Pimelic acid, oxidation

The application of this addition to aminomethylene ketones provides a convenient synthesis of monoamides of pimelic acid (508). It should be noted that the corresponding oxidation of hydroxy methylene cyclohexanone leads to ring contraction and formation of cyclopentanoic acid. 

Lysine is formed in bacteria by decarboxylation of meso-diamino-pimelic acid (Fig. 24-14). Glycine is decarboxylated oxidatively in mitochondria in a sequence requiring lipoic acid and tetrahydrofolate as well as PLP (Fig. 15-20). A methionine decarboxylase has been isolated in pure form from a fem. ° The bacterial dialkylglycine decarboxylase is both a decarboxylase and an aminotransferase which uses pyruvate as its second substrate forming a ketone and L-alanine as products (See Eq. 

Ihe double bond, leaving the acetoxyl and hydroxyl groups unchanged. 3-Acetoxy-l-iionanonoic acid (4) was isolated in 92% yield, together with an hydroxy acid (5), which was oxidized with alkaline permanganate to pimelic acid in 71% yield. 

Exhaustive methylation of a-methyltropidine followed by a Hofmann degradation eliminates the nitrogen as trimethylamine and the low boiling cycloheptatriene (tropilidene) was isolated in good yield (22,121). Tropane may be converted through the intermediate methyltropane to A -cyclo-heptadiene (hydrotropilidene) by a similar process. In the conversion of methyltropane methohydroxide to cycloheptadiene (139), 20% of the methyltropane is reformed by the loss of methanol, a side reaction which occurs in most Hofmann degradations to a greater or lesser extent. Cycloheptatriene and cycloheptadiene have been reduced to cycloheptane (194) which in turn has been oxidized (nitric acid) to pimelic acid. 

Picoline-l-oxide, 36, S4 PiMELIC ACID, 7-0X0-, DIETHYL ESTER,... 

Boyle (1661) mentions that olive and almond oils become thick when acted upon by red fuming aqua fortis (which dissolves camphor), but the observation was not noticed imtil J. J. E. Poutet, a Marseilles apothecary, found that olive oil solidifies when shaken with a solution of mercury in nitric acid, and he proposed this as a test for olive oil. It was found, however, that other oils behaved similarly. Felix Boudet, a Paris apothecary, found that the mercury solution acts only when it contains free nitrous acid, and showed that a new substance is formed which he called elaidin, and considered to be a compound of glyceryl oxide and a new acid, elaidic acid. Laurent, by the action of nitric acid on oleic acid obtained eladaic acid. He isolated from the product what he called suberic, pimelic, adipic, and azelaic acids, which he formulated adipic pimelic and azelaic His pimelic acid... 

CYP107H1 (Biol) Bacillus subtilis 3EJB, 3EJD, 3EJE Hexadec-9Z-enoic acid-(ACP), octadec-9Z-enoic acid-(ACP) Oxidative cleavage of ACP-bound fatty acids in pimelic acid biosynthesis TisI ... 

Fig. 6.31 The C-C bond cleavage reaction catalyzed linked fatty acids by Biol (CYP107H1) from B. subtilis by P450 Biol. The reaction schemes show the three-step in the formation of pimelic acid, an intermediate in the oxidative reaction that leads to bond cleavage between the bacterial biotin synthesis pathway [131]...

Scheme 13.4. In the upper part, a representation of the oxidation of tropine to an N-methyl-pyrrolidinedioic acid (tropinic acid) and the subsequent production of piperylenedicarboxylic acid and pimelic acid (heptanedioic acid). In the lower part, a representation of the electrolytic conversion of glutaric acid (pentanedioic acid) to suberic acid (octanedioic acid) and carbon dioxide (CO2) and thence to cycloheptanone and, in two different ways, to cycloheptene.

Liquid-phase oxidation investigations of polyesters based on adipic and pimelic acids, together with kinetic studies, have also been reported." ... 

Pimelic acid (n=5) this acid (heptanedioic acid), from the Greek pimelh (pimele fat), as adipic acid, was isolated from oxidized fats. It was obtained in 1884 by Ganttner F et al. as a product of ricinoleic acid (hydroxylated oleic acid) from castor oil. 

Most microorganisms, fungi and higher plants synthesise biotin from pimelic acid and alanine. Pimelic acid is a product of oxidative cleavage of higher fatty acids. The primary product of the biosynthesis is dethiobiotin (5-85), which reacts with methionine and gives biotin. Biotin is found as a prosthetic group... 

Tropolone has been made from 1,2-cycloheptanedione by bromination and reduction, and by reaction with A -bromosuccinimide from cyolo-heptanone by bromination, hydrolysis, and reduction from diethyl pimelate by acyloin condensation and bromination from cyclo-heptatriene by permanganate oxidation from 3,5-dihydroxybenzoic acid by a multistep synthesis from 2,3-dimethoxybenzoic acid by a multistep synthesis from tropone by chlorination and hydrolysis, by amination with hydrazine and hydrolysis, or by photooxidation followed by reduction with thiourea from cyclopentadiene and tetra-fluoroethylene and from cyclopentadiene and dichloroketene. - ... 

To glutaric, adipic, pimelic, and suberic acids which serve as sources of carbon and energy these compounds are formed by terminal oxidation followed by an unusual oxidation at the carbon atom 3 to the ether bond (Modrzakowski and Finnerty 1980). 

Two independent studies with free fatty acids have been reported (Figure 4). For Green etal. the first step is an CiJ-hydroxylation that should take place on rather rare odd chain fatty acids to lead to pimelate by successive /3-oxidations (Figure 4, a), whereas Cryle et observe an in-chain hydroxylation that occurs... 

PIMELIC KETONE (108-94-1) Forms explosive mixture with air (flash point 111°F/44°C). Incompatible with amines, oxidizers, hydrogen peroxide, strong acids. Violent reaction with nitric acid above 165°F/73°C. Dissolves plastics, resins, and rubber. Attacks red metals and lead. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Cyclohexanone. KetohexamethyJene pimelic ketone Hyrrol O Anone Nadone. C4H 0O mol wt 98.14. C 73,43%, H 10.27%, O 16.30%. Obtained from cydohexanol by catalytic dehydrogenation or by oxidation (which yields cyclohexanone and adipic acid) Or from cyclohexane by oxidation (yielding cyclohexanone and cydohexanol) Brit,... 

Alicyclic ketones produce esters of a, (o-dicarboxylic acids (entries 5, 6). An example is cyclohexanone, which gives dimethyl pimelate. These compounds, used for the production of polyesters and polyamides, have traditionally been synthetized in industry by oxidation of alicyclic ketones (74). 

Cyclohexanone - hek-so- non (ca. 1909) (pimelic ketone, ketohexamethylene) n. CH2(CH2)4C=0. a colorless liquid produced by the oxidation of cyclohexane or cyclohexanol. Its most important use is for the manufacturer of adipic acid for nylon 6/6, and caprolactam for nylon 6. It is also an excellent high-boiling, slowly evaporating solvent for many resins including cellulosics, acrylics and vinyls. It is one of the most powerful solvents for PVC, and is often used in lacquers to improve their adhesion to PVC (See image). 

---