2-keto adipic

Keto adipic aciduria 2-Keto adipic dehydrogenase... 

Scow et al. 1986, 1989 Zaidi et al. 1988, 1989). The products of biodegradation have also been studied with pure cultures of microorganisms. Catechol, beta-keto adipic acid, and nitrite have been identified as products of aerobic biodegradation of 2-nitrophenol (Zeyer and Kearney 1984) and 4-nitrocatechol, hydroquinone, gamma-hydroxymuconic semialehyde, and nitrite from 4-nitrophenol (Raymond and Alexander 1971 Spain et al. 1979). On the other hand, 2-aminophenol and 4-aminophenol have been isolated from anaerobic biodegradation of 2-nitrophenol and 4-nitrophenol, respectively (Adhya et al. 1981 Villanueva 1961). 

Finally, this tricyclic phenol (75) was utilized142 to synthesize the natural metabolite aflatoxin B2 (5) by the condensation with diethyl0-keto adipate, in von Pech-mann fashion, to afford the acyclic ester (79). Upon treatment of the derived acid chloride (80) with Lewis Acid (A1C13), there was obtained a single product which... 

The urinary elimination of glutaric acid increases in rats after administration of L-lysine (T15), a fact which is in accordance with the known metabolic route leading from lysine to glutaric acid via pipecolic acid (R8) (Fig. 5). Another intermediate of that metabolic sequence, a-keto-adipic acid, is foimd in urine after administration of lysine to the rat, the amount representing about 2 % of that of the administered L-lysine... 

Experiments made on pyridoxal-deficient animals suggested that pyridoxal phosphate and iron are required for the biosynthesis of porphyrin. It was later established that pyridoxal phosphate is required for the formation of -amino levulinic acid, probably by participating in the formation of active glycine. The condensation of succinate and glycine leads to the formation of a very labile a-amino-j -keto adipic acid. The participation of a-amino-jS-keto adipic acid as an intermediate in the reaction was established in experiments proving the acid to be an efficient precursor of porphyrin biosynthesis in vitro. An enzyme system capable of catalyzing the succinyl CoA-glycine condensation and the decarboxylation of the intermediate to yield amino levulinic acid has also been obtained from a particular fraction of chicken erythrocyte. In liver, an enzyme has been found in the mitochondria [132]. 

Subsequent metabolism of m,cw-muconic acid by Pseudomonas results in the formation of j3-ketoadipic acid, which is further degraded as its coenzyme A-thioester to acetyl coenzyme A and succinyl coenzyme A (Katagiri and Hayaishi, 1957). Sistrom and Stanier (1954) have identified the two enzymes that together produce ]8-ketoadipic acid. The first, lactonizing, enzyme equilibrates w,w-muconic acid with (-f)-y-carbo-xymethyl-zl -butenolide this product is irreversibly converted to jS-keto-adipic acid by the second, delactonizing, enzyme. 

Further bacterial degradation of m,m-muconic acid in cell-free enzyme extracts occurs via y-carboxymethylene butenolide — )3-keto-adipic acidsuccinic acid -b acetyl coenzyme A (Evans et al., 1951 Dagley et al., 1960 Katagiri and Hayaishi, 1957). 

It is worthwhile mentioning the reduction of p-keto butanoates substituted at the a position [362-369], of 4-substituted 3-oxobutanamides [370,371], of prochiral 3-keto adipates [372], and of the heteroanalogous keto esters 253 (Fig. 63) that gave -hydroxy-phosphonates 254 upon BY reduction [373,374]. 

The Dieckmann condensation of diethyl adipate yields a keto-ester product. 

Products detected or isolated from these oxidations include the corresponding a-hydroxy ketone and a-diketone and also adipic acid (from cyclohexanone) in up to 95 % yield. However, IrCI gives a-chloroketone in quantitative yield . Evidently when the rate of oxidation exceeds enolisation attack is on the keto form, probably via a complex, although this is definite only for Ce(IV) perchlorate, to give a radical, e.g. 

In the case of the dicarboxylic esters of adipic and pimelic acids, intramolecular condensation gives cyclic esters of /8-keto-carboxylic acids (Dieckmann) ... 

Methyl n-amyl carbinol. 247, 254 Methyl n-amyl ketone, 482 Methylaniline (mono), pure, from commercial methylaniline, 562, 570 P-Methylanthraquinone, 728, 740 Methyl benzoate, 780, 781 p-Methyl benzyl alcohol, 811,812 Methyl benzyl ketone, 727, 735 Methyl y-bromocrotonate, 926, 927 2-Methyl-2-butene, 239 Methyl n-butyl carbinol, 247,255 Methyl n-butyl ether, 314 Methyl n-butyl ketone, 475, 481 4-Methylcarbostyril, 855 p-Methylcinnamic acid, 719 4-Methylcoumarin, 853, 854 Methyl crotonate, 926, 927 Methylethylacetic acid, 354, 358 Methylethylethynyl carbinol, 468 Methyl ethyl ketone, 335, 336 purification of, 172 Methyl n-hexyl ether, 314 Methyl n-hexyl ketone, 335, 336 Methyl n-hexyl ketoxime, 348 Methyl hydrogen adipate, 938 Methyl hydrogen sebacate, 938,939 4-Methyl-7-hydroxycoumarin, 834 Methyl iodide, 287 Methyl isopropyl carbinol, 247,255 Methyl 4-keto-octanoate, 936... 

Keywords diethyl adipate, diethyl pimelate, Dieckmann condensation, cyclic fi-keto ester... 

Disconnection of the cylic j8-keto ester (23) gives the dipolar synthon (25), the reagent equivalent of which is diethyl adipate. 

For example, the calcium salt of adipic acid yields on distillation, adipoketone (keto-pentamethylene),... 

TL 24 2009 (1983) (0-keto ester) 25 1241 (fi-diketones to /J-hydroxy ketones), 4623 (3-oxo glutarate and adipate esters), 5083 (a-sulfenyl-/J-keto esters) (1984) 26 101 (/J-keto esters), 771 (a-PhS ketone), 4213 (/J-keto esters) (1985) 27 565 (/J-diketones to /J-hydroxy ketones), 1915 (a-keto esters) 2091 (/J-keto esters), 2657 (/J-keto esters), 3547 (2-acyl- 1,3-dithianes 2-acylthiazoles), 4737 (a-chloro ketones), 4817 (a-PhSOj ketone), 5275 (/J-keto esters and amides), 5281 (/ -keto esters), 5397 (a-chloro ketone, /J-keto ester), 5405 (/J-keto thio- and dithioesters) (1986) 28 2709 (/ -chloro-a-keto ester), 3189 (/J-keto ester) (1987) 29 4769 (3- and 4-nitro ketones), 4865 (/J-keto ester), 6167 (5-acetyl-2-isoxazolines) (1988) 30 2707 (yS-keto ester), 3701, 5705 (/J-keto ester) (1989) 31 1159 (/J-keto ester), 1615 (/J-keto ester), 1811, 3631 (/J-keto esters), 4025 (a-hydroxy ketone), 4195 (2-acyl-2-alkenoate ester), 5575 (y- and 5-keto sulfones), 7463 (/J-diketone to /f-hydroxy ketone)... 

A keto acid ester such as allyl levulinate may be crosaUxlced by adipic acid hydrazide, and some unsaturated diketones or keto-acids would probably react similarly. Polymers have been descriled in bead form, but conditions could probably be found to enstire emulsion stability. (55)... 

Dieckmann eyclixatioo f diethyl adipate can be deacribed by the two Huooeasive equilibria shown below Use SpartanView to obtain the enerfdes of diethyl adipate, the keto ester, th keta eater eaolate ion, ethanail, and eUtoatde anion, and calculate AM" for both atepa Which seep as more fanorable ... 

Phenol, btomobenzene, i-butylbenzene, and acenaphthene give keto acids in good yields. The reaction is applicable to other aliphatic dibasic acid anhydrides like glutaric anhydride, adipic poly anhydride, and maleic anhydride, furnishing w-aroyl acids. An excellent discussion including experimental conditions and procedures has been given. Optimum conditions for the reaction of naphthalene, biphenyl, and chlorobenzene with phthalic anhydride have been determined. The Corresponding keto acids are obtained in 90-98% yields. In this type of condensation, nitrobenzene is stated to be far superior to other solvents with respect to solvent power and ability to slow side reactions. ... 

Dieckmann cyclization of diethyl adipate can be described by the two successive equilibria shown below. Use SpartanView to obtain the energies of diethyl adipate, the keto ester, the keto ester enolate ion, ethanol, and ethoxide anion, and calculate AH° for both steps. Which step is more favorable ... 

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