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  • 2000-2004
  • 1990-1994  (853)
  • 1920-1924
  • 1991  (853)
  • Organic Chemistry  (822)
  • MRI
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Rheumatology international 11 (1991), S. 183-186 
    ISSN: 1437-160X
    Keywords: MRI ; Rheumatoid arthritis ; Spondyl-arthropathy ; Gonarthritis ; Arthritis ; Radiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The knees of fifty-two patients suffering from rheumatoid arthritis (RA), 22 patients with seronegative spondylarthopathies (SA) as well as of 20 healthy volunteers were examined by magnetic resonance imaging (MRI). Osseous erosions (RA 52%-SA 18%; P〈0.005), Baker cysts (RA 56%-SA 12%; P〈0.005), pannus formation (RA 67%-SA 36%; P〈0.05), and cartilage thinning with narrowing of the joint space (RA 46%-SA 18%; P〈0.05) proved to be more frequent MRI findings in patients with RA. Additionally, in patients with RA erosions were more extensive. Follow-up MRI examinations of 19 patients revealed an improvment in MRI changes in SA within an average interval of 6 months. No substantial changes were noted in 7 of 13 RA patients. Quantitative and qualitative MRI findings of knee arthritis differ in patients with RA and SA and this was statistically significant. However, as there is considerable overlap of the MRI and radiographic changes in both groups the discriminating diagnostic value in the individual case was limited.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1437-2320
    Keywords: Basilar arteries ; cerebellar arteries ; MRI ; trigeminal nerves ; trigeminal neuralgia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The most common cause of the idiopathic trigeminal neuralgia are tortuous arteries in the prepontine space. The trigeminal nerve can be compressed by the superior cerebellar artery, the inferior cerebellar artery, or the basilar artery. Seldom the nerve is traumatised by an enlarged vein. Because an operative decompression of the nerve can relieve pain, a preoperative evaluation is needed. Angiography of the vertebral arteries is able to predict a tortuous artery close to the trigeminal nerve but cannot show the nerve itself. MRI can show tortuous vessels and the trigeminal nerve together on one single image by means of a 3D gradient-echo FLASH sequence with an effective slice thickness of approximately 1 mm and secondary reconstructions in every desired plane. MRI thus provides an efficient tool for the evaluation of patients with trigeminal neuralgia.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-2161
    Keywords: High-resolution magnetic resonance imaging (MRI) of finger joints ; MRI ; Arthritis ; Osteoarthritis ; Hand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract High-resolution magnetic resonance imaging (MRI) of the interphalangeal joints of the fingers is being employed to study arthritis. To facilitate this research, a clear understanding of the structures visualisable by MRI is necessary. A gradient echo (GE) sequence was developed that produced good contrast between cartilage and other joint structures. These detailed images, with an in-plane resolution of 200 × 100 μm, enable resolution of three cartilage zones which can be interpreted as a superficial layer at the cartilage/cartilage interface, an intermediate layer and calcified cartilage in contact with bone; these correlate well with known anatomy. Further analysis of the images indicates that although a chemical shift artifact causes changes in the images at the field strength used (0.5 T), it does not cause enough distortion to necessitate suppression of the effect. Furthermore, the only detectable susceptibility artifact at these low field strengths was a loss of signal in bone trabeculae at the bone/cartilage interface. There is clearly potential in the study of the articular structures, in particular cartilage, in detail, using high-resolution MRI.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    The international journal of cardiovascular imaging 7 (1991), S. 1-5 
    ISSN: 1573-0743
    Keywords: newborns ; MRI ; congenital heart disease ; systemic shunts ; oblique views
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Eight infants with systemic-pulmonary Blalock-Taussig shunts were evaluated by spin-echo ECG-gated MRI. Contrary to Echocardiography, MRI using coronal oblique projections successfully visualized all palliative shunts entirely in one single plane (including one carried out on a right aberrant subclavian artery). MRI allowed assessment of size, course and patency of the shunt, including pulmonary and subclavian insertion. The proximal portion of the pulmonary and subclavian arteries were also visualized. We conclude that MRI with axial scans completed by coronal oblique planes is a promising, non invasive method for imaging the anatomical features of Blalock-Taussig shunts.
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  • 5
    ISSN: 1573-0905
    Keywords: developmental dysphasia ; dyslexia ; temporal processing ; MRI ; thalamic nuclei ; caudate nuclei
    Source: Springer Online Journal Archives 1860-2000
    Topics: Education
    Notes: Abstract Over the past twenty years, Tallal and colleagues have directed their research toward defining the neuropathological mechanisms responsible for developmental dysphasia. We have hypothesized that higher level auditory processing dysfunction, which has previously been associated with developmental dysphasia, may result from more basic temporal processing deficits which interfere with the resolution of rapidly presented, brief duration stimuli. This temporal processing deficit interferes with adequate perception of specific verbal stimuli which require resolution of brief duration formant transitions, resulting in disordered language development. The temporal processing deficit occurs across multiple sensory modalities, and also affects rapid and sequential motor production skills. Despite relatively normal clinical neuroradiological examinations, in vivo morphological analysis, utilizing magnetic resonance imaging techniques for quantitative volumetric measurements of specific brain structures, has identified abnormalities in superior parietal, prefrontal, and temporal cortices, as well as diencephalic and caudate nuclei. Abnormalities in structures which are involved in multimodal processing and sensory motor integration is consistent with the behavioral profile of developmental dysphasia. Two alternative hypotheses regarding the neurophysiological basis of the multimodal temporal processing disorder include: dysfunction in specific cellular systems which subserve rapid, transient processing; and abnormal gating of sensory relay by intralaminar and reticular thalamic nuclei.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Acta neurochirurgica 110 (1991), S. 140-145 
    ISSN: 0942-0940
    Keywords: Cavernous haemangioma ; intraventricular tumour ; CT ; MRI ; management ; results
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Since the availability of CT diagnostis 23 cases of intraventricular cavernous angioma (IVCA) have been published in the literature. Three additional cases have been operated upon in our Department. Based on these 26 cases the clinical data, radiological findings, treatment and outcome of IVCAs are reviewed.
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  • 7
    ISSN: 1279-8517
    Keywords: Levator ani muscle ; MRI ; Anorectal anomalies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé A partir de l'étude comparative de coupes anatomiques dans les plans transversal, frontal, sagittal et des coupes IRM correspondantes du petit bassin, les auteurs déterminent quels sont les plans de coupe et les modes IRM les plus performants pour l'étude morphologique des muscles élévateurs de l'anus. Cette étude montre l'intérêt de l'examen IRM dans le bilan des malformations ano-rectales opérées.
    Notes: Summary A comparative study of serial anatomic sections in the transverse, frontal and sagittal planes with corresponding MRI sections of the pelvis allowed the authors to define the most suitable sectional planes and MRI modes for a morphologic study of the levator ani muscle. This study shows the value of MRI examination in the assessment of anorectal malformations.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Surgical and radiologic anatomy 13 (1991), S. 197-201 
    ISSN: 1279-8517
    Keywords: MRI ; Brain ; Reference plane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Définition en résonance magnétique d'un plan de référence céphalique alignant le point chiasmatique et la commissure postérieure, facilement déterminé sur une coupe sagittale médiane et permettant d'orienter les coupes horizontales selon une direction proche du sillon latéral, et de façon quasiment orthogonale à l'axe du tronc cérébral.
    Notes: Summary A cephalic reference plane is described through the chiasmatic notch and the posterior commissure, which is easily identified on mid-sagittal cuts using magnetic resonance imaging. The horizontal cuts so obtained are almost parallel to the lateral fissure and are perpendicular to the axis of the brain stem.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Acta neurochirurgica 110 (1991), S. 120-123 
    ISSN: 0942-0940
    Keywords: Cerebello-pontine angle lesions ; acoustic schwannoma ; cyst ; CT ; MRI ; differential diagnosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Three cases with large space-occupying cysts in the cerebellopontine angle are reported. CT and MRI findings were not typical for acoustic schwannomas but at operation, besides the large cysts, small acoustic schwannomas could be detected and removed. The clinical and neuroradiological features of this unusual varietyand the CT and MRI differential diagnosis of cerebellopontine angle lesions are discussed.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Acta neurochirurgica 108 (1991), S. 40-44 
    ISSN: 0942-0940
    Keywords: Pineal cyst ; enlarged pineal gland ; infratentorial supracerebellar approach ; MRI ; occlusive hydrocephalus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Seven patients with non-neoplastic symptomatic lesions of the pineal gland have been operated on in our department since 1988. Clinical symptoms were slight and there were intermittent signs of a space occupying lesion in the quadrigeminal area, i.e. visual and gait disturbances. In three patients, obstructive hydrocephalus with related symptoms was found. Diagnosis was confirmed by use of MRI in sagittal planes, revealing a cystic lesion in five and a solid tumour in two patients. All patients were operated on without complications using an infratentorial supracerebellar approach. Histological examination showed glial cysts of the pineal gland in five patients. In the two solid specimens, normal pineal tissue was found. These lesions seem to be of special interest, as the only pathological property are their size: Both lesions — “too large pineal glands” — caused obstruction of the outlet of the third ventricle with subsequent hydrocephalus. Surgical treatment was curative in all cases with prompt relief of the symptoms. Clinical symptoms and signs, diagnostic and pathological findings, as well as the surgical results of these cases will be reported.
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  • 11
    ISSN: 0942-0940
    Keywords: MRI ; spinal subdural haematoma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Spinal subdural haematoma (SSH) is a rare cause of spinal cord or cauda equina compression which occurs mainly in patients with a bleeding diathesis. This report presents a case of subacute lumbar subdural haematoma demonstrated by magnetic resonance imaging. MRI appears to be more sensitive than myelography and CT.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Acta neurochirurgica 109 (1991), S. 154-157 
    ISSN: 0942-0940
    Keywords: Sacral meningocele ; MRI ; ultrasound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary With the presentation of a case of giant anterior sacral meningocele, the evident superiority of magnetic resonance imaging over any other methods for the diagnosis of this rare condition is demonstrated. Ultrasound as a screening tool is often the first to reveal the presence of the intrabdominal cystic abnormality and furthermore is an excellent means for checking the post-operative course. In addition this particular case is interesting because the dural stalk linking the meningocele to the dural abdominal sac was not entirely free from nervous structures inspite of macroscopic appearances to the contrary.
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  • 13
    ISSN: 1432-1084
    Keywords: Arteriovenous Malformations ; Celebral ; Endovascular Therapy ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Of 86 patients with whose cerebral arteriovenous malformations (AVMs) were embolised in the period 1985–1990 29 were examined by high-field spin-echo (SE) magnetic resonance imaging (MRI) after endovascular therapy with gistoacryl-lipiodol. Embolisation-related changes in the nidus of the AVM and in the surrounding brain parenchyma were assessed. Results were compared with pretreatment MR and CT, and with follow-up angiograms in all patients. In accordance with angiographic findings, complete obliteration of pathological vessels was noted in 7 patients (24.1%) and partial occlusion in 22 (75.9%); small ischaemic infarcts were observed in 8 patients (27.6%) and extravascular deposits of blood breakdown products were seen in 3 (10.3%). MRI is a valuable noninvasive technique for assessing morphology and haemodynamics of cerebral AVMs before and after treatment. However, following embolotherapy, variable effects on signal intensity in vascular lumina caused by flowing blood, thrombosis and the embolisation agent have to be carefully analysed. To assess the exact site of histoacryl-lipiodol in embolised nidus territories or small areas of possible intracerebral hemorrhage, the time interval between endovascular therapy and MR examinations may have to be modified.
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  • 14
    ISSN: 1432-1920
    Keywords: Carotid artery ; Vertebral artery ; Dissection ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Fifteen patients were observed between 1987 and 1990: there were six with angiographically confirmed vertebral artery dissection, and 9 with carotid artery dissection. Results showed concordance of MRI and angiographic findings, in all cases but one. The dissected portion consistently showed a semilunar hyperintensity narrowing the residual eccentric signal void of the lumen when the artery was not completely occluded. In one angiographically occluded vessel, MR detected a small signal void within the hyperintensity, indicating that the artery was not completely occluded. The length of the dissected portion was clearly demonstrated by MR. Follow up MR and angiographic studies confirmed the regression of the dissection, and also allowed examination of the cerebral parenchyma.
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  • 15
    ISSN: 1432-1920
    Keywords: Subacute sclerosing panencephalitis ; MRI ; Relapsing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Serial MRI was performed on a 15 year old girl with Subacute Sclerosing Pan-encephalitis (SSPE). After a period of remission she entered a phase of progressive deterioration. A repeat MRI showed significant resolution of the previous abnormalities. Her pathology and MRI scans are discussed.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Neuroradiology 33 (1991), S. 260-263 
    ISSN: 1432-1920
    Keywords: Primitive neuroectodermal tumor ; Leptomeninx ; CT ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Primitive neuroectodermal tumor (PNET) without an obvious intraparenchymal mass lesion and with diffuse spread in the subarachnoid space is rare. We report such a rare case and discuss the computed tomography (CT) and magnetic resonance (MR) features.
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  • 17
    ISSN: 1432-1920
    Keywords: MRI ; Gadolinium-DTPA ; Medulloblastoma ; Subarachnoid dissemination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We report two cases with subarachnoid dissemination of medulloblastoma depicted clearly by Gadolinium-DTPA enhanced MRI. We also demonstrate the superiority of Gadolinium-DTPA enhanced MRI over nonenhanced MRI, CT, myelography and postmyelographic CT for diagnosing subarachnoid dissemination and for monitoring the response to therapy.
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  • 18
    ISSN: 1432-1920
    Keywords: Radiation myelopathy ; MRI ; Gadolinium ; DTPA enhancement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We described two cases of chronic progressive radiation myelopathy (CPRM), in which magnetic resonance imaging (MRI) was of great value for the diagnosis. Gadolinium-DTPA (Gd-DTPA) enhancement delineated precise lesions responsible for Brown-Séquard syndrome caused by CPRM in both cases. This safe, sensitive procedure will be a requisite study in patients who are suspected of CPRM.
    Type of Medium: Electronic Resource
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  • 19
    ISSN: 1432-1920
    Keywords: MRI ; Uncal herniation ; Arachnoid cyst ; CT
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary We report a case of arachnoid cyst in the Sylvian fissure which progressed to uncal herniation. MRI was shown to be superior in visualizing uncal herniation.
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  • 20
    ISSN: 1432-1920
    Keywords: MRI ; Myelopathy ; Posterior longitudinal ligament
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Ossification of the posterior longitudinal ligament is a potentially curable cause of thoracic myelopathy. As this case illustrates, MRI can confirm the diagnosis, demonstrate other concomitant pathology such as disc herniation, and help assess the clinical significance of OPLL by showing spinal word compression.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    European radiology 1 (1991), S. 58-64 
    ISSN: 1432-1084
    Keywords: MRI ; Larynx ; Hypopharyngeal tumours ; Contrast media
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Twenty-eight patients with tumours of the larynx, divided into supraglottic, glottic, and subglottic lesions, and of the hypopharynx were examined by different MRI techniques using the paramagnetic contrast medium Gd-DTPA. The results of preoperative MRI were compared with clinical laryngoscopy and the pathological tumour classification. The examinations were carried out using plain T1-wand T2-weighted and Gd-DTPA enhanced T1-weighted sequences. Most studies included three slice orientations for optimal assessment of different tumour locations. The most accurate diagnostic information was given by Gd-DTPA-enhanced sequences. The combination of plain images, contrast-enhanced images and subtraction enabled precise assessment of deep infiltration. T2-weighted and proton density sequences conveyed more information about cartilage invasion and liquid-filled structures, but gave more artefacts than T1-weighted images. Laryngoscopy had advantages in T1-classified tumors, as the extent of the tumor could be seen, and offered histological information via biopsy. Diagnostic findings of MRI correlated in 85.7% with the pathologist's report, and laryngoscopy provided exact classification in only 64.3% of patients. Gd-DTPA-enhanced MRI is an important adjunct to non-contrast MR studies, and forms an ideal diagnostic supplement to laryngoscopy.
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neurology 238 (1991), S. 49-50 
    ISSN: 1432-1459
    Keywords: Basilar artery ; Aneurysm ; MRI ; Brainstem
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The use of MRI in the diagnosis of vascular anomalies of the basilar artery is demonstrated in two cases. The first patient had a partially thrombosed giant aneurysm of the basilar artery; the second had an atypical course of the basilar artery. MRI is indicated whenever other imaging procedures do not provide a definite diagnosis or the use of contrast medium for conventional X-ray examination or computed tomography is contraindicated.
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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    Child's nervous system 7 (1991), S. 139-146 
    ISSN: 1433-0350
    Keywords: Vascular cerebral malformations ; Cavernous angiomas ; Epilepsy ; Childhood ; CT ; MRI ; Cavernoma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cavernomas are vascular malformations composed of a compact mass of sinusoidal-type vessels that are immediately contiguous with one another and have no intervening parenchyma. Cavernous malformations were previously held to be a rare pathology occurring predominantly in adults. New neuroradiological techniques such as computed tomography (CT) and magnetic resonance imaging (MRI) demonstrate, on the contrary, that these lesions are also more frequent during childhood than was previously thought. In our institution we observed 17 cases of cavernous malformations in patients aged between 18 months and 16 years, 16 of whom were diagnosed after 1982. In 4 of these cases there was a documented familial history; in 2 multiple malformations were present. The most common site was the subcortical frontal region, but in 1 case the malformation was located in the pineal region. The most frequent (in 12 cases) initial symptom was hemorrhage, with the characteristics of an intracerebral hematoma. In 4 cases the initial symptom consisted of epileptic fits and 2 of these patients subsequently suffered hemorrhage. In one case the symptoms observed were those of an expansile process. All our patients underwent cerebral angiography and only in 1 case did this show a vascular abnormality. CT, performed in 16 patients, gave positive results in all cases. MRI, performed in 12 patients, gave highly significant images in all cases. Radical surgical removal of the malformation was performed in 15 of the 17 patients, and the results can be considered excellent in the majority of cases. Cavernous malformations are, therefore, more frequent lesions than had previously been thought, especially in pediatric patients. MRI offers the most conclusive means of diagnosis and, considering the possibility of family predispositions, this is also the method to be used in screening a patient's family members. The operation is easy, at least for the most frequent location, and is justified in view of the risk of hemorrhage and relapses.
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  • 24
    Electronic Resource
    Electronic Resource
    Springer
    Langenbeck's archives of surgery 376 (1991), S. 346-350 
    ISSN: 1435-2451
    Keywords: Spine fracture ; MRI ; Validity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Validität der Kernspintomographie bei der Beurteilung der traumatisierten Bandscheibe wurde im Rahmen einer prospektiven diagnostischen Studie im Vergleich zur intraoperativen Diskographie als Goldstandard ermittelt. Die Untersuchungen wurden an beiden dem Frakturwirbel benachbarten Bandscheiben von 27 Patienten, deren Wirbelfraktur operativ behandelt worden war, durchgeführt. Die Sensitivität der Kernspintomographie als nichtinvasives Untersuchungsverfahren betrug 96%, die Spezifität 75%. Diese Werte entsprechen einer Validität von 88%.
    Notes: Summary The validity of the magnetic resonance imaging (MRI) in the diagnosis of injured intervertebral discs was examined by a prospective diagnostic study. The golden standard being intraoperative discography. The examinations were carried out on both intervertebral discs adjoining the fractured vertebral body. There were 27 patients with 54 injured discs. The sensitivity of the MRI as a noninvasive method is 96%, the specifity is 75%. These results comply with a validity of 88%.
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Brain topography 3 (1991), S. 381-390 
    ISSN: 1573-6792
    Keywords: EEG laterality ; MRI ; The 10–20 system ; Alpha rhythm
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Bilateral EEG recording is a common practice when brain laterality needs to be assessed in cognitive neurophysiology and psychiatry research. Its precision and validity remain uncertain. With structural brain imaging methods, it is possible to examine EEG electrode placements according to the 10–20 system and the validity of inferences made on derived data. Frequent sources of placement errors are examined along with important factors that contribute to EEG imbalance. Examples are mentioned where asymmetries of EEG/ERP caused by cranial and parenchymal brain asymmetries may be mistaken for cognition-related laterality changes. Because external skull landmarks are not reliable predictors of cranial and parenchymal brain asymmetries, laterality assessment cannot be guaranteed by the 10–20 system. Consequently, a return, on a case-to-case basis, to nonstandard montages, assisted by structural brain imaging is seen as an acceptable alternative.
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  • 26
    ISSN: 1573-6792
    Keywords: CT ; Dipole ; EEG ; Epilepsy ; Multimodality Matching ; MEG ; MRI ; Volume Visualization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Interpretation of EEG (electroencephalography) or MEG (magnetoencephalography) derived three-dimensional dipole localizations is hampered by poor visualization. This paper describes a method for combining dipole data with structural image data of the same patient. To ensure high precision this method utilizes external markers that are easy to apply. These markers can achieve subslice accuracy and can even be used to pinpoint reference points outside the scanned volume. Accurate matching is thus provided even in standard imaging protocols employing thick slices and/or large interslice gaps. The results of the matching method are presented in 2D and 3D visualizations. The hybrid images facilitate the interpretation of dipole localizations with respect to the patient's anatomy.
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  • 27
    ISSN: 1573-6792
    Keywords: High-resolution EEG ; Evoked potential ; MRI ; Spatial signal enhancement ; Deblurring ; Finite element model ; Laplacian derivation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary There is a vast amount of untapped spatial information in scalp- recorded EEGs. Measuring this information requires use of many electrodes and application of spatial signal enhancing procedures to reduce blur distortion due to transmission through the skull and other tissues. Recordings with 124 electrodes are now routinely made, and spatial signal enhancing techniques have been developed. The most advanced of these techniques uses information from a subject's MRI to correct blur distortion, in effect providing a measure of the actual cortical potential distribution. Examples of these procedures are presented, including a validation from subdural recordings in an epileptic patient. Examples of equivalent dipole modeling of the somatosensory evoked potential are also presented in which two adjacent fingers are clearly separated. These results demonstrate that EEGs can provide images of superficial cortical electrical activity with spatial detail approaching that of O15 PET scans. Additionally, equivalent dipole modeling with EEGs appears to have the same degree of spatial resolution as that reported for MEGs. Considering that EEG technology costs ten to fifty times less than other brain imaging modalities, that it is completely harmless, and that recordings can be made in naturalistic settings for extended periods of time, a greater investment in advancing EEG technology seems very desirable.
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  • 28
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substituted 2,2-dialkyl-2,3-dihydro-4H-pyran-4-ones of type II and III have been prepared by acid-catalyzed cyclization of the corresponding substituted acetylenic ketones I in good to excellent yields (Scheme 1). These 2,2-dialkyl-2,3-dihydro-4H-pyran-4-ones II and III have been used for the in situ preparation of highly reactive dienes of type IV-VI (Scheme 2) in carbonyl-alkyne exchange reactions with electron-poor alkynes VII to yield the highly substituted aromatic compounds VIII and IX. These reactions proceed in good yields and with excellent degree of regioselectivity. Aryl-substituted 2,2-dialkyl-2,3-dihydro-4H-pyran-4-ones III (R1 = Ar) subsequently yield highly substituted biaryls. Reaction mechanisms are presented for the formation of the 2,2-dialkyl-2,3-dihydro-4H-pyran-4-ones as well as for the carbonyl-alkyne exchange reactions with electron-poor acetylenes.
    Additional Material: 3 Tab.
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  • 29
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal and molecular structure of bis[dinitrato-(2,4,8,15,18,21-hexaoxatricyclo[20.4.0.09,14]hexacosane)europium(III)]pentakis(nitrato)europiate(III) [Eu(NO3)2LB]2([Eu(NO3)5]), has been determined at 170 K from single-crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P21/n (ITC No. 14): a = 16.338(3) Å, b = 15.704(3) Å, c = 24.474(4) Å, β = 97.73(1)°, Z = 4. The structure was refined to a final R value of 0.058 (Rw = 0.060). The asymmetric unit contains three independent ions lying on general positions: [Eu(NO3)5]2- and two distinct [Eu(NO3)2LB]+ cations with the macrocyclic ligand in the cis-anti-cis conformation (B-isomer). The EuIIIions are 10-coordinate with the following mean bond lengths: Eu-O(nitrate) = 2.48(2) Å in the anion and 2.45(2) Å in the two cations, Eu-O(ether) = 2.56(8) and 2.55(5) Å. Small but significant differences are observed between the two complex cations, especially with respect to the positions of the cyclohexyl substituent. A conformational analysis performed on the six O-atoms of the complex cations confirms the predictions of a simple model. The metal ion sites of the complex have been probed by high-resolution excitation and emission spectra at 296 and 77 K. The 5D0←7F0 excitation spectrum displays two main bands along with several other minor components. A detailed analysis of the corresponding and selectively excited emission spectra leads to the observation of three types of spectra corresponding to the three crystallographically different EuIII ions. Moreover, three minor sites are identified, one anionic and two cationic, with a population equal to ca. 10% of the population of the main sites. We interpret this finding as reflecting the presence of molecules with slightly different conformations.
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  • 30
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    Helvetica Chimica Acta 74 (1991), S. 103-109 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The C2-symmetrical chiral pyrrolidines 2 and 3 are of opposite helicity. The corresponding N-acylnitroso dienophiles 6 and 7 react in good yield with cyclohexadiene, leading thereby with excellent diastereoisomeric excess to the expected Diels-Alder cycloadducts (see Scheme). The [2.2.2] bicyclic moieties of the major diastereoisomers 9 and 11 proved to be of opposite configuration, as expected. Their configuration is best explained by assuming the acylnitroso dienophile to be in the s-cis conformation in the transition state, the approach of the diene being endo (see Fig.).
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  • 31
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An enzyme is extracted from the red peel of Amanita muscaria which cleaves the C(2)-C(3) and the C(4)-C(5) bond of the aromatic ring of L-dopa (1) to form a mixture of 4,5-secodopa (= salt of 6-amino-2-hydroxy-4-(2′-oxoethylidene)hept-2-enedioic acid; 2) and 2,3-secodopa ( = salt of 7-amino-5-formyl-2-hydroxyocta-2,4-dienedioic acid; 3), two hitherto hypothetical biosynthetic intermediates (see Scheme). Though isolation of these products has not been possible, structural evidence is inferred from reaction products, kinetics, and spectroscopical characteristics in comparison with known compounds. Secodopas 2 and 3 are characterized in dilute solution by HPLC and UV/VIS spectroscopy (anions; λmax 424 and 414 nm, resp., ∊420 = 25500; on acidification, shift to 380 and 372 nm, resp.). They cyclize without enzyme catalysis, optimally at pH 4.5-5; 3 produces muscaflavin (5) and 2 betalamic acid (4). The products arc identified by direct comparison with authentic samples in HPLC, by 1H-NMR of 5, and by condensation of 4 with L-proline to form the well known betalain indicaxanthin (7). The enzymatic conversion of L-dopa (1) via 2 to betalamic acid (4; (S)) and its condensation with L-proline leads to pure natural indicaxanthin (7; (2S,115)); correspondingly, the enzymatic conversion of D-dopa to (R)-betalamic acid and its condensation with L-proline produces isoindicaxanthin ((2S,11R)) which is unknown in nature. Particularly relevant is the fact that the same enzyme cleaves pyrocatechol to produce a solution of the enolate form of the known 2-hydroxy-6-oxohexa-2,4-dienoate (secopyrocatechol; 9; see Fig. 5). Dissociation constants of the corresponding enolic functions in the cleavage products are determined by spectrometric titration and compared to those of known systems.
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  • 32
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    Helvetica Chimica Acta 74 (1991), S. 225-231 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical behaviors of the pyrazinone derivatives 5,6,7,8-tetrahydroquinoxalin-2(1H)-ones 1a-c and 1,5,6,7,8,9-hexahydro-2H-cyclohepta[b]pyrazin-2-one 1d were investigated. Dye-sensitized photo-oxygenation of 1a-c gave the 1:1 adducts 5a-c of the corresponding 3,8a-epidioxy-3,5,6,7,8,8a-hexahydroquinoxalin-2(1H)-one 4 and H2O, whereas 1d gave 3,9a-epidioxy-1,3,5,6,7,8,9,9a-octahydro-2H-cyclohepta[b]pyrazin-2-one 4d (Scheme 2). The different kind of products was interpreted as being the result of the ring strain and steric hindrance of endoperoxides produced from 1a-d with singlet oxygen. Irradiation of 1a-b in the presence of alkenes gave tricyclic azetidine derivatives 9 by [2 + 2] cycloaddition of the C=N bond of 1 to the alkene.
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  • 33
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The piperidines 12-18, piperidmose analogues of Neu5Ac (1) with a shortened side chain, were synthesized from N-acetyl-D-glucosamine via the azidoalkene 32 and tested as inhibitors of Vibrio cholerae sialidase. Deoxygenation at C(4) of the uronate 22, obtained from the known D-GlcNAc derivative 20, was effected by β-elimination (→ 23), exchange of the AcO at C(3) with a (t-Bu)Me2SiO group and hydrogenation (→ 26; Scheme 1). Chain extension of 26 by reaction with Me3SiCH2MgCl gave the D-ido-dihydroxysilane 28, which was transformed into the unsaturated L-xylo-mesylate 29 and further into the L-lyxo-alcohol 30, the mesylate 31, and the L-xylo-azide 32. The derivatives 29-31 prefer a sickle zig-zag and 32 mainly an extended zig-zag conformation (Fig. 2). The piperidinecarboxylate 15 was obtained from 32 by ozonolysis (→ 33), intramolecular reductive animation (→ 34), and deprotection, while reductive animation of 34 with glycolaldehyde (→ 35) and deprotection gave 16 (Scheme 2). An intramolecular azide-olefin cycloaddition of 32 yielded exclusively the fused dihydrotriazole 36, while the lactone 39 did not cyclize (Scheme 3). Treatment of 36 with AcOH (→ 37) followed by hydrolysis (→ 38) and deprotection led to the amino acid 18. To prepare the (hydroxymethyl)piperidinecarboxylates 12 and 17, 32 was first dihydroxylated (Scheme 4). The L-gluco-diol 40 was obtained as the major product, in agreement with Kishi's rule. Silylation of 40 (→ 42), oxidation with periodinane (→ 44), and reductive animation gave the L-gluco-piperidine 45. It was, on the one hand, deprotected to the amino acid 12 and, on the other hand, N-phenylated (→ 46) and deprotected to 17. While 45 and 12 adopt a 2C5 conformation, the analogous N-Ph derivatives 46 and 17 adopt a 5C2 and a B3,6 conformation, respectively, on account of the allylic 1,3-strain. The conformational effects of this 1,3-strain are also evident in the carbamate 47, obtained from 45 (Scheme 5), and in the C(2)-epimerized bicyclic ether 48, which was formed upon treatment of 47 with (diethylamino)sulfur trifluoride (DAST). Fluorination of 40 with DAST (→ 49) followed by treatment with AcOH led to the D-ido-fluorohydrin 50. Oxidation of 50 (→ 51) followed by a Staudinger reaction and reduction with NaBH3CN afforded the (fluoromethyl)piperidine 52, while reductive amination of 51 with H2/Pd led to the methylpiperidine 55, which was similarly obtained from the keto tosylate 54 and from the dihydrotriazole 36. Deprotection of 52 and 55 gave the amino acids 13 and 14, respectively. The aniline 17 does not inhibit V. cholerae sialidase; the piperidines 12-16 and 18 are weak inhibitors, evidencing the importance of an intact 1,2,3-trihydroxypropyl side chain.
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  • 34
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    Helvetica Chimica Acta 74 (1991), S. 438-444 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Monomorin I, a Trail Pheromone of the Pharao Ant (Monomorium pharaonis)Katalytic hydrogenation of the 4-nitroalkanone 5 yielded the cis-pyrrolidine ester 6 (Scheme). The preparation of 5 was accomplished by ethanolysis of the nitrocyclohexanone derivative 4. Iodination at C(α) of 6, followed by cyclization, gave a nearly 5:6 mixture of the two C(5)-epimers 10/9 of octahydroindolizine. Epimerisation of the undesired 10 to 9 and subsequent transformation of the latter gave racemic monomorine I (1; 34% yield from 5).
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  • 35
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    Helvetica Chimica Acta 74 (1991) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 36
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    Helvetica Chimica Acta 74 (1991), S. 326-330 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystal Structure of a Thiazolorifamycine: Rifamycine PThe crystal structure of a natural thiazolorifamycin, rifamycin P, as an adduct with EtOH and H2O, has been determined by X-ray crystallography by a combination of direct methods and Patterson techniques. Block-diagonal least-squares refinement using 5996 independent reflections and 1475 parameters led to an R factor of 0.092 (two independent molecules of rifamycin P). The middle part of the ansa chain, essential for activity against the bacterial DNA-dependent RNA polymerase (DDRP) resembles that of active rifamycins. The four OH groups lie on the same side of the molecule and are almost in the same plane. Interatomic distances between the O-atoms agree well with a spatial model derived from X-ray studies, performed on semisynthetic active rifamycins.
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  • 37
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oximes are used in the therapy of organophosphate poisoning. They form an interaction product with the organophosphate which is claimed to be more toxic than the organophosphate itself. We have synthesized one of these compounds which would be formed by the reaction of pyridine-4-carbaldehyde oxime methiodide with sarin (GB). Thus, reaction of oxime 1 with sarin chloridate (2), yielded 4-{{[(isopropyloxy)methylphosphoryloxy]-imino}methyl}-1-methylpyridinium iodide (4) which was characterized by NMR spectroscopy and X-ray crystallography.
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  • 38
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    Helvetica Chimica Acta 74 (1991), S. 531-542 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Substitued N-(isoxazol-4-yl)thioureas 1 undergo a transformation in the presence of hexacarbonylmolybdenum and acid to yield functionalized thiazoles 3 in a one-pot reaction. In a few cases, 1,4,5-trisubstituted dihydroimidazolethiones 4 are also isolated as side products. Mechanistic considerations are outlined and scope and limitations of this new methodology discussed.
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  • 39
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    Helvetica Chimica Acta 74 (1991), S. 565-571 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aphelandrine (1) is shown to be biosynthesized in the root cells of Aphelandra tetragona (VAHL) NEES from labelled putrescine (4), spermidine (5), and cinnamic acid (3). Whether spermine (6) and the (p-hydroxycinnamoyl)spermidine 8 are precursors of 1 is uncertain, since the latter is hydrolysed to a large extent before incorporation, and the former is metabolized to 4 and 5. Methionine (7) is the source of the 3-aminopropyl unit of 5 and 6.
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  • 40
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermolysis of the glycosylidene-derived O-benzylated diazirine 1 in the presence of N-phenylmaleimide (2), acrylonitrile (3), dimethyl fumarate (4), or dimethyl maleate (5) led in good yields to mixtures of the spirocyclopropanes 6/7, 8-11, 12/13, and 12/13/16/17. The diastereoselectivity depends upon the alkene. The cycloaddition of 1 to 5 is not diastereospecific, in keeping with previous results. Deprotection of 12, 13, 16, and 17 yielded the tetrols 14,15, 18, and 19, respectively.
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  • 41
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The course of solid-phase peptide-coupling reactions as well as the swelling properties of a peptide-resin are influenced by the addition of inorganic salts (LiCl, LiBr, LiClO4, KSCN). Used as additives, these salts can (i) improve coupling yields (e.g., for Fmoc-(Ala)5-Phe-resin → Fmoc-(AIa)6-Phe-resin in DMF/CH2Cl2 1:1 from 89.4 to 97.1% (for polyethylene oxide) on polystyrene (= PEO-PS) resin) or from 77.5 to 93.8% (for poly-(N,N′-dimethylacrylamide) on ‘Kieselgur’ (=PDMAA-KG) resin) without and with 0.4M LiCl, respectively), (ii) increase resin swelling (e.g. for Fmoc-(Ala)5-Phe-(polystyrene resin) from 2.42- to 5.73-fold in 1-methylpyrrolidin-2-one (=NMP) without and with LiCl, (respectively), and (iii) change coupling rates. Example;; of coupling reactions and swelling behaviour (degree and rate) in different solvents (DMF, DMF/CH2Cl2 1:1, THF, NMP, N,N-dimethylpropyleneurea (= DMPU) with and without salts) using different resins (polystyrene (PS); PEO-PS, and PDMAA-KG) and an improved analysis of alanine oligomers up to Ala12-Phe by HPLC and FAB-MS are reported.
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  • 42
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rearrangement of methyl 2-(methylthio)benzenesulfonate (1) to the zwitterionic 2-(dimethyl-sulfonium)benzenesulfonate (2) is known to proceed in solution by intermolecular Me transfers. The same rearrangement has been observed to occur in crystalline 1, but the crystal structure shows that the molecular packing is not conducive to intermolecular Me transfer. The reaction has been carried out with mixed crystals composed of 1 and deuteriomethylated (D6)-l. By fast-atom-bombardment mass spectroscopy, it has been shown that the product consists of a 1:2:1 mixture of the non-, tri-, and hexadeuterated species, the mixture expected, if the solid-state reaction proceeds by intermolecular Me transfers. From this result, together with the slower rates of conversion in the single crystal compared with the melt, it can be concluded that the reaction must occur not topochemically but rather at defects such as microcavities, surfaces, and other irregularities in the ordered crystal arrangement.
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  • 43
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    Helvetica Chimica Acta 74 (1991), S. 717-726 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the complexes 3 of various metals ligated to chiral 4,5-dihydro-2-(2′-oxidophenyl-ϰO)oxazoles-ϰN is described (Scheme). Three of them, i.e. 3a, 3e, and 3f containing CuII, ZnII and NiII, respectively, were analyzed by X-ray diffraction studies. A series of CuII complexes (6a-d) with differently substituted dihydrooxazoles have been synthesized.
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  • 44
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    Helvetica Chimica Acta 74 (1991), S. 748-760 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-(2′-Deoxy-β-D-threo-pentofuranosyl)thymine (= 1-(2′-deoxy-β-D-xylofuranosyl)thymine; xTd; 2) was converted into its phosphonate 3b as well as its 2-cyanoethyl phosphoramidite 3c. Both compounds were used for solid-phase synthesis of d[(xT)12-T] (5), representing the first DNA fragment build up from 3′-5′-linked 2′-deoxy--β-D-xylonucleosides. Moreover, xTd was introduced into the innermost part of the self-complementary dodecamer d(G-T-A-G-A-A-xT-xT-C-T-A-C)2 (9). The CD spectrum of d[(xT)12-T] (5) exhibits reversed Cotton effects compared to d(T12) (6; see Fig. 1), implying a left-handed single strand. With d(A12) (7) it could be hybridized to form a propably Left-handed double strand d(A12) · d[(xT)12-T] (7·5) which was confirmed by melting experiments in combination with temperature-dependent CD spectroscopy. While 5 was hydrolyzed by snake-venom phosphodiesterase, it was resistant towards calf-spleen phosphodiesterase. The modified, self-complementary duplex 9 was hydrolyzed completely by snake-venom phosphodiesterase, at a twelvefold slower rate compared to unmodified 8; calf-spleen phosphodiesterase hydrolyzed 9 only partially.
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  • 45
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Temperature-dependent 1H- and 13C-NMR spectra reveal that polyhalogenated marine β-chamigrenes or synthetic derivatives thereof which are trans-diequatorially, substituted at C(8) and C(9), such as rogiolol ((-)-2), obtusol ((+)-3), and their acetates (+)-1 and (-)-4, undergo slow ring-A chair-chair inversion. Conformational equilibria and kinetics are investigated with the aid of synthetic model compounds and molecular-mechanics calculations. Thus, steric repulsions between Brax-C(2) and Heq-C(7) are seen to disfavour thermodynamically conformers 1b, 2b, 3b, and 4b, which can only be detected through cross-saturation transfer, while additional steric repulsions between Meax-C(1) and OHax-C(3) make conformer 8b of obtusol epimer so scarcely populated that it can not be detected. In agreement, with (+)-9 and (+)-10, which have a trigonal C(2), two conformers can be directly observed by NMR. The kinetic barriers, which are seen to arise mainly from steric repulsions between Hax-C(14) and the axial H or halogen atoms at C(8) and C(10), are calculated and discussed with respect to well documented exocycliemethylidene-substituted cyclohexane(ene) systems. This helps to rationalize why in rogiolol acetate ((+)-1) ring B is unusually inert towards Zn/Et2O/AcOH which causes bromohydrine-group elimination from ring A.
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  • 46
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cycloviolaxanthin (= (3S,5R,6R,3′S,5′R,6′R)-3.6:3′,6′-Diepoxy-5,6,5′,6′-tetrahydro-β,β-carotene-5,5′-diol), a Novel Carotenoid from Red Paprika (Capsicum annuum)From red paprika (Capsicum annuum var. longum nigrum) cycloviolaxanthin was isolated as a minor carotenoid and, based on spectral data, assigned the symmetrical structure 8.
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  • 47
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    Helvetica Chimica Acta 74 (1991), S. 807-818 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of quinic acid (4) via epoxide 13, starting from shikimic acid (5), is described (Scheme 1). Treatment of 13 with thiophenol yielded not only 17, but also the γ-lactones 18 and 19 as result of migration of silyl groups within a cis- and trans-diol system. The conversion provides a direct stereoselective epoxidation of a shikimic-acid derivative as well as an alternative pathway for the preparation of 4. A shorter approach via the disilylated epoxide 22 was unsuccessful because the γ-lactone 25 was obtained in place of the desired α-hydroxy ester 24 (Scheme 2).
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  • 48
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The four protected diastereoisomcrs 7a/7b and 8a/8b P-thioadenylyl-(3′-5′)-P-thioadenylyI-(3′-5′)-adenosine were synthesized, separated, and deblocked to the free oligonucleotides (Scheme). Biochemical characterization of these (3′-5′)phosphorothioate analogues of adenyiate trimer indicate that these compounds, and the corresponding 5′-monophosphates, neither bind to nor activate RNase L, and are considered to be valuable control compounds in screening experiments.
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  • 49
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    Helvetica Chimica Acta 74 (1991), S. 825-877 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures of four inclusion compounds of 2,6-dimethylideneadamantane-1,3,5,7-tetracarboxylic acid (4) are described, which involve the following guest species: (a) a mixture of 4-methylpent-3-en-2-one, 2,6-dimethylhepta-2,5-dien-4-one, and mesitylene (condensation products of acetone); (b) mesitylene; (c) a mixture of 4-methylpent-3-en-2-one and mesitylene; (d) (tert-butyl)benzene. In all four cases, the host architectures consist of two interpenetrating super-diamond networks built up by the tetra-acid molecules via pairwise H-bonds between the tetrahedrally directed COOH groups. In the first three cases (tetragonal crystal symmetry), the two diamond-like host lattices interpenetrate symmetrically, in the fourth case (monoclinic) asymmetrically. This asymmetry is brought about by the increased steric bulk of the (tert-butyl)benzene guest molecules. Attempts to enforce an inclusion compound of 4 with a single, extremely hollow diamond-like host lattice by offering still bulkier guest molecules have as yet not been met with success. The generally very high propensity of 4 to form inclusion compounds was envisaged and designed beforehand by appropriate evaluation and modulation of the crystal structure of the parent adamantane-1,3,5,7-tetracarboxylic acid, which represents a fivefold diamond-like self-inclusion compound. Crystals of the free, uncomplexed 4 appear to be extremely unstable and could so far not be obtained. On the other hand, from aqueous solution a very stable monohydrate of 4 may be crystallized (4-H2O), which was also subjected to X-ray analysis. The (triclinic) crystal structure of 4·H2O involves an interesting dichotomy inasmuch its pattern of H-bonding may be rationalized either in terms of a double, cross-linked super-zincblende (sphalerite) architecture, or as a system of porous, puckered 4-connected sheets, which interpenetrate each other pairwise and are cross-linked by the H2O molecules. Various structure and (space group) symmetry characteristics of the supramolecular solid-state complexes reported here are highlighted by pointing out analogies with comparable structures retrieved from the literature.
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  • 50
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    Helvetica Chimica Acta 74 (1991) 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 51
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As the root bark CH2Cl2 extract of Bauhinia rufescens showed antifungal activity in a bioassay with the plant pathogenic fungus Cladosporium cucumerinum, a phytochemical investigation was undertaken on material collected in Niger. Activity-guided fractionation of this extract, using different preparative chromatographic methods, allowed the isolation of the four new antifungal tetracyclic compounds 1-4. Their structures were established by 1H- and 13C-NMR data, and single-crystal X-ray analyses were used to confirm the structures of 1 and 3. The isolated compounds seem to be biogenetically related to a stilbene.
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  • 52
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    Helvetica Chimica Acta 74 (1991), S. 800-806 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new route to completely protected α-methylated α-amino acids starting from alanine is described (see Scheme). These derivatives, which are obtained via base-catalyzed opening of the oxazolidinones (2S,4R)- and (2R,4S)-2, can be directly employed in peptide synthesis. The synthesis of both enantiomers of Z-protected α-methylaspartic acid β-(tert-butyl)ester (O4-(tert-butyl) hydrogen 2-methylaspartates (R) or (S)-4a), α-methyl-glutamic acid γ-(tert-butyl) ester (O5-(tert-butyl) hydrogen 2-methylglutamate (R)- or (S)-4b), and of Nε-bis-Boc-protected α-methyllysine (N6,N6-bis[(tert-butyloxy)carbonyl]-2-methyllysine (R)- or (S)-4c) is described in full detail.
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  • 53
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Via the phosphotriester approach, new structural analogs of (2′-5′)oligoadenyiates, namely 3′-deoxyadenylyl-(2′-5′)-3′-dcoxyadenylyl-(2′-ω)-9-(ω-hydroxyalkyl)adenines 18-21, have been synthesized (see Scheme) which should preserve biological activity and show higher stability towards phosphodiesterases. The newly synthesized oligonucleotides 18-21 have been characterized by 1H-NMR spectra, TLC, and HPLC analysis.
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  • 54
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    Helvetica Chimica Acta 74 (1991), S. 905-906 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of [Leu5]enkephalin-related glycoconjugates with an ester-, ether-, or amide-type linkage were synthesized and evaluated for antiviral activity against HIV-1 in a cell-culture system using peripheral blood lymphocytes. All tested glycoconjugates exhibited a certain antiviral activity which was significantly higher than the activity of the parent peptide compound itself. These results indicate that synthetic glycoconjugates of opioid peptides are good candidates for the development of anti-HIV agents.
    Additional Material: 1 Tab.
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  • 56
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Developmental efforts to improve the yield of the chemical synthesis of (3R,3′R)-zeaxanthin resulted in the isolation, partly by chromatography from reaction mixtures, and full spectroscopic characterization by 1H-NMR, UV/VIS, and CD spectrosocpy of eleven (Z/E)-isomers of zeaxanthin: (7Z)-, (9Z), (13Z)-, (15Z)-, (7Z,7′Z)-, (9Z,9′Z)- (7Z,9Z,7Z)-, (7Z,11Z,7′Z)-, (9Z,13Z,9′Z)-, (7Z,9Z,7′Z,9′Z)-, and (7Z,9Z,11Z,7′Z,9′Z)-zeaxanthin. Five of these isomers were obtained by specific synthesis, namely the (7Z)-, (7Z,7′Z)-, (9Z,9′Z)-, (7Z,9Z,7′Z)-, and (7Z,9Z,7′Z-9Z)-isomers.
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  • 57
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring Enlargement of 1,2-Thiazol-3(2H)-one-1,1-dioxides and 3-Amino-2H-azirines to 4H-1,2,5-Thiadiazocin-6-one-1,1-dioxidesReaction of 3-amino-2H-azirines 2 with the 1,1-dioxides 4 and 7 of 1,2-thiazol-3(2H)-ones and 1,2-thiazoli-din-3-ones, respectively, in i-PrOH at room temperature leads to 4H-1,2,5-thiadiazocin-6(5H)-one-1,1-dioxides 5 (Scheme 2, Table) and the corresponding 7,8-dihydro derivatives 8 (Scheme 4), respectively. The structure of some of the new 8-membered heterocycles as well as the structure of the minor by-product 6 (Scheme 3) have been established by X-ray crystallography (Chapt. 4). The proposed reaction mechanism for the ring expansion to 5 and 8 (Scheme 2) is in accordance with previously published results of reactions of 2 and NH-acidic heterocycles and is further supported by the results of the reaction of 4a and the (1-15N)-labelled aminoazirine 2a*.
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  • 58
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of 1,2-Thiazoles; A Convenient Approach to 1,2-Thiazol-3(2H)-one 1,1-DioxidesThe 1,2-thiazoles obtained from 3-chloroalk-2-enals and ammonium thiocyanate (7 → 9, Scheme 1) are easily transformed to 1,2-thiazol-3(2H)-one 1,1-dioxidcs 10 on treatment with H2O2 in AcOH at 80°. Hydrogenation of 10 in AcOH yields the corresponding saturated 1,2-thiazolidin-3-one 1,1-dioxides 16 (Scheme 3). Cycloalka[c]-1,2-thiazoles 18 are prepared from 2-[(thiocyanato)methyliden]cycloalkan-1-ones and ammonia (Scheme 4). Surprisingly, oxidation of 18a with H2O2 in AcOH yields the tricyclic oxaziridine 19.
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  • 59
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    Helvetica Chimica Acta 74 (1991), S. 1095-1101 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Synthesis of Derivatives of Pyrido[1,2-a]lazepineThe conjugated pyridinium ylides of type 4 undergo 8π -electrocyclisation affording the heterobicyclic allenes 5 which, in the presence of H2O and H2O2, are subsequently transformed into the substituted pyrido[1,2-a]-azepinones 6, a novel heterocyclic system. The chemical behaviour of 6a,b is dominated by cleavage of the lactam bond and subsequent reaction to pyridinc and isoquinoline derivatives, respectively; e.g. reaction of 6a, b with 4,5-dihydro-4-methyl-3H-1,2,4-triazole-3,5-dione affords the cycloadducts 11 and 12 almost quantitatively. The successful transformation of 6b into 15 is described, the latter being the first representative of the presently unknown, potentially antiaromatic pyrido[1,2-a]azepine (1).
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  • 60
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    Helvetica Chimica Acta 74 (1991), S. 1156-1156 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Regio- and stereospecific labeling experiments are conducted to unravel the mechanistic features of the Fe+-induced dehydrogenation of octane-1,8-diol in the gas phase. With regard to the regioselectivity, ca. 20% of molecular hydrogen originates from the C(3)/C(4) or the equivalent C(5)/C(6) positions. The remaining 80% are, provided by the C(4)/C(5) methylene units. The steps, preceding the reductive elimination of hydrogen, are irreversible, and the overall reaction follows a 1,2-elimination mode. The loss of HD from C(3)/C(4) is associated with a kinetic isotope effect KH2/KHD = 1.68. Formation of D2 from the positions C(4)/C(5) has an isotope effect of KH2/KD2 = 4.7; this figure is slightly dependent on the configuration at C(4)/C(5). Most interesting is the finding that the configuration at C(4)/C(5) in [4,5-D2]octane-1,8-diol, i.e. 5c vs. 5d, plays a pivotal role in the dehydrogenation of the central C(4)/C(5) part. This unexpected and unprecedented result is explained in terms of conformational analysis. A staggered-like conformation serves as a precursor to generate a trans-fused bicyclic intermediate 6. It is this very intermediate from which most of the molecular hydrogen is eliminated. Of minor importance is the as-fused chelate 7, which is formed from an eclipsed-like conformation of the octane-1,8-diol/Fe+ complex. The contribution of 6 and 7 to the product formation is controlled by the relative configuration at the labeled positions C(4)/C(5). For the D,L-form 5c, we estimate a ratio of ca. 9:1 for the contribution of 6 vs. 7; due to an isotope effect, this ratio drops to 1:85:1 for the meso-form 5d. This finding constitutes the first example for the existence of isotopically sensitive branching (‘metabolic switching’) in gas-phase organometallic chemistry.
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  • 62
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures of the LaIII, EuIII, and TbIII complexes of macrobicyclic [bpy.bpy.bpy] ligands, [La3+ ⊂ 1]3 Cl- ( = 3-La), [Tb3+ ⊂ 1]3 Cl- ( = 3-Tb), and [Eu3+ ⊂ 2]3 C1- ( = 3-Eu), have been determined. They confirm the cryptate nature of these species, the cations being bound to the eight N-sites of the ligand. The macrobicycle presents two open faces, thus allowing additional coordination of two species, Cl- ions or H2O molecules, to the bound cations. These data provide structural support for the photophysical studies of the luminescent properties of the EuIII and TbIII cryptates, which indicated residual coordination of H2O molecules.
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  • 63
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of 4-alkylpyrocatechols 2 by means of an insect diphenoloxidase (laccase) or K3 [Fe(CN)6] yields, in the presence of resorcinols 1 (R2 = H), complex mixtures of products from which biphenyltetrols 3 (R3 = H) and dibenzofuranones 5 and 6 were isolated. It is suggested that similar homo-coupling products are formed from pyrocatechols 2b and 2c in insects during cuticle sclerotization.
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  • 64
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    Helvetica Chimica Acta 74 (1991), S. 1236-1238 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-pressure 17O- and 13C-NMR show that [Ru(H2O)6]2+ reacts quantitatively with carbon monoxide (50 bar) in water to form [Ru(CO)(H2O)5]2+.
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  • 65
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    Helvetica Chimica Acta 74 (1991), S. 1264-1272 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of ‘Push-Pull’-OligoAcetylenes‘Push-pull’ triacetylenes 11a, b, c, as well as ‘push-pull’ tetraacetylene 13b have been prepared by reaction of the corresponding trichloroene(oligoinyl)amines 9 and 10 with 2 mol-equiv. of BuLi followed by acylation. The sequences (Schemes 3 and 4) are very simple and straightforward, they could in principle be applied to the synthesis of ‘push-pull’ pentaAcetylenes 15 and hexaacetylenes 17 (Scheme 5). Main limitations are the moderate yields as well as the low thermal stability of push-pull oligoacetylenes.
    Additional Material: 1 Tab.
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  • 66
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sphydrofuran (1) was isolated from the culture filtrate of Streptomyces sp. (strain Gö 28 and Tü 3616) by chemical screening methods. Metabolite 1 is an anomeric and ring-chain tautomeric mixture and could easily be transformed into the stable furan derivative 2 under acidic conditions. The constitution and relative configuration of 1 was established by X-ray crystallography of its 8-O-methyl derivative 3a. The absolute configuration at C(4) of 1 and thus of the whole molecule (3R,4S,5S) could be determined starting from 2 using the Helmchen method.
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  • 67
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On treatment with H2SO4/MeOH, epimerization of hexamethyl cis-5,6-dihydroxycobyrinate c,8-lactam (3) takes place quantitatively at C(6), yielding the corresponding trans-diol 4. The corresponding lactone 7, whose structure has been established by X-ray analysis, is obtained from xanthocorrinoids 5 and 6 under similar conditions.
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  • 68
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    Helvetica Chimica Acta 74 (1991), S. 1314-1328 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of biologically relevant O4-phospho-L-tyrosine-containing peptides have been synthesized by either the global phosphorylation of the side-chain-unprotected L-tyrosine moiety in presynthesized resin-bound peptides or alternatively by the incorporation of suitably protected O4-phospho-L-tyrosine building blocks in the continuous-flow method of Fmoc solid-phase peptide synthesis. Different phosphate-protecting groups have been applied.
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  • 69
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    Helvetica Chimica Acta 74 (1991), S. 1352-1361 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoselective Synthesis von Pyrrolizidin Alkaloids from NitroalkanonesReduction of 5-nitropentadecane-2,8-dione (11), synthesized by a Michael reaction from nitromethane, methyl vinyl ketone, and dec-1-en-3-one, gave, depending on the conditions, two epimeric 3-heptyl-2,3,5,6,7,7a-hexahydro-5-methyl-1H-pyrrolizines as the main products: Catalytic hydrogenation (Pd/C) afforded the expected 7aα-hydro epimer 1b with cis-orieted H-atoms at C(3), C(5), and C(7a). NaBH3CN/NH4OAc reduction of the nitrodione 11 yielded all four diastereoisomers with the 7aβ-hydro epimer 1a as the predominant component; 1a is a pheromone of the cryptic thief ant Solenopsis sp. The N-atom of the pyrrolizidine ring stems from NH4OAc exclusively as shown by reduction of 11 with NaBH3CN/(15N)H4OAc.
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  • 70
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    Helvetica Chimica Acta 74 (1991), S. 1362-1372 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the first glycosylidene-derived 2-acetamido-2-deoxydiazirine 4 from N-acetylglucosamine 6 is described. Thus, 6 was transformed into the 3-O-mesylglucopyranoside 9 by glycosidation with allyl alcohol, benzylidenation, and mesylation (Scheme 2). Solvolysis of 9 gave the allopyranoside 10 which, upon benzylation and glycoside cleavage, yielded the hemiacetals 12. Using our established method (via the lactone oxime 14 and the diaziridines 16), 12 gave the diazirine 4. Thermolysis of this diazirine in the presence of i-PrOH gave the dihydro-1,3-oxazole 5 (Scheme 1); in the presence of acrylonitrile, the four diastereoisomeric spirocyclopropanes 17-20 and the acetamidoallal 21 were obtained and separated by prep. HPLC (Scheme 3). Assignment of the configuration of 17-20 is based on NOE measurements and on the effect of diamagnetic anisotropy of the CN group. The ratio of the four cyclopropanes, which is in keeping with earlier results, is rationalized.
    Additional Material: 4 Tab.
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  • 71
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O-Methylation of the optically active 3′-hydroxycoclaurines 3a and 3b and of the N-methylated analogs 5a,b with S-adenosyl-L-[methyl-14C]methionine in presence of mammalian COMT was investigated in vitro. The N-unsubstituted (1S)- and (1R )-isomers 3a and 3b, respectively, afforded almost equal amounts of the corresponding N-norreticuline 4 and N-nororientaline 19, besides two unknown by-products (see Fig. and Table 1). The N-methylated (1S)-isoquinoline 5a, on the other hand, afforded largely (S)-orientaline ((S)-19), while an almost equal mixture of (R)-reticuline (6b) and (R)-orientaline ((R)-19) was obtained from the (1R)-enantiomer 5b. The isoquinolines 3a,b and 5a,b were prepared by a Bischler-Napieralski cyclization yielding O-benzyl-protected isoquinoline 10 (Scheme 1). The optical resolution of 10 was accomplished with 2′-bromotartranilic acid. The N-methylated isoquinolines were prepared by N-formylation of 10a,b and reduction of the formamides 13a,b with diborane (→ 14a,b). Deblocking of the benzyl-ether moieties of 10a,b and 14a,b was accomplished by catalytic hydrogenation in presence of HCl, affording directly 3a,b·HCl and 5a,b·HCl, respectively.
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  • 72
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetone extraction of cultures of the marine ascomycete Leptosphaeria oraemaris (LINDER) on cornmeal disk gave the novel polyketide derivative leptosphaerolide ( = (+)-7-[(1E)-l,3-dimethylpent-1-enyl]-10-hydroxy-3-methoxybenzo[1,2-b:5,4-c′]dipyran-2(9H)-one; (4+)-8) besides the o-dihydroquinone 3-[(1E)-1,3-dimethylpent-1-euyl]-8,10-dihydroxy-7-methoxy-8-(2-oxopropyl)-1H-naphtho[2,3-c]pyran-9(8H)-one (1) as a 10:9 mixture of epimers. retro-Aldol reaction of 1 gave leptosphaerodione ( = (-)-3-[(1E)-1,3-dimethylpent-1-enyl]-10-hydroxy-7-methoxy-1H-naphtho[2,3-c]pyran-8,9(8H)-dione; (-)-6) which was also present in small amounts in the extracts and which gave 1 on reaction with acetone. It is thus likely that 1 is an artefact of the extraction by acetone. Biogenetically (+)-8 might derive from (-)-6 via an unusual oxidation with loss of CO2.
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  • 73
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    Helvetica Chimica Acta 74 (1991), S. 1600-1607 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical addition to 2-cyclohexyl-5-methylidene-6-methyl-1,3-dioxan-4-one (2) affords stereoselectively 5,6-trans-products trans-3. The size of the radical has no influence on the selectivity. These trans-acetals are converted into threo-3-hydroxy-butanoates 4. Methyl 2-methylidene-3-[(tert-butyl)diphenylsilyloxy]butanoate (5), treated under the same conditions, leads mainly to the erythro-isomer of 4 after deprotection. An influence of the steric bulkyness of the radical is observed. The stereochemical course of the reactions is discussed.
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  • 74
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    Helvetica Chimica Acta 74 (1991), S. 1609-1621 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a complete set of 2H-labeled isotopomers, the gas-phase reactions of Ti+ to Zn+ with butyl isothio-cyanate are studied. The main product for most of the metal ions is MHNCS+ formed by an ion/dipole mechanism. Exceptions are Cr+, which yields significant amounts of H2 and H2S loss, Mn+, which is the only ion that does not form MHNCS+ at all but produces mainly C2H4 and C3H6, and Zn+, which predominantly reacts by charge transfer.
    Additional Material: 6 Tab.
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  • 75
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Oxathiolanc Synthesis: Spirocyclic 1,3-Oxathiolanes from the Lewis-Acid-Catalyzed Reaction of Cyclic Trithiocarbonates and OxiranesThe cyclic trithiocarbonates 1.3-dithiolane-2-thione (4) and 1,3-dithiole-2-thione (9) in 1,2-dichloroethane and MeCN, respectively, react with alkyl- and phenyl-substituted oxiranes 2 in the presence of Lewis acids to give 1-oxa-4,6,9-trithiaspiro[4.4]nonanes 5 and 6 (Scheme 2) and 1-oxa-4,6,9-trithiaspiro[4.4]non-7-enes 10 and 11 (Scheme 3), respectively. The reactions proceed regioselectively yielding 2-alkyl (5, 10) and 3-phenyl derivatives (6, 11) as the main products. From the reaction of 4 and 2-phenyloxirane (2e) with TiCl4, 2-phenyl-1,4,6,9-tetrathia-spiro[4.4]nonane (7) is isolated as a minor product. The molecular structures of 5a, 6e, and 7 are established by X-ray crystallography.
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  • 76
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    Helvetica Chimica Acta 74 (1991), S. 1533-1543 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformations in solution of six selected chiral 1,1′-bis (diphenylphosphino)ferrocenyl ligands bearing functionalized side chains, the diastercoisomers 4 and 5 and 6-9, have been elucidated by 2D-NMR methods (COSY, TOCSY, NOESY, and 1H,31P and 1H,13C correlations). The possible relationship between the preferred conformation and the stereoselectivity observed in the gold(I)-catalyzed asymmetric aldol condensation in the presence of these ligands is discussed.
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  • 77
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    Helvetica Chimica Acta 74 (1991), S. 1591-1599 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bimetallic inclusion complexes have been synthesized by a secondary coordination interaction between the guest complex [Fe(η5-C5H5)(CO)2(NH3)][PF6] and copper(II) complex 1a or nickel(II) complex lb containing crown-ether hosts. The X-ray crystal-structure analysis established that the Cu,Fe inclusion complex 2 crystallize as a centrosymmetric dimer with a Cu—Cu separation of 3.73 Å and a novel out-of-plane Cu—N interaction. The magnetic parameters for 2 were obtained by ESR and ENDOR spectroscopy. ESR susceptibility measurements down to 6 K exclude the presence of any antiferromagnetic coupling interaction between the CuIIcenters of the dimer.
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  • 78
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    Helvetica Chimica Acta 74 (1991), S. 1636-1642 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The revised structure of the indole alkaloid aristolasicone (2) was confirmed through a convergent total synthesis of the racemic form of this metabolite. The key step involves a one-pot condensation/cyclization reaction between 1-(4-methoxyphenylsulfonyl)-1H-indole-2-acetaldehyde (9) and (±)-trans-5-(2,6-difluorobenzyloxy)-p-menth-l-en-8-amine ((±)-7). The resulting allohobartine derivative (±)-13, obtained in 84% yield, was deprotected and oxidized to (±)-alloscrratenone ((±)-15) which cyclized smoothly to the target molecule (±)-2 upon exposure to BF3 · Et2O.
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  • 79
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acylnitroso dienophiles 4 reacted instantly with 1-(silyloxy)butadiene 5α and led in good yield to the regioisomeric cycloadducts 6 (major) and 7 (minor; Scheme 2, Table 1). cis-Hydroxylation of these primary cycloadducts with OsO4 (catalyst) occurred stereospecifically and in high yield (→8 and 9, resp.; Scheme 2). It was followed by reductive ring cleavage to give either 1-amino-1-deoxy-DL-erythritol or 4-amino-4-deoxy-DL-erythrose derivatives 10 and 14, respectively, depending on the nature of the reducing agent (Schemes 3 and 4).
    Additional Material: 7 Tab.
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  • 80
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991), S. 1679-1688 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The autoxidation of CuI in aqueous MeCN has been studied using a Clark oxygen electrode in the presence and absence of Cu11. The reaction is inhibited by Cu11 in the pH range of 0.5 to 5.0, reaching a lower limiting value at the highest concentrations. The reaction order changes from 1 to 2 with respect to CuI under the influence of Cu2+ ion. Detailed kinetics analysis of a total of 275 measurements has shown that an unstable primary adduct CuO+2 decomoses to give .O2- or HO2., depnding on pH, and also reacts directly with a second Cu+ ion, avoiding one-electrton reduction of O2 by this path. Reaction of HO2. is faster with CuI than with Cu11 by a factor of 20, and single-electron transfer within CuO+2 to Cu2+ and .O2- predominates over reaction with a second copper ion for [CuItot] 〈 2. 10-3M in the absence of Cu2+. The most likely value for the reaction of .O2- with CuI is 5.3 · 108 M-1S-1, but even this high rate constant is at the limit of significance. All secondary reactions followinfg the initial formation of CuO+2 are shown to be very fast, a fact that should be properly considered in the discussion of mechanisms of copper-catalyzed oxidations and oxygenations.
    Additional Material: 4 Ill.
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  • 81
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    Helvetica Chimica Acta 74 (1991), S. 1834-1842 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular-mechanics calculations of the sexidentate coordinated complexes of the pendant arm macrocyclic hexaamines trans- (L1) and cis-6,13-dimethyl-3,4,8,11-tetraazacyclotetradecane-6,13-diamine (L2) reveal that the trans-isomer shows a preference toward small metal ions, whereas the L2 may coordinate a wider range of metal ions without significant intramolecular strain. Conformational disorder in previously reported crystal structures of complexes of L1 is interpreted, and predictions for some, as yet, unknown complexes of L2 are made.
    Additional Material: 3 Ill.
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  • 82
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    Helvetica Chimica Acta 74 (1991), S. 1790-1800 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligonucleotides continuing 3-deaza-2′-deoxyguanosine (I) or its N7-regioisomer 2 were prepared by solid-phase synthesis using P111 chemistry. Protection of 1 or 2 with N,N V-dimethylformamide diethyl acetal followed by 4,4′-dimethoxytritylation afforded imidazo[4,5-c]pyridines 10b and 11b, respectively. The latter were converted into the 3′-phosphonates 10c or lie, respectively; the cyanoethyl N,N-diisopropylphosphoramidite 10d was also prepared. The oligonucleotide building blocks were employed in automated solid-phase synthesis. 1 he self-complementary oligomers 13, 15, and 17 were prepared and characterized by enzymatic hydrolysis with snake-venom phosphodiesterase followed by alkaline phosphatase. There CD spectra exhibited the general structure of a B-DNA.
    Additional Material: 5 Ill.
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  • 83
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991), S. 1808-1816 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Force-field parameters have been developed for the molecular-mechanics calculation of tertiary carbenium ions with tricyclane structure, for tertiary cyclobutyl and cubyl cations. The cyclobutyl parameters are also applicable to tertiary 7-norbornyl cations. Satisfactory plots are obtained for correlation of the rates of solvolysis with the differences in steric energies between carbenium ions and the corresponding bromides.
    Additional Material: 2 Ill.
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  • 84
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991), S. 934-940 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chiral bicyclic imidazol derivatives 7 and 8 were obtained from D-glucose derivative 9 by a sequence of selective protection/deprotection and intramolecular SN2 reactions. Triols 7 and 8 are analogues of 6-epica-stanospermine (4) and of 3,7a-diepialexine (6), respectively, and are potential glycosidase inhibitors. However, their anti-HIV activity proved to be only marginal.
    Additional Material: 1 Ill.
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  • 85
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raclopride, an antipsychotic 6-methoxysalicylamide (= 2-hydroxy-6-methoxybenzamide) derivative, was shown by titrimetry and UV-pholometry to exist in zwitterionic form at physiological pH. Calculations revealed that the neutral and zwitterionic forms differ considerably in their conformational behavior, the latter form being energetically favored by an intramolecular phenolate-ammonium ionic bond. These findings indicate that raciopride and other halogenated 6-melhoxysalicylamides with a highly acidic phenolic group may not resemble other ortho-methoxybenzamides in their stereoelectronic structure and mode of binding to the dopamine D2 receptor.
    Additional Material: 9 Ill.
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  • 86
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    Helvetica Chimica Acta 74 (1991), S. 1-6 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bridged bis(dihydrooxazole) compound (-)-2 and its silylated derivative (-)-3 have been synthesised as building blocks for chiral ligands. The complex of (-)-3 with CuII has been obtained, and its crystal structure has been determined. The CuII ion is bound to two deprotonated ligands in a twisted tetracoordinated geometry.
    Additional Material: 1 Ill.
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  • 87
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    Helvetica Chimica Acta 74 (1991), S. 55-64 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In presence of crown ether, 2-alkoxy-1,1-dichlorocyclopropanes react with t-BuOK/THF preferentially via ring opening to 2-chloroalk-2-en-1-ones and alkynones or to chlorocyclopropenes. The latter may be intercepted with 1,3-diphenylisobenzofuran, but in the absence of trapping agent, the rearrangement to vinylcarbenes does not occur.
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  • 88
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The efficiency of aromatic ketones as singlet-oxygen (1O2(1Δg)) sensitizers can vary considerably with the electronic configuration of their lowest triplet state and the solvent used. Near-infrared measurements of tie luminescence of singlet oxygen have shown that the quantum yield of singlet-oxygen production (ΦΔ) by 1H-phenalen-1-one (1) is close to unity in both polar (ΦΔ = 0.97±0.03 in methanol) and non-polar solvents (ΦΔ = 0.93±0.04 in benzene). Analysis of the absorption spectra of the ground state and phosphorescence measurements show that the lowest singlet and triplet states have dominant π, π* electronic configurations. The quantum yield of intersystem crossing (ΦISC) of 1, determined by laser flash photolysis (partial-saturation method), is equal to unity. In comparison with other aromatic ketones, these parameters are important for the discussion of the surprisingly high ΦISC of 1 and the efficient energy transfer from its triplet state to molecular oxygen. The 1H-phenalen-1-one (1), being one of the most efficient singlet-oxygen sensitizers in both polar and non-polar media, could be used as a reference sensitizer, in particular in the area of relatively high energies of excitation.
    Additional Material: 3 Ill.
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  • 89
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ingestion of yellow star thistle (Centaurea solstitialis L.) by horses produces parkinsonism due to nigro-pallidal degeneration. The toxin responsible has not been identified so far. A CH2Cl2 extract from the aerial parts of C. solstitialis exhibited significant neurotoxicity against primary neuronal cultures of foetal rat brain. Activity-guided fractionation yielded the known sesquiterpene lactones solstitialin A (1), 13-0-acetylsolstitialin A (3), cynaropicrin (4), and the hitherto unknown 3-O-acetylsolstitialin A (2). In the bioassay with rat foetal full cell culture, 3 and 4 were toxic in a concentration-dependent manner and may be responsible for the ability of the plant to cause neurodegenerative changes in the brain of horses.
    Additional Material: 1 Ill.
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  • 90
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Methoxycarbonyl-Substituted 2,3-Dihydropyridin-4(1H)-one(= Methyl 1,2,3,4-Tetrahydro-4-oxopyridine-1-carboxylate) as Chromophore for Photochemical [2 + 2]-CycloadditionsWith olefins having an electron-acceptor as well as with olefins having an electron-donor substituent, 1-methoxycarbonyl-substituted dihydropyridinone 12 undergoes [2 + 2] cycloaddition in good preparative yields. The photochemical cycloaddition is highly regioselective. For preparative purposes, the ring junction can be equilibrated to the thermodynamically more stable cis-junction. Only the ‘endo’/‘exo’ selectivity at the C-atom bearing the olefin substituent cannot be controlled. The photodimerization of 12 is the only side reaction. Using a slight excess of the olefin, the photodimerization can be suppressed. The protecting group at the N-atom of the dihydropyridinone can be varied in order to introduce an internal sensitizer, as shown with 1-acyl-substituted compound 29, which underwent the cycloaddition process even with sunlight.
    Additional Material: 3 Ill.
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  • 91
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of enantiomerically pure, C2-symmetric 4,4′,5,5′-tetrahydro-2,2′-methylenebis[oxazoles] and 4,4′,5,5′-tetrahydro-2,2′-bi(oxazoles) is reported. Copper complexes with anionic tetrahydromethylenebis[oxazole] ligands are efficient catalysts for the enantioselective cyclopropane formation from olefins and diazo compounds (up to 96% ee in the reaction of styrene with menthyl diazoacetate). Tetrahydrobi(oxazole)iridium(I) complexes were found to catalyze transfer hydrogenations of aryl alkyl ketones with i-PrOH (up to 91% ee). Tetrahydrobi(oxazole)palladium complexes can be used as enantioselective catalysts for allylic nucleophilic substitution (up to 77% ee in the reaction of PhCH=CHCH(OAc)Ph with NaHC(COOMe)2).
    Additional Material: 2 Tab.
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  • 92
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991) 
    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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  • 93
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of isomers and analogs of the neurotoxin 1-methyl-4-phenylpyridinium (MPP+) were examined for their lipophilic behavior. Their partition coefficients in the 1-octanol/H2O system were measured by centrifugal partition chromatography (CPC), which, being much faster and markedly more precise than the classical shake-flask method, proved a very promising alternative for assessing lipophilicity. A smaller-than-expected lipophilicity was shown by the ortho-isomer of MPP+ (M2PP+) and is explained in terms of electronic effects and rigidity, as revealed by UV and NMR spectroscopy, and conformational analysis. Implications of lipophilicity in modulating the in vivo dopaminergic neurotoxicity of the examined compounds are also discussed.
    Additional Material: 2 Ill.
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  • 94
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The regioselectivity of the hydro-alkoxycarbonylation of methyl acrylate, methacrylate, and crotonate catalyzed by [PdCl2L2] complexes (L = phosphine ligands) can be largely controlled by variation of the ligands. PPh3, promotes preferential carbonylation at the α-position, whereas with [(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis-(methylene)]bis[diphenylphosphine] as ligand, the β-position is overwhelmingly carbonylated.
    Additional Material: 1 Tab.
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  • 95
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    Helvetica Chimica Acta 74 (1991), S. 336-342 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic boronolide (1) is prepared in six steps in 4.4% overall yield from acrolein dimer 6 and 1-(trimethyl-silyl)hex-1-yne (8). The latter, by hydromagnesiation, is condensed with 6 to give the corresponding threo-allylic alcohol 13 (Scheme 2). Conversion of 13 to the erythro-allylic alcohol 5 (Scheme 3), bis-hydroxylation, and acetylation afford 1.
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  • 96
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tripeptide and hexapeptide derivatives Boc-Gly-Sar-MeLeu-OH (5b), Boc-Ala-Sar-Sar-OH (6b), Boc-Ala-Sar-MeLeu-OH (7b), and Boc-Abu-Sar-MeLeu-Val-MeLeu-Ala-OH (12b) can be poly-deprotonated (tri- and pentalithio derivatives K and P, respectively), and thus C-alkylated on sarcosine (Sar) moieties with MeI and allyl or PhCH2Br. The polylithiated species are solubilized in THF, and their reactivity modified by excess base (lithium diisopropylamide (LDA)), by added LiCl, and/or the cosolvent N,N′-dimethylpropyleneurea (DMPU). Optimization of the reaction conditions for methylation in the cases of 7b (Table 3) and 12b (Scheme 8) gave products in which the Sar residue of the educt has been transformed into a Me-D-Ala unit in yields of 80 (9c/8c) and 67% (14c/13c), respectively, and with a diastereoselectivity of ca. 4:1. Less selective methylations and benzylations were observed with the tripeptides 5b and 6b containing only one stereogenic center; also, excess base and alkyl halide may lead to double alkylations in those latter two cases (Tables 1 and 2). No epimerization of stereogenic centers was detected under the strong-base conditions. The analysis of the products was accomplished by a combination of NMR and FAB-MS spectroscopy, as well as by hydrolysis to the parent amino acids, subsequent formation of derivatives with isopropyl isocyanate, and GC analysis on the chiral column Chirasil-Val®.
    Additional Material: 3 Tab.
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  • 97
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A large series of orthopramides (= 2-methoxybenzamides), 6-methoxysalicylamides, and 2,6-dimethoxy-benzamides were examined for their affinity to the dopamine D2 receptor. The binding data were correlated with physicochemical parameters and 13C-NMR chemical shifts using the cross-validated partial least-squares method and multiple linear regression analysis. The results quantitate the influence of electronic factors and lipophilicity to D2 receptor binding. They also show that the N-[(1-ethylpyrroIidin-2-yl)methyl] and N-(1-benzylpiperidin-4-yl) side-chains affect the mode of binding of these compounds.
    Additional Material: 4 Ill.
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  • 98
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    Helvetica Chimica Acta 74 (1991), S. 297-303 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acylation of 2,5-dihydro-2,2-dimethyl-1,3-thiazoles leads to 3-acyl-2,3-dihydro-2,2-dimethyl-1,3-thiazoles as potential starting materials for the total synthesis of racemic cephalosporins.
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  • 99
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991), S. 315-322 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The glycosylation of indazolyl anions derived from 4a, b with 2-deoxy-3,5-bis-O-(4-methylbenzoyl)-α-D-erythro-pentofuranosyl chloride (5) is described. The reaction was Stereoselective - exclusive β-D-anomer formation - but regioisomeric N1- and N2-(2′-deoxy-β-D-ribofuranosides) (i.e. 6a and 7a, resp., and 6b and 7b, resp.) were formed in about equal amounts. They were deprotected to yield 8a, b and 9a, b. Compound 1, related to 2′-deoxyadenosine (3), and its regioisomer 2 were obtained from 8b and 9b, respectively, by catalytic hydrogenation. The anomeric configuration as well as the position of glycosylation were determined by 1D NOE-difference spectroscopy. The first protonation site of 1 and 2 was found to be the NH2 group. The N-glycosylic bond of 1H-indazole N1-(2′-deoxyribofuranosides) is more stable than that of the parent purine nucleosides. Compound 1 is no substrate for adenosine deaminase.
    Additional Material: 3 Tab.
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  • 100
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    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 74 (1991), S. 390-396 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An asymmetric synthesis of the analogue 4a of isoproterenol and of di-o-pyvaloylepinephrine 3 which provides both enantiomers in optically pure state is reported. The key step of the method is the highly diastereo-selective reduction (using DIBAL or DIBAL/ZnCl2) of a β-ketosulfoxide 7 which leads, as desired, to the (S)- or the (R)-configuration at C(1) (Schemes 4 and 5).
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