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  • MRI
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  • 101
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Liquordynamik ; Aquädukt ; Quantifizierung ; MRT ; Phasenkontrast ; Normalwerte ; Key Words: CSF dynamics ; Aqueduct ; Quantification ; MRI ; Phase contrast ; Normal values
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: With the 2D-phase-contrast technique the volume flow of the CSF via the cerebral aqueduct can be quantified by MRI-means. In this study the stroke volume of CSF via the aqueduct per cardiac cycle (SVcc) is used to measure the extent of the volume flow. Normative values for the SVcc are not yet defined, however, they are indispensable for the clinical utility of this non-invasive method. The aim of the presented investigation is to evaluate, if the interthalamic width of the third ventricle is useful as a reference system for the extent of the SVcc via the aqueduct and if a normal CSF-flow can be defined. Hundred and seven patients (56 female, 51 male; age distribution 8 to 89 years) without clinical or imaging findings of a CSF-flow disturbance were examined on a standard 0.5 T MRI-scanner (Gyroscan, Philips). The measurements of the SVcc via the aqueduct were performed in a single slice perpendicular to the aqueduct in the level of its median third with a retrospective cardial-gated quantitative 2D-phase-contrast sequence. The interthalamic width of the third ventricle was measured in a transversal slice (bicommissural orientation, standard T1-weighted spin-echo sequence) in the level of the upper margin of the tectorial membrane. In 83 patients with a normal heart rate and without any further abnormalities in their imaging studies the SVcc is essentially dependent (r = 0.822) on the interthalamic width of the third ventricle (between 1 and 16 mm). Eleven patients with either a subcortical atrophy without leucencephalopathy, megacisterna magna, Dandy-Walker variant or bradycardia showed a significant increase of the SVcc (p 〈 0.05). On the other hand a significant decrease of the SVcc (p 〈 0.05) is seen in 13 patients with either tachycardia, Arnold-Chiari Type-1 malformation, relative aqueductal stenosis and/or severe periventricular leucencephalopathy. These results are in good agreement with the current conceptions on the physiology of the CSF-flow. As the above mentioned criterias of influence have ho pathological significance concerning a CSF-flow disturbance requiring therapy, we used the linear regression with y = B1*× +b0 (b1 = 22.2 ± 2.9; b0 = 43,5 ± 21.1) in all 107 patients to evaluate the extent of the SVcc (y) versus the interthalamic width of the third ventricle (x). This correlation offers the possibility to differentiate a hyperdynamic (above +3 standard error SE), a hypodynamic (below −3 SE) and a normodynamic (between ± 3 SE) CSF-flow via the cerebral aqueduct for the first time. Additional imaging findings and the heart rate must find their influence in the evaluation.
    Notes: Zusammenfassung: Mit Hilfe der 2D-Phasenkontrasttechik kann der Volumenfluss des Liquors über dem Aquädukt magnetresonanztomographisch quantifiziert werden. Als Maß für die Höhe des Volumenflusses dient in vorgestellter Untersuchung das Schlagvolumen pro Herzzyklus (SVcc). Normwerte für die Höhe des SVcc konnten bislang nicht definiert werden. Sie sind jedoch für eine klinische Nutzung dieses nichtinvasiven Verfahrens unerläßlich. Ziel vorliegender Untersuchung ist es zu prüfen, ob die interthalamische Weite des dritten Ventrikels als Bezugssystem für die Höhe des SVcc über dem Aquädukt geeignet ist und sich ein normaler Liquorfluss definieren läßt. Die Untersuchungen erfolgten bei 107 Patienten (56 Frauen, 51 Männer im Alter von acht bis 89 Jahren) ohne klinische und bildmorphologische Hinweise auf eine Liquorzirkulationsstörung an einem Standardsystem 0,5 T (Gyroscan, Fa. Philips). Die Messung des SVcc über dem Aquädukt wurde in einer Eizelschicht senkrecht zum Aquädukt in Höhe des mittleren Drittels mit einer retrospektiv kardial getriggerten 2D-quantitativen Phasenkontrastsequenz durchgeführt. Die Messung der interthalamischen Weite des dritten Ventrikels erfolgte im Transversalschnitt (Bikommissuralebene, Standard-T1-gewichtete SE-Sequenz) in Höhe des Oberrandes der Lamina tecti. Für 83 kardial normofrequente Patienten ohne zusätzliche bildmorphologische Auffälligkeiten wird die Höhe des SVcc maßgeblich von der interthalamischen Weite des dritten Ventrikels (1 bi 16 mm) bestimmt (r = 0,822). Bei elf Patienten mit einer subkortikal betonten Atrophie ohne Leukenzephalopathie, Megacisterna magna, Dandy-Walker-Variante oder Bradykardie ist das SVcc signifikant erhöht (p 〈 0,05). Dagegen ist das SVcc für 13 Patienten mit Tachykardie, Arnold-Chiari-Malformation Typ 1, relativer Aquäduktestenose und/oder fortgeschrittener periventrikulärer Leukenzephalopathie signifikant erniedrigt (p 〈 0,05). Diese Ergebnisse lassen sich gut mit den geltenden Vorstellungen über die Physiologie des Liquorflusses in Einklang bringen. Da den vorgenannten Einflusskriterien keine pathologische Bedeutung hinsichtlich einer therapiebedürftigen Liquorzirkulationsstörung beigemessen werden kann, nutzen wir zur Bewertung der Höhe des SVcc (y) gegenüber der interthalamischen Weite des dritten Ventrikels (x) die lineare Regression mit y = b1*× + b0 (b1 = 22,2 ± 2,9; b0 = 43,5 ± 21,1) für alle 107 Patienten. Diese Beziehung gibt erstmals die Möglichkeit, einen hyperdynamen (〉 +3 SE), hypodynamen (〈 −3 SE) und normodynamen (in den Grenzen ± 3SE) Liquorfluss über dem Aquädukt zu differenzieren. In die Bewertung müssen das Vorliegen zusätzlicher bildmorphologischer Einflussfaktoren und die Höhe der Herzfrequenz einfließen.
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  • 102
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Medulloblastom ; Pubertas praecox ; MRT ; Kontrastmittel ; Key Words: Medulloblastoma ; Subarachnoid metastases ; Precocious puberty ; MRI ; Contrast enhancement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: Medulloblastoma, the most frequent pediatric brain tumor, has known propensity for subarachnoid dissemination. Spinal metastases indicate a poor prognosis. Intraventricular spread is much less common. We report a case of primary intraventricular dissemination with precocious puberty as the first clinical symptom due to a metastasis at the infundibulary stalk. This has not been reported so far as initial symptom of a medulloblastoma. Furthermore, we encountered an unusually mild contrast enhancement of the spinal and intraventricular metastases. Delayed scanning after contrast administration and FLAIR sequences proved to be particularly valuable in this case.
    Notes: Zusammenfassung: Medulloblastome des Kleinhirns sind die häfigsten malignen Hirntumoren im Kindesalter. Ihre Neigung zur Ausbreitung im Subarachnoidalraum ist bekannt und Prognose bestimmend. Wir berichten über den ungewöhnlichen Fall eines Medulloblastoms mit ausgeprägter intraventrikulärer Aussaat. Eine Metastase im Reccessus infundibularis führte hierbei zum Auftreten einer Pubertas praecox als initiales Krankheitssymptom, eine Beobachtung, die bisher nicht beschrieben wurde. Bemerkenswert war zudem die ungewöhnlich schwache Kontrastmittelaufnahme der intraventrikulären und spinalen Metastasen. Für die Diagnostik erwiesen sich FLAIR-Sequenzen und Spätaufnahmen nach Kontrastmittelgabe als besonders wertvoll.
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  • 103
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Vena ophthalmica superior ; Thrombose ; Sinus caverosus ; Computertomographie ; Kernspintomographie ; Key Words: Superior ophthalmic vein ; Thrombosis ; Sinus cavernosus ; CT ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: A 65-year-old woman with persistant headache since a few weeks is presented. The day before hospitalization there was a sudden onset of protrusio bulbi and progredient swelling of the soft-tissue of the left eye. In the clinical examination left side protrusio bulbi, double-vision, chemosis and swelling of the eye-lid were found. Blood sample showed an elevation of inflammation indicators. MRI and CT revealed a thrombosis of the left superior ophthalmic vein with partial thrombosis of the left cavernous sinus.
    Notes: Zusammenfassung: Eine 65-jährige Patientin stellt sich mit seit Wochen bestehenden Kopfschmerzen vor. Am Tag vor der Aufnahme war morgens akut eine Protrusio bulbi mit einem periorbitalen Ödem aufgetreten. Klinisch fanden sich eine Protrusio bulbi mit Chemosis und Oberlidschwellung links, Doppelbildern sowie einer Erhöhung der Entzündungsparameter. Kernspintomographisch und computertomographisch ließ sich eine Thrombose der Vena ophthalmica superior links mit Teilthrombose des linken Sinus cavernosus nachweisen.
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  • 104
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 83 (2000), S. 363-369 
    ISSN: 1439-6327
    Keywords: Key words Achilles tendon moment arm ; MRI ; Maximum voluntary contraction ; In vivo ; Tendon excursion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The aim of the present study was to estimate and compare in vivo measurement-based Achilles tendon moment arm lengths at rest and during isometric plantarflexion maximum voluntary contraction (MVC) using the centre-of-rotation (COR) and the tendon-excursion (TE) methods. Both methods were based on morphometric analysis of sagittal-plane magnetic resonance images of the foot. Using the COR method, moment arms were obtained at ankle angles from 15° of dorsiflexion to 30° of plantarflexion in steps of 15°, digitizing the perpendicular distance from a moving centre of rotation in the tibio-talar joint to the Achilles tendon action line. The TE method was based on measurement of calcaneal displacement along the tibial axis during 15° rotations of the ankle joint, from 30° of dorsiflexion to 45° of plantarflexion. The two methods gave similar estimations at rest varying from 4.3 to 5.6 cm. Using the COR method, the Achilles tendon moment arm during MVC was larger by 1–1.5 cm (22–27%, P 〈 0.01) than the respective resting value. In contrast, no difference (P 〉 0.05) was found between the resting and MVC moment arm estimations of the TE method. The disagreement in moment arms during MVC may be attributed to differences in the assumptions made between the two methods. The TE method has more limitations than the COR method and its estimations during MVC should be treated with caution. Resting Achilles tendon moment arm estimations of the COR method should be multiplied by 1.22–1.27 when maximal isometric plantarflexion joint moments, musculotendon forces and stresses are predicted using modelling.
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  • 105
    ISSN: 1573-7373
    Keywords: SCLC ; brain matastases ; neurologic asympotomatic ; MRI ; prophylactic radiotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose. In this study we evaluated the usefulness of MR-imaging in the detection of asymptomatic brain metastases (BM) at the initial diagnosis in patients with small cell lung cancer (SCLC) and studied the follow-up of these patients. Patients and methods. One-hundred and twenty-five patients with SCLC were investigated with MR-imaging. Results. In 112 patients with normal neurological findings, MR-imaging of the brain demonstrated BM in 17 patients (15%). Six of these 17 patients were therefore upgraded to extensive disease (ED). Two of these 17 patients died during chemotherapy because of progressive disease and 3 patients became neurologic symptomatic with progressive disease on MR-imaging of the brain. After completion of chemotherapy a repeated MR-imaging of the brain in the remaining 12 patients showed 1 complete remission, 4 partial remission and 7 progressive disease of the BM. Conclusion. This study showed that at presentation an unexpectedly high percentage of SCLC patients had asymptomatic BM on MR-imaging. We propose that MR-imaging of the brain should be included in the staging of SCLC patients as well for staging, prognosis and therapy.
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  • 106
    ISSN: 1573-7373
    Keywords: astrocytoma ; 201thallium SPECT ; MRI ; MR spectroscopy ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose To compare chemotherapy treatment monitoring in astrocytoma by 201thallium single photon emission computed tomography (SPECT) and photon magnetic resonance spectroscopy (1H-MRS) with magnetic resonance imaging (MRI), and to evaluate the influence of morphological tumor changes on cerebral 201thallium uptake and metabolic changes in 1H-MRS. Materials and methods Six patients with highly malignant astrocytomas were followed with quantitative 201thallium SPECT, MRI, and 1H-MRS during chemotherapy. Maximum follow-up included six examinations per patient by either method during 18 months. Criteria were set for: (1) regression (≥ 25% tumor reduction), (2) status quo (〈 25% reduction and 〈 25% increase), and (3) progression of disease (≥ 25% tumor increase). Results were compared with the clinical state of disease. Changes of tumor volume, contrast enhancement, necrosis, hemorrhage and edema on MRI were compared to changes in 201thallium uptake volumes and 1H-MRS metabolite ratios. Results Six patients were followed with a total of twenty-four examinations with 201thallium SPECT, MRI and 1H-MRS, respectively, between February 1997 and October 1998. Five patients developed clinical progression of disease, 4 out of 5 cases showed SPECT progression, 4 out of 5 cases MRI progression, and 1 out of 2 interpretable cases 1H-MRS progression at final assessment before clinical deterioration. During the phase of clinically stable disease; (A) the criterion for regression or status quo was met in 10 out of 13 assessments with SPECT, 11 out of 13 with MRI, and 8 out of 9 interpretable 1H-MRS; (B) the criterion for progression was met in 3 out of 13 with SPECT, 2 out of 13 with MRI, and 1 out of 9 interpretable 1H-MRS. The accuracy of SPECT, MRI, and 1H-MRS in identifying changes of tumor burden concordant with patients' clinical course was 78%, 83%, and 82%, respectively. SPECT regression was associated with MRI decrease of tumor size, contrast enhancement, edema and hemorrhage. SPECT progression was associated with MRI increase of the same parameters and the increase of necrosis. 1H-MRS regression was associated with decrease of edema. 1H-MRS progression was associated with increase of tumor size, hemorrhage, and increase or decrease of contrast enhancement. Conclusions Both 201thallium SPECT and 1H-MRS evaluation showed sensitivity for detection of astrocytoma progression. We did not find a higher accuracy of SPECT or MRS than of MRI in astrocytoma chemotherapy monitoring. Treatment induced MRI changes were associated with 201thallium uptake variations. 1H-MRS was difficult to apply for astrocytoma treatment monitoring. Improvements regarding size of measurement area such as multivoxel MRS and fat suppression pulses appeared desirable, and also the use of functional techniques with superior resolution such as dual isotope SPECT. However, our results suggest that 201thallium SPECT and 1H-MRS can provide additional information to MRI for chemotherapy efficacy evaluation in selected cases.
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  • 107
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 47 (2000), S. 195-210 
    ISSN: 1573-7373
    Keywords: MRI ; spinal cord ; tumor ; intramedullary
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The advent of MRI has significantly changed the diagnosis of spinal cord tumors. Standard imaging provides excellent localization and characterization of the tumor in a noninvasive fashion. Exact histologic diagnosis of the two most common tumors, ependymoma and astrocytoma, remains elusive but there are some suggestive imaging characteristics. It is hoped that some of the newer MR imaging sequences will improve characterization of the tumor and thereby influence therapy. Several of these pulse sequences are already used routinely in brain imaging. Evaluation of new imaging sequences in the spine has lagged behind brain MR imaging, mainly due to technical factors. Work on animal spine models and extrapolation from brain imaging studies suggest that it is only a matter of time before some of these techniques become clinically relevant.
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  • 108
    ISSN: 1573-7373
    Keywords: brain ; brain tumors ; MRI ; MR spectroscopy ; diffusion imaging ; glioma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This study sought to correlate quantitative presurgical proton magnetic resonance spectroscopic imaging (1H- MRSI) and diffusion imaging (DI) results with quantitative histopathological features of resected glioma tissue. The primary hypotheses were (1) glioma choline signal correlates with cell density, (2) glioma apparent diffusion coefficient (ADC) correlates inversely with cell density, (3) glioma choline signal correlates with cell proliferative index. Eighteen adult glioma patients were preoperatively imaged with 1H-MRSI and DI as part of clinically-indicated MRI evaluations. Cell density and proliferative index readings were made on surgical specimens obtained at surgery performed within 12 days of the radiologic scans. The resected tissue location was identified by comparing preoperative and postoperative MRI. The tumor to contralateral normalized choline signal ratio (nCho) and the ADC from resected tumor regions were measured from the preoperative imaging data. Counts of nuclei per high power field in 5–10 fields provided a quantitative measure of cell density. MIB-1 immunohistochemistry provided an index of the proportion of proliferating cells. There was a statistically significant inverse linear correlation between glioma ADC and cell density. There was also a statistically significant linear correlation between the glioma nCho and the cell density. The nCho measure did not significantly correlate with proliferative index. The results indicate that both ADC and spectroscopic choline measures are related to glioma cell density. Therefore they may prove useful for differentiating dense cellular neoplastic lesions from those that contain large proportions of acellular necrotic space.
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  • 109
    ISSN: 1615-6692
    Keywords: Key Words Cardiac imaging ; MRI ; Heart ; Ventricular function ; Schlüsselwörter Kardiale Bildgebung ; Magnetresonanztomographie ; Herz ; Ventrikelfunktion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die kardiale Dysfunktion ist eine der Hauptursachen kardiovaskulärer Morbidität und Mortalität. Eine genaue und reproduzierbare Bestimmung der Herzfunktion ist essentiell für die Diagnosestellung, Prognoseabschätzung und Beurteilung des Therapieeffekts beim einzelnen Patienten. Die kardiovaskuläre Magnetresonanztomographie (CMR) bietet eine Messmethode für die globale und regionale Herzfunktion, die nicht nur genau und reproduzierbar, sondern auch nichtinvasiv, ohne ionisierende Strahlung und unabhängig von geometrischen Annahmen und einem akustischen Fenster ist, das den Einsatz der Echokardiographie limitiert. Mit der Verfügbarkeit schnellerer MR-Scanner und automatisierter Analysesysteme sowie mit zunehmender Verbreitung und reduzierten Kosten wird CMR bald den Referenzstandard für die Messung der Herzfunktion darstellen.
    Notes: Abstract Cardiac dysfunction is a major cause of cardiovascular morbidity and mortality. Accurate and reproducible assessment of cardiac function is essential for the diagnosis, the assessment of prognosis and evaluation of a patient's response to therapy. Cardiovascular Magnetic Resonance (CMR) provides a measure of global and regional function that is not only accurate and reproducible but is noninvasive, free of ionising radiation, and independent of the geometric assumptions and acoustic windows that limit echocardiography. With the advent of faster scanners, automated analysis, increasing availability and reducing costs, CMR is fast becoming a clinically tenable reference standard for the measurement of cardiac function.
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  • 110
    Electronic Resource
    Electronic Resource
    Springer
    Herz 25 (2000), S. 365-383 
    ISSN: 1615-6692
    Keywords: Key Words Congenital heart disease ; MRI ; Blood flow ; MRA ; Postoperative ; Pulmonary arteries ; Schlüsselwörter Kongenitale Herzerkrankung ; MRT ; Blutfluss ; MR-Angiographie ; Postoperativ ; Pulmonalarterien
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Weltweit werden jährlich etwa 1,5 Millionen Kinder mit kongenitalen Herzerkrankungen (CHD, congenital heart disease) geboren. Durch Verbesserung der verschiedenen chirurgischen und interventionellen Techniken ist die Überlebensrate von CHD-Patienten drastisch gestiegen. Immer mehr Patienten mit postoperativen Residuen, Folgezuständen und Komplikationen benötigen eine umfassende Nachsorge. Die Darstellung und Quantifizierung morphologischer und funktioneller kardiovaskulärer Anomalien erfordern zuverlässige und vorzugsweise nichtinvasive bildgebende Verfahren. Die Röntgenkontrastangiokardiographie, der bisherige Goldstandard, eignet sich nicht zur wiederholten Anwendung. Die transthorakale Echokardiographie (TTE) ist die meistverwendete nichtinvasive Methode, doch bei älteren Patienten, insbesondere mit komplexen oder operativ behandelten Malformationen, sind die damit gewonnenen Informationen unter Umständen unbefriedigend. Narben-, Knochen- und Lungengewebe sowie Thoraxdeformitäten können mit dem Schallfenster interferieren. Die transösophageale Echokardiographie (TEE) liefert bei Erwachsenen mit verschiedenen CHD-Formen eindeutig einen weitaus besseren Bildausschnitt, ist jedoch als semiinvasiv einzustufen. Bei Kleinkindern ist die TEE für die auf Intensivstationen und in Operationssälen erforderliche unmittelbare prä- und postoperative Überwachung inzwischen unentbehrlich. Die Kernspintomographie (Magnetresonanztomographie, MRT) hat sich zu einem klinischen nützlichen Verfahren zur Untersuchung des Herzens entwickelt, vor allem bei angeborenen Fehlbildungen. Sie gilt heute als etablierte nichtinvasive Methode, mit der sich die Anatomie des Herzens in jeder gewünschten Ebene mit hoher Auflösung und naturgetreuen Kontrast zwischen kardialen Strukturen und strömendem Blut darstellen läßt. Das konventionelle Spin-Echo eignet sich hervorragend zur morphologischen Beurteilung, liefert jedoch nicht unbedingt funktionelle Informationen. Die durch neuere Impulssequenzen mögliche funktionelle Analyse verleiht der MRT ihren besonderen Wert. Mehrere dieser neuen MRT-Verfahren werden gegenwärtig klinisch eingesetzt. Die Gradienten-Echo-MRT liefert ein Bild des Blutflusses. Mit ihr können Stenosen, Regurgitation oder Shunts aufgrund der durch diese hämodynamischen Läsionen verursachten Strömungsturbulenzen entdeckt werden. Außerdem ermöglicht die Gradienten-Echo-MRT eine fortlaufende Schleifendarstellung der Ventrikelwandbewegung und eine Quantifizierung der Kammerfunktion. Mit der quantitativen Phasenkontrast-MR-Angiographie lassen sich Blutströmungsgeschwindigkeit und Volumendurchfluss in den mittleren und großen Gefäßen messen. Diese Besonderheit der MRT läßt sich zur Quantifizierung von Stenosen, Regurgitation, intrakardialen Shunts und des differentiellen pulmonalen Blutstroms nutzen. Vor allem ihre Fähigheit zur Messung des Volumendurchflusses ist ein klarer Vorteil der MRT. Die kontrastverstärkte MR-Angiographie ist besonders nützlich zur Darstellung der Pulmonalarterienäste und des Aortenbogens. Pulmonaler Blutfluss, rechtsventrikuläre Funktion, pathologische Aortenbefunde und Fontan-Umgehungskreislauf sind u. a. hochinteressante Fragestellungen, die mit multifunktioneller MRT untersucht wurden. Bei Patienten mit Pulmonalstenose oder Fallot-Tetralogie lassen sich mittels MRT Morphologie und Schwere jeder pulmonalen (Rest-)Stenose beurteilen, die rechtsventrikuläre Hypertrophie bewerten sowie eine postoperative Insuffizienz der Pulmonalklappe oder ventrikuläre Dysfunktion quantifizieren. Bei Patienten, die wegen Koarktation operiert wurden, kann die Morphologie von Rest- oder Restenosen MR-tomographisch mit Hilfe von Spin-Echo-Bildern und der kontrastverstärkten MR-Angiographie des Aortenbogens beurteilt werden. Die quantitative Phasenkontrastangiographie erlaubt zusätzlich, den Druckgradienten über der Stenose und das Ausmaß des Kollateralflusses zu bestimmen. Patienten mit Transposition der großen Arterien werden in der Regel mit Umkehroperationen auf Vorhofebene behandelt. Eine Dysfunktion des rechten systemischen Ventrikels ist bei diesen Patienten eine wesentliche Frage, die mit funktionellen MRT-Verfahren untersucht wurde. Andere Komplikationen nach Vorhofumkehroperation wie Obstruktionen im pulmonalen oder systemisch-venösen Kreislauf lassen sich mit der Gradienten-Echo-MRT mühelos aufdecken. Der Fongan-Umgehungskreislauf bleibt nach wie vor ein faszinierendes, in vielerlei Hinsicht noch nicht völlig verstandenes Thema. Zahlreiche Modifikationen der ursprünglichen Fontan-Operation wurden eingeführt, mit jeweils eigenen hämodynamischen Charakteristika. Zweifellos kann die kombinierte morphologisch-funktionelle MRT zur Entwicklung weiterer Verbesserungen des Fontan-Verfahrens beitragen. Trotz aller technischen Verbesserungen, insbesondere der Einführung des Atemanhalteverfahrens, bleibt die MRT nach wie vor eine Ergänzung zu Echokardiographie und Angiokardiographie. Verfügbarkeit, Ortsgebundenheit und die bei Säuglingen und Kindern erforderliche Sedierung sind bekannte Hindernisse. Nicht zuletzt gilt es, gegen die relativ begrenzte Einbeziehung von Kardiologen in die MRT-Abteilung und die eingeschränkte Verfügbarkeit von Radiologen mit Erfahrung in CHD anzugehen, um die MRT zu einem “vollwertigen Mitglied im Klub” der bildgebenden Verfahren bei CHD zu machen.
    Notes: Abstract With the increasing number of patients surviving after therapeutic intervention for congenital heart disease (CHD), accurate and frequent follow-up of their morphologic and functional cardiovascular status is required, preferably with a noninvasive imaging technique. Echocardiography, either transthoracic or transesophageal, has been the first choice for this purpose, and will probably keep that status, at least in a large segment of the CHD spectrum. Magnetic resonance imaging (MRI) is an established method for high-resolution visualization of cardiovascular morphology. In the past decade, newer MRI techniques have been developed that allow functional evaluation of CHD patients. Particularly the introduction of breath-hold imaging, contrast-enhanced MRA and user-friendly computer software for image analysis may move functional MRI of CHD from the science laboratory to clinical use. It is already evident that MRI is superior to echocardiography in certain areas of limited echocardiographic access, such as the pulmonary artery branches and the aortic arch in adult patients. But MRI has also a unique potential for accurate volumetric analysis of ventricular function and cardiovascular blood flow, without any geometric assumptions. If supported by increased cooperation between cardiologists and radiologists, MRI will grow into a useful noninvasive imaging tool that, together with echocardiography, will obviate the need for invasive catheter studies for diagnostic purposes.
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  • 111
    ISSN: 1434-3924
    Keywords: Schlüsselwörter Arthroskopie ; Klinische Untersuchung ; Kniegelenk ; MRT ; Key words Arthroscopy ; Clinical examination ; Knee ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Magnetic resonance imaging (MRI) is used frequently in the diagnosis of knee injuries. The aim of this study was to compare the accruracy of MRI and clinical examination in diagnosing meniscal and cruciate ligament tears. Between January 1997 and June 1998, a total of 883 patients had undergone knee joint arthroscopy, operated on by one orthopedic surgeon. Of these, 144 patients had a preoperative MRI (group 1). This group was compared with 309 patients who had undergone arthroscopy without MRI between January 1997 and June 1997 (group 2). Sensitivity, specificity and accuracy for tears of the medial meniscus were 80.6%/58.8%/72.9% in group 1 and 83.3%/78.5%/80.3% in group 2, respectively, for tears of the lateral meniscus 44.4%/88.9%/83.3% in group 1 and 60.6%/98.8%/92.5% in group 2 and for tears of the anterior cruciate ligament 58.1%/92.0%/¶84.7% in group 1 and 80.1%/96.6%/¶89.6% in group 2. This study demonstrates that an experienced orthopedic surgeon can rely on the clinical diagnosis and decide whether arthroscopy is necessary in most cases without MRI. He will find intraarticular pathology in almost all cases if arthroscopy is performed. MRI should be reserved for special cases and should not be performed without first conducting a thorough clinical examination. The orthopedic surgeon should decide whether MRI is needed.
    Notes: Zusammenfassung Mit zunehmender Häufigkeit wird beim Verdacht auf einen Kniebinnenschaden die Magnetresonanztomographie (MRT) eingesetzt. Ziel der vorliegenden Arbeit war es, die Treffsicherheit von MRT und klinischer Untersuchung bei der Diagnose von Meniskusläsionen und Kreuzbandverletzungen zu vergleichen und daraus zu schlussfolgern, wann ein MRT am Kniegelenk indiziert ist. Vom 1.1.1997 bis zum 30.6.1998 wurden 883 Kniegelenkarthroskopien durchgeführt. Bei 144 Kniegelenken lag präoperativ ein MRT vor (Gruppe 1). Dieser Gruppe wurde eine Vergleichsgruppe, bestehend aus allen vom 1.1.1997 bis zum 30.6.1997 arthroskopierten Kniegelenken ohne präoperatives MRT (n = 309) gegenübergestellt (Gruppe 2). Sensitivität, Spezifität und Präzision betrugen für den medialen Meniskus 80,6%, 58,8% bzw. 72,9% in Gruppe 1 und 83,3%, 78,5% bzw. 80,3% in Gruppe 2, für den lateralen Meniskus 44,4%, 88,9% bzw. 83,3% in Gruppe 1 und 60,6%, 98,8% bzw. 92,5% in Gruppe 2 und für das vordere Kreuzband 58,1%, 92,0% bzw. 84,7% in Gruppe 1 und 80,1%, 96,6% bzw.89,6% in Gruppe 2. Mit einer sorgfältigen klinischen Untersuchung können in Verbindung mit Standardröntgenaufnahmen in den meisten Fällen die Diagnose und damit die Indikation zur Arthroskopie mit ausreichender Sicherheit gestellt werden. Die Magnetresonanztomographie sollte Spezialindikationen vorbehalten bleiben und durch den Operateur veranlasst werden.
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  • 112
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    Arthroskopie 13 (2000), S. 132-137 
    ISSN: 1434-3924
    Keywords: Schlüsselwörter Qualitätssicherung ; Knorpeldefekte ; MRT ; Scores ; Keywords Quality control ; Cartilage repair ; MRI ; Clinical scores
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Most procedures currently in use for the treatment of full thickness cartilage defects lack solid data as a proof of quality. Various techniques for quality control are advisable. Meticulous documentation of adverse events and treatment failures is crucial. Patient self-assessment and clinical scores are often biased but focussed on the basis of medical efforts: the well-being of the patient. Second-look arthroscopies produce fewer facts for quality control than expected but enable therapeutical intervention. Magnetic resonance imaging will be essential for cartilage assessment in the future. To date, the evaluation of tissue quality is experimental. Histology and immunohistochemistry are widely accepted as precise tools to characterize cartilaginous tissue. Ethical reasons prohibit daily use. Quality control following the repair of cartilage defects is complicated, expensive, and of variable outcome, but dangerous if neglected. Multiple insignificant results can lead to a sharp image of the postoperative condition and may enable quality control of treatment and surgery.
    Notes: Die meisten Verfahren zur Behandlung von Gelenkknorpeldefekten werden angewendet, ohne dass ihre Qualität zweifelsfrei nachgewiesen ist. Verschiedene Möglichkeiten der Qualitätssicherung können derzeit mit vertretbarem Aufwand routinemäßig eingesetzt werden. Die Beurteilung der Sicherheit einer Behandlung hinsichtlich Komplikationen und Therapieversagern ist von eminenter Bedeutung. Patientenfragebögen und klinische Scores sind subjektiv, orientieren sich aber am eigentlichen Ziel einer Therapie: der Wiederherstellung des Wohlbefindens des Patienten. Noch in den Anfängen, aber mit hervorragenden Perspektiven für die Zukunft steht die Magnetresonanztomographie. Knorpelqualität und -aktivität können heute noch nicht beurteilt werden. Die Kontrollarthroskopie nach der Behandlung von Gelenkknorpeldefekten liefert weniger harte Daten für die Qualitätssicherung als erwünscht, ermöglicht aber therapeutische Maßnahmen. Histologische Untersuchungen stehen im Ruf der unbestechlichen Präzision. Dem breiten Einsatz stehen jedoch fehlende Standards und berechtigte ethische Bedenken entgegen. Qualitätssicherung nach der operativen Behandlung von Gelenkknorpeldefekten ist schwierig, teuer und häufig ungenau – keine Qualitätssicherung ist oft gefährlich. Aus vielen, isoliert gesehen ungenauen Befunden werden die Bewertung eines Zustands immer sicherer und die Beurteilung der Qualität einer Behandlung möglich.
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  • 113
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    Cancer and metastasis reviews 19 (2000), S. 39-43 
    ISSN: 1573-7233
    Keywords: angiogenesis ; MRI ; permeability ; in vivo imaging ; hypoxia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Magnetic resonance imaging (MRI) provides a range of non-invasive measures for visualization of tumor angiogenesis in the clinic as well as in experimental tumor models. MRI methods were developed for assessment of spatial and temporal changes in perfusion, blood volume fraction, vascular permeability, vascular function, vascular maturation, vessel diameter and tortuosity. Molecular targeted contrast agents were used for mapping specific markers of neovasculature. These approaches were applied for analysis of a number of regulatory mechanisms controlling tumor angiogenesis and for preclinical evaluation of tumor response to antiangiogenic agents.
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  • 114
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    Journal of neural transmission 107 (2000), S. 1427-1436 
    ISSN: 1435-1463
    Keywords: Keywords: Brain ; MRI ; PSP ; MSA ; parkinsonism.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary. To establish diagnostic magnetic resonance imaging (MRI) criteria for differentiating progressive supranuclear palsy (PSP) from multiple system atrophy (MSA), magnetic resonance images from eight patients with probable PSP, 30 with probable MSA {nine striatonigral degeneration (MSA-P) and 21 olivopontocerebellar atrophy (MSA-C)}, and ten age-matched controls were retrospectively studied. Anteroposterior diameters in the midline sagittal T1-weighted image of the rostral (RMT) and caudal midbrain tegmentum (CMT), caudal pons and medulla were measured. Divergence of the red nuclei (RN) in the axial T2-weighted image was judged. All PSP images had a smaller RMT diameter than the lower limit of the normal range, showed RN divergence, and had a pontine diameter within the normal range. All MSA images had a CMT diameter within the normal range; no MSA images showed divergence of RN. Forty-four percent (4/9) of MSA-P and 76% (16/21) of MSA-C images had a pontine diameter smaller than the lower limit of the normal range. On basis of the results, we propose MRI diagnostic criteria for differentiating PSP from MSA.
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  • 115
    ISSN: 1436-2023
    Keywords: Key words Osteonecrosis ; Femoral head ; Bone marrow edema ; MRI ; Histology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Sequential magnetic resonance imaging (MRI) was performed on a 38-year-old woman with systemic lupus erythematosus who had received corticosteroid and had developed non-traumatic osteonecrosis of the femoral head. The initial MR finding was a band lesion on the T1-weighted image, which had been present before the onset of symptoms. At the onset of symptoms, a diffuse bone marrow edema pattern, with a low signal intensity on T1 and high signal intensity on T2-weighted images, was noted around the band lesion, extending to the femoral neck. Histopathologically, this region was found to consist of serous exudate, focal interstitial hemorrhage, and mild fibrosis, without any evidence of extension of osteonecrosis. It should be noted that extension of a low signal intensity area on MRI after the onset of hip pain may not be the result of the extension of osteonecrosis, but may represent concomitant edema due to collapse.
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  • 116
    ISSN: 1573-6792
    Keywords: EEG ; MRI ; Co-registration ; Spline ; Source localization ; Head model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two classes of functional neuroimaging methods exist: hemodynamic techniques such as PET and fMRI, and electromagnetic techniques such as EEG/ERP and MEG. In order to fusion these images with anatomical information, co-registration with volumetric MRI is needed. While such co-registration techniques are well established for hemodynamic images, additional steps are needed for electromagnetic recordings, because the activity is only recorded on the scalp surface and inverse solutions based on specific head models have to be used to estimate the 3-dimensional current distribution. To date most of the experimental and clinical studies use multi-shell concentric sphere models of the head, solve the inverse problem on this simplistic model, and then co-register the solution with the MRI using homogeneous transform operations. Contrary to this standard method, we here propose to map the MRI to the spherical system by defining transformation operations that transform the MRI to a best-fitting sphere. Once done so, the solution points are defined in the cerebral tissue of this deformed MRI and the lead field for the distributed linear inverse solutions is calculated for this solution space. The method, that we call SMAC (Spherical Model with Anatomical Constrains) is tested with simulations, as well as with the following real data: 1) estimation of the sources of visual evoked potentials to unilateral stimulation from data averaged over subjects, and 2) localization of interictal discharges of two epileptic patients, one with a temporal, the other with an occipital focus, both confirmed by seizure freedom after resection of the epileptogenic region.
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  • 117
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    Neurological sciences 21 (2000), S. 53-55 
    ISSN: 1590-3478
    Keywords: Key words Genetic Creutzfeldt-Jakob disease ; Deafness ; MRI ; 14-3-3 protein
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We describe a case of genetic Creutzfeldt-Jakob disease (CJD) with deafness at the onset. We report clinical features, 14-3-3 protein positivity, electroencephalography and brain stem auditory evoked potential abnormalities, and high signal on magnetic resonance imaging in basal ganglia and temporal cortex. Similarities with CJD Heidenhain variant are discussed.
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  • 118
    ISSN: 1590-9999
    Keywords: Key words Disc herniation ; Lumbar spine ; Migration ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The majority of symptomatic lumbar disc herniations are located in a posterolateral position with resultant nerve root compression. Although caudal, rostral and lateral migrations of disc fragments are common, posterior epidural migration of an extruded free fragment from a lumbar disc herniation is a rare occurrence and sometimes may cause a dural sac compression with cauda equina syndrome. This retrospective case report describes a 63-year-old man with intractable lower back pain and cauda equina syndrome. Emergency magnetic resonance imaging (MRI) revealed a posterior epidural soft tissue compressing the dural sac. The lesion was hypointense on T1-weighted images, hyperintense on T2-weighted images and showed rim enhancement after intravenous injection of gadolinium. A laminectomy at L3 was performed and the extruded disc fragment was removed with dural sac decompression. Postoperatively the patient's radicular symptoms completely resolved. At the 2-year follow-up visit, the patient had recovered full motor, sensory and urinary functions. MRI is the modality of choice in the evaluation of an extruded free disc fragment and a cauda equina compression. In such cases a wide decompressive laminectomy is recommended.
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  • 119
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    Neurological sciences 21 (2000), S. 151-155 
    ISSN: 1590-3478
    Keywords: Key words Epilepsy ; Venous angioma ; MRI ; Vascular malformations ; Focal cortical dysplasia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The purpose of this study was to evaluate the frequency and characteristics of epilepsy associated with cerebral venous angiomas (VA). We examined epileptic patients in which magnetic resonance imaging (MRI) showed VA. The characteristics of epilepsy and its relationships to VA were studied. Out of 1020 epileptic patients submitted to MRI in a 10-year period, 4 presented with VA. All had partial seizures, most frequently complex partial, with secondary generalizations in 3. Drug resistance was observed in 2. One patient had a small area of cortical dysplasia near the VA; another had a cutaneous angioma. In 2 patients, there was no topographic concordance between the VA and the focus on electroencephalography. Our study reveals that VA are rarely found in epileptic patients, differently from other vascular malformations, in particular cavernomas. Topographic and/or etiological relationships between VA and epilepsy are still undefined.
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  • 120
    ISSN: 1573-3297
    Keywords: Extended twin study ; methodology ; structural equation modeling ; intermediate phenotype ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Psychology
    Notes: Abstract The hunt for genes influencing behavior may be aided by the study of intermediate phenotypes for several reasons. First, intermediate phenotypes may be influenced by only a few genes, which facilitates their detection. Second, many intermediate phenotypes can be measured on a continuous quantitative scale and thus can be assessed in affected and unaffected individuals. Continuous measures increase the statistical power to detect genetic effects (Neale et al., 1994), and allow studies to be designed to collect data from informative subjects such as extreme concordant or discordant pairs. Intermediate phenotypes for discrete traits, such as psychiatric disorders, can be neurotransmitter levels, brain function, or structure. In this paper we conduct a multivariate analysis of data from 111 twin pairs and 34 additional siblings on cerebellar volume, intracranial space, and body height. The analysis is carried out on the raw data and specifies a model for the mean and the covariance structure. Results suggest that cerebellar volume and intracranial space vary with age and sex. Brain volumes tend to decrease slightly with age, and males generally have a larger brain volume than females. The remaining phenotypic variance of cerebellar volume is largely genetic (88%). These genetic factors partly overlap with the genetic factors that explain variance in intracranial space and body height. The applied method is presented as a general approach for the analysis of intermediate phenotypes in which the effects of correlated variables on the observed scores are modeled through multivariate analysis.
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  • 121
    ISSN: 1434-1948
    Keywords: NMRD ; MRI ; Contrast agents ; Carbonic anhydrase ; Sulfonamides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel Gd-DTPA derivative with a built-in sulfonamide (SA) was synthesized as a contrast agent for MRI. The complex was designed to selectively target the enzyme carbonic anhydrase. It is shown that the longitudinal relaxation rates of aqueous solutions of Gd-DTPA-SA in the presence of carbonic anhydrase increase significantly. The binding constant is determined to be 15,000 ± 5,000 M-1. This value ensures substantial formation of the carbonic anhydrase adduct at imaging concentrations of Gd-DTPA-SA. The complex interacts with erythrocytes, presumably due to a high affinity for the carbonic anhydrase present on the outer surface of the latter. This takes place even though the enzyme has a low abundance and is easily saturated by small amounts of Gd-DTPA-SA. The interaction of Gd-DTPA-SA with serum proteins is negligibly small. Therefore, the complex could potentially be tested as a selective contrast agent for compartments outside the blood pool.
    Additional Material: 4 Ill.
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  • 122
    ISSN: 1437-2320
    Keywords: CNS ; imaging techniques ; MRI ; tissue contrast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Magnetic resonance imaging (MRI) has undergone a rapid development which is still continuing. In this article a survey is given of the present status of this new diagnostic tool in the evaluation of diseases of the central nervous system. When atoms with uneven numbers of protons or neutrons in a homogeneous magnetic field are tilted against the main vector of this field by a radiofrequency pulse, nuclear magnetic resonance can be observed. During the relaxation of the little dipoles back to the direction of the underlying magnetic field, a resonance signal is generated. The superposition of variable field gradients enables the scanning of sectional images in the axial, frontal and sagittal plane. The variables of H+-magnetic resonance which can be utilized for imaging are: the proton density, the relaxation times T1 (spin-lattice) and T2 (spin-spin) and flow effects. While the proton density in organic tissue fluctuates only by some 10%, the relaxation times may vary by several hundred per cent. Tissue contrast, therefore, is mainly based on relaxation times differences. The image character can also be influenced by variations of imaging parameters (i.e. repetition rate, interpulse delay, read out or echo delay) in different imaging sequences, such as the spin-echo and the inversion recovery technique. Depending on these imaging parameters T1 and T2 will contribute to the signal to a varying degree. This fact is most important for the diagnostic information of MRI. In initial clinical experiences in the diagnosis of diseases of the central nervous system, MRI has demonstrated high sensitivity in the detection of lesions (such as oedema, neoplasms, demyelinating disease), but less significance in lesion discrimination. In spinal disease the direct sagittal imaging of MRI enables MRI-myelography without contrast medium, superior to conventional myelography in many cases. For detailed evaluation of disc disease, however, the spatial resolution still has to be improved. Promising results have been obtained from flow effects. Depending on the flow velocity of blood, vessels appear white with intensive signals (slow flow) or black due to low signal intensities (rapid flow). MRI-angiography including measurement of blood flow seems possible. MRI-contrast media are not yet available for routine clinical use. Promising results have been reported on the basis of rare-earth elements, such as gadolinium Gd3+. These substances decrease T1 and T2 with subsequent increase in signal intensity. Concerning harmful side-effects of MRI, three possible sources have to be considered: the static magnetic field, the changing magnetic field, and radiofrequency heating. No permanent damage to organisms has been described up to the present time, in relation to the magnetic field strength used in MRI. However, there is known risk for patients who carry cardiac pace makers or metal implants such as aneurysm clips.
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  • 123
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    Helvetica Chimica Acta 67 (1984), S. 47-53 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The He(Iα) photoelectron (PE) spectra of tris(perfluorocyclobuta)benzene 4(F)3,3,4,4,7,7,8,8,11,11,12,12-Dodecafluorotetracyclo[8.2.0.02,5.06,9]dodeca-1,5,9-triene, tris(perfluorocyclopenta)benzene 5(F)1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Octadecafluoro-2,3,4,5,6,7,8,9-octahydro-1H-trindene., tetrakis(perfluorocyclobuta)cyclooctatetraene 6(F)3,3,4,4,7,7,8,8,11,1l,l2,l2,l5,15,16,16-Hexadecafluoropentacyclo[12.2.0.02,5.06,9.010,13]hexadeca-1,5,9,13-tetraene., and of tetrakis(perfluorocyclopenta)cyclooctatetraene 7(F)1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-Tetracosafluoro-1,2,3,4,5,6,7,8,9,10,11,12-dodeca-hydrotetracyclopenta[a,c,e,g]cyclooctene. are reported. A tentative assignment of the PE spectra is derived by empirical correlation with those of relevant reference compounds. The results suggest that 6(F) retains the D4h-conformation in the gas phase, i.e. A conformation with a planar cyclooctatetraene ring, as observed in the crystal. All four compounds exhibit a sharp increase of their first ionization energies, relative to the corresponding parent hydrocarbons, due to the perfluoro effect.
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  • 124
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene (1) has been used to prepare complexes of the type [PtL(1)] (L = C2H4, CH2=CH—CO2Me, PhC≡CPh, MeC≡CMe, MeO2CC≡CCO2Me, (i-Pr)O2CC≡CCO2(i-Pr), Ph3P and CO). It is shown that these complexes are less labile than the corresponding species [PtL(Ph3P)2]. The preparation of complexes trans-[PtX(R)(1)] by oxidative addition of RX (RX = PhCH2Br and Mel) to [Pt(C2H4)(1)] is described. The isolation of [PtO2(CH3)2CO(1)] is also reported.
    Additional Material: 3 Tab.
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  • 125
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical anions of the compounds N1N, N3N and N5N, in which two naphthalen π-systems are separated by 1, 3 and 5 spirobonded cyclobutane rings, respectively, and tha tof the reference compound N1, containing one naphthalene π-system and one cyclobutane ring, have been studied by ESR and ENDOR spectroscopy under a variety of experimental conditions. The intramolecular electrons spin transfer between the two π-moieties in N3N.⊖ and N5N.⊖ is slow on the hyperfine time-scale, irrespective of the applied conditions. It is also slow in N1N.⊖, except for media of high solvating power. In such media, with a slight reduction of N1N to its radical anion, a paramagnetic species is observed, the hyperfine data for which are consistent with N1N to its radical anion, a paramagnetic species is observed, the hyperfine data of which are consistent with N1N.⊖, undergoing a fast intramolecular electron spin tansfer. The ESR and ENDOR spectra of this species are superimposed on those characteristic of a slow transfer. It is suggested that the fast and slow transfer involve the syn- and anti-conformations, respectively, since the distance, r, between the two naphthalene π-systems of N1N.⊖ is considerably shorter in the former than in the latter (r = 740 vs. 880 Pm for the distance between the centres of the π-systems). Glassy solutions of exhaustively reduced N1N display signals of the dianion triplet state, whereas no such signals are found for N3N and N5N. The zero-field splitting parameter, D, is 4.7 mT, corresponding to r ≈ 480 pm.
    Additional Material: 5 Ill.
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  • 126
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Loss of CH3., CH4, C2H4, C3H5., C3H6 and C3H7 from the molecular ions of a number of 13C-labeled analogs of 4,4-dimethyl-1-pentene was studied both in normal (source) 70-eV electron impact (EI) spectra dn in metastable spectra. For loss of CH3. in the source, 96% of the methyl comes frm positions of 5, 5′ and 5″, while the remainder comes from position 1. In the metastable spectra, loss of C-1 (16%) and C-3 (9%) is increasing in importance. The loss of ethylene is a particular case: either C-1 or C-3 are lost with any other C-atom from positions 2,5,5′, and 5″ (8 × 10%) in the metastable spectra, the probability for simultaneous loss of C-1 and C-3 being 6%. If C-1 seems to these two positions become completely equivalent in the metastable time range. The T-values (kinetic energy release) for the different positions show small, but statisticaly different values and a small isotope effect. Loss of C3H5 (allylic cleavage) is 100% C-1, C-2 and C-3, i.e., no evidence for skeletal rearrangement is seen. This is also true for loss of C3C6 (McLafferty rearrangement) within the source, but in metastable decay the other positions gain in importance. The neutral fragment C3H7. appears to be the the result of consecutive loss of CH3. and C3H4, rather than a one-step loss of propyl radical or the inverse reactions sequence. No metastable reaction can be seen for this reaction. Decomposition of labeled C6H11+ and C5H10+ secondary ions occurs in an essentially random fashion.
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  • 127
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    Helvetica Chimica Acta 67 (1984), S. 450-454 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Up to now the synthesis of para-substituted phenyl-terpyridine ligands was difficult with respect to the purification of the reaction products. We have found that these compounds can easily be isolated as hydrobromides from acetic acid. Starting from the hydrobromides the purification turned out to be easy. Synthesis of para-substituted Cl-, Br-, H3C-, H2BrC-, HO- 2,6-Bis(2-pyridyl)-4-phenylphyridine is reported.
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  • 128
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    Helvetica Chimica Acta 67 (1984), S. 441-449 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexation of Silver(I) by Cyclic TetraminesThe nature of Ag(I)-complexes with 1,4,8,11-tetraazacyclotetradecane (1), 1,5,9,13-tetraazacyclohexadecane (2) 1,5,10,14-tetraazacyclooctadencane (3) and 1,6,11,16-tetraazacycloeicosane (4) is studied. The effect of ring size on disproportionation of the Ag() cation in the presence of ligand is reported. The stability of Ag(I)-complexes with 3 and 4 in aqueous solution is determined by means of potentiometric titration.
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    Helvetica Chimica Acta 67 (1984), S. 625-627 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 130
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    Helvetica Chimica Acta 67 (1984) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 131
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    Helvetica Chimica Acta 67 (1984), S. 625-639 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical Ions of Bridged [14] Annulenes. Investigations on the Influence of Frontier Orbitals on Reactivity and BondingThe radical anions and the radical cations derived from trans-15, 16-dimethyl-1, 4:8,11-ethandiyliden[14]annulene (6), trans-15-methyl-1,4:8,11-ethandiyliden[14]annulene (7) and cis-15, 16-propano-1,4:8,11-ethandiyliden[14]annulene (8) are described. The hyperfine data of the radical anions 6, 7 and 8 resemble those of the structurally related radical anions of trans-10b, 10c-dimethyldihydropyrene (4) and trans-10b, 10c-dihydropyrene (5). This finding leads to the conclusion, that the change in the relative arragement of the saturated bridge within the fourteen-membered π-perimeter by passing from 4 (5) to 6 (7, 8) does not in fluence the energetic sequence of the lowest unoccupied molecular orbitals. The behavior of 6 and 7 towards oxidation parallels the photochemical reactivity of 4. The hyperfine coupling constants of the radical cations derived from 6 and 7 indicate that the removal of an electron is accompanied by an isomerization of the molecular framework. The investigation of the electron transfer process gby cyclic voltammetry supports these findings. The radical cations prefer the cyclophane-like structures 6a and 7a, in which the central σ-bond (C(15)-C(16) bond) is broken.
    Additional Material: 7 Ill.
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  • 132
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    Helvetica Chimica Acta 67 (1984), S. 664-668 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical behaviour of the title compound 1a is compared to that of the non-fluorinated parent ketone 2-methylcyclohexanone (1b). Substitution of the CH3- group on C(2) by a trifluoromethyl group strongly enhances 2H- and RH- reduction product formation in cyclohexane or 2-propanol and oxetane formation in the presence of 2-methylpropene as olefinic component. Under all these conditions 1b exclusively undergoes a-cleavage, a process observed for 1a only in non-reducing solvents as benzene or tert-butyl alcohol.
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  • 133
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of β-keto-acetals, derived from non-enolisable β-diketones, with sulfonic acids in boiling benzene resuots in a smooth retro-Claisen-type fragmentation. The acetal-C-atom is thereby transformed into a carboxylic ester via a dialkoxycarbenium ion, which is dealkylated by the sulfonate counter-ion. Application of this reaction to the diastereomeric monoacetals 3 and 4, derived from cis-9-methyl-decalin-1,8-dione (1), followed by transesterification with CH3OH, yields optically pure 4-(2′-methyl-3′-oxocyclohexyl)butyrate 9 ((+)-9 from 3, (-)-9 from 4) and the monosulfonate of Meso-2,3-butanediol (-)-13 (Scheme 2). Unexpectedly, this cleavage proceeds as well with monoacetal 26, obtained by acetalization of trans-9-methyl-decalin-1,8-dione (27) with 2,2-dimethyl-1,3-propanediol (Scheme 7). Some attempts, aiming at an isomerization of the cis- and trans-decalin derivatives 3 and 24, or 25 and 26, via the postulated carboxonium intermediate, were not successful.
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  • 134
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    Helvetica Chimica Acta 67 (1984), S. 856-865 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkylation of bicyclo[3.3.0]octane-2,8-dione (1), which is prepared by a modification of the procedure described in the literature, gives the methyl- and propynyl-derivatives 6 and 7 (Scheme 1). In addition to the method described previously (Scheme 2), 9-methyl-cis-decalin-1,8-dione 9 is obtainable stereoselectively either by cyclization of keto-acid 16, or by aldol cyclization of keto-aldehyde 26 and oxydation of the resulting alcohols 24 and 25 (Scheme 4). The β-keto-alcohols 24 and 25 undergo a base-catalyzed isomerization; the trans-decalin isomers 27 and 28 are not detected in this equilibrium mixture (Schemes 4 and 5)l. Monoreduction of cis-dione 9 gives the endo-alcohol 25, while 27 is the favored product of the reductin of trans-dione 10 (Scheme 4). Optically pure (+)-25 can be prepared from (9S,10R)-monoacetal 29 (Scheme 5).
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  • 135
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new tripeptide (dimer), bis[(L-cysteine-S-acetyl)-L-hemicystinyl(S2 → S2)-D-valine] (6) was synthesized by coupling N-(tert-butoxycarbonyl)-S-carboxymethyl-L-cysteine benzyl ester (1) with S-trityl-L-cysteinyl-D-valine benzyl ester and subsequent removal of the protecting groups. After reduction of the disulfide, the free tripeptide Cys (CH2CO-Cys-D-Val) (Ib) was used as a substrate of isopenicillin-N synthetase in a cell-free conversion to 6-[2-((D-2-amino-2-carboxyethyl)thio)acetamido]penicillanic acid (IIa).
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  • 136
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    Helvetica Chimica Acta 67 (1984), S. 902-905 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the title compounds is described.
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  • 137
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    Helvetica Chimica Acta 67 (1984), S. 927-927 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 138
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Resolution of racemic cis-3-(2-aminophenylthio)-2-hydroxy-3-(4-methoxyphenyl) propionic acid (2) via the cinchonidine salt 3, and brucine salt 4, isolation of the calcium salts (+)- and (-)-5, as well as their cyclization to enantiomeric 1,5-benzothiazepines (+)- and (-)-1, are described. X-Ray single-crystal analysis reveals (2S, 3S) absolute configuration of (+)-1 on the basis of tentative comparison of CD data with those for the 1,4-benzodiazepine derivative (+)-8 of known absolute configuration.
    Additional Material: 4 Ill.
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  • 139
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    Helvetica Chimica Acta 67 (1984) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 140
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    Helvetica Chimica Acta 67 (1984), S. 927-933 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis ad Structure of Zinc Complexes of 2-Amino-1-azetinesThe 2-dimethylamino-3,3-dimethyl-1-azetines 7a and 7b have been synthesized in analogy to the procedure reported by Ghosez et al. [1] (Scheme). The crystal structure of 1-benzhydryl-azetidindimethyliminium chloride 5a, a precursor of azetine 7a, has been established by X-ray diffraction analysis. Treatment of azetines 7a and 7b with ZnBr2 in CH2Cl2/MeCN yielded tetrahedral bis (azetine)dibromozinc complexes 8a and 8b, respectively (Scheme 2). The molecular structure of 8a has been determined by X-ray diffraction analysis too.
    Additional Material: 3 Ill.
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  • 141
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    Helvetica Chimica Acta 67 (1984), S. 947-952 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioselective synthesis of (+)- and (-)-cis-2-methyl-4-propyl-1,3-oxathine 8 and 9 form (E)-2-hezen-1-ol (1) as common starting material is described. The two enantiomeric forms exhibit different organoleptic properties.
    Additional Material: 2 Tab.
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  • 142
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    Helvetica Chimica Acta 67 (1984), S. 959-963 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyanothyl-subsituted cylohexyl cyclohexanoates, bi(cyclohexanes) and phenyl cyclohexanes were synthisized. Their mesmorphic behaviour is compared to that of the corresponding cyano derivatives. (Cyanoethyl)cyclohexyl cyclohenxanoates show mesmorphic properties in contrast to the corresponding cyano derivative. Separation of the cyano substituent from the rigid core of an anisotropic aliphatic compound by methylene groups enhances the thermodynamic stability of the mesophase. In aromatic compound, the cyanoethyl group leads to lower clearing points. These phenomena are attributed to teh influence of steric effects on the packing density and to the dependence of the clearing point on molecular association.
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  • 143
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    Helvetica Chimica Acta 67 (1984), S. 1000-1002 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nα-L-Iysine with a 2-carboxy-4, 6-dinitrophenyl (Dncp) haptenic group on the ε-amino function is a potent anaphylactogen in the guinea pig. We prepared Nε -Dncp- Nα-benzoly-L-Iysinamide and Nε-Dncp-Nα-benzoyl-L-lysyl-1-aminopropane where the carboxyl group of Iysine is blocked. Both compounds were non-elections of anaphylaxis.
    Additional Material: 1 Tab.
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  • 144
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    Helvetica Chimica Acta 67 (1984), S. 21-28 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C45- and C50-Carotenoids. Synthesis of Optically Active Acyclic C15-End GroupsThe optically active C15-end groups (S)-12, (S)-13 and (R)-14 were prepared from the C12-synthon (S)-11 in good chemical and optical yield. These C15-end groups are suitable compounds for the synthesis of optically active C45- and C50-carotenoids.
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  • 145
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the crystal structure of the title compound at 98 K the dimethylamino group has pyramidal geometry. The nitrogenlone pair is not directed towards the triple bond; instead, one N—CH3 bond lies almost in the plane of the disubstituted ring, directed away from the triple bond, while the other N—CH3 bond and the lone pair are directed to opposite sides of the plane, nearer to the acetylene. There is a remarkably short intramolecular contact (2.39 Å) between a methyl H- and an acetylenic C-atom. The Taft σI parameter of the arylethynyl substituent appears to be similar to that of a carboxylic ester, judging from the bond-angle deformation at the ipso-C-atom.
    Additional Material: 5 Ill.
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  • 146
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Heart Glycosides of the Arrow Poison of Lophopetalum toxicum LOHERFrom the cytotoxic and positive inotropic acting bark extract of the Philippinan Lophopetalum toxicum eight heart glycosides have been isolated and their structures have been elucidated mainly by field-desorption-MS- and 1- and 13C-NMR spectroscopy. Besides the known k-Strophanthidin (1), Antiarigenin (6) and β-Antiarin (Antiarigenin-3-β-O-α-L-rhamnoside, 10) the following mono- and diglycosides could be identified: strophanthidin-3-β-O-α-6-desoxy-D-allopyranoside (strophalloside, 2), strophanthidin-3-β-O-β-6-desoxy-D-glucopyranoside (= Strophanthidin chinovoside, 3), strophanthidin-3-β-O[-4Oβ-D-allopyranosyl-β-6-desoxy-D-allopyranoside] (4), strophanthidin-3-β-O-[3-O-β-D-glucopyranosyl-β-6-desoxy-D-talopyranoside] (5), antiarigenin-3-β-O-[3-O-β-D-gulopyranosyl-β-6-desoxy-D-talopyranoside] (7), antiarigenin-3-β-O-[4O-β-D-allopyranosyl-β-6-desoxy-D-allopyranoside] (8), and antiarigenin-3-β-O-β-6-desoxy-D-allopyranoside (antiallosid) (9). The structure of strophanthidinchinovoside (3) could be confirmed by synthesis.
    Additional Material: 3 Ill.
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  • 147
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A recent controversy on the interpretation of the ESR spectrum of ionized oxirane is clarified on the basis of the electronic absorption spectra of ionized tetramethyloxirane and 9,10-octalineoxide. The results favour a ring-opened structure for oxirane molecular cation, resulting from C—C bond cleavage and being iso-π-electronic to allyl radical.
    Additional Material: 3 Ill.
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  • 148
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Acylation of Acetylenes with β,γ-Unsaturated Acid Chlorides, A New Synthesis of 5-Substituted 2-CyclopentenonesThe acylation of acetylenes with α,α-disubstituted, β,γ-unsaturated acid chlorides under Friedel-Crafts-type conditions leads to 5-substituted 2-cyclopentenones. Phenols are formed with β,γ-unsaturated acid chlorides bearing at least one α-H-atom. These transformations are explained by the intramolecular cyclization of the initially formed vinyl cation, which, in the cases of α,α-disubstituted acid chlorides, is followed by ring contraction. The reaction leading to 2-cyclopentenones is applied to the synthesis of some spiro[4.4]nona- and spiro[4.5]deca-2,6-dienones.
    Additional Material: 1 Tab.
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  • 149
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    Helvetica Chimica Acta 67 (1984), S. 113-119 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Arylazonaphthalenes with all the potential cyclopalladation sites (one peri- and three ortho-positions) substituted by methyl or ethyl groups react with stoicheiometric or catalytic amounts of sodium tetrachloropalladate(II) to the corresponding 2-arylbenzo[g]indazoles. Possible mechanisms for the catalytic cyclization reaction are proposed.
    Additional Material: 1 Tab.
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  • 150
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1n, π*-Excitation of the γ,δ-epoxy-enone (E)-3 leads exclusively to the conformers (Z)-3A + B. On 1π, π*-excitation of (E)-3, in addition to (Z)-3A + B, products 6-9 arising from a carbene intermediate e are formed. However, products of an isomerization via C(γ), O-bond cleavage of the oxirane were not formed on either mode of excitation. On thermolysis, at 80° the conformer (Z)-3A is transformed into (Z)-3B, which on photolysis returns to (Z)-3A and (E)-3. At 160°, however, (Z)-3B rearranges to the isomers 6, 10 and 11.
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  • 151
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    Helvetica Chimica Acta 67 (1984), S. 866-869 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selective oxidation of benzylic methylene groups through UV irradiation in acetone/water/FeCl3 mixtures is reported. This method applied to a series of model compounds, provides an easy access to the corresponding 1-oxo derivative. Thus, tetralin gives a 100% yield of 1-tetralone, indane leads to 60% of 1-indanone, and diphenylmethane is oxidized to benzophenone with 80% yield. However, under the same conditions, alkyl-substituted aromatic hydrocarbons such as toluene, ethyl- and propylbenzene lead to low yields of aldehydes or ketones. Isochromane furnishes a mixture of two substances which can be interconverted, namely the expected l-isochromanone (9%) and the corresponding hydroxy acid (23%). We failed to apply the method to nitrogen heterocycles containing benzylic groups such as 1,2,3,4- and 5,6,7,8-tetrahydroquinoline as they do not react due to the formation of complexes which precipitate from the solutions.
    Additional Material: 1 Tab.
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  • 152
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pure pencillin N α-sulfoxide (1) and penicillin N β-sulfoxide (2) were obtained by HPLC and tested as substrates for deacetoxycephalosporin C synthetase (DXCS). Neither one of the sulfoxides was utilized under conditions of conversion of penicillin N (8) to deacetoxycephalosporin C (9). The cephalosporin C α and β-sulfoxides (3 and 4, resp.) were also prepared. Relative stabilities of the sulfoxides 3 and 4 are discussed by interpretation of the 13C-NMR spectra.
    Additional Material: 9 Ill.
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  • 153
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Business C,D,E,F,G,H,J,K,L und M, Ten New Tetranortriterpenes from Entandrophragma Bussei HarmsTen new tetranortriterpenes, busseins C, D, E, F, G., H, J, K, L and M have been isolated from the petroleum ether extract of the timber of Entandrophragma bussei Harms. utilizing separation by high-pressure liquid chromatography (HPLC). The structural assignments are based mainly on spectral evidence. For the 1H-NMR spectroscopy extensive use of nuclear Overhauser effects (NOE) was made.
    Additional Material: 2 Ill.
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  • 154
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    Helvetica Chimica Acta 67 (1984), S. 928-930 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 155
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alcohols and phenols are efficiently nitrated with thionyl chloride nitrate or thionyl nitrate, even in the presence of an aromatic moiety. While thionyl chloride nitrate is suitable for nitration of primary OH-groups in carbohydrates, thionyl nitrate is reactive enough to react with secondary OH-groups as well. These reagents permit the highly selective nitration of the 5′-,2′5′- and 3′, 5′-OH-groups of ribonucleosides to produce either mono-or diprotected nitro derivatives in high yields. Carbon acids and the enol form of some ketones are efficiently nitrated with trifluoromethanesulfonyl nitrate/potassium tert-butoxide. Lutidine N-oxide (2,6-(CH3)2C5H3N O) was found to have a marked effect on nitration reactions. Similarly, thionyl chloride nitrite and thionyl nitrite exhibit an excellent capacity for nitrosation of the aforementioned substrates.
    Additional Material: 5 Tab.
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  • 156
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    Helvetica Chimica Acta 67 (1984), S. 934-938 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical cations and the radical of 1,2-bis(phenalen-1-ylidene)ethane (1), 1,2-bis(phenalen-1-ylidene)ethene (2) and pentaleno[1,2,3-cd: 4,5,6-c′ d′]diphenalene (3) have been characterized by ESR and ENDOR spectroscopy. The ease of formation of these radical ions and their π-spin distributions are interpreted in terms of a simple model correlates the frontier orbitals of 1, 2 and 3 with the nonbonding MO's of two phenalenyl π-systems.
    Additional Material: 3 Ill.
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  • 157
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    Helvetica Chimica Acta 67 (1984), S. 939-946 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 1-(2-propynyl)pyridinium salts 3 described. Compounds 3 react with a second pyridine molecule, in the presence of the corresponding hydrochloride, to form products of type 4, Certain bases cause the 1-(2-propynyl)pyridinium salts 3 to rearrange into 1-propadienylpyridinium salts. 5. Diethylamine converts compounds 3 into 1-acetonylpyridinium salts 8. Moreover, treatment of 3 or 5 with sodium methoxide gives enol ether sof type 9, which can be hydrolyzed to teh ketones 8. Addition of bromine to some of teh unsaturated compounds is also reported.
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  • 158
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    Helvetica Chimica Acta 67 (1984), S. 953-958 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: IR-spectroscopic investigations of light-induced rearrangement reactions of nitrosooxymethane (CH3ONO3), nitrosooxyethane (CH3CH2ONO) and N,N-dimethylnitrosamine ((CH3)2NNO) in low-temperature rare-gas matrices have established that these molecules are transformed in two photolysis steps to the previously unknown C-nitroso compounds nitrosomethanol (CH2(OH)(NO)), 1-nitrosoethanol (CH3CH(OH)(NO)), and methyl(nitrosomethyl)amine CH2(NO)(NH)(CH3). Evidence for a similar rearrangement reaction has been advanced for N-Nitrosopyrrolidine which is converted to C-nitrosopyrrolidine . The matrix-isolation technique in combination with wavelength-selective irradiation allowed to trap and characterize an intermediate of rearrangement which revealed to be nitroxyl (HNO) complex (CH2…HNO, CH3CHO…HNO, CH3N = CH2…HNO, and ). Since these findings have a close resemblance with rearrangement reactions of more complex nitrosooxy compounds, nitrosamines, or nitrosohydrazines used in organic synthesis, it is suggested that also in these reactions nitroxyl is present as an intermediate species.
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  • 159
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    Helvetica Chimica Acta 67 (1984), S. 964-967 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Epoxycarotenoids: Isolation of 1,2-Epoxy-1,2-dihydrolycopene from TomatoesThe optically active, 1,2-epoxy-1,2-dihydrolycopene was isolated from tomatoes. Its constitution was established by comparison with the racemic synthetic compound.
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  • 160
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Epoxycarotenoids: Synthesis, 1H-NMR and CD Studies of (S)-1,2-Epoxy-1,2-dihydrolycopene and (S)-1′,2′-Epoxy-1′, 2′ -dihydro-γ-caroteneThe synthesis of (S)-1,2-epoxy-1,2-dihydrolycopene ((S)-1) and (S)-1′, 2′ -epoxy- 1′, 2′ -dihydro-γ-carotene ((S)-2) are described. The CD spectra of the (all-E)-isomers and of the isomers (7Z, S)-1 and (7′Z, S)-2 are discussed. The comparison of the CD spectra of the synthetic (S)-1 and the compound isolated from the tomatoes proves the (S)-configuration of the natural product.
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  • 161
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    Helvetica Chimica Acta 67 (1984), S. 1003-1011 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plectranthons A, B, C, and D. Diterpenoid Phenanthrene-1,4-diones from Leaf-glands a Plectranthus sp. (Labiatae)The following structures of four new 1,4-phenanthraquionones, isolated in minute amounts from the coloured leaf-glands of a Plectranthus sp. obtained from the borders of Lake Kiwu2, Rwanda, are proposed: plectranthon A (1; 3-hydroxy-5, 7,8-trimethyl-2-(2-propenyl)phenanthrene-1, 4-dione), plectranthon B (2; 2-(2ξ-acetoxypropyl)-3-hydroxy-5,7,8-trimethylphenanthrene-1,4-dione), plextranthon C (3; 3-hydroxy- 7,8-diemethyl-2-(2-propenyl)phenanthrene-1,4-dione), and plectranthon D (4; 3-hydroxy-7,8,10-trimethyl-2-(2-propenyl)phenanthrene-1,4-dione). 2-(2ξ-Hydroxypropyl)-3,6-dihydroxy-5,7,8-trimethylphenanthrene-1,4-dione (11), a compound very similar to 1-4, was prepared by a Wagner-Meerwein, rearrangement of coleon E (5). Biogenetically, the plectranthons are derived from abietanoic precursors. The compounds 1, 2 and 4 are the first natural C20-phenanthrenes of diterpenoid origin.
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  • 162
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative hydroboration of exo- (1) and end-Fe(CO)3 (2) complexes of 5,6-dimethylidenebicyclo[2.2.2]oct-2-ene are highly stereoselective and give endo -alcohol 3 and exo -alcohol 4 as major products, respectively, Collins oxidations of 3 and 4 furnish the corresponding exo -Fe(CO)3 -complexed 5,6-dimethylidene-2-bicyclo-[2.2.2]octanone 7 and 8. NaBH4 reduction of exo-complexes 7 gives a mixture of 3 and isomeric exo-alcohol 18, whereas reduction of endo-complexes 8 gives the endo-alcohol, endo-complexes 19, as the sole product. The base-catalyzed H/D exchange of 7 and 8 afford the dideuterated exo-complex 35 and the monodeuterated endo-complex 32, respectively. Oxidative hydroborations of the exo-(9) and endo-Fe(CO)3 (10) complexes of 5,6-dimethylidenebicyclo[2.2.1]hept-2-ene give the corresponding exo-alcohols 39 and 40. Oxidation of 39 and 40 gives the exo- and endo-complexes 41 and 42, respectively, of 5,6-dimethylidene-2-bicyclo[2.2.]heptanone. Only Hexo —C(3) can be exchanged in 42, wheres both H-atoms at C(3) in 41 are exchangeable. The endo-Fe(CO)3 group in 8 and 42 blocks the base-catalyzed H/D exchange of Hendo —C(3), thus providing a test for the configuration of Fe(CO)3 group in these systems. These studies have led to a revision of the iron configurations proposed by Hansen et al, [2] for 1, 2, 9 and 10.
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  • 163
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    Helvetica Chimica Acta 67 (1984), S. 361-364 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 164
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvolysis rate constants in MeOH and t-BuOh are compared for β-methyl and β-phenyl derivatives of two cycloakyl systems. It appears that the β-phenyl derivatives solvolyse at te same rate as the β-methyl ones. The lack of deceleration is attributed to phenyl assistance. It is established by configurational analysis of the reaction products, that those products which necessarily originate from a cationic species are the most abundant ones. It is suggested that these reactions could proceed through ion-pair intermediates, which are nucleophilically solvated by phelyl or by the solvent. A parallel between phenyl assistance and ‘SN2 (intermediate)’ mechanism, suggested by Bentely & Schleyer, is drawn.
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  • 165
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    Helvetica Chimica Acta 67 (1984), S. 361-372 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the water self-diffusion coefficients (D), as well as those of low- and high-field (stationary and time-dependent) specific conductivities (K), have been determined in the percolation regime of ternary mixtures of water, AOT, and oil. For the first time a pronounced similarity in the behavior of D and κ was detected giving instructive hints about the large variations in the specific conductivities of these systems. Results from kinetic and stationary experiments are consistent with a network-structure model of micro phases in the percolation regime in which the micro phases retain their discrete character.
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  • 166
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Facile synthesis of derivatives of 2,4-diphenyl-3-azabicyclo[3.3.1]nonane and 7,9-diphenyl-8-azabicyclo[4.3.1]decaneThe facile synthesis of hydantoins, cyanhydrins and aminonitriles derived from 2,4-diphenyl-3-azabicyclo[3.3.1]nonanone and 7,9-diphenyl-8-azabicyclo[4.3.1]decanone is described. Configurations at C(9) or C(10) of the new compounds wth pharmaceutical and synthetical utility is deduced from their spectral properties.
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  • 167
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    Helvetica Chimica Acta 67 (1984), S. 1328-1347 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the D-arabino- and D-ribo-ortholactones 13a-f and 15b-f and their treatment with Zn leading to the unsaturated esters 14a-d and 16a-d are described. Possible fragmentation mechanisms are discussed. The results were only compatible wit a concerted, nonsynchronous process, where both the axial lone pair of the ring oxygen atom and the lone pair formed during rupture of the C(5), O-bond participate in the elimination of the axial and of the equatorial C(1)-alkoxy groups, respectively.
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  • 168
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    Helvetica Chimica Acta 67 (1984), S. 1368-1373 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This communication reports ESR-spectroscopic investigations of the radical anion of 1,8-dimethyl[14]annulene (1) which possesses a flexible molecular framework allowing configurational and conformational mobility. The ESR and ENDOR spectra indicate that at higher temperatures (T 〉 160 K), \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{- \atop \dot{}} $\end{document} exists as a mixture of several distinct isomers. One of them, the sole product at T 〈 160 K, is found to be energetically preferred. The configuration and the conformation of this species can be determined by interpretation of the hyperfine data in terms of a singly occupied MO of the 14-membered π-perimeter.
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  • 169
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    Helvetica Chimica Acta 67 (1984), S. 1386-1396 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-(tert-Butyl)-3,7-dehydrotropone (7-(tert-butyl)bicyclo[3.2.0]hepta-1(7),2,4-trien-6-one; 1) was found to dimerize reversibly to 2A by [2 + 4]-cycloaddition/cycloreversion reaction. The equilibrium lies on the side of the highly strained dimer 2A in the solid state, and on the side of the monomer 1 in solution. The [2 + 4]-reaction is fully perisite-, regio- and stereoselective. Above room temperature, 1 irreversibly formed a decarbonylated dimer 6, probably via the intermediate 9A or 9B, which resulted either from a dimerisation of 1 by [4 + 6]-cycloaddition or from a sigmatropic rearrangement of the originally formed dimer 2A or 2B. Similary, the 6-bromo derivative 14 afforded the corresponding decarbonylated dimer 15. Should the formation of 6 and 15 be due to a primary cycloaddition then that reaction is fully peri-, site- and regioselective. Mild LiAlH4-reduction of 6 and subsequent acetylation yielded the acetate 11, the structure of which was established by an X-ray analysis. More vigorous LiAlH4-treatment also reduced the terminal fulvenoid double bond of 6 and acetylation of the crude product led to the acetated 12 and 13.
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  • 170
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    Helvetica Chimica Acta 67 (1984), S. 1427-1428 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 171
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    Helvetica Chimica Acta 67 (1984), S. 1427-1438 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electromotive Behaviour of Liquid-membrane Electrode Assemblies Based on Enantiomer-selective Chiral IonophoresA comprehensive theoretical treatment is given for the potentiometric behavior of enantiomer-selective membrane electrodes based on chiral ionophores and plasticizers. The membrane model allows for free and complexed enantiomeric or racemic ions (e.g. ephedronium and l-phenylethylammonium ions) as well as for achiral interfering ions. Experiments are derived for the determination of the stoichiometry and the relative stability of enantiomeric ion/enantiomeric ligand complexes, and for the analytical measurement of the enantiomeric excess of ions in solution.
    Additional Material: 5 Ill.
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  • 172
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water exchange of square-planar Pd(H2O)24+ has been studied as a function of temperature (240 to 345 K) and pressure (0.1 to 260 MPa, at 324 K) by measuring the 17/O-FT-NMR line-widths of the resonance from coordinated water at 27.11 and 48.78 MHz. The following exchange parameters were obtained: k298ex = (560 ± 40) s-1, ΔH* = (49.5 ± 1.9) kJ mol-1, ΔS* = - (26 ± 6) J K-1 mol-1 and ΔV* = - (2.2 ± 0.2) cm3 mol-1. The values refere to an aqueous perchlorate medium with an ionic strength between 2.0 and 2.6 m and a perchloric-acid concentration between 0.8 and 1.7 m, and are interpreted in terms of an associative (a) activation for the exchange. The exchange rate for Pd(H2O)24+ is 1.4 × 106 times faster than for Pt(H2O)24+ at 298 K. A comparison with reactions between other nucleophiles and Pd(H2O)24+ is also made.
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  • 173
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of Organometallic Compounds, XX. Selectivity of 1,4-Addition of Benzyltitanium Compounds with BenzylildenacetoneTetrabenzyltitanium and dialkoxydibenzyltitanium compounds give essentially 1,4- addition with trans-4-phenyl-3-buten-2-one.
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  • 174
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aminative Reductive Coupling of Aromatic Aldehydes to N,N,N′,N′-Tetraalkyl-1,2-diarylethylenediamines, Induced by Tris(dialkylamino)methylvanadium (IV)In a novel type of reaction, certain aromatic aldehydes (benzaldehyde, p-methoxybenzaldehyde, 1-naphthaldehyde, furan-2-carbaldehyde) and secondary amines are coupled to give N,N,N′,N′-tetraalkyl-1,2-diarylethylenediamines 1-6. The reagents are tris(dialkylamino)methylvanadium(IV) compounds (cf. Eqn. 2). These are generated in situ either from isolable chlorotris(dialkylamino) vanadium(IV) (Eqn. 3), or preferably, from an Et2O/pentane solution of VCl4 which is treated sequentially with 3 equiv. of lithium dialkylamide, 1 equiv. of MeLi, and 0.8 equiv. of an aromatic aldehyde, to give the products 1-6 in a one-pot preparation (Scheme 2). The yields range from 14 to 54%. The diastereoisomeric mixtures (meso- and (±)-forms) obtained are separated by chromatography (Al2O3, petroleum ether/Et2O/Et3N), and the pure stereoisomers fully characterized. A mechanism of the reductive coupling induced by CH3V (NR2)3 is proposed (Scheme 1).
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  • 175
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    Helvetica Chimica Acta 67 (1984), S. 1506-1514 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several oxidative, reductive and C,C-cleavage reactions were performed starting from the three bicyclo[4.2.1]nona-3,7-diene-2-one derivatives 1, 5 and 18. The oxidations were selective and led to the diols 2,8 and 9, and the epoxides 6,9, and 20. The reductions were selective only in the case of 20 21; otherwise they led to mixtures of the alcohols 10 and 11, and of the dienes 14 and 15. The periodate ring cleavages afforded the functionalized cycloheptane derivatives 3, 12, 13 and 16. Configurational assignments were made on the basis of detailed 1H-NMR and X-ray analysis of 20.
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  • 176
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    Helvetica Chimica Acta 67 (1984), S. 1531-1534 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Red-Coloured Abietanoids from Leaf-Glands of Plectranthus strigosus BENTH.Chromatographic examination of the red-coloured diterpenoids from the South-African title plant yielded the following compounds: parviflorone A(1), parviflorone B (2), parviflorone C(3), parviflorone E (4) parviflorone D (5), parviflorone F (6), parviflorone G (7), and parviflorone H (8). Compounds 7 and 8 represent new variants of these quinone methides.
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  • 177
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polar Diterpenoids from Leaf-Glands of Plectranthus argentatus S. T. BLAKEFrom the red leaf-glands of the Australian Plectranthus argentatus the following novel diterpenoids were isolated: coleon-U-quinone (1), 8α,9α-epoxycoleon-U-quinone (3), 6β-formyloxy-7α-hydroxyroyleanone (7), and 5,6-dihydrocoleon U (10), besides the already known compounds 6β, 7α-dihydroxyroyleanone (4), 7α-acetoxy-6β-hydroxyroyleanone (5), and 7α-formyloxy-6β-hydroxyroyleanone (6). Epoxydation of 1 by perborate led in 32% yield to the epoxyquinone 3.
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  • 178
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    Helvetica Chimica Acta 67 (1984), S. 1568-1571 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Partially protected 4- or 5-hydroxy-sugar oximes were transformed into 5- or 6-membered 1-C-nitroglycosyl chlorides, respectively, by reaction with NaOCl under phase-transfer conditions. With the exception of the oxidation of the gluco-derivative 1 giving the anomers 6 and 7, the reactions were completely diastereoselective.
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  • 179
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    Helvetica Chimica Acta 67 (1984), S. 1572-1579 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and the liquid-crystal temperatures of sixty 4-cyano-2-fluorophenyl and 4-cyano-3-fluorophylen 4-substituted benzoates are described. The nematic-isotropic liquid transition temperatures of the most of these novel esters are only marginally lower than those of the corresponding esters containing an H-atom in place of the F-substituent. In several instances, the clearing points of the F-substiuted-phenyl esters are higher than those of the non-substituted-phenyl esters. The nematic ranges of several of the new esters are markedly broader than those of the analogous non-F-substituted-phenyl esters.
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  • 180
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    Helvetica Chimica Acta 67 (1984), S. 1588-1592 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-NMR and vapor-pressure osmometry results are presented, which indicate the occurrence of a rapid equilibrium involving the head-to-head dimerization of β44-helices in chloroform solutions of HCO-L-Ile-(D-AIle-L-Ile)4-OMe. This equilibrium typifies the one that, in Urry's view, would be responsible for the formation and breaking down of the ion-conducting channels formed by gramicidin A in lipid bilayers.
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  • 181
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and liquid-crystal transition temperatures of forty ester derivatives of 2-fluoro-4-hydroxybenzonitrile and 3-fluoro-4-hydroxybenzonitrile are reported. The esters contain the trans-1,4-disubstituted cyclohexane or the 1,4-disubstituted bicyclo[2.2.2]octane rings (some contain an additional phenyl ring). Many of the novel F-substituted esters exhibit substantially higher nematic-isotropic transition temperatures than the corresponding unsubstituted esters. The order of clearing points of these laterally substiuted esters differing only in the presence of a benzene ring and the above-mentioned rings id established.
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  • 182
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    Helvetica Chimica Acta 67 (1984), S. 1598-1602 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of New Morphine Partial Structure 15,16-SecomorphinanThe synthesis of a new morphine partial structure, 15,16-secomorphinan, is described. One of the series, (±)-15, 16-secocyclorphan (5), has the analgesic potency of morphine and exhibits good binding to the opiate receptor.
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  • 183
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diastereoselective Synthesis of Novel Mannich (Bases1) through Titanium ReagentsTrichlorotitanium dialkylamino-alkoxides (2; titanates of N, O-hemiacetals) are generated either from the corresponding lithium alkoxides and titanium tetrachloride (Scheme 1) or by addition of trichloro-dialkuylamino-titanium to aldehydes. The electrophilic (dialkylamino) alkylating reagents 2 are used to convert lithium enolates to β-dialkylamino-ketones and -esters 5 (Mannich bases), see Scheme 2 and Table. One diastereoisomer of the products 5g-5p thus obtained with cyclohexenolate is formed preferentially (66-84%). The configuration of the products of this first diastereoselective version of the Mannich reaction could not yet be determined. A typical procedure for carrying out the reaction is given.
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  • 184
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    Helvetica Chimica Acta 67 (1984), S. 1612-1615 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new, practical method for the optical resolution of bicyclic ketones if illusttrated by the preparation of (+)-(1R,4R)-7-oxabicyclo[2.2.1]bept-5-en-2-one ((+)-1) and (+)-(1R, 2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yul acetate ((+)-4). It involves the diastereoselective formation of a brucine complex with the corresponding cyanhydrine mixture.
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  • 185
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of three-coordinate bis(dialkylphosphinomethyl)benzo[c]phenanthrene Ag(I) complexes, alkyl= t-Bu, (1b), and cyclohexyl, (1c), anion = BF4, CIO4, CIO4, NO3, Cl, Br, I, have been prepared and thier 31P-NMR characteristics recorded. The solid state structures of [Ag(1b)Br], [Ag(1b)Cl] and [Ag(1b)CIO4] have been determined by X-ray diffraction. The Ag atom in these complexes shows distorted trigonal geometry. Selected bond lengths and angles are as follows: Ag-P = 2.463(4) Å and 2.433(5) Å, P-Ag-P=141.6(2)° in the bromo complex, Ag-P = 2.457(2) Å and 2.427(2) Å, P-Ag-P = 142.6(1)° ion the chloro complex, and Ag-P = 2.394(2) and 2.393 (2) Å, P-AG-P = 161.5(1)° in the perchlorato complex.
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  • 186
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    Helvetica Chimica Acta 67 (1984), S. 1625-1629 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new syntheses of verrucarinic acid (2S, 3R-dihydroxy-3-methylpentanoic acid) and its derivatives, suitably protected for the further conversion to macrocyclic trichothecenes, are described. The first one makes use of a diastereoselective alkylation of a (-)-(S)-malic acid ester and the regioselective reductin of one carboxyl function toa methyl group. The second approach involves a stereoselective addition of an allylsilane to a chiral glyoxylate.
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  • 187
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Control of the Catalytic Synthesis of Pyridine from Alkynes and Nitriles by the (η6-Borinato)-Nigands at Cobaltη6-Borinato groups as ligands at cobalt have unique effects on the chemo- and negioselectivity of the catalytic co-cyclization of alkynes and nitriles. The turnover number of the conversion of acrylonitrile and acetylene to give 2-vinylpyridine is considerably enhanced. Cyano compounds wih polar substitutents such as amino or thio groups can also be reacted. The homogeneous reaction of HCN with acetylene giving pyridine has been achieved for the first time.
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  • 188
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The endocyclic double bond C(2), C(3) in 5,6-dimethylidene-7-oxabicyclo[2.2.1]-hept-2-ene (1) can he coordinated selectively on its exo-face before complexation of the exocyclic s-cis-butadiene moiety. Irradiation of Ru3(CO)12 or Os3(CO)12 in the presence of 1 gave tetracarbonyl [(1R,2R, 3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo[2.2.1]-hept-2-ene)]ruthenium (6) or -osmium (8). Similarly, irradiation of Cr(CO)6 or W(CO)6 in the presence of 1 gave pentacarbonyl[(1R, 2R, 3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene)]chromium (10) or -tungsten (11). Irradiation of complexes 6 and 11 in the presence of 1 led to further CO substitution giving bed-tricarbonyl-ae-bis[(1R,2R,3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene)]ruthenium (7) and trans-tetracarbonyl[(1R,2R,3S,4S)-2,3-η-(5,6-dimethylidene-7-oxabicyclo-[2.2.1]hept-2-ene)]tungsten (12), respectively. The diosmacyclobutane derivative cis-m̈-[(1R,3R,3S,4S)-(5,6-dimethylidene-7-oxabicyclo[2.2.1]hepta-2,3-diyl)]bis(tetracarbonyl-osmium) (Os-Os) (9) wa also obtained. The Diels-Alder reactivity of the exocyclic s-cis-butadiene moiety in complexs 7 and 8 was found to be significantly higher than that of the free triene 1.
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  • 189
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products generated by heating 5,6-dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene (1) with Fe2(CO)9, Ru3(CO)12, Os3(CO)12, Cr(CO)3(MeCN)3, (or W(CO)5(MeCN) or by treatment with Fe-atoms have been characterized by spectroscopic methods. Apart from the expected η2- and η4-complexes of the triene 1, condensation products are formed which arise from the formal [4 + 2]-cyclodimerization of 1 involving the endocyclic double bond of one molecule and the diene moiety of a second. The [4 + 2]-cyclodimerization is catalyzed by Os3(CO)12 in MeOH and gives 1,4-epoxy-7-methoxy-2,3-dimethylidene-1,2,3,4,4a,9,9a,10-octahydroanthracene (15)). Fe-Atoms induce a stereoselective [2 + 2]-cyclodimerization pf 1 which involves its endocyclic double bond and produces the dimer 8.
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  • 190
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    Helvetica Chimica Acta 67 (1984), S. 1647-1649 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of 2,3-Unsubstituted N-Acylindoles by [3,3]-Rearrangement of the N-Phenyl-O-vinylhydroxylamine DerivativesSummary, Treatment of N-phenylhydroxamic acids with vinylacetate in the presence of Li2PdCl4 affords 2,3-unsubstituted N-acylindoles via hetero-Cope-rearrangement of the intermediate N-O-vinylhydroxylamine derivatives.
    Additional Material: 1 Tab.
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  • 191
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    Helvetica Chimica Acta 67 (1984), S. 1669-1669 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 192
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 193
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation of (RS,SR)-3-Phenyl-6-hepten-2-ol (3n) gave the photoproducts 6n-10n. Some reactions of 6n and 8n are reported. The regio- and diastereoselectivity observed in the photoreaction of substituted 5-phenylpentenes is discussed with respect to conformational preferences of the compounds to be irradiated.
    Additional Material: 1 Tab.
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  • 194
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new convenient synthesis of dihydrolysergic acid is described, which allows the preparation of substituted derivatives, especially those with different substitutents in the aromatic ring. Starting from appropriately substituted 5-nitro-2-tetralones, the synthesis leads via a tricyclic isonitrile to the indole-ring closure as the last step, thus circumventing the troublesome protection/deprotection of the latter.
    Additional Material: 1 Tab.
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  • 195
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The portions of the N3H3 singlet potential energy surface corresponding to triaziridines (1), azimines (2) and triazenes (3) have been calculated by ab initio SCF using 3-21G, 6-31G, and 6-31G** basis sets. Minima and transition states were located by force gradient geometry optimization. The most important computation results are: (1) Triaziridines (1): The configuration at the 3 N-atoms is pyramidal. There are 2 stereoisomers, 1a and 1b. The c,t-isomer 1a has less energy than the c,c-isomer 1b. The 2 stereoisomerizations by N-inversion hve rather high activation energies. The N,N bonds in 1 are longer and weaker (STO-3G estimation) than in hydrazine. The N-homocycle 1 exhibits less ring strain than the C-homocycle cyclopropane or three-membered heterocycles. (2) Azimine (2): All 6 Atoms are in the same plane. There are 3 stereoisomers, 2a, 2b, and 2c. The order of ground state energies is (Z,Z) 〈 (E,Z) ≫ (E,E). The 2 N,N bond lengths correspond to multiplicity 1½. The electronic structure of 2 corresponds to a 1,3-dipole with almost equal delocalization of the 4 π-electrons over all 3 N-atoms. The negative net charge at the central N-atom is much less than that at the terminal N-atoms. Azimines should behave as π-donors in complexation with transition metals (3) Triazene (3): All 6 atoms are in the same plane. There are 2 stereoisomers, 3a and 3b. The order of ground-state energies is (E) 〈 (Z). The stereoisomerization proceeds as pure N-inversion. N-Inversion has a high energy barrier inversion at N(1) is faster than at N(2). One of the N,N bond lengths is typical for a double, the other for a single bond. The electronic structure of triazene 3 entails rather localized π- and p-electron pairs at N(1),N(2) and at N(3). Triazenes should behave as p-donors in complexation with transition metals. (4) -N3H3-Isomers: The order of ground-state energies is 3 〈 2 〈 1. The energy differences between these constitutional isomers are much larger than between the stereoisomers of each. The [1,2]-H shifts for conversions of 2 to 3 and the [1,3]-H shift for tautomerization of 3 have relatively high activation energies; both shifts can be excluded as modes of thermal, unimolecular transformations.
    Additional Material: 2 Ill.
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  • 196
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    Helvetica Chimica Acta 67 (1984), S. 1952-1956 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 4-hydroperoxy-2,4,6-trimethylcyclohexa-2,5-dienone with acetaldehyde using trimethylsilyl trifluoromethanesulfonate as catalyst gives 1,1′-bis[(1,3,5-trimethyl-4-oxo-2,5-cyclohexadienyl) peroxy]diethyl ether (7) in 70% yield. The structure of this unusual acetal was determined by X-ray analysis.
    Additional Material: 1 Ill.
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  • 197
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structures of the antimalarials dihydroqinghaosu (2), artemether (3), and artesunic acid (7a) derived from qinghaosu were elaborated by 1H-NMR spectroscopy, and supported with X-ray data obtained for 2 and 3. Several new derivatives, useful for the chemical characterization of dihydroqinghaosu (2) and artesunic acid (7a), were prepared.
    Additional Material: 2 Ill.
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  • 198
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    Helvetica Chimica Acta 67 (1984), S. 1562-1567 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chain elongation of the deoxy-nitroribose 6 by a Michael addition to the vinyl-phosphonate 7 followed by a solvolysis gave the heptulosephosphonate 11 (87%). From 11, the key intermediates 15 and 16 (77%) were obtained by a highly diastereoselective reduction, followed by detritylation, periodate cleavage, and silylation. Methoxycarbonylation of 15 and 16 gave 17 and 18 which were converted into methyl shikimate (21; 79%) by intramolecular olefination and partial deprotection. Similarly, phosphonoylation of 16 gave 22 (99%) which was transformed into the diethyl phosphashikimate 2 (53% from 6).
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  • 199
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    Helvetica Chimica Acta 67 (1984), S. 2029-2030 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 200
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    Helvetica Chimica Acta 67 (1984), S. 2028-2028 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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