Lipase-catalyzed synthesis of monostearoylglycerol in organic solvents from 1,2-O-isopropylidene glycerol

Hess, Robert A.; Bornscheuer, Uwe T.; Capewell, A.; Scheper, Thomas

doi:10.1016/0141-0229(94)00126-c

Cited by 25 publications

(12 citation statements)

References 19 publications

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“…Thus isooctane was the solvent of choice, since its use also eliminated any error that might have been caused by evaporation of a more volatile solvent. A similar dependency of activity on solvent has also been found in the P. cepacia-catalyzed reaction between a fatty acid or fatty-acid ester with IPG (11). In that study, n-heptane was reported to be a better solvent with a threefold enhancement of the initial rate compared with those in other hydrocarbon solvents.…”

Section: Resultssupporting

confidence: 72%

“…It has been suggested that the initial rate of synthesis might be related to the log P value of the solvent used, and that the rate should decrease as the solvent is changed from hydrophobic to hydrophilic [i.e., as log P of the solvent is decreased (11,18)]. However, the exact nature of the effect of solvent on enzyme kinetics has yet to be confirmed.…”

Section: Resultsmentioning

confidence: 99%

“…Over 90% conversion was re-ported (10) by direct synthesis of IPG-oleate from IPG and oleic acid catalyzed by Mucor miehei (Lipozyme®, Fluka, Buchs, Switzerland) and using an oleic acid/IPG ratio >3. Hess et al (11) reported 84% conversion of stearic acid or ethyl stearate to IPG-esters by using Pseudomonas cepacia as the catalyst in hexane. Enol esters have also been used as acyl donors which shift the position of the equilibrium because they cause irreversible tautomerization of the vinyl alcohol or isopropenyl alcohol by-product.…”

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confidence: 99%

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Kinetics of enzymatic synthesis of isopropylidene glycerol esters by goat pregastric lipase

Lai

Hattori

O’Connor

1999

J Americ Oil Chem Soc

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The goat pregastric lipase-catalyzed esterification of isopropylidene glycerol with caproic acid, to form isopropylidene glycerol caproate, followed a ping pong bi bi mechanism incorporating an acyl-enzyme intermediate. The maximum rate was estimated to be 96 µmol min -1 mg -1 in isooctane at 35°C, and the Michaelis-Menten constants for isopropylidene glycerol and caproic acid were 0.23 and 0.32 M, respectively. The catalyzed rate also correlated well with the partition coefficient of caproic acid between the organic and aqueous phases. The results suggest that the desolvation energy of the substrate from the bulk medium to the active site of the enzyme dominates the reaction rate for the enzyme-catalyzed reaction in organic media.Paper no. J9049 in JAOCS 76, 845-851 (July 1999).

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Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Kinetics of enzymatic synthesis of isopropylidene glycerol esters by goat pregastric lipase

Lai

Hattori

O’Connor

1999

J Americ Oil Chem Soc

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“…Acylation of the isopropylidene derivative of glycerol has been widely used for the synthesis of monoacylglycerols (8)(9)(10). Our initial studies with isopropylidene glycerol were carried out in hexane solvent at 60°C using Lipozyme TM as the catalyst and dimethyl sebacate as the acyl donor.…”

Section: Resultsmentioning

confidence: 99%

“…The latter strategy, however, deals with substrates that often have very different solubility characteristics, which often inhibits their reaction with each other. A number of publications have addressed this problem by devising different methods to modify the solubility of glycerol, for example by adsorption onto inert supports (5-7), use of the isopropylidene protecting group (8)(9)(10), or complexation with phenyl boronic acid (PBA) (11,12). Other approaches to overcoming the glycerol solubility limitation include carrying out the reaction with substrates in biphasic systems (13), by microemulsion (14), or by addition of water to the reaction media (15).…”

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confidence: 99%

Synthesis of polyfunctional glycerol esters: Lipase‐Catalyzed esterification of glycerol with diesters

Villeneuve

Foglia

Mangos

et al. 1998

J Americ Oil Chem Soc

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The enzymatic esterification of glycerol with dicarboxylic acids or esters was studied to produce mono-and/or diesterified glycerol adducts. Such materials are useful synthons in the synthesis of biodegradable polymers and surfactants. In this work two strategies were studied for preparing these prepolymeric glycerol derivatives: the lipase-catalyzed esterification of free glycerol with diacids or esters and the reaction of supported or protected glycerol with diesters. For example, reaction of isopropylidene glycerol with dimethyl sebacate gave a >95% yield of isopropylidene glycerol-monomethyl sebacate ester. Reaction of glycerol supported on silica with dimethyl adipate gave a 40% yield of glycerol-monomethyl adipate ester. Best yields of glycerol-mono-and diesters (70% and 10%, respectively) were obtained by direct esterification of free glycerol with a diester in a solvent-free system containing small amounts of water (<4%). JAOCS 75, 1545-1549 (1998).The lipase-catalyzed esterification of aliphatic dicarboxylic acids with diols has been studied extensively for the production of bifunctional precursors in the synthesis of biodegradable polymers (1-3). In this regard, the enzymatic esterification of glycerol with diacids also would be attractive (Scheme 1). The latter reaction should result in the formation of monoand/or diesterified glycerol products that can be used as trifunctional synthons in the synthesis of glycerol-derived biopolymers or surfactants. The synthesis of such partial glycerides can be achieved using either chemical or enzymatic methods (4). Chemical methods typically are carried out with inorganic catalysts at high pressure and temperature and suffer several drawbacks such as low yields, unwanted side reactions, and decomposition products that result in discolored reaction products. Enzymes (lipases), on the other hand, operate under milder conditions and hence offer advantages over chemical methods. Basically, three strategies have been used in the lipase-catalyzed synthesis of partial glycerides: (i) partial hydrolysis of triacylglycerols; (ii) glycerolysis of triacylglycerols; and (iii) direct esterification of glycerol with acyl donors. The latter strategy, however, deals with substrates that often have very different solubility characteristics, which often inhibits their reaction with each other. A number of publications have addressed this problem by devising different methods to modify the solubility of glycerol, for example by adsorption onto inert supports (5-7), use of the isopropylidene protecting group (8-10), or complexation with phenyl boronic acid (PBA) (11,12). Other approaches to overcoming the glycerol solubility limitation include carrying out the reaction with substrates in biphasic systems (13), by microemulsion (14), or by addition of water to the reaction media (15). One objective of our present study is the synthesis of polyfunctional glycerol esters of dicarboxylic acids for use as prepolymeric synthons. Attempts to prepare these synthons using the above enzymatic ...

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Preparation of 1-monoacyIgIyceroIs from gIycidoI and fatty acids cataIyzed by the chromium(III)-fatty acid system

Janiš¹,

Krejčí²,

Klásek³

2000

Eur. J. Lipid Sci. Technol.

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A description is given for preparing 1‐monoacylglycerols by the reaction of fatty acids with glycidol catalyzed by Cr(III)‐fatty acid complexes. These complexes were found to possess catalytic efficiency substantially greater than catalysts employed earlier. Effects of catalyst type, its content in the mixture, molar ratio of reactants, and reaction temperature during the course of acid conversion were studied. With a catalyst content of 0.5% by mass of charged reactants and at 90 °C a 90— 95% conversion of the acid can be achieved within 60 min. In addition to the corresponding 1‐monoacylglycerol, only unreacted starting substances and the catalyst were detected in resulting reaction mixtures.

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Lipase-catalyzed synthesis of monostearoylglycerol in organic solvents from 1,2-O-isopropylidene glycerol

Cited by 25 publications

References 19 publications

Kinetics of enzymatic synthesis of isopropylidene glycerol esters by goat pregastric lipase

Kinetics of enzymatic synthesis of isopropylidene glycerol esters by goat pregastric lipase

Synthesis of polyfunctional glycerol esters: Lipase‐Catalyzed esterification of glycerol with diesters

Preparation of 1-monoacyIgIyceroIs from gIycidoI and fatty acids cataIyzed by the chromium(III)-fatty acid system

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