomeric excess of 90—96% of both enantiomers [64], opening new preparative aspects. 

Transesterification takes place under both acidic and basic conditions, so that acyl substituents in partially esterified carbohydrates are prone to migration (Figure 6.27). Presumably for steric reasons, acyl groups tend to migrate to primary positions - the well-known migration of acyl groups from the 4- to the... 

Whereas, the co PEIs 39a-c, 40a-f and 4a-c are characterized by a partial replacement of the dicarboxylic acid 27b, a series of co PEIs (42) was described in a patent [56] where the composition of the diphenols was varied. Higher contents of hydroquinone raise the melting point and the crystallinity higher contents of ferf-butylhydroquinone raise the T . These series of co PEIs which allow a broad variation of the Tg were prepared by transesterification of PET with combinations of the dicarboxylic acid 27b and acetylated methyl hydroquinone, ferf-butylhydroquinone or phenylhydroquinone (43a-c)[57]. Figure 10 displays the influence of the molar composition on the Tg and on the E-modulus of the co PEIs 43b. All these co PEIs are noncrystalline and nematic up to a molar fraction of 75-80% PET. At higher PET contents crystallization of long PET blocks takes place and the LC-phase has completely vanished. A further modification of these LC-PEIs can be achieved by cocondensation of 4-acetoxybenzoic acid or 6-ace-toxy-2-naphthoic acid [58]. 

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