3 -Hydroxydecanoic acid

Alkali Fusion. Tha alkaU fusion of castor oil using sodium or potassium hydroxide in the presence of catalysts to spHt the ricinoleate molecule, results in two different products depending on reaction conditions (37,38). At lower (180—200°C) reaction temperatures using one mole of alkah, methylhexyl ketone and 10-hydroxydecanoic acid are prepared. The 10-hydroxydecanoic acid is formed in good yield when either castor oil or methyl ricinoleate [141-24-2] is fused in the presence of a high boiling unhindered primary or secondary alcohol such as 1- or 2-octanol. An increase to two moles of alkali/mole ricinoleate and a temperature of 250—275°C produces capryl alcohol [123-96-6] CgH gO, and sebacic acid [111-20-6] C QH gO, (39—41). Sebacic acid is used in the manufacture of nylon-6,10. 

The nature of the product strongly depends on the length of the hydroxy acid generally when the hydroxyl group is remote the yield of lactone drops significantly. For example, 10-hydroxydecanoic acid [1679-53-4] does not produce any decanoUde instead, the reaction proceeds by intermolecular oligomerization, and a complex mixture of di-, tri-, tetra-, and pentalactones results (90). However, when Pseudomonas sp. or Candida iylindracea]i 2Lses are incubated with 16-hydroxyhexadecanoic acid [506-13-8] hexadecanoUde is the predorninant product (91). 

Block copolymers were synthesized by a combination of fipase-catalyzed polymerization and atom transfer radical polymerization (ATRE). " " At first, the polymerization of 10-hydroxydecanoic acid was carried out by using lipase CA as catalyst. The terminal hydroxy group was modified by the reaction with a-bromopropionyl bromide, followed by ATRP of styrene using CuCE2,2 -bipyridine as catalyst system to give the polyester-polystyrene block copolymer. Trichloromethyl-terminated poly(e-CL), which was synthesized by lipase CA-catalyzed polymerization with 2,2,2-trichloroethanol initiator, was used as initiator for ATRP of styrene. 

In 1985, a lipase-catalyzed polymerization of 10-hydroxydecanoic acid was reported. The monomer was polymerized in benzene using poly(ethylene glycol) (PEG)-modified lipase soluble in the medium [12]. The degree of polymerization (DP) of the product was more than 5. PEG-modified esterase from hog Ever and lipase from Aspergillus niger (lipase A) induced the oligomerization of glycolic acid [13]. 

Sha et al. applied the commercially available dual initiator ATRP-4 for the chemoenzymatic synthesis of block copolymers. In a first series of publications, the group reported the successful synthesis of a block copolymer comprising PCL and polystyrene (PS) blocks [31, 32]. This concept was then further applied for the chemoenzymatic synthesis of amphiphilic block copolymers by macroinitiation of glycidyl methacrylate (GMA) from the ATRP functional PCL [33]. This procedure yielded well-defined block copolymers, which formed micelles in aqueous solution. Sha et al. were also the first to apply the dual enzyme/ATRP initiator concept to an enzymatic polycondensation of 10-hydroxydecanoic acid [34]. This concept was then extended to the ATRP of GMA and the formation of vesicles from the corresponding block copolymer [35]. 

Macrolides. Nine- and ten-membered lactones cannot be obtained from treatment with Cs2C03 in DMF because of preferred inlcrmolecular cyclization (9, 100).2 However, the mesylate of 9-hydroxydecanoic acid is cyclized by Cs2C03 in DMF to phoracantholid 1 (1) in 45% yield together with I lie diolide (25% yield). Similar treatment of the mesylate of 10-hydroxydecanoic acid results in the lactone and the diolide in the ratio 7 3. Cyclization proceeds in very low yield when an a,/5-double bond is introduced.3... 

Reported hydroxyacids that are self-condensable by enzyme catalysis include 6-hydroxyhexanoic acid [25], 10-hydroxydecanoic acid [26], 5-hydroxyhexanoic acid [27], 5-hydroxydodecanoic acid [27], 11-hydroxydecanoic acid [28],... 

O Hagan, D., and Zaidi, N. (1993) Polymerisation of 10-hydroxydecanoic acid with the lipase from Candida cylindracea. J. Chem. Soc. Perkin Trans. 1, (20), 2389-2390. 

Table 12.1 Initiators and monomer used in dual initiator approach to block copolymers. CL caprolactone 4MCL 4-methyl caprolactone MMA methyl methacrylate CMA glycidyl methacrylate FOMA perfluorooctyl methacrylate 10-HA 10-hydroxydecanoic acid.

The production requires 2 fermentations. In the first fermentation, lipase enzymes liberate the unsaturated fatty acids of flaxseed oil. During the first feraientation, the hydrolyzed fatty acids, linolenic acid, linoleic acid and oleic acid, are converted to (respectively) 10-hydroxy-12(Z),15(Z)-octadecadienoic acid, 10-hydroxy-12(Z)-octadecenoic acid and 10-hydroxydecanoic acid by Pseudomonas sp. NRRL-2994. Pseudomonas sp. produced stereochemically pure d (R)-isomers of each of the hydroxy fatty acids (>95.8%) 23) at a concentration of >12 g/L in the fermentation broth. The resulting hydroxy fatty acids were recovered by phase separation technique, and used for the second fermentation. 

All 0X0- and hydroxy acids were characterized for the first time as enzymic degradation products from linoleic acid. The major components 1-octen-3-ol and 1,5-octadien-3-ol were optically active. This was proved by formation of an ester with an optically active acid and capillary separation. The methods used will be published in the near future (Tressl and Engel 1981). These results indicate a highly specific enzyme-system in Agaricus campestris catalyzing the conversion of linoleic acid into (-)-1-octen-3-ol and 10-hydroxydecanoic acid resp. into ( )-2-octen-1-ol and 9-hydroxydecanoic acid. As demonstrated in Table VI linolenic acid is transformed into the corresponding C8 Components containing two C = C bonds. 

Hydroxydecanoic acid Ac, in H-00239 Undecanedioic acid Mono-Me ester, in... 

Polyesterifications of various diacids/diols and linear hydroxy acids were studied using lipase-catalysis. The different diols studied include 1,4-butaiw, 1,6-hexane, and 1,8-octane diol. The diacids studied include succinic, glutaric, adipic, and sebacic acid. The different hydroxy acids studied were 6-hydroxyhexanoic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, and 16-hydroxyhexadecanoic. The effect of the chain length of the diol and diacids and hydroxy acids on the build-up of polymer chains by lipase-catalyzed polycondensation reactions was studied. The effect of reaction parameters on product molecular weight averages and chain dispersity were assessed. 

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