1.3- Cyclohexanedione acylation

Lace bugs in the genus Corythucha produce the isomeric 2-acyl-3,6-dihy-droxy-2-cyclohexene-l-ones, with a different pattern of oxygenation [45, 51, 52]. These were synthesized from 1,3-cyclohexanedione 11 (Scheme 3), with key steps being acylation to give 12, protection of the 1,3-dicarbonyl as the isox-... 

Table 2.1.9 Changes of blood amino acids in various primary inherited defects and as a result of secondary changes. ASA Argininosuccinic acid, CPS carbamoyl phosphate synthase, LPI Lysinuric protein intolerance, MAD multiple acyl-CoA dehydrogenation, MSUD maple syrup urine disease, NAGS N-acetylglutamate synthase, NKH nonketotic hyperglycinemia, NTBC 2-(2-nitro-4-3 trifluoro-methylbenzoyl)-1,3-cyclohexanedione, OCT Ornithine carbamoyltransferase,...

Y,s-Diketo esters This reagent effects C-acylation of ketones. It is suitable for C-acylation of 1,3-cyclohexanedione. 

In a specific work, it has been shown that chemical modification of hyperforin by acylation, oxidation and alkylation produce detrimental effects on the molecule activity as inhibitor of serotonin uptake [89], and the presence of the enolized cyclohexanedione moiety in its structure has been related to its efficacy on the re-uptake of neurotransmitters. 

Early work on aryloxyphenoxypropionates failed to show any metabolic effects except those on acyl lipid synthesis. The general inhibition of labeling of all acyl lipid classes but not that of sterols or terpenoids led to the idea that de novo fatty acid synthesis was being reduced. In fact, there is little effect on fatty acid elongation (e.g.. Table 3.13). Of the two enzyme systems involved in de novo synthesis, it has now been established that the aryloxyphenoxypropionates and cyclohexanediones only affect acetyl-CoA carboxylase. Moreover, this carboxylase from dicotyledons (resistant) appears to be different from that in monocotyledons (sensitive) because the selectivity of herbicides (including stereospecificity) is retained during in vitro measurements (Table 3.14). 

Cyclohexanedione dioxime under these conditions (120°C, 1 h) gives, together with 2,2 -dipyrrole (3%), 2-pyridyl (2%), 2-acyl (3%) pyrrole derivatives as well as the product from total deoximation of the initial dioxime, 1,2-cyclohexanedione (14%) (Scheme 1.77) [270]. 

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