Synthesen von Heterocyclen, 135. Mitt.: Chinolizine und Indolizine,VI: eine Synthese von 2-Hydroxy-benzo[a] chinolizin-4-onen

Zusammenfassung 2-Hydroxy-6,7-dihydro-4H-benzo[a]chinolizin-4-one (3a—p) werden durch Kondensation von 1-Alkyl-3,4-dihydro-isochinolinen (1a—g) mit Malonsäure-bis-2,4,6-trichlorphenylestern (2a—e) erhalten. Die Ausbeuten sowie die erforderlichen Reaktionszeiten und Temperaturen sind stark von der Art der Substituenten abhängig.

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Syntheses of heterocycles, CXXXV: Quinolizines and indolizines, VI. A synthesis of 2-hydroxy-4H-benzo[a]quinolizin-4-ones

The condensation of 1-alkyl-3.4-dihydro-isoquinolines (1a tog) with 2.4.6-trichlorophenyl malonates (2a—e) yields 2-hydroxy-6,7-dihydro-4H-benzo[a]quinolizin-4-ones (3a—p). Yields, required reaction-periods and temperatures are depending on the nature of the substituents present in the malonyl and isoquinoline residue.

     

Chinolizine und Indolizine,XIII. Acyl-2-hydroxy-4-chinolizinone

The reaction of 2-picolylketones (1 a, b) with reactive trichlorophenyl malonates (2 a–f) leads to 1-acyl-2-hydroxy-4-quinoliziones (3 a–i) which can be easily deacylated by boiling hydrochloric acid yielding 4-quinolizinones4 a–f. The 3-acetyl-2-hydroxy-4-quinolizinones6 and8 are obtained byKlosa-Ziegler acylation of4 a and7, respectively. The reaction of the acetyl compound3 a with acetic anhydride yields the 2-pyrone derivative9, whereas the propionyl derivative3 g yields the 4-pyrone10 under the same conditions. Nitration of3 e does not give the 1-nitro derivative12 but rather the 1,3-dinitro compound11.     

Ultrafast magnetic resonance imaging of the brain

The purpose of this study was to compare the diagnostic efficacy of single shot fast spin echo sequence (SSh-FSE), and single shot GRASE-sequence (SSh-GRASE) to the conventional T(2)-weighted fast spin echo-sequence (T(2)-FSE) in the imaging of brain disorders. Thirty three patients with high signal intensity lesions on T(2)-weighted images (n = 28), or intracerebral hemorrhage (n = 5), were examined on a 1.0 T MR scanner, with 23 mT/m gradient strength. The scan time for the conventional T(2)-FSE-sequence was 2 min 57 s, the scan time for the single shot-FSE-, and single shot-GRASE-sequences was 11 sec, and 17 sec, respectively. Twenty-one patients remained still during the examination, whereas 12 could not stay still with consecutive marked motion artifacts. Images were reviewed by three radiologists. Lesion conspicuity, image quality, and artifacts were scored on a subjective scale. Signal-to-noise ratios of lesions and normal tissue and contrast-to-noise ratios (CNR) were measured by region of interest (ROI). In the patient group without motion artifacts conspicuity for lesions > or =5 mm did not show a significant difference on conventional T(2)-FSE, single shot-FSE and single shot-GRASE. Detectability of the smaller lesions was significantly inferior on single shot-FSE-, and single shot-GRASE-sequences in artifact free images. For the patient group with motion artifacts SSh-FSE and SSh-GRASE were markedly superior to the conventional T(2)-FSE. Grey-white differentiation was better on conventional T(2)-FSE. Physiologic ferritin as well as pathologic hemosiderin depositions were slightly darker and therefore better visible on SSh-GRASE than on SSh-FSE. Conventional T(2)-FSE showed significantly more artifacts. In conclusion, SSh-FSE and SSh-GRASE imaging can be used for rapid imaging of the brain in those patients who are claustrophobic or in patients with involuntary movements due to extrapyramidal disorders, as well as in children in whom anesthesia is contraindicated or sedation is not possible.     

Chinolizine und Indolizine,XIV Umlagerungen von Heterocyclen,X Ringumwandlungen von 1-Acyl-2-hydroxy-4-chinolizinonen

By heating with ammonia or aniline 1-acyl-2-hydroxy-4-quinolizinones (1 a–e) are transformed to 4-hydroxy-5-(2-pyridyl)-2-pyridones (3 a–f), with4 a–d as minor sideproducts. The structure of the rearranged compound3 f was established by an independent synthesis starting with6 and7. The reaction of1 a, d with ethyl β-aminocrotonate (β-ACE) yields pyrono-quinolizinones8 a, b and pyronopyridones9 a, b as byproducts; the latter are obtained in high yield by reaction of3 a, b with β-ACE. The ringtransformation reaction cannot be extended to 1-methoxycarbonyl-quinolizinones, such as10; in this case 2-amino-4-quinolizinone11 is the main product of the reaction with ammonia.     

Synthesen kondensierter „Hydroxy-aza- und-oxa-chinolizinone”

The synthesis of some condensed 4-hydroxy-2-pyridone derivatives by the reaction of 2,4,6-trichlorophenyl malonates (2) with azomethines incorporating the C=N bond in a ring system is reported. The reaction of 3-aryl- or 3-haloquinoxalines (1 a, b) with2 yields monopyrido-condensed quinoxalines (3 a-d), while 3-alkyl-quinoxalines (1 c, 9) react to give dipyrido-derivatives (4 and5). Dehydrogenation of5 with Pd/C is used to confirm the structure of the known product of the reaction between2 and 5,10-dihydrophenazine (8). The reaction of2 with monosubstituted quinoxalones10 a-d yields the corresponding monopyridoquinoxalones11 a-e.

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10. Mitt.:Th. Kappe, M. Hariri undF. S. G. Soliman, Arch. Pharm.309, 684 (1976).

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Aus der DissertationY. Linnau, Universität Graz, 1969.

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Aus der DissertationW. Stadlbauer, Universität Graz, 1975.