ABSTRACT
New colour reactions for the identification of drug compounds have been devised. For example, butazolidine is oxidized with permanganate in basic medium to azobenzene and butyric acid; after reduction and coupling, the former is transformed to a red azodye. On nitration, gluthetimide gives the p-nitrophenyl derivative and a second nitro group is substituted at position 3. With hydroxylamine in basic medium, this o-dinitro compound reacts to furnish a violet colour when the dinitro derivative is reduced to the ortho-quinoidal dialkali metal salt. Dipolar cycloadditions of BNO, ANO and DPNI to norbornane- and cyclohexane-condensed 1,3-oxazine dipolarophiles have been utilized to synthesize adducts containing 1,2,4-oxadiazole and -triazole rings. The norbornene double dipolarophiles contain both C=N and C=C bonds; for steric reasons, ketene formed in situ adds primarily to the C=C. The addition of dipoles with high steric demands can lead to a change in conformation. By means of retro Diels-Alder reactions, hetero- mono-, bi- and tricyclic compounds may be synthesized. With bifunctional reagents, norbornene amino acids and hydrazides are transformed to condensed cyclic derivatives; when these are heated, cyclopentadiene is cleaved off to give mostly new target compounds.
Subject(s)
Pharmaceutical Preparations/chemistry , Chemistry, Organic/methods , Oxidation-ReductionABSTRACT
The reactions of 2-carboxybenzaldehyde (1) with 1,3- or 1,4-aminoalcohols (2a-i, 3a,b) were used to prepare partially or fully saturated tetra- and pentacyclic compounds containing a condensed 1,3-oxazino- or oxazepinoisoindolone moiety and one terminal saturated carbocycle. Isoindolo[2,1-a][3,1]benzoxazinones (4a-d, 6, 7), stereoisomeric isoindolo[1,2-b][2,4]benzoxazepinones (5a-c) hexahydrocyclopentane[b]pyrrolo[1,2-a][3,1]-benzoxazinone (10a,b), octahydroindolo[1,2-b]- and decahydroindolo[1,2-a]benzoxazinone (11a,b and 12a,b) and related pentacyclic derivatives (4e-g) were prepared. The diastereomers 5a-c differ in the ring annelation or in the position of the NCHO hydrogens and annelational hydrogens. The stereostructures of these compounds were elucidated by means of 1H and 13C NMR spectroscopy, including DNOE, DEPT, 2D-HSC measurements and X-ray analysis.
Subject(s)
Oxazines/chemistry , Indicators and Reagents , Models, Molecular , Molecular Conformation , Molecular Structure , Nuclear Magnetic Resonance, Biomolecular , Oxazines/chemical synthesis , Stereoisomerism , Structure-Activity RelationshipABSTRACT
In chronic septic complications of the ankle joint bony fusion can be achieved with radical resection of necrotic tissues, special positioning of the foot and extrafocal stabilisation. For non-cooperative patients with bland infections intramedullary stabilisation can be used after which early full weight bearing is possible. The correct technique of operation together with adjuvant therapy with a Septopal chain increases the healing chances of patients and reduces the time and costs of therapy.
ABSTRACT
Prevention of recurrence after consolidation of infected femur and tibia fractures and nonunions is based on two principles. First necrotic bone is eliminated with reaming and rinsing the intramedullary canal after metal removal. As missing inramedullary tissue granulates gradually, prevention of retention cavities is achieved by a drainage tube that is gradually removed in the direction of gravity. In chronic cases the method is combined with application of a Septopal chain. Since 1978 this method has been used in 39 cases of which 32 have been succesful.
ABSTRACT
The authors present the late results of 10 male patients with open leg fractures and nonunions treated between 1978 and 1985 with tibiofibular synostosis. This was achieved by autologous cancellous bone grafting. The average time of the follow-up study was 11 years at which time all patients were free of fistulas, fully weight-bearing and able to work. In their subjective opinion these advantages compensated for reduced ankle motion and tolerable periodic pain.
ABSTRACT
The Friedel-Crafts reaction of benzene with cis-4-cyclohexene-1,2-dicarboxylic anhydride (1) yields trans-5-phenyl-cis-2-benzoylcyclohexanecarboxylic acid (2), which gave cyclohexane-condensed pyridazinone (3) with hydrazine, and cis-4,5-tetramethylene-1,2-oxazin-8-one (4) with hydroxylamine. From 2 with ethylenediamine, the saturated imidazol[2,3-a]iso-indolone (5) was prepared, while the reaction of 2 with 1,3-diaminopropane furnished a mixture of two isomeric pyrimido[2,3-a]isoindolones (6a,b) in the relative positions of the benzene ring and cyclohexane annelation hydrogens. From the reaction of 2 with 3-aminopropanol, the oxazino[2,3-a]isoindolone (7) was obtained. The reaction of 2 with cis-2-hydroxymethylcyclohexylamine gave the tetracyclic (8), while 2 and diendo-3-hydroxymethylbicyclo[2.2.1]hept-5-enyl-2-amine yielded the isomers (9a,b), which differ in the mutual positions of the phenyl group on the quaternary carbon and cyclohexane annelation hydrogens. 1H and 13C-nmr spectra and DNOE and 2D-HSC measurements proved that the 5-phenyl group is cis-equatorial to the two annelated hydrogens of the cyclohexane ring.
Subject(s)
Indoles/chemical synthesis , Hydrazines , Indicators and Reagents , Indoles/chemistry , Magnetic Resonance Spectroscopy , Molecular Conformation , Molecular Structure , OxazinesABSTRACT
Electron impact ionization mass spectrometry indicates that the behavior of W-unsubstituted pyrirnidin-4-ones with CH2-R type substitution at C-2 differs from homologs that are N-substituted and/or 2-aryl- or 2-methyl-substituted. A dominant intramolecular cycliza-tion was found to occur between 3ZV (in agreement with the predominance of the 3NH tautomers) and the ortho positions of the aryl moiety in compounds with a CH2-aryl substitution at C-2. Theoretical calculations with an AMI SCFR method on 2-, 6-, and 2, 6-disubstituted pyrimidin-4-ones support the mass spectrometric observations.
