bluuebunny/crossref_metadata_2025 huggingface dataset:
Sustainable organizations and the green supply chain
Authors: Da Costa Fernando José Pereira , Rodrigues Manoel Gonçalves
Published: February 2024

The theme of green chains arises from the importance assumed by the supply chains affected by the green choice of companies. In other words, management of the green supply chain is increasingly present in organizations, due to the current concern with the environment, which leads organizations to adopt measures to preserve their clientele, one of which is the management of green supply chain. Indeed, by management of a green supply chain is understood the integration between all members of the chain and their partners, with the aim of improving environmental performance. It seeks to reduce waste and to cost savings, promoting the improvement of the image of a sustainable business. Thus, the company gains a competitive advantage. In fact, today many customers seek to buy products and services in business environments that are concerned with this type of issue. The concern becomes environmental management, involving all the members of the chain.
Socio-emotional skills in the context of the Covid-19 Pandemic
Authors: Serafim Ana Luísa , Veloso Cláudia Miranda , Fernandes Sara Veiga , Rivera-Navarro Jesús
Published: February 2024

Emotional competence in teaching is a topic that reveals a lot of interest nowadays, since in addition to being extremely important that teachers feel good about the tasks they are tasked with in terms of work it is also very important that for them to concretize efficiently and feel good on an emotional level. Due to the context of Pandemic by COVID-19 that we are all experiencing, there were several changes that teachers had to adjust to provide a good learning experience for students, which is the reason for this study, so the objective of this investigation is to know the profile of emotional competence of the teachers of the School Groups of the district capital of Bragança in the context of Pandemic by COVID-19, using an anonymous and confidential questionnaire applied to the teachers of the Group of the district capital of Bragança, divided into two parts: a first part, contemplating socio-demographic and professional variables and a second part consisting of the "Veiga Emotional Competence Scale" (EVCE) (Veiga-Branco, 2005, 2011, 2015, 2016, 2017, 2018). The results obtained reveal that there is no influence of sociodemographic or professional variables on the teachers' emotional competence profile or dimensions.
Diagnostic Accuracy of Transabdominal Ultrasonography in Evaluation of Gastric Malignancies: A Cross-sectional Study
Authors: Basti Ram Shenoy , Ganesh MK , Mynalli Soujanya , Braggs Anston Vernon , Kabbinad Banuprakash V
Published: February 2024

Introduction: Gastric cancer (GC) is the fifth most common malignancy worldwide. Transabdominal Ultrasonography (TA- USG) is a non invasive and inexpensive imaging modality that is widely available. However, there is a lack of knowledge regarding the utility of USG among radiologists in the diagnosis of GC. Aim: To evaluate the accuracy of TA-USG in the detection of gastric malignancy. Materials and Methods: This was a cross-sectional study conducted in the Department of Radiodiagnosis at Father Muller Hospital, Mangaluru, Karnataka, India from October 2021 to February 2023. Patients with Upper Gastrointestinal (UGI) symptoms and suspected Gastric Carcinoma, who underwent UGI scopy (n=107) referred from the Departments of Gastrosurgery, Medical Gastroenterology, and Oncosurgery, were included. The sensitivity, specificity, Positive Predictive Value (PPV), and Negative Predictive Value (NPV) of TA-USG in the diagnosis of GC were determined. Results: The TA-USG could diagnose 94 out of 107 cases of malignancy, with the best results in detecting antropyloric malignancy. TA-USG performed worst in early GC. The authors had four cases of early GC, all of which were not diagnosed with TA-USG. The sensitivity, specificity, PPV, NPV, Positive Likelihood Ratio (PLR), Negative Likelihood Ratio (NLR), and accuracy were calculated to be 87.85%, 93.83%, 86.24%, 94.61%, 14.23, 0.13, and 92%, respectively, with a p-value of <0.001. Conclusion: The TA-USG is a valuable tool for detecting gastric malignancy, especially in patients with gastric outlet obstruction, a non distensible stomach, or other risk factors that preclude endoscopy. It can also play a role in regions where UGI endoscopy is not available.
An interprofessional approach to collaborative management of low-back pain in primary care: A scholarly analysis of a successful educational module for prelicensure learners
Authors: Peranson Judith , Weis Carol Ann , Slater Morgan , Plener Joshua , Kopansky-Giles Deborah
Published: February 2024

Objective

In 2008, an interprofessional education (IPE) working group was formed to develop a module on interdisciplinary low-back pain management to fill a curricular gap at our institution. This article describes the program evaluation outcomes and highlights factors contributing to its successful implementation over 8 years through reference to Brigg’s Presage-Process-Product (3-P) Model of Teaching and Learning.

Methods

Program evaluation occurred through administration of a pre- and postmodule Health Professional Collaborative Competency Perception Scale, with scores compared using paired t tests. Descriptive statistics were analyzed from 5-point Likert scales for module session components.

Results

A total of 853 students from 9 health care occupations (medicine, chiropractic, physiotherapy, pharmacy, nursing, nurse practitioner, occupational therapy, physiotherapy assistants, and occupational therapist assistants) participated in 51 iterations of the module from 2011 to 2019, averaging 16 participants each session. All Health Professional Collaborative Competency Perception Scale items significantly improved from pre- to postintervention (p < .001) for learners from 6 health professions. Module components were rated highly, with the majority of learners rating these as 4 (helpful) or 5 (very helpful) for their learning. Participants also improved their scores in perceived history and physical exam comfort, knowledge of pharmacotherapy, management options, and attitudes regarding an interprofessional approach to back pain (p < .001).

Conclusion

This article describes the presage, process factors, and products of this model IPE program that provides learners from various health care professions with an opportunity to gain a deeper understanding of the interdisciplinary management of low-back pain, as demonstrated through improvement in collaborative competencies.
A Review on Various Bio-Resources as a Tool to Reduce Water Pollution Via Eco-Friendly Adsorption Technology
Authors: Devasena S. Subhashree , Padmavathy P. , Rani V. , Ganesan P. , Pereira J. Jaculine
Published: February 2024

Pollution of water bodies is a raising concern in today’s world. Water pollution occurs when harmful compounds enter water bodies and lowers the water quality. It is necessary to treat wastewater before its final disposal into aquatic bodies and environment. Among all the conventional water treatment techniques, adsorption technology attracted much attention owing to its simplicity and eco-friendly nature. Several studies were reported with the application of different kinds of adsorbents in the treatment of both organic and inorganic pollutants in wastewater. However, demand for the development of more suitable adsorbent with selective pollutant removal capacity and good economic feasibility is still rising. Therefore, this review aims to provide a detailed review about the adsorption technology and its mechanisms in pollutant removal process. The adsorption ability of certain important adsorbents were discussed along with future perspectives. Effective, economical, and environmentally friendly wastewater management should be the ultimate objective of any wastewater treatment process. Keeping that in view, this review article highlighted the importance of wastewater management and treatment via adsorption technology.
Systematic literature review of the impact of psychiatric pharmacists
Authors: Ho Jessica L. , Roberts Jenna , Payne Gregory H. , Holzum Dorothy N. , Wilkoff Hannah , Tran Tran , Cobb Carla D. , Moore Tera D. , Lee Kelly C.
Published: February 2024

Introduction

Pharmacists focusing on psychotropic medication management and practicing across a wide variety of healthcare settings have significantly improved patient-level outcomes. The Systematic Literature Review Committee of the American Association of Psychiatric Pharmacists was tasked with compiling a comprehensive database of primary literature highlighting the impact of psychiatric pharmacists on patient-level outcomes.

Methods

A systematic search of literature published from January 1, 1961, to December 31, 2022, was conducted using PubMed and search terms based on a prior American Association of Psychiatric Pharmacists literature review. Publications describing patient-level outcome results associated with pharmacist provision of care in psychiatric/neurologic settings and/or in relation to psychotropic medications were included. The search excluded articles for which there was no pharmacist intervention, no psychiatric disorder treatment, no clinical outcomes, no original research, no access to full text, and/or no English-language version.

Results

A total of 4270 articles were reviewed via PubMed, with 4072 articles excluded based on title, abstract, and/or full text in the initial pass and 208 articles selected for inclusion. A secondary full-text review excluded 11 additional articles, and 5 excluded articles were ultimately included based on a secondary review, for a final total of 202 articles meeting the inclusion criteria. A comprehensive database of these articles was compiled, including details on their study designs and outcomes.

Discussion

The articles included in the final database had a wide range of heterogeneity. While the overall impact of psychiatric pharmacists was positive, the study variability highlights the need for future publications to have more consistent, standardized outcomes with stronger study designs.
The impact of early direct-contact experiences on reducing mental health stigma among student pharmacists: A pilot study
Authors: Tran Amber R. , Patel Saumyaa A. , Loera Lindsey J. , Smith Tawny , Catanzano Samantha
Published: February 2024

Introduction

Mental health–related stigma is a barrier to treatment and recovery for serious mental illnesses (SMIs). Educational training programs demonstrate positive changes in health professional students’ attitudes and stigma toward SMI; however, student pharmacists have minimal opportunity to directly engage with the SMI population. This study aims to assess and compare student pharmacists’ stigma related to SMI before and after participating in a pilot series of direct-contact workshop experiences.

Methods

The 15-item Opening Minds Scale for Healthcare Providers survey was administered to student pharmacists before and after the workshop experiences to measure stigma toward SMI. Five 2-hour workshops were provided to members of a local nonprofit organization serving people with SMI by student pharmacist volunteers detailing a health and wellness topic. The postworkshop survey included free text responses to obtain student feedback.

Results

Twenty-four complete preworkshop surveys were obtained, and most of them had positive attitudes and beliefs at baseline. Thirteen postworkshop surveys were obtained from student pharmacists who participated in a workshop event, and 9 were completed by student pharmacists who did not participate in a workshop event, which were used as a comparator group. Stigma decreased after participating in a workshop event, and those who participated demonstrated a lower degree of stigma versus the comparator group.

Discussion

Direct-contact experiences allow student pharmacists to interact with people with SMI earlier in their training and help reduce stigma toward those with psychiatric disorders. Future research is needed to identify large-scale changes in pharmacy student stigma.
Über Desaminierungsreaktionen I [1]. Zum Abbau primärer aliphatischer Amine mit Hilfe von Aryldiazoniumionen in schwach basischem Milieu
Authors: Moll H. , Vuille R.
Published: December 2004

The deamination of primary aliphatic amines by N‐copulation with diazotized sulfanilic acid in weekly alkaline aqueous solution is investigated.
Strahlungschemie von Kohlenwasserstoffen. 14. Mitteilung. Mögliche Radikalreaktionen in Benzol
Authors: Zimmerli Bernhard , Gäumann Tino
Published: December 2004

The behaviour of benzene and its mixtures with naphthalene, anthracene, cyclohexene and cyclohexadienes under the influence of γ‐irradiation is examined. A mechanism of the product formation in pure benzene is proposed and discussed, that is mainly based on radical reactions between cyclohexadienyl and phenylcyclohexadienyl radicals. The existence of phenyl radicals is shown by the formation of phenylnaphthalenes with naphthalene as additive. The inhibiting effect of cyclohexene and cyclohexadiene on the biphenyl and phenylcyclohexadiene formation can be explained by hydrogen abstraction by the phenyl radicals.
Azofarbstoff‐ CrIII‐Komplexe mit orthokondensierten Sechs‐ und Siebenringen
Authors: Schetty G.
Published: December 2004

From the azo dyestuff 2‐aminophenyl acetic acid → β‐naphthol two isomeric 1:2 chromium complexes could be prepared, which probably are coordinated in the sandwich arrangement. The dyestuff 2‐aminophenyl acetic acid → phenyl‐methyl‐pyrazolone is forming only one 1:2 chromium complex, probably coordinated in the DREW‐PFITZNER arrangement. These complexes are the first proved examples for metal‐containing azo dyestuffs with ortho condensed 6‐ and 7‐membered rings.
Thyrocalcitonin IV. Die Totalsynthese des α‐Thyrocalcitonins
Authors: Riniker B. , Brugger M. , Kamber B. , Sieber P. , Rittel W.
Published: December 2004

The total synthesis of the hypocalcaemic hormone α‐thyrocalcitonin (I) isolated from porcine thyroid glands is reported in detail. By the fragment condensation approach, using coupling procedures known to avoid racemisation, the fully protected dotriacontapeptide sequence II was synthesised. In the build up of II the disulfide ring bridge connecting the cysteine residues 1 and 7 was preformed in the protected nonapeptide fragment 1–9. Simultaneous removal by acidolysis of the nine protecting groups present in II yielded synthetic α‐thyrocalcitonin (I) in a state of high purity and possessing full biological activity; the disulfide bond remained intact during the de‐protection step. On repeated biological assay the synthetic preparation I in the test system of KUMAR et al. [2] was found to possess an activity of 130.8 U/mg peptide.
Die Glykoside von Vincetoxicum hirundinaria, MEDIKUS. 2. Mitteilung: Hydrierungen und Umlagerungen der Genine sowie Massenspektren
Authors: Stöckel K. , Stöcklin W. , Reichstein T.
Published: December 2004

The course of hydrogenation of hirundigenin (7) (C21H30O5), either in acetic acid or ethanol, is strongly influenced by the solvent used. In acetic acid tow moles of hydrogen were taken up very quickly under saturation of the double bond and hydrogenolysis of the hydroxyl group. In ethanol, first the cyclohemiketal ring was slowly opened to a triol, and subsequently the double bond was saturated very slowly. In the case of anhydrohirundigenin (11) hydrogenation of the δ5‐double bond occurred rapidly in acetic acid. Subsequently, the δ8, 14‐ethylenic linkage was also slowly hydrogenated under formation of two stereomeric trans‐derivatives. Vincetogenin consumed two moles of hydrogen in acetic acid, and this resulted in the formation of two isomers as well. Hirundigenin and anhydrohirundigenin are stable toward alkaline hydrolysis, but do rearrange in the presence of acids. One of the isomerisation products of dihydro‐anhydrohirundigenin has been isolated in pure form.
Sur le rôle métabolique de la proferrorosamine A produite par Pseudomonas roseus fluorescens J. C. MARCHAL 1937
Authors: Pouteau‐Thouvenot M. , Choussy M. , Barbier M. , Viscontini M.
Published: December 2004

La biosynthèse de la proferrorosamine A produite par Pseudomonas roseus fluorescens est inhibée par le tryptophane et cette inhibition est levée par l'acide shikimique. A la suite de l'ensemble des résultats acquis, des hypothèses concernant le rôle métabolique de la proferrorosamine A sont formulées et discutées.
Strahlungschemie von Kohlenwasserstoffen. 18. Mitteilung. Hexan‐N2O
Authors: Menger Andrée , Gäumann Tino
Published: December 2004

N2O has the following effects on the radiolysis of light and heavy hexane: It decreases the bimolecular part of the hydrogen production. A corresponding N2‐production amounts to the double of this decrease. The speed of competition is very much faster at higher temperature. The amount of CC bond split yielding alkyl radicals is decreased but not suppressed. The initial amount of hexyl radicals formed is not changed and shows no isotope effect, whereas an additional production of these radicals shows such an effect. They are probably formed by the abstraction by OH‐radicals that are products of the neutralization reaction of N2O− with the hexyl cation. This additional amount contributes mainly to the 3‐hexyl‐isomer. The part of the additional hexene formation that exceeds the amount produced by disproportionation from hexyl radicals is formed in a unimolecular process yielding water as the second product. This is a main product, hexanols and hexanones have not been found. A partial product balance involving hydrogen, hexyl and hexene is presented. The disproportionation/combination ratio for hexyl radicals is according to this balance 0.75.
Note sur les réctions d'échange de restes alcoyle chez des monoesters orthophosphoriques et benzènephosphonique
Authors: Cherbuliez E. , Baehler Br. , Marszalek J. , Weber G. , Rabinowitz J.
Published: December 2004

Experimental data obtained from the study of the behaviour of monoalkyl phosphates ROP(O)(OH)O− or monoalkyl phosphonates C6H5P(O)(OR)O− in aquo‐alcoholic (H2O + R′OH) solutions suggest: (1) in the case of monoalkyl phosphonates the exchange of R and R′ must proceed by a direct alcoholysis; (2) in the case of monoalkyl phosphates, where the scission of the ester at about pH 4,5 proceeds via the intermediate formation of metaphosphate ion PO3−, R′OPO3H− can also be formed by the addition of R′OH to PO3− (competitive to the addition of water) besides direct alcoholysis of ROPO3H−.
Über ein neues Verfahren zur Herstellung von. Acetylenverbindungen. Vorläufige Mitteilung
Authors: Wieland P.
Published: December 2004

A new method for the preparation of acetylenes by reating α‐halogeno‐ or α‐sulfonyloxyketones with p‐toluenesulfonylhydrazine is reported.
Die Glykoside von Marsdenia erecta R. Br. 1. Mitteilung: Isolierungen. Glykoside und Aglykone, 325. Mitteilung
Authors: Saner A. , Zerlentis C. , Stöcklin W. , Reichstein T.
Published: December 2004

Dried leaves of Marsdenia erecta R. Br. gave over 6% of a crude glycoside mixture, the main portion of which consisted of weakly polar material, soluble in ether or chloroform. By mild acid hydrolysis it yielded crude sugars and aglycones. The following four crist. sugars were isolated: D‐cymarose, D‐oleandrose and two bioses: pachybiose and marsectobiose (C14H24O8, new). By PC. and TLC. the presence of digitoxose, canarose, thevetose and 3‐O‐methyl‐6‐deoxyallose could be demonstrated. The crude acyl‐genin mixture contained β‐sitosteryl‐β‐D‐glucopyranoside and three highly hydroxylated pregnane derivatives: drevogenin‐P, 17 β‐marsdenin (C21H32O6, new) and marsectohexol (C21H34O6, new), all partly esterified with acetic, tiglic and benzoic acid. Five crist. acyl‐genins (A1–A5) were isolated by chromatography, but most of them still were mixtures. After alkaline hydrolysis of the crude acyl‐genins 6 acyl‐free compounds were obtained. 4 of them were identical with the above mentioned substances, the other two: 17‐iso‐drevogenin‐P and marsdenin (17 α‐marsdenin) are formed from drevogenin‐P and 17 β‐marsdenin by isomerisation.
Reaktivität von Koordinationsverbindungen XXII [1]. Zur Kinetik der O2‐Aufnahme von Kobalt(II)‐Chelaten 3‐zähniger Amine und Amide
Authors: Donatsch P. , Gerber K. H. , Zuberbühler A. , Fallab S.
Published: December 2004

The kinetics of the interaction between molecular oxygen and the Co2+‐complexes of the three terdentate ligands Z, N‐(2‐picolyl)‐ethylenediamine (PEN), N‐(2‐picolyl)‐oxamide (POA) and diethylenetriamine (DIEN) have been studied spectrophotometrically and using an O2 specific Clark electrode. Starting from the respective 1:1‐ and 1:2‐complexes, the binuclear species ZCoO2(OH)CoZ and Z2CoO2CoZ2 are formed with each ligand. The existence of the former product shows that a minimum of three chelating nitrogen donors is sufficient to make a Co2+‐complex reactive towards O2.

As derived from the empirical rate laws the same general reaction mechanism must be valid for all three systems. In the case of PEN‐ and DIEN‐complexes the oxygen adducts are metastable intermediates and formed in stoichiometric quantities. With POA irreversible formation of cobaltic species is rapid, and O2‐adducts are present in steady state concentrations only, except in strongly basic solutions.
Die Wohl‐Ziegler‐Bromierung von Tiglin‐ und Angelika‐säureestern
Authors: Löffler A. , Pratt R. J. , Rüesch H. P. , Dreiding André S.
Published: December 2004

The Wohl‐Ziegler bromination (with N‐bromo‐succinimide = NBS) of methyl tiglate (1b) gave a 2:1 mixture of methyl γ‐bromotiglate (3b) and methyl β′‐bromotiglate (5b). This ratio of γ‐ to β′‐bromination was unaffected by changes of solvent, catalyst or size of the ester alkoxy group. The same products were obtained from the NBS treatment of methyl angelate (2b). This NBS‐bromination appears to be thermodynamically controlled, since both angelic and tiglic acid as well as their methyl esters were brought into equilibrium (1 ⇆ 2 = > 9:1) with catalytic amounts of NBS.
Versuche zur Synthese von 9β, 10α‐Steroiden; B,C,D‐tricyclische Verbindungen
Authors: Saucy G. , Koch W. , Müller M. , Fürst A.
Published: December 2004

In a search for a new and efficient synthesis of the compound 7, the cyclization of 5 (obtained by a Michael‐reaction from 3 and 4) was studied. Treatment of 5 with strong acid furnished the known dienedione 8. Mild acidic conditions gave the bridged alcohol 9 and other, unidentified products, rather than the desired enone 6. Under basic conditions, 5 did not cyclize to 6, but underwent retro‐Michael reaction. Attempts were then made to convert the dienedione 8 to the 14α‐enone 19. However, both catalytic hydrogenation and lithium‐ammonia reduction of 8 yielded mainly 14β‐products. In some hydrogenation experiments, isomerization of the dienedione 8 to the phenols 13 (major) and 14 (minor) occurred. The stereochemistry of the new isomeric des‐A‐androst‐9‐en‐5, 17‐diones (16, 17 and 20) was determined by chemical and spectroscopic methods.
Versuche zur Biotinsynthese. Herstellung von (3aS, 6aR)‐1, 3‐Dibenzyl‐tetrahydro‐4H‐thieno[3, 4‐d]imidazol‐2,4(1H)‐dion
Authors: Gerecke M. , Zimmermann J.‐P. , Aschwanden W.
Published: December 2004

A modification of the biotin synthesis of Goldberg & Sternbach is described, enantiomers being separated in the first steps and wrong isomers recyclised. The conversion of the lactone 15 to the thiolactone 16 is done by a new method using potassium thioacetate in high boiling solvents.
Absolute Konfiguration von Semi‐α‐carotinon aus Murraya exotica
Authors: Buchecker R. , Yokoyama H. , Eugster C. H.
Published: December 2004

Semi‐α‐carotenone isolated from the fruit of Murraya exotica (Rutaceae) has the same chirality (6‐R) as (+)‐α‐carotene.
3β‐Hydroxy‐14, 15β‐epoxy‐16β‐acetoxy‐5β, 14β‐card‐20(22)‐enolid aus Gitoxigenin. Partialsynthetische Versuche in der Reihe der Herzgifte, 4. Mitteilung [1]
Authors: Boffo Ursul , Linde Horst H. A. , Meyer Kuno
Published: December 2004

Die Teilsynthese von 3β‐Hydroxy‐14, 15β‐epoxy‐16β‐acetoxy‐5β, 14β‐card‐20 (22)‐enolid (IX) wird beschrieben.
Die Ermittlung von realen Gefügezuständen mit Hilfe der technologischen Kalorimetrie — Aussagemöglichkeiten üblicher Abkühlungskurven. Vorläufige Mitteilung
Authors: Wlodawer R.
Published: December 2004

The cooling curve of a casting, recorded by thermocouples, reflects the heat transfer during the solidification periods. E. g. during the intervall from point 3 → 5 (see fig. 1) the primary austenite crystallises. The more austenite there is in the cast iron, the more crystallisation heat from the austenite becomes free, and the larger is the intervall 3 → 5.

Knowing the fusion heat (cal/g austenite), the specific heat (cal/°C g), and the square relationsship time/heat, it is possible to transform the cooling curve into a calorimeter curve (fig. 2). In the logarithmic scale system, the curve‐inclination m ⋍ 1:2. This technological calorimeter curve shows the quantities of heat relatively exactly. From the above findings the quantities of primary austenite and the other texture components can be calculated. In every case we find considerably more austenite than in the equilibrium.

With the aide of this mathematical artifice any cooling curve is the key for the quantitative determination of all texture components, as demonstrated here on the example of cast iron; in principle this is possible for other alloys too.
Préparation de quelques dérivés de l'acétylamino‐5‐thiophénecarbaldéhyde‐2 per Bernard Miche de Malleray
Authors: de Malleray Bernard Miche
Published: December 2004

L'actylamino‐5‐thiophénecarbaléhyde‐2, dont la préparation a été a améliorée, a été condensé avec des corps à méthylène actif. Certains des produits obtenus ont servi è prépaparer des acides aminés thiophéniques puis finalement le monochlorhydrate d'homolysine, corps nouveau. La condensation de l'acétylamino‐5‐thiophénecarbaldéhyde‐2 avec l'acide malonique a fourni non pas l'acide propionique ß‐aminé correspondant, mais l'acide (acétylamino‐5‐thénylidène‐2)‐malonique.
C‐Glycosides V: Données mécanistiques sur l'halogénation d'hydrazones et d'oximes dérivées de sucres. Communication préliminaire
Authors: Tronchet J. M. J. , Baehler Br. , Le‐Hong N. , Livio P. F.
Published: December 2004

The bromination of aldehydo‐sugars p‐nitrophenylhydrazones has been studied and the gem‐bromo‐azo intermediates isolated and characterized in some cases. In the same way, in the chlorination of aldehydo‐sugars oximes gem‐chloro‐nitroso intermediates have been obtained and in some instances isolated. These observations support a SE2′ mechanism for such reactions.
Determination of ΔH°, ΔG°, and ΔS° of the Interaction of Ions with Carrier Antibiotics by Computerized Microcalorimetry
Authors: Früh P. U. , Clerc J. T. , Simon W.
Published: December 2004

ΔH°, ΔG°, and ΔS° — and thereby the equilibrium constant of the interaction of carrier antibiotics with ions — are determined using a microcalorimeter on‐line with a dedicated computer. Thermodynamic data of the interaction of monensin, macrotetrolides and valinomycin with sodium and potassium ions in methanol at 25°C are given.
Die Kristallstruktur von Trikobalt(II)‐dihydroxidsulfat‐dihydrat, Co3(OH)2(SO4)2 · 2 H2O
Authors: Dubler E. , Oswald H. R.
Published: December 2004

Tricobalt (II)‐dihydroxidesulfate‐dihydrate, Co3(OH)2(SO4)2 · 2H2O, is orthorhombic: a = 7.21, b = 9.77, c = 12.86 Å, V = 905.9 Å3, space group D‐Pbcm with four formula units per cell. The atomic positions have been determined by threedimensional Patterson and Fourier synthesis and full‐matrix least‐squares refinement of single crystal X‐ray diffraction data.

The structure shows infinite chains [001] of CoO octahedra sharing one edge with each other. These chains are linked together by alternating SO4 tetrahedra and additional CoO octahedra, thus giving rise to a three‐dimensional network of polyhedra. There is no similarity to the well known layer structures of most hydroxide salts of divalent metals. The SO4 tetrahedra are regular while the CoO octahedra show considerable distortion. The water molecule is coordinated to one Co atom and bonded to sulfate oxygen by two weak hydrogen bridges.
Infrarotspektroskopische und thermoanalytische Untersuchung von Trikobalt(II)‐dihydroxidsulfat‐dihydrat, Co3(OH)2(SO4)2 · 2H2O
Authors: Dubler E. , Oswald H. R.
Published: December 2004

The infrared spectra between 600 and 4000 cm−1 of Co3(OH)2(SO4)2 · 2H2O, Co3(OH)2(SO4)2, and Co3(OD)2(SO4)2 · 2D2O are reported and discussed. The spectra are mainly examined in relation to the binding state of the water molecules. The results are in good agreement with the previously described crystal structure studies. Thermogravimetry, differential thermal analysis and X‐ray diffraction methods were used to investigate the unusual thermal decomposition behaviour of Co3(OH)2(SO4)2 · 2H2O. The kinetics of the dehydration reaction are discussed.
The UV.‐spectrum and the photochemical properties of 1‐ethoxycarbonylimino‐pyridinium ylide
Authors: Gleiter Rolf , Schmidt Dieter , Streith Jacques
Published: December 2004

The UV. spectrum of 1‐ethoxycarbonylimino‐pyridinium ylide 1 has been measured using the stretched film technique. From a Pariser‐Parr‐Pople model the first two bands can be assigned to π* → π transitions. The photorearrangement of 1 leading to the diazepine 3 is discussed.
The Synthesis and Reactions of Yomogi Alcohol. Conversion of the artemisyl skeleton to the santolinyl skeleton by a 1,2‐shift of a vinyl group. Synthesis of santolinatriene
Authors: Thomas Alan F. , Pawlak (née Bucher) Waltraud
Published: December 2004

The synthesis of yomogi alcohol (2, 5, 5‐trimethylhepta‐3,6‐dien‐2‐ol, 2) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out. Acidic reagents open the ring of yomogi alcohol epoxide (16) at with participation of the 6,7‐double‐bond, a shift of the vinyl group results to yield a compound with the santolinyl skeleton. The same reagents are without effect when this double bond reduced. Action of butyllithium of the benzaldehyde acetal (41) of 2, 5‐dimethyl‐4‐vinyl‐2, dihydroxy‐hex‐5‐ene (28), obtained by acid‐catalyzed ring opening of yomogi alcohol epoxide in the presence of benzaldehyde, leads to santolinatriene (42).

This vinyl shift is not observed in the case of O‐acetyl yomogi alcohol epoxide (46), from white a compound believed to be an oxetan 48 (R  COCH3) is formed with concomitent shift of the acetate group. Further unusual reactions of the oxetan are described, and some observation about the epoxidation of sterically hindered allyl alcohols and their acetates are made.
A Total Synthesis of the Alkaloid Rhoeadine. Preliminary communication
Authors: Klötzer W. , Teitel S. , Brossi A.
Published: December 2004

Die Umwandlung des Phtalidisochinolins (–)‐Bicucullin (1) in das Benzazepinalkaloid (+)‐Rhoeadin (8) und in sein unnatürliches Isomeres werden beschrieben.
B, B, B‐Trimethyl‐N, N, N‐triäthylborazin‐ und B, B, B‐Triäthyl‐N, N, N‐trimethylborazin‐molybdäntricarbonyl
Authors: Deckelmann K. , Werner H.
Published: December 2004

The title compounds have been prepared in low yields starting with cis‐(CH3CN)3‐Mo(CO)3 or Mo(CO)6 (photochemical route). The new complexes are generally less stable than the corresponding hexaalkylborazine‐chromium compounds and react very smoothly with Lewis bases by cleavage of the borazine‐metal bond. The IR.‐spectra indicate the similarity of type of bonding in hexaalkylborazine‐molybdenum and ‐chromium complexes.
On the Complex Formation of Tris‐(dipivalomethanato)‐europium with Pyridine
Authors: Huber H. , Seelig J.
Published: December 2004

The complexation of the shift reagent tris‐(dipivalomethanato)‐europium with pyridine in deuteriochloroform has been studied by means of 1H‐NMR. Shift parameters S = 28.0, 9.9, and 9.2 ppm respectively for pyridine protons 2, 3 and 4 are obtained. The results indicate that the shift reagent complexes a single pyridine molecule with an association constant K1 > 100 mole−1l.
Arbeiten über Phosphorsäure‐ und Thiophosphorsäure ester mit einem heterocyclischen Substituenten. 2. Mitteilung. Eine verbesserte Methode zur Herstellung von 1, 3, 4‐Oxadiazol‐2(3H) onen und von Thio‐ und Dithiophosphorsäure‐O, O‐dialkyl‐S‐[(1, 3, 4‐oxadiazol‐2(3H)‐on‐3‐yl)‐methyl]‐estern
Authors: Rüfenacht K.
Published: December 2004

Some 1,3,4‐oxadiazol‐2(2H)‐ones with aliphatic substituents in 5‐position are prepared in good yields and converted via the 3‐hydroxymethyl derivatives to the corresponding 3‐chloromethyl derivatives which are suitable starting materials for the preparation of insecticidal O,O‐dialkyl‐S‐[(5‐subst.‐1,3,4‐oxidiazol‐2(3H)‐one‐3‐yl)‐methyl]‐thiophosphates and dithiophosphates.
Stoffwechselprodukte von Mikroorganismen. 108. Mitteilung. Kristallstrukturanalyse des Chlorothricolid‐methylesters
Authors: Brufani M. , Cerrini S. , Fedeli W. , Mazza F. , Muntwyler R.
Published: December 2004

The X‐ray crystal structure analysis of the Caesium salt of Chlorothricolide methylester, derived from the aglycone of the antibiotic chlorothricin, is described.
3α‐ und 3β‐Amino‐3‐desoxy‐digitoxigenin. Partialsynthetische Versuche in der Reihe der Herzgifte, 5. Mitt.
Authors: Sawlewicz Ludwika , Weiss Ekkehard , Linde Horst H. A. , Meyer Kuno
Published: December 2004

Zusammenfassung. Es wird die Synthese der im Titel genannten 3‐Amino‐cardenolide beschrieben.
Über atropisomere Biphenyl‐Derivate mit einer Pseudoasymmetrieachse
Authors: Helmchen G. , Prelog V.
Published: December 2004

Diastereomeric biphenyl derivatives VIIIa and b have been prepared as first examples of compounds with an axis of pseudoasymmetry. Compound VIIIa was prepared by an unambiguous synthesis from (+)‐V. The absolute configuration of the latter was determined by correlation with (+)‐(R)‐2‐amino‐2′,6‐dimethyl‐6′‐nitro‐biphenyl (XII) and hence the configuration of VIIIa (and therefore also of VIII b) was established.
Application de la réduction polarographique des sulfones aromatiques et des p‐toluènesulfonates d'alkyle à des problèmes de structure
Authors: Gerdil Raymond
Published: December 2004

The polarographic reduction potentials of a series of aromatic sulfones and homologous alkyl tosylates in anhydrous NN‐dimethylformamide have been measured. The relation between reduction potential and structure is discussed on the basis of HMO. calculations, under the assumption that compounds PhSO2X (X = NR1R2, OR, halogens) are sulfone derivatives A critical approach is made of the use of the Taft‐Hammett relation for correlating half‐wave potentials. The different reduction mechanisms at the electrode observed in aprotic and protic media for the above compounds are satisfactorily accounted for by simple MO. calculations.
Etude par spectrométrie de masse de la fragmentation du cyclopentènediol‐3,5‐trans
Authors: Singy G. A. , Buchs A.
Published: December 2004

The decomposition modes of trans cyclopentene‐3, 5‐diol under electron impact have been studied on deuterium labelled analogues. Fragmentation mechanisms are proposed.
Synthese von Haschisch‐Inhaltsstoffen. 5. Mitteilung
Authors: Petrzilka T. , Lusuardi W. G.
Published: December 2004

A (−)‐Δ8‐6a,10a‐trans‐tetrahydrocannabinol analogue, with a methyl‐(3‐dimethyl‐amino‐propyl)‐amino side‐chain instead of the n‐pentyl radical in the naturally occurring product, has been synthesized by condensing 5‐methylamino‐resorcinol tosylate with (+)‐trans‐p‐2,8‐menthadien‐1‐ol.
Isolierung und Aminosäuresequenz von Substanz P aus Pferdedarm
Authors: Studer Rolf Otto , Trzeciak Arnold , Lergier William
Published: December 2004

The isolation and amino acid sequence of substance P from horse intestine is reported. The sequence, H‐Arg‐Pro‐Lys‐Pro‐Gln‐Gln‐Phe‐Phe‐Gly‐Leu‐Met‐NH2 is identical with the sequence reported for substance P isolated from bovine hypothalami.
Die Cyclopropylcarbinyl‐Cyclobutyl‐Homoallyl‐Umlagerung. I. Teil. Synthese von Tricyclo[3.2.1.02,7]octan‐3‐ol, endo‐ und exo‐Tricyclo[3.2.1.03,6]octan‐4‐ol und exo‐Bicyclo[3.2.1]‐oct‐2‐en‐7‐ol
Authors: Geisel Manfred , Grob Cyril A. , Santi Werner , Tschudi Werner
Published: December 2004

Tricyclo[3.2.1.02,7]octan‐3‐ol (1) and its 4‐isomer 7 were obtained by hydroboration of tricyclo[3.2.1.02,7]oct‐3‐ene (5). The former alcohol 1 is quantitatively converted to the isomeric alcohol exo‐bicyclo[3.2.1]oct‐2‐en‐7‐ol (3) by treatment with aqueous acid.

Photolysis of 1‐diazo‐3‐(cyclopent‐3‐enyl)‐propan‐2‐one (12c) gave a high yield of tricyclo[3.2.1.03,6]octan‐4‐one (10a). Reduction of the latter ketone produced a mixture of endo‐ and exo‐tricyclo[3.2.1.03,6]octan‐4‐ol 2 and 9, respectively. Oxidation of these secondary alcohols with silver carbonate in benzene furnished a mixture of the ketone 10a and the lactone 14 of 6‐hydroxy‐bicyclo[2.1.1]heptane‐2‐carboxylic acid. The latter is thought to be formed by oxydation of the hydrate of the strained ketone 10a.
Etude des mécanismes de réarrangement dans la fragmentation des benzoyloxy‐cyclopentànes par impact électronique
Authors: Singy Gérard A. , Buchs Armand
Published: December 2004

The fragmentation modes of 3‐benzoyloxy‐cyclopentene and of 4‐benzoyloxy‐cyclopentene have been studied on deuterium‐labelled analogues. A mathematical model is proposed for the study of the rearrangement reactions which occur during the expulsion of H2O and of \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CO}_2 {\rm H}^. $\end{document} from the molecular ion of 3‐benzoyloxy‐cyclopentene.
Elektronenspinresonanz freier Radikale bei photochemischen Reaktionen von Ketonen in Lösung
Authors: Paul H. , Fischer H.
Published: December 2004

Transient alkyl and acyl radicals are detected and identified by electron spin resonance during UV.‐Irradiation of dialkyl and alkyl aryl ketones in liquid solutions. They are formed by the primary processes of α‐cleavage, intermolecular photoreduction or α‐chloro elimination. For several ketones a temperature dependent competition between α‐cleavage and photo‐reduction is observed indicating a higher energy of activation for the cleavage than for the reduction process. The results are discussed with respect to the photochemical behaviour of the ketones.

Electron spin resonance parameters are reported for a variety of radicals. In particular 13C coupling constants support a sigma type structure of acyl radicals and require a nearly planar radical center of t‐butyl and isopropyl radicals.
Addition of Xanthenyl and Thioxanthenyl Halides to Asymmetric Diarylethylenes and Their 2‐Halogeno‐Derivatives
Authors: Tadros Wadie , Sakla Alfy Badie , Awad Sami Bassili , Abdul‐Malik Nadia Fouad
Published: December 2004

Xanthenyl and thioxanthenyl halides added readily to asymmetric diarylethylenes and their 2‐halogeno‐derivatives to give after dehydrohalogenation 1,1‐diaryl‐2‐[xanthen(orthioxanthen)‐9‐yl]‐ethylenes and 1,1‐diaryl‐2‐halogeno‐2‐[xanthen(or thioxanthen)‐9‐yl]‐ethylenes. The thioxanthenylethylenes were also obtained by another way.

Reactions of these ethylenes with bromine, chlorine or sulfuryl chloride were influenced by the halogen and the nature of the p‐substituent.

Dehydrohalogenation of the 2‐halogenoxanthenyl(or thioxanthenyl) ethylenes gave the corresponding 1,1‐diaryl‐2‐[xanthen(or thioxanthen)‐9‐ylidene]‐ethylenes.
Conformational Study by ESR. of Some Alkyl Substituted 6a‐Thiathiophthene Radical Anions
Authors: Gerson Fabian , Heinzer Josef , Stavaux Madeleine
Published: December 2004

ESR. data are reported for the radical anions (II⊖ to VI⊖) of five alkyl substituted 6a‐thiathiophthenes. Rates and activation parameters for the inversion of the 3,4‐trimethylene chain in IV⊖, V⊖ and VI⊖ have been obtained by means of an iterative least squares computer program ESRCEX. Preferential conformations of the alkyl substituents are discussed in terms of the 〈cos2θ〉 dependence of the β‐proton coupling constants and with the aid of molecular models. Experimental evidence strongly suggests that the partial rotation of the ethyl and isopropyl groups in V⊖ and VI⊖ is correlated with the inversion of the 3,4‐trimethylene chain.
Eine neue Synthese des 3‐[3,4‐Dihydroxy‐phenyl]‐L‐alanins (L‐DOPA) aus L‐Tyrosin
Authors: Bretschneider Hermann , Hohenlohe‐Oehringen Kraft , Kaiser Ado , Wölcke Uwe
Published: December 2004

L‐Tyrosin wird mit Acetylchlorid in Gegenwart von Aluminiumchlorid in 3‐Acetyl‐L‐tyrosin übergeführt, das mit Wasserstoffperoxid in alkalischem Milieu zu L‐DOPA oxydiert wird.
Aromatische [1,5s]‐sigmatropische H‐Verschiebungen in Arylallenen
Authors: Heimgartner Heinz , Zsindely Janos , Hansen Hans‐Jürgen , Schmid Hans
Published: December 2004

1‐Mesityl allene (1), 1‐mesityl‐3‐methyl allene (2) and 1‐mesityl‐3,3‐dimethyl allene (3) rearrange thermally at 150–190° in decane via [1,5s]sigmatropic H‐shifts to yield the o‐quinodimethanes 4, which cyclise to give the 1,2‐dihydronaphthalenes 5 and 6 and/or undergo [1,7 a]sigmatropic H‐shifts to give 1‐mesityl‐(Z)‐buta‐1, 3‐dienes (Z)‐7 and (Z)‐8, respectively (Schemes 1,3,4 and 5) in almost quantitative yields. The activation parameters of these isomerisations are given in Table 1. 1‐Mesityl‐1‐methyl allene (9) isomerises at 190° to give 4,5,7‐trimethyl‐1,2‐dihydronaphthalene (17) in 50% yield (Scheme 6).

2′‐Isopropylphenyl allene (10) in decane rearranges at 170° to 1‐(Z)‐propenyl‐2‐isopropenyl‐benzene ((Z)‐19, Scheme 7). Deuterium labelling experiments show that the rate determining step is an aromatic [1,5s]sigmatropic hydrogen shift from an sp3‐ to an sp‐hybridised carbon atom. The primary kinetic isotopic effect (kH/kD) is 3.45, while the secondary βisotopic effect is 1.20 (Scheme 7 and Table 2).
α‐Chlor‐nitrone IV: Zur Stereochemie der λ‐Lacton‐Synthese und eine Methode zum Aufbau von α‐Methyliden‐λ‐lactonen aus Olefinen. Über synthetische Methoden, 8. (vorläufige) Mitteilung
Authors: Petrzilka Martin , Felix Dorothee , Eschenmoser Albert
Published: December 2004

The Ag+‐induced reaction between N‐cyclohexyl‐α‐chloro‐propionaldonitrone and the two diastereomeric 2‐butenes in liquid SO2 is a stereospecific cis‐addition. The use of N‐cyclo‐hexyl‐α,β‐dichloro‐propionaldonitrone in this type of reaction provides a preparative route from olefines to α‐methylidene‐butyrolactones.
[4+2]‐Cycloadditionen von 1,2‐Dicyanocyclobuten und seine thermische Ringöffnung zum 2,3‐Dicyanobutadien‐1,3
Authors: Belluš Daniel , Bredow Klaus Von , Sauter Hanspeter , Weis Claus D.
Published: December 2004

Facile synthetic routes to 1,2‐dicyanocyclobutene (3), cyclobutene‐1,2‐dicarboxylic acid (56) and derivatives thereof are presented, starting from 1,2‐dicyanocyclobutane (1), a commercially available acrylonitrile cyclodimer.

The favored mode of [4+2]‐cycloadditions of 3 to cyclic dienes with sp3carbon atoms is the endo‐addition (above 90% relative yields of adducts with endo‐cyclobutane ring). Exo‐cycloaddition, however, is preferred by dienes having no sp3‐carbon atom (e.g. furane). Cyclisation reactions involving cis‐vicinal substituents in [4+ 2]‐cycloadducts afford (m.n. 2)‐azapropellanes 18, 74 and 77. 1H‐ and 13C‐NMR. spectra of the stereoisomeric adducts are discussed in detail. The structures of the furane adducts 14 and 15 were determined by 1H‐NMR. using the shift reagent Eu(dpm)3.

Reactive butadienes 32, 53‐55 are obtained in high yield and purity by gasphase thermolysis (380–420°) of the correspondingly substituted cyclobutenes. 2,3‐Dicyanobutadiene‐l, 3 (32) gives good yields of [4 + 2]‐cycloadducts with strained cycloolefines, moderate yields with vinylethers and non‐activated olefins, and no adducts at all with electrophilic dienophiles (8.g. maleic anhydride, fumaronitrile). Thus, reactions of 32 are typical Diels‐Alder reactions with ‘inverse electron demand’.

Some of these primary [4+2]‐cycloadducts (38, 39 and 45) were dehydrogenated to new aromatic ortho‐dinitriles 46‐48.
Synthesis of 2,5‐Diphenylbenzocyclopropene and 7,7‐Dideuteriobenzocyclopropene
Authors: Müller Paul
Published: December 2004

Die Reduktion von 7,7‐Dichloro‐2,5‐diphenylbenzocyclopropen1 (1) mit Aluminiumhydrid liefert in 50% Ausbeute 2,5‐Diphenylbenzocyclopropen (2). Aluminiumdeuterid wandelt 7,7‐Difluorobenzocyclopropen (3) in 7,7‐Dideuteriobenzocyclopropen um.
Synthèses dans la série des bis‐indéno‐fluorènes, IX. Le dihydro‐13,15‐7H‐bis‐indéno[2.1‐b; 2′.1′‐h]fluorène et son dérivé méthylé en position 6
Authors: Chardonnens Louis , Barras Jean‐Luc
Published: December 2004

By condensation according Ullmann of 2‐iodo‐9‐oxo‐fluorene with 3‐bromo‐2‐cyano‐9‐oxo‐fluorene, followed by cyclisation and reduction, the new linear 13,15‐dihydro‐7H‐diindeno[2.1‐b; 2′.1′‐h]fluorene (III) is synthesized in 3 steps. The 6‐methyl‐derivative of II is also obtained in a similar way.
Beckmann Fragmentation and Rearrangement. Part VII. Fragmentation and cyclization of α‐methylthio‐ketoximes. Fragmentation reactions no. 27
Authors: Grob Cyril A. , Ide Junya
Published: December 2004

α‐Methylthio‐propiophenone anti‐oxime p‐toluenesulfonate (tosylate) (12b) fragments quantitatively in 80% ethanol yielding benzonitrile and a methylidenesulfonium ion 15. The syn‐isomer, however, undergoes a Beckmann rearrangement. The fragmentation of α‐methylthio‐isobutyropher one anti‐oxime tosylate (13b) is accompanied by cyclization to the 1, 2‐thiazetin‐1‐ium ion 27, which is hydrolyzed via the sulfimine 29 to the keto sulfide 20 and the keto sulfoxide 30. A comparison of the rates of the α‐alkylthio anti‐ketoxime tosylates 12b and 13b and of the homomorphous oxime tosylates 16b and 17b shows that fragmentation and cyclization are strongly assisted by the sulfur atom. Whereas both the anti‐ and syn‐isomers of α‐amino ketoxime derivatives fragment quantitatively, only the anti‐isomers of α‐alkylthio ketoxime derivatives undergo facile fragmentation.
Totalsynthese von Humaninsulin unter gezielter Bildung der Disulfidbindungen. Vorläufige Mitteilung
Authors: Sieber Peter , Kamber Bruno , Hartmann Albert , Jöhl Albert , Riniker Bernhard , Rittel Werner
Published: December 2004

A preliminary account is given of a total synthesis of human insulin involving directed formation of the three disulfide bonds at different stages of the fragment‐condensation approach. The synthesis was facilitated by the application of two new methods for the selective removal of protecting groups. In the first, two S‐Trt‐protected cysteine residues are converted to the disulfide without affecting S‐Acm‐protected cysteine residues. The second new method consists in a very mild, pH‐controlled, acidolysis of N(α)‐Trt, leaving intact N(α)‐Bpoc and other acid‐labile protecting groups. The last step of the synthesis was the formation of the disulfide bridge between the Acm‐protected cysteine residues A7 and B7 by iodine. Extensive counter‐current distribution yielded the synthetic hormone in pure form. It was compared and found to be identical with natural human insulin. Identification was achieved by means of thinlayer chromatography and electrophoretic procedures, as well as by comparing the pattern of break‐down by enzymes (finger‐printing). The natural and synthetic hormones were crystallized under identical conditions. The synthetic human insulin was found to possess full biological activity in an in vitro system.
Bildung von Estern und Lactonen durch Silberionen‐Katalyse
Authors: Gerlach Hans , Thalmann Adolf
Published: December 2004

A mild and efficient method for the preparation of esters has been found in the silver ion induced reaction of alcohols with 2‐pyridyl esters of thiocarboxylic S‐acids. Examples are given to show the utility of this push button activation for the rapid formation of macrocyclic lactones and esters at room temperature under non‐basic conditions.
Präparative Herstellung von 5‐Desoxy‐L‐arabinose, Xylit und D‐Ribose aus «Diacetonglucose»
Authors: Kiss Joseph , D'Souza Richard , Taschner Paul
Published: December 2004

Simple, reproducible preparative methods are described for the production of the title compounds from diacetone glucose.