Search results for "cyclic"

Synthesis and properties of polymers with unusual structure

1985

This lecture summarize some recent results of our current research. The first part describes the homopolymerization and copolymerization of a monocyclic and two bicyclic unsaturated acetals. In this way polyacetals with 1,4-cis-butadiene units and cyclohexene units respectively are obtained. Secondly, the N-substitution of polyamides is described. By N-metalation and subsequent alkylation comb-like polyamides are available. Longer branches cause a side-chain crystallinity. The anionic “grafting-from” technique forms irregular branched polyamides. By termination reaction between living ends of poly(2-isopropenylnaphthalene) and suitable electrophiles new macromonomers are available. The last…

- conformational preference of , -9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid

1985

Abstract The 1 H and 13 C nmr spectra of exo , exo -9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid, 3, in DMSO-d 6 or alkaline D 2 O, clearly show that it exists in a boat - chair -conformation with equatorial carboxyl groups, thus being the first case of boat - chair preference of a bicyclo[3.3.1] nonan-9-one due to the presence of exo , exo -2,4- substituents.

Dihydrodiol Dehydrogenase: An Important Enzyme in Dihydrodiol-Epoxide Pathway — Mediated Benzo(A)Pyrene Mutagenicity

1978

Benzo(a)pyrene is metabolized to two major groups of mutagenically reactive metabolites: Monofunctional epoxides and dihydrodiol-epoxides. Various monooxygenase forms catalyze the various pathways at very different rates. In metabolic situations where the contribution by dihydrodiol-epoxides is small, epoxide hydratase represents a very efficient protective system. However, in situations where the mutagenic effect is predominately due to dihydrodiol-epoxide, the effect of epoxide hydratase is complicated and weak. We have now obtained evidence that a dihydrodiol dehydrogenase represents an efficient protective system in the latter situation. The enyzme was purified to homogeneity and the pu…

Dihydrodiol Dehydrogenase: Substrate Specificity, Inducibility and Tissue Distribution

1982

The present study shows that: Dihydrodiol dehydrogenase activity is present in the 100,000 g supernatant fraction of extrahepatic tissues. Dihydrodiol dehydrogenase is able to oxidize the hydroxy group and to reduce the keto group of a number of xenobiotics including quinones derived from polycyclic aromatic hydrocarbons. Dihydrodiol dehydrogenase was not inducible by various substances including hormones, polycyclic aromatic hydrocarbons, substrates of the enzyme and potent inducers of monooxygenases, epoxide hydrolase and glutathione S-transferases. Only in the case of thyroxine was a weak induction with a high dose of the hormone observed.

Individual Differences in DNA Repair Capacities in Man

1987

After metabolic activation of benzo[a]pyrene to the 7,8-dihydrodiol- 9,10-epoxide, this ultimate carcinogen preferentially binds to the exocyclic amino group of guanine. In order to investigate possible interindividual differenes in the capacity of repair of the DNA adducts formed from benzo[a]- pyrene 7,8-dihydrodiol 9,10-epoxide, their persistence in freshly isolated lymphocytes of several donors was studied. The results show a surprisingly large interindividual variation in DNA adduct formation and their persistence in freshly isolated lymphocytes. This range included several individuals with an apparent complete lack of repair capability for these adducts. Compared with controls, smoker…

Front Cover: Synthesis and Unusual NMR-Spectroscopic Behavior of a Strained Bicyclic Ammonium Salt (Eur. J. Org. Chem. 10/2018)

2018

Heterocyclic rearrangements.N,N-diphenylhydrazones, oximes andO-methyloximes of 3-benzoyl-5-phenyl-1,2,4-oxadiazole

1985

The behaviour of (E)- and (Z)-N,N-diphenylhydrazones and O-Methyloximes of 3-benzoyl-5-phenyl-1,2,4-oxadiazole has been studied. When refluxed in benzene, or in dioxane-water (1:1), the (Z)-N,N-diphenylhydrazone 8Z gave the indazole 11 or the substituted semicarbazide 12, respectively. The O-methyloxime 14Z did not give any rearrangement. A criticism of the oximation reaction of 3-benzoyl-5-phenyl-1,2,4-oxadiazole is also reported.

Einführung einer Dreifachbindung in das Bicyclo[6.1.0]nonan-Gerüst

1987

Ausgehend von den auf verschiedenen Wegen zuganglichen Ketonen 1a–c wird die Einfuhrung einer Dreifachbindung in das Bicyclo[6.1.0]nonan-Gerust mit Hilfe der Selenadiazol-Methode untersucht. Dabei Konnen die hochgespannten Bicyclo-[6.1.0]nonine 2a und 2b in reiner Form isoliert werden. Masgeblich fur die Position der Dreifachbindung ist die Regioselektivitat der Ringschlusreaktion bei der Selenadiazolbildung. Introduction of a Triple Bond into the Bicyclo[6.1.0]nonane Skeleton The introduction of a triple bond into the bicyclo[6.1.0]nonane skeleton is investigated by applying the selenadiazole method to the ketones 1a–c, accessible on different pathways. The highly strained bicyclo[6.1.0]no…

ChemInform Abstract: First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis-Hillman Reaction Between Alkyl Vinyl Ketones and Aryl …

2008

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …

Cycloaddition of benzothiete and electron-deficient nitriles

1991

The o-quinoid 8π electron system 2, generated by thermal ring opening of benzothiete (1), enters regio-specific [8π + 2π] cycloaddition reactions with electron-deficient nitriles 3a-d, yielding the 4H-1,3-benzothiazines 4a-d. A competitive dimerization of 1 leads to 1,5-dibenzo[b,f]dithiocin (5). Depending on the nitrile further competitive or subsequent reactions (2 + 3b 7b, 2 + 3d 4d 8d) can occur. The cycloadducts 10e and 11e gained from 3e anticipate a primary cleavage of 3e to methylisothiocyanate 9e which reacts at the CN double bond as well as at the CS double bond.