bluuebunny/crossref_metadata_2025 huggingface dataset:
Reduced Surface Runoff Losses of Metolachlor in Narrow‐Row Compared to Wide‐Row Soybean
Authors: Krutz L. Jason , Koger Clifford H. , Locke Martin A. , Steinriede Robert W.
Published: July 2007

Cultural management practices that reduce the off‐site transport of herbicides applied to row crops are needed to protect surface water quality. A soybean [Glycine max (L.) Merr.] field study was conducted near Stoneville, MS on Sharkey clay to evaluate row spacing (50 cm vs. 100 cm) effects on metolachlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(methoxy‐1‐methylethyl) acetamide] transport. One day after the foliar application of metolachlor to 2.03 m wide by 2.43 m long plots, 60 mm h−1 of simulated rainfall was applied until 25 min of runoff was generated per plot. The calculated mass of metolachlor intercepted by the soybean foliage was greater in narrow‐row than wide‐row soybean, 0.39 kg ha−1 vs. 0.23 kg ha−1, respectively. Field and laboratory studies indicated that less than 2% of the metolachlor intercepted by the soybean foliage was available for foliar wash‐off 1 d after application. Antecedent soil water content at the start of the simulations was lower in narrow‐row soybean. In turn, there was a 1.7‐fold greater time to runoff on narrow‐row plots. The greater time to runoff likely contributed to lower metolachlor concentration in runoff from narrow‐row plots. Cumulative metolachlor losses were significantly greater in wide‐row than narrow‐row soybean, 3.7% vs. 2.2%, respectively. Findings indicate that narrow‐row planting systems may reduce metolachlor runoff following a post‐emergence application.
Skeletal Myocyte Types and Vascularity in the Black Sicilian Pig
Authors: Velotto S. , Varricchio E. , Prisco M. R. Di , Stasi T. , Crasto A.
Published: July 2007

The objective of this study was to verify the presence of giant fibres in the Black Sicilian pig skeletal muscle and to evaluate the effect of sex on histochemical and morphometric characteristics of the myocytes (myofibres) as well as vascularity of the muscle. Twenty Black Sicilian pigs (10 males, 10 females) from a farm in Sicily (Italy) were slaughtered at two years of age. Muscle tissues were obtained from three muscles: psoas major, longissimus dorsi, and trapezius. Myofibres were stained for myosin ATPase, succinic dehydrogenase, and α-amylase-PAS. For all fibre types, area and perimeter were measured. Slow-twitch oxidative fibres, fast-twitch glycolytic fibres and fast-twitch oxidative-glycolytic fibres were histochemically differentiated; an image-analyzing system was used. The results showed no differences between males and females in percentage of the fibre types, but there were significant differences between sexes in size of all the three fibre types. Psoas major muscle had a high percentage of slow-twitch oxidative fibres and contained more capillaries per fibre and per mm2 than trapezius and longissimus dorsi, in which fast-twitch glycolytic fibres dominated. The cross-sectional area of all fibres types was larger in longissimus dorsi than in trapezius and psoas major muscles; the giant fibres were absent in all the muscles studied. Fibre type composition may contribute to the variation of meat quality.
Efficiency of Carbonyl Iron in Prevention of Anaemia in Piglets
Authors: Svoboda M. , Ficek R. , Synková B. , Drábek J.
Published: July 2007

The aim of this study was to evaluate efficiency of elemental iron preparation in the form of carbonyl iron in prevention of iron deficiency in piglets. The piglets in group I (n = 14) were given 210 mg of carbonyl iron orally at the age of 3 days. The piglets in group II (n = 15) received 210 mg of carbonyl iron orally on days 3 and 9. In group III (n = 14) the piglets were injected i.m. with 200 mg Fe3+ as iron dextran. Fourteen days after birth, haemoglobin concentration in group I started to decrease and the piglets developed anaemia. In group II, at the age of 28 days, Hb dropped below 80 g/l and the piglets developed anaemia. Under conditions of this trial, the oral administration of carbonyl iron did not prevent development of iron deficiency in piglets.
Dynamics of Calcaemia, Phosphoraemia and Magnesaemia at Different Prepartal Intakes of Calcium in Dairy Cows
Authors: Zelený T. , Zelený J. , Kroupová V. , Slavík P.
Published: July 2007

The objective of this study was to compare the efficiency of high and low Ca intake in cows with analytically defined levels of calcaemia, phosphoraemia and magnesaemia in the prepartal period, on their postpartal changes important for the diagnosis of postpartal diseases. In dairy cows (Czech Pied cattle) receiving a winter feed ration, the prepartal intake of Ca was adjusted from day 241 of pregnancy to 80% in group A (n = 15) and to 160% of the standard in group B (n = 9). In both groups the concentrations of Ca, P and Mg in blood serum were measured at the beginning of experimental diets, on day 12 before the expected parturition, and on days 1, 2, 3 and 4 after parturition. At the beginning of the experiment (42 days before parturition) the value of calcaemia was 1.82 ± 0.10 mmol l-1, phosphoraemia 1.61 ± 0.37 mmol l-1 and magnesaemia 0.74 ± 0.6 mmol l-1 of blood serum. After the 30-day feeding of experimental diet (day 12 before the expected parturition) higher hypocalcaemia was recorded in group A persisting to day 3 post partum. Phosphoraemia and magnesaemia were at the lower limit of reference values only from day 12 before the expected parturition to day 4 post partum. In group A three cows became recumbent until day 3 post partum with a decrease in magnesaemia below 0.5 mmol l-1. Phosphoraemia and magnesaemia were at the lower limit of reference values only from day 12 before the expected parturition to day 4 post partum. In group A three cows became downed until day 3 post partum with a decrease in magnesaemia below 0.5 mmol l-1. In group B with 160% intake of Ca, 12 days before the expected parturition calcaemia amounted to 2.20 ± 0.27 mmol l-1 and hypocalcaemia ranging from 1.60 ± 0.45 to 1.80 ± 0.26 mmol l-1 of blood serum persisted from day 1 to day 4 post partum. The average level of phosphoraemia in group B was maintained above 1.80 mmol l-1 and magnesaemia was within the range of 0.93 - 1.21 mmol l-1 of blood serum. The results of the nutrition experiment document that for the prepartal adjustment of Ca intake aimed at a reduction in the incidence of the postpartal downer cow syndrome, it is necessary to determine calcaemia, phosphoraemia and magnesaemia in late-pregnant cows. In hypocalcaemia, hypophosphoraemia and especially hypomagnesaemia the prepartal diet with 80% coverage of Ca need leads to a higher risk of the downer cow syndrome accompanied by higher hypomagnesaemia.
Effects of Fungicide Euparen Multi (Tolylfluanid) on Development of Preimplantation Embryos in Mouse
Authors: Domaracký M. , Rehák P. , Legáth J. , Koppel J.
Published: July 2007

The effect of the fungicide Euparen Multi (containing 50% tolylfluanid) on the development of mouse preimplantation embryos was evaluated. Euparen Multi was daily administered per os to female mice (ICR strain) at four different doses of 118, 294, 588 and 1177 mg/kg b.m., beginning on day 1 of pregnancy. Embryos obtained on day 4 of pregnancy were stained by morphological triple staining (Hoechst 33342, propidium iodide, Calcein AM), and the number of nuclei, blastocyst formation, distribution of embryos according to the nucleus number and cell death incidence were determined. Embryos in the experimental groups (except for the lowest dose 118 mg/kg b.m.) showed a highly significant dose-dependent reduction in total cell numbers corresponding to the lower proportion of blastocysts. The occurrence of cell death was significantly increased in all experimental groups, indicating that Euparen Multi is able to cause cell death at relatively low doses. Our data demonstrate that Euparen Multi could induce significant alterations in the preimplantation embryo development.
Influence of Gamma Irradiation on DNA Methylation in Liver of Male Rats and their Offspring
Authors: Kožurková M. , Letavayová L. , Mišúrová E.
Published: July 2007

In the present work, the influence of gamma radiation (3 Gy) on DNA methylation in slowly proliferating liver tissue of adult male rats and their offspring was studied. Total methylation of DNA was determined on the basis of presence of 5-methylcytosine at the inner cytosine of the C-C-G-G sequence by using restriction enzymes, endonuclease Msp I and its isoschisomer Hpa II. It was found that in the liver of control animals, molecular weight distribution of both Msp I and Hpa II digestion products of DNA and the level of DNA methylation were influenced by age mainly between the 3rd and the 7th days of life. At this time, significant difference was found especially in products of cleavage with enzyme Msp I, where an increase in DNA fragments of medium molecular weight (1 - 7 kb) occurred. The changes in the molecular weight distribution of DNA digestion products in the offspring of control rats were accompanied by an increase in the level of total DNA methylation from 29.8% to 67%. In the offspring of irradiated males, the level of DNA methylation was higher in comparison with the offspring of non-irradiated control males, especially on the 3rd day after birth. We suppose that this finding is conjoined with a transgeneration transfer of radiation-induced genome damage.
Neonatal Transient Hypothyroidism in Two Whippet Puppies
Authors: Kolevská J. , Brunclík V. , Bartošová L.
Published: July 2007

The work describes a case of neonatal transient hypothyroidism in two whippet puppies aged 10 weeks. The condition was caused by iodine deficiency either in the diet solely or in combination with a partial peroxidase defect. Goitre developed in the puppies, fed giblets and poultry meat. Laboratory examinations in both puppies showed symptoms of hypothyroidism: non-regenerative anaemia, hypercholesterolaemia, significant decrease in the concentration of total thyroxine and increased concentration of thyrotropin. Ultrasonographic examination demonstrated enlarged thyroid glands. Cytological examination confirmed hyperplastic epithelial cells of the thyroid gland. The clinical condition improved within two months after the diet was changed to commercial dog food and after oral iodine supplementation was started. The iodine substitution was gradually discontinued. Four years later, the clinical and laboratory examinations were carried out in one of the presented patients under completely different circumstances (examination after a car accident). Haematological, biochemical and hormonal examinations were entirely within the reference range.
Effects of Freezing Milk Samples on the Recovery of Alimentary Pathogens and Indicator Microorganisms
Authors: Hubáčková M. , Ryšánek D.
Published: July 2007

The objective of the present study was to determine the effects of freezing and subsequent storage on quantitative results of bacteriologic culturing of selected alimentary pathogens and indicator microorganisms in milk. Two model experiments were carried out. In the first experiment, raw milk samples were frozen and stored at -20 °C for 72 hours, 7 days or 21 days. After thawing, the following counts of indicator microorganisms were assessed: total bacteria count and counts of coliform and psychrotrophic microorganisms. The counts of these microorganisms determined before freezing served as control. In the second experiment, milk samples were inoculated with strains of shigatoxigenic Escherichia coli, enterotoxigenic Staphylococcus aureus and bacteria Listeria monocytogenes and frozen. After storage for the above times, recovery was performed and colony-forming unit counts per millilitre were assessed. It was documented that freezing had a considerable adverse effect on the recovery of shigatoxigenic E. coli (P < 0.01) after 7 days of storage. A decline in counts of coliform bacteria (P < 0.01) and psychrotrophic microorganisms (P < 0.01) was detected as soon as after 72 hours storage. The decline in counts of E. coli and psychrotrophic microorganisms continued with the time of storage - 72 hours and 7 days (P < 0.05); 72 hours and 21 days (P < 0.01). In contrast, no effect was recorded for L. monocytogenes and total bacterial count. Freezing caused a slight increase (P < 0.05) in S. aureus counts in milk samples after 72 hours and 7 days of storage. The results of this study indicate that the freezing of milk samples is unsuitable for sample storage before the assessment of hygienic quality because potential risk of misdiagnosis may be high.
Quality of Honey Harvested and Processed Using Traditional Methods in Rural Areas of Kenya
Authors: Muli E. , Munguti A. , Raina S. K.
Published: July 2007

The honey consumed in most of Africa is harvested from traditional hives and processed using traditional methods. This work presents the quality characteristics of honey samples (n = 72) processed using traditional methods and on sale in various important beekeeping zones in Kenya: West Pokot, Baringo, Mwingi, Tana, North Kinangop, Mbeere, Nandi Hills, Mida Creek, Kakamega and Taita. The quality of the honey was compared to international standards as proposed in the Codex Alimentarius. The quality markers analyzed were moisture, hydromethylfurfural (HMF), sugar content, diastase, proline content, and free acidity. Moisture was determined using a honey refractometer, HMF and Diastase content were determined through spectrophotometry, sugars were determined by High Performance Liquid Chromatography (HPLC), proline was determined through spectrophotometry and free acidity quantified by volumetry - titration technique. Average constituent values were at 16.00 - 21.20% (moisture); 3.70 - 389.36 mg/kg (HMF); 20.83 - 300.6 mg/kg (proline); 8.03 - 56.98 Schade units (diastase); 57.03 - 102.66% (fructose and glucose levels) and 18.00 - 71.85 50 mg/kg (free acidity). Most of the samples had constituent levels within the limits set in the Codex Alimentarius. Traditional honey harvesting and processing methods seem not to have negative effects on the major honey constituents. However, excessive smoking during harvesting had compromised the aroma and flavour of some samples. In an effort to promote beekeeping as an eco-friendly, sustainable alternate source of livelihoods, training in best apiculture practices, improved extension services and establishment of honey marketplaces is being done to improve honey quality in Kenya.
Is Sanfilippo type B in your mind when you see adults with mental retardation and behavioral problems?
Authors: Moog Ute , van Mierlo Ingrid , van Schrojenstein Lantman‐de Valk Henny M.J. , Spaapen Leo , Maaskant Marian A. , Curfs Leopold M.G.
Published: July 2007

Sanfilippo type B is an autosomal recessive mucopolysaccharidosis (MPS IIIB) caused by deficiency of N‐acetyl‐α‐D‐glucosaminidase, a lysosomal enzyme involved in the degradation of heparan sulfate. It is characterized by neurologic degeneration, behavioral problems, and mental decline. Somatic features are relatively mild and patients with this disorder can reach late adulthood. It is the most common subtype of MPS in the Netherlands and probably underdiagnosed in adult persons with mental retardation (MR). In order to increase knowledge on the adult phenotype and natural history in Sanfilippo type B, we present the clinical data of 20 patients with this disorder. Sixteen of them were followed for one to three decades. Six died between 28 and 69 years of age, mainly from pneumonia and cachexia; the surviving patients were 18–63 years old. Apart from the youngest, they had lost mobility at 36–68 years. Most had developed physical problems, in particular in the 4th–6th decade of life: cardiac disease (cardiomyopathy, atrial fibrillations), arthritis, skin blistering, swallowing difficulties requiring feeding by a gastrostomy tube, and seizures. The course of the disease was dominated in most of them by challenging behavioral problems with restlessness, extreme screaming and hitting, difficult to prevent or to treat pharmaceutically. Even in absence of knowledge of the history of an elderly patient with MR, the presence of behavioral problems should prompt metabolic investigation for MPS. © 2007 Wiley‐Liss, Inc.
OCC prepares new insurance guidelines
Authors: Stone Edward J.
Published: July 2007

The guidelines are expected to cover about a dozen key topics.
Bank insurance execs still play second fiddle
Authors: Stone Edward J.
Published: July 2007

Bank insurance executives don't get the respect they deserve. They're still playing second file to other department heads at many banks.
OCC answers questions about advisory letter
Authors: Stone Edward J.
Published: July 2007

Bankers have a lot of questions about the OCC's latest advisory letter.
Expect hot debate on modernization bill
Authors: Stone Edward J.
Published: July 2007

The administration has been working on its own bill to modernize the financial services industry.
Will agents' “stealth” strategy catch bankers napping?
Authors: Stone Edward J.
Published: July 2007

Agents' clever multistate strategy may reverse recent gains before bankers know what hit them.
Buying an agency: More problems than you think
Authors: Stone Edward J.
Published: July 2007

You may face more problems than you realize—even before you open the doors.
NAIC hearing: Many voices, little agreement
Authors: Stone Edward J.
Published: July 2007

Many voices spoke at the recent NAIC hearing. But there was little agreement among opposing groups.
NY parity bill squeaks through before recess; OH and FLA also make changes
Authors: Stone Edward J.
Published: July 2007

It was uncertain whether the bill would pass at all.
Cold shoulder for Ludwig's plea to consumer groups?
Authors: Stone Edward J.
Published: July 2007

Comptroller Ludwig asked consumer groups to fight restrictive state hank insurance laws.
OCC: Banks can sell crop insurance
Authors: Stone Edward J.
Published: July 2007

The OCC declared that crop iiisirrance is incidental to banking hecairse it protects loans to farmers.
Citicorp‐travelers merger creates dilemma for regulators
Authors: Stone Edward J.
Published: July 2007

Glass‐Steagall is not officially dead. But don 9t tell that to citicorp or the Travelers Group.
Bankers lose: House passes financial modernization bill
Authors: Stone Edward J.
Published: July 2007

The House has passed a bill tearing down the walls separating banking, insurance, and equities.
Fragile H.R. 10 coalition may fall apart
Authors: Stone Edward J.
Published: July 2007

When Congress reconvenes, the fragile coalition that supported the bill may fall apart.
Are bank insurance web sites courting legal disaster?
Authors: Stone Edward J.
Published: July 2007

Technology has leapfrogged far ahead of the law. Your bank may be operating in treacherous, unchartered waters. To avoid matching customers with inappropriate products, you must design your Web site carefully.
Court severely curbs bank crop insurance powers
Authors: Stone Edward J.
Published: July 2007

A new court ruling has severely limited national banksypower to sell crop insurance.
House passes financial modernization bill
Authors: Stone Edward J.
Published: July 2007

The final version has customer privacy measures that could hamper marketing. Also, new restrictions on title insurance sales will frustrate bankers.
Ohio case may have broad impact
Authors: Stone Edward J.
Published: July 2007

The lawsuit defeated three restrictive Ohio statutes—including one or more controlled business laws.
Critical factors in database marketing
Authors: Stone Edward J.
Published: July 2007

It's crucial to get top‐down commitment. But it's equally crucial to get proper database marketing system financing.
Liquid chromatographic analysis of certain commercial formulations for non‐opioid analgesics
Authors: Bhushan R. , Gupta Deepak , Mukherjee Aparna
Published: July 2007

A simple and sensitive method for separation and quantitative determination of non‐opioid analgesics from pharmaceutical preparations has been developed and validated. Commercial formulations of three non‐opioid analgesics, viz. paracetamol, ibuprofen and diclofenac, were chosen for present studies. These were extracted, isolated, purified and recrystallized and were characterized by melting point, λmax and IR. Quantitative determination was carried out using HPLC and TLC supplemented with UV spectrophotometry. Copyright © 2007 John Wiley & Sons, Ltd.
A rapid and highly sensitive method for the determination of glimepiride in human plasma by liquid chromatography–electrospray ionization tandem mass spectrometry: application to a pre‐clinical pharmacokinetic study
Authors: Chakradhar Lagishetty , Kallem Rajareddy , Karthik Arumugam , Sundari Bala Tripura , Ramesh Srirangam , Mullangi Ramesh , Srinivas Nuggehally R.
Published: July 2007

A sensitive and specific liquid chromatography–positive electrospray ionization–tandem mass spectrometry method has been developed and validated for the determination of glimepiride (GPD) in human plasma. GPD and the internal standard (IS, glibenclamide) were extracted from a small aliquot of human plasma (200 µL) by a simple liquid–liquid extraction technique using ethyl acetate as extraction solvent. The compounds were separated on a YMC Propack, C18, 4.6 × 50 mm column using a mixture of ammonium acetate buffer, acetonitrile and methanol (30:60:10, v/v) as mobile phase at 0.5 mL/min on an API 4000 Sciex mass spectrometer connected to an Agilent HPLC system. Method validation and pre‐clinical sample analysis was performed as per FDA guidelines and the results met the acceptance criteria. GPD and IS were detected without any interference from human plasma matrix. The method was proved to be accurate and precise at linearity range of 0.02–100.00 ng/mL with a correlation coefficient of 0.999. The method was robust with a lower limit of quantitation of 0.02 ng/mL. Intra‐ and inter‐day accuracies for GPD were 88.60–113.50 and 96.82–103.93%, respectively. The inter‐day precision was better than 12.21%. This method enabled faster and reliable determination of GPD in a pre‐clinical study. Copyright © 2007 John Wiley & Sons, Ltd.
Structure–Fluorescence Contrast Relationship in Cyanine DNA Intercalators: Toward Rational Dye Design
Authors: Fürstenberg Alexandre , Deligeorgiev Todor G. , Gadjev Nikolai I. , Vasilev Aleksey A. , Vauthey Eric
Published: July 2007

The fluorescence enhancement mechanisms of a series of DNA stains of the oxazole yellow (YO) family have been investigated in detail using steady‐state and ultrafast time‐resolved fluorescence spectroscopy. The strong increase in the fluorescence quantum yield of these dyes upon DNA binding is shown to originate from the inhibition of two distinct processes: 1) isomerisation through large‐amplitude motion that non‐radiatively deactivates the excited state within a few picoseconds and 2) formation of weakly emitting H‐dimers. As the H‐dimers are not totally non‐fluorescent, their formation is less efficient than isomerisation as a fluorescent contrast mechanism. The propensity of the dyes to form H‐dimers and thus to reduce their fluorescence contrast upon DNA binding is shown to depend on several of their structural parameters, such as their monomeric (YO) or homodimeric (YOYO) nature, their substitution and their electric charge. Moreover, these parameters also have a substantial influence on the affinity of the dyes for DNA and on the ensuing sensitivity for DNA detection. The results give new insight into the development and optimisation of fluorescent DNA probes with the highest contrast.
Scaling of neuron number and volume of the pulvinar complex in new world primates: Comparisons with humans, other primates, and mammals
Authors: Chalfin Brandon P. , Cheung Desmond T. , Muniz José Augusto P.C. , de Lima Silveira Luiz Carlos , Finlay Barbara L.
Published: July 2007

The lateral posterior nucleus and pulvinar (LP‐pulvinar complex) are the principal thalamic nuclei associated with the elaborate development of the dorsal and ventral streams of the parietal cortex in primates. In humans, a novel site of origin for a subpopulation of pulvinar neurons has been observed, the ganglionic eminence of the telencephalon. This additional site of neuron origin has been proposed to contribute to the pulvinar's evolutionary expansion (Letinic and Rakic [ 2001] Nat Neurosci 4:930–936). Studies of neuron number in the LP‐pulvinar complex in gibbon, chimpanzee, and gorilla compared to humans, however, did not show that the human LP‐pulvinar was unexpectedly large (Armstrong [ 1981] Am J Phys Anthropol 55:369–383). Here we enlarge the allometric basis for comparison by determining neuron number in the LP‐pulvinar complex of six New World primates (Cebus apella, Saimiri ustius, Saguinus midas niger, Alouatta caraya, Aotus azarae, and Callicebus moloch) as well as measuring LP‐pulvinar volume in a further set of 24 species including additional primates, carnivores, and rodents. The volume of the LP‐pulvinar complex scaled with positive allometry with respect to brain volume across all species examined. The scaling of the number of neurons in the LP‐pulvinar complex was extremely similar in New World primates and anthropoid apes, with the human LP‐pulvinar value close to the regression line. Comparison of the relative volumes of the LP‐pulvinar in the larger sample confirmed this observation, and further demonstrated that both primates and carnivores showed a “grade shift” in its size compared to rodents, with the pulvinar comprising a greater proportion of total brain volume across the board. Diurnal, nocturnal, or crepuscular niche did not discriminate LP‐pulvinar size across taxa. J. Comp. Neurol. 504:265–274, 2007. © 2007 Wiley‐Liss, Inc.
Expression of connexins in embryonic mouse neocortical development
Authors: Cina Cima , Bechberger John F. , Ozog Mark A. , Naus Christian C.G.
Published: July 2007

During embryonic development, young neurons migrate from the ventricular zone to the cortical plate of the cerebral cortex. Disturbances in this neuronal migration have been associated with numerous diseases such as mental retardation, double cortex, Down syndrome, and epilepsy. One possible cause of these neuropathologies is an aberration in normal gap junctional communication. At least 20 connexin (Cx) genes encode gap junction proteins in mice and humans. A proper understanding of the role of specific connexins in the developing brain requires the characterization of their spatial and temporal pattern of expression. In the current study we performed all the experiments on mouse developing cortex at embryonic days (E) 14, 16, and 18, timepoints that are highly active with regard to cortical development. Using reverse transcription‐polymerase chain reaction, Western blot analysis, and immunohistochemistry, we found that among the family of gap junction proteins, Cx26, Cx36, Cx37, Cx43, and Cx45 were expressed in the developing cortex of mice, Cx30 and Cx32 were absent, while Cx40 was expressed at a very low level. Our results demonstrate that Cx26 and Cx37 were evenly distributed in the cortical layers of developing brain, while Cx36 and Cx43 were more abundant in the ventricular zone and cortical plate. Cx45 distribution appeared to be more abundant at E18 compared to the other timepoints (E14 and E16). Thus, the present study provides identification and the distribution pattern for Cxs associated with cortical development during normal neuronal migration. J. Comp. Neurol. 504:298–313, 2007. © 2007 Wiley‐Liss, Inc.
Synthesis of Highly Functionalized Anthraquinones and Evaluation of Their Antitumor Activity
Authors: Tietze Lutz F. , Gericke Kersten M. , Schuberth Ingrid
Published: July 2007

Highly functionalized anthraquinones which derive from the natural products mensacarcin, islandicin, and chrysophanol have been efficiently synthesized using a Diels–Alder reaction as key step. The introduction of the proposed pharmacophoric side chain unit has been achieved by an addition of an aryllithium species onto different aldehydes. Furthermore, the antitumor activity of these novel compounds has been studied by the in vitro growth inhibition of human lung carcinoma cells of line A549.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
A Stereoselective Approach to 1,3‐Amino Alcohols Protected as Cyclic Carbamates: Kinetic vs. Thermodynamic Control
Authors: Broustal Garance , Ariza Xavier , Campagne Jean‐Marc , Garcia Jordi , Georges Yohan , Marinetti Angela , Robiette Raphaël
Published: July 2007

Direct enantiocontrolled access to 1,3‐amino alcohols protected as cyclic carbamates is described. The approach is based on the addition of a silyl dienolate to aldehydes in the presence of 10 % of Carreira's catalyst (vinylogous Mukaiyama‐aldol addition). The obtained δ‐hydroxyesters were reduced to pent‐2‐ene‐1,5‐diols, which were converted into the corresponding dicarbamates with tosyl isocyanate. Stereoselective cyclization of these dicarbamates proceeded with 1,3‐asymmetric induction under either thermodynamic or kinetic control to afford enantioselectively six‐membered‐ring cyclic carbamates. Calculations enabled us to rationalize the observed stereoselectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Fabrication of two‐weir structure‐based packed columns for on‐chip solid‐phase extraction of DNA
Authors: Zhong Runtao , Liu Dayu , Yu Linfen , Ye Nannan , Dai Zhongpeng , Qin Jianhua , Lin Bingcheng
Published: July 2007

Microchip‐based packed column SPE of DNA was performed using the microfabricated two‐weir structure within a microchannel. We developed two methods to fabricate the two‐weir structured glass chips: a “two‐side etching/alignment” method and a simplified “one‐side/two‐step etching” method. The former method required a straightforward alignment step, while the latter approach comprised a simplified wet etching process using paraffin wax as the temporary protective layer. Both methods were convenient and rapid as compared to the previous approaches. Through a reversibly sealed bead‐introduction channel, beads can be fed into or out of the chip columns, thus enabling refreshment of the packing materials. Using the proposed chip columns, highly efficient λ‐DNA extractions (average recovery >80%) were performed with good chip‐to‐chip reproducibility (RSD <10%). The on‐chip SPE procedure was completed within 15 min at the flow rate of 3 μL/min and the bulk of the loaded DNA was eluted within a small volume of ∼8 μL. Application of the microchip‐based packed columns was demonstrated by purifying PCR‐amplifiable genomic DNA from human hepatocellular carcinoma (HepG2) cells and human whole blood samples.
Tumor‐reactive CD8+ T‐cell clones in patients after NY‐ESO‐1 peptide vaccination
Authors: Karbach Julia , Gnjatic Sacha , Pauligk Claudia , Bender Armin , Maeurer Markus , Schultze Joachim L. , Nadler Kerstin , Wahle Claudia , Knuth Alexander , Old Lloyd J. , Jäger Elke
Published: July 2007

A major objective of peptide vaccination is the induction of tumor‐reactive CD8+ T‐cells. We have shown that HLA‐A2 positive cancer patients frequently develop an antigen‐specific CD8+ T‐cell response after vaccination with NY‐ESO‐1 peptides p157‐165/p157‐167. These T‐cells are highly reactive with the peptides used for vaccination, but only rarely recognize HLA‐matched, NY‐ESO‐1 expressing tumor cell lines. To address the apparent lack of tumor recognition of vaccine‐induced CD8+ T‐cell responses, we used autologous tumor cells for in vitro stimulation and expansion of pre‐ and postvaccine CD8+ T‐cells. In contrast to standard presensitization methods with peptide‐pulsed antigen‐presenting cells, mixed lymphocyte tumor culture favored the selective expansion of low‐frequency tumor‐reactive T‐cells. In four patients, we were able to demonstrate that antigen‐specific and tumor‐reactive T‐cells are detectable and are indeed elicited as a result of NY‐ESO‐1 peptide vaccination. Further analyses of postvaccine antigen‐specific T‐cells at a clonal level show that vaccine‐induced antigen‐specific T‐cells are heterogeneous in functional activity. These results suggest that the methods of immunomonitoring are critical to identify the proportion of tumor‐reactive T‐cells within the population of vaccine‐induced antigen‐specific effector cells. Our results show that immunization with NY‐ESO‐1 peptides leads to strong tumor‐reactive CD8+ T‐cell responses. Our findings suggest that approaches to peptide vaccination may be improved to induce higher numbers of antigen‐specific T‐cells and to selectively increase the proportion of CD8+ T‐cells that have the capacity to recognize and eliminate tumor cells. © 2007 Wiley‐Liss, Inc.
Borverbindungen, VIII Pyrolyse von Alkyl‐ und Cycloalkylboranen
Authors: Köster Roland , Larbig Wolfgang , Rotermund Gerhard W.
Published: July 2007

Beim Erhitzen von Trialkylboranen auf 200° und höher erhält man je nach Art und Länge der Alkylreste organische Borverbindungen verschiedener Struktur. Die Dehydroborierung (Bildung von B–H‐Verbindungen) ist der eigentlichen pyrolytischen Umwandlung vorgelagert. Die Zusammensetzung der entstehenden Alken‐Gemische wird erläutert. Trialkylborane mit kleinen Alkylresten liefern infolge C–C‐Spaltung im wesentlichen Methylborane. Aus Alkylboranen mit mittleren und langen Alkylgruppen erhält man unter Alken‐ und Wasserstoff‐abspaltung monocyclische sowie bicyclische Borverbindungen. Cycloalkylborane wandeln sich in Bor‐Heterocyclen mit endo‐Bor‐Atomen um. Präparativ ist die Pyrolyse zur Darstellung bestimmter Bor‐Heterocyclen gut geeignet. – Bei fortschreitender Pyrolyse äthylierter Diborane konnten als Reaktionsprodukte auch Organocarborane nachgewiesen werden.
Über zwei neue Verfahren zur Einführung der Propinyliden‐Gruppe
Authors: Eiter Karl , Oediger Hermann
Published: July 2007

Triphenyl‐propargyl‐phosphoniumbromid liefert in flüssigem Ammoniak mit Aldehyden Verbindungen, die den Propinyliden‐Rest HCC–CH enthalten. Diese Verbindungen werden besser aus Aldehyden bzw. Ketonen und der aluminiumorganischen Verbindung des Propargylbromids erhalten, indem man die zunächst entstehenden Hydroxyverbindungen halogeniert und mit 1.5‐Diaza‐bicyclo[4.3.0]nonen‐(5) dehydrohalogeniert.
Cycloaddition von Diazoalkanen an Isothiocyanate
Authors: Martin Dieter , Mucke Wolfgang
Published: July 2007

Isothiocyanate reagieren mit Diazoalkanen, Diazoessigester und ω‐Diazo‐acetophenon unter Bildung substituierter 1.2.3‐Thiadiazole. Substituenteneinfluß und fehlende Lösungsmittelabhängigkeit kennzeichnen die Reaktion als 1.3‐dipolare Cycloaddition. 5‐Phenoxycarbonylamino‐4‐äthoxycarbonyl‐1.2.3‐thiadiazol (IVi) reagiert mit Aminen unter Phenolabspaltung zu Thiadiazolylharnstoffen, die mit Natronlauge zu 5.7‐Dioxo‐4.5.6.7‐tetrahydro‐1.2.3‐thiadiazolo‐[5.4‐d]pyrimidinen VIII cyclisieren.
Über Alkin‐amine, IX Die Umsetzung von 1‐Brom‐3‐Methyl‐pentin‐(1)‐ol‐(3) und dessen Methyläther mit sekundären Aminen
Authors: Wolf Viktor , Block Wolfgang , Piater Helmut
Published: July 2007

3‐Methyl‐1‐brom‐pentin‐(1)‐ol‐(3) reagiert mit Diäthylamin und Piperidin unter Substitution und Addition am C‐Atom 1. Vorwiegend wird der Acetylenalkohol jedoch in Butanon und ein Essigsäurederivat gespalten und zum α‐Ketol hydratisiert. Methoxy‐brom‐methylpentin zeigte erwartungsgemäß keine Ketonspaltung und nur untergeordnete Hydratisierung, jedoch vorwiegend Addition und Substitution am C‐1. Die Konstitution der Spaltprodukte und der Folgeprodukte ß‐Methyl‐ß‐äthyl‐acrylsäure‐diäthylamid (XVII) und 1.1‐Bis‐diäthylamino‐3‐methyl‐pentadien‐(1.3) wurde gesichert.
Zur Kenntnis der Thiosäuren, VI Kondensationsreaktionen der Thioessigsäure 6a‐Thia‐thiophthene und 2‐Thioxo‐2H‐thiapyrane
Authors: Behringer Hans , Grimm Axel
Published: July 2007

Thioessigsäure liefert in Gegenwart von Natriumacetat mit Acetylaceton 2.5‐Dimethyl‐6a‐thia‐thiophthen (I), mit Alkyl‐phenyläthinyl‐ketonen vom Typ II 3‐substituierte 2‐Methyl‐5‐phenyl‐6a‐thia‐thiophthene (III), während Aryl‐phenyläthinyl‐ketone (IV) 4‐Aryl‐6‐phenyl‐(2)‐thioxo‐2H‐thiapyrane (IX) geben. Bei diesen Kondensationen reagiert die Thioessigsäure als Carbonyl‐ bzw. Methylenkomponente; sie wirkt ferner als Schwefelüberträger und bei der Entstehung von I und III auch als Dehydrierungsmittel. – Ein einfaches Verfahren zur Gewinnung von 3.5‐Diphenyl‐ und 3‐Methyl‐5‐phenyl‐dithioliumsalzen (VIII) wird beschrieben.
Aminoacyl‐Derivate des α‐Selenonaphthols und ihre Verwendung zur Peptidsynthese
Authors: Jakubke Hans‐Dieter
Published: July 2007

N‐Carbobenzoxy(Cbo)‐aminosäure‐[α‐selenonaphthylester] lassen sich bequem aus den Cbo‐Aminosäuren und α‐Selenonaphthol nach der Anhydrid‐Methode synthetisieren. Die gut kristallisierenden und beständigen aktivierten Ester geben bei der Amid‐ und Peptid‐Synthese Ausbeuten von 60–97%. Die Entacylierung mit HBr/Eisessig führt zu wenig hygroskopischen Ester‐hydrobromiden, die wiederum mit Cbo‐Aminosäuren zu carboxylaktivierten Cbo‐Peptiden umgesetzt werden können. Bei der Synthese von Cbo‐Glycyl‐L‐phenyl‐alanyl‐glycinäthylester aus Cbo‐Glycyl‐L‐phenyl‐alanin‐[α‐selenonaphthylester] und Glycinäthylester (Anderson‐Callahan‐Test3)) tritt keine Racemisierung ein.
Reaktionen mit Diazocarbonylverbindungen, XXI1). Umsetzung von o‐Chinondiaziden mit ß‐Amino‐crotonsäureäthylester
Authors: Ried Walter , Kleemann Axel
Published: July 2007

o‐Chinondiazide reagieren mit ß‐Amino‐crotonsäureäthylester und dessen N‐Monoalkyl‐derivaten zu o‐Hydroxyarylhydrazonen des 2‐Oxo‐3‐imino‐buttersäureäthylesters. Durch saure Hydrolyse werden diese in die o‐Hydroxyarylhydrazone des 2.3‐Dioxo‐buttersäureäthylesters übergeführt. Die Hydrolyseprodukte lassen sich in vielen Fällen auch durch Kupplung von o‐Chinondiaziden mit Acetessigester gewinnen. Die o‐Hydroxyarylhydrazone des 2.3‐Dioxo‐buttersäureäthylesters liefern mit Phenylhydrazin o‐Hydroxy‐arylazo‐pyrazolone‐(5).
Über Kupfer(I)‐Komplexe mit 8‐Methylmercapto‐ und 8‐Benzylmercapto‐chinolin
Authors: Hein Franz , Vogt Karl‐Heinz
Published: July 2007

Darstellung und Eigenschaften von Kupfer(I)‐Komplexen des Typs [CuL2]X (L = 8‐Methyl‐mercapto‐chinolin; X = [Cu⊖Cl2]⊖, SO4H⊖, ClO4⊖, CO3H⊖ und L = 8‐Benzylmercaptochinolin; X = ClO4⊖) werden beschrieben.
Über die Hexaacetoxy‐diphensäure
Authors: Reichel Ludwig
Published: July 2007

Es wird über die Gewinnung der Hexaacetoxy‐diphensäure aus dem acetylierten Gerbstoffgemisch der Zerreiche (Quercus cerris) berichtet.
Die Oberfläche von Buchen‐Zellstoffasern und ‐Gefäßen mit abnehmendem Lignin‐ und Hemicellulosengehalt im elektronen‐mikroskopischen Bild
Authors: Jayme Georg , Azzola Friedrich Karl
Published: July 2007

Durch Auswertung elektronenoptischer Aufnahmen von Buchen‐Halbzellstoff wird bewiesen, daß bei der stufenweisen Entfernung von Hemicellulose und Lignin in Abhängigkeit von der Ausbeute an den Oberflächen der Zellelemente charakteristische Änderungen der Textur und der topochemischen Verteilung der Komponenten Lignin, Hemicellulose und Cellulose auftreten.
Zur Chemie des Benzolglykols, XIV1). Synthese des 2‐Desoxy‐streptamins2) und des (±)‐Hyosamins
Authors: Nakajima Minoru , Hasegawa Akira , Kurihara Norio
Published: July 2007

2‐Desoxy‐streptamin (1a) wurde stereoselektiv aus 3‐Desoxy‐epi‐inosit dargestellt. Analog wurde rac‐Hyosamin (N‐Methyl‐2‐desoxy‐streptamin) erhalten.
Zur theoretischen Deutung der Massenspektren organischer Verbindungen
Authors: Spiteller Gerhard , Spiteller‐Friedmann Margot
Published: July 2007

Die Zerfallsprozesse organischer Verbindungen im Massenspektrometer lassen sich qualitativ gug verstehen, wenn im Gegensatz zu den bisherigen Anschauungen angenommen wird, daß das angreifende Elektron beim Durchqueren des Moleküls die in seinem Wirkungsbereich liegenden Elektronenorbitale zunächst anregt; dann erst erfolgt die Ionisation, wobei die Wahrscheinlichkeit zur Abspaltung eines Elektrons aus π‐Bindungen wesentlich höher ist als diejenige von Elektronen aus σ‐Bindungen. — Diese Anschauungen erfahren eine Stütze durch das Abfangen massenspektrometrischer Zwischenabbauprodukte, was durch Absenken der thermischen Energie der Moleküle und der kinetischen Energie der angreifenden Elektronen gelingt.
Organische Fluorverbindungen, IX1). Fluorisoprenole
Authors: Machleidt Hans , Grell Wolfgang
Published: July 2007

Lithiumalanat reduziert α.β‐ungesättigte γ‐Fluorcarbonsäureester (z. B. 1) bei —78° zu γ‐Fluorisoprenolen. Bei höherer Temperatur tritt als nächster Reaktionsschritt die reduktive Eliminierung des Fluors ein. Daneben findet, weitgehend Temperatur‐unabhängig, über einen Additions‐Eliminierungsmechanismus eine intramolekulare nucleophile Substitution des Fluors statt. Fortschreitende Reduktion führt zu Hydroxymethyl‐cyclopropanen (z. B. 9). 8‐Fluor‐geraniol (39) läßt sich nicht auf klassischem Wege darstellen. Intermediär gebildetes 6‐Fluormethyl‐3‐carbäthoxy‐hepten‐(5)‐on‐(2) (24) stabilisiert sich durch intramolekulare nucleophile Substitution des Fluors unter Allylumlagerung zum Dihydrofurancarbonsäure‐(3)‐ester 26. Die Synthese von 39 gelingt jedoch durch Carbonyl‐Olefinierung von Fluoraceton mit 4.4‐Äthylendioxy‐pentyliden‐triphenylphosphoran (32), C2‐Verlängerung des resultierenden Fluorketons 30 und Reduktion des 8‐Fluor‐geraniumsäureesters 38 mit LiAlH4.
Umsetzungen von Diazoverbindungen mit Azoverbindungen, III1). 1.3.4‐Oxdiazoline und Hydrazondicarbonsäureester aus der Umsetzung von Diazoessigsäureestern mit Azodicarbonsäureestern: IR‐ und 1H‐NMR‐spektroskopische Untersuchung
Authors: Fahr Egon , Königsdorfer Karl , Scheckenbach Franz
Published: July 2007

Die Umsetzung von Diazoessigsäureestern mit Azodicarbonsäureestern führt nicht, wie bisher angenommen wurde, zu Diaziridin‐Derivaten, sondern bei Reaktionstemperaturen unterhalb 80—100° zu 1.3.4‐Oxdiazolinen (4), oberhalb 80—100° zu Hydrazondicarbonsäureestern (2). Die Struktur der Reaktionsprodukte wird durch IR‐ und 1H‐NMR‐spektroskopische Untersuchungen bewiesen. — Diazoketone liefern mit Azodicarbonsäurediäthylester ausschließlich Hydrazondicarbonsäureester.
Über Isothiazole, IV1). Zur Reaktivität von Methylisothiazolen
Authors: Hofmann Hansdieter
Published: July 2007

Von den C‐methylierten Isothiazolen kondensiert nur 5‐Methyl‐isothiazol (1) mit aktivierten aromatischen Aldehyden (m‐Nitro‐benzaldehyd) zu 1.2‐disubstituierten Äthenen (3). Einführung einer Nitrogruppe in 4‐Stellung von 1 bewirkt auch eine Kondensation der 5‐Methyl‐Gruppe mit nicht‐aktivierten aromatischen Aldehyden (Benzaldehyd), wobei 4 entsteht.
Untersuchungen am Graphitoxyd, IV1). Vergleich der Darstellungsverfahren für Graphitoxyd
Authors: Boehm Hanns‐Petter , Scholz Werner
Published: July 2007

Drei verschiedene Darstellungsverfahren für Graphitoxyd wurden verbessert und die erhaltenen Präparate miteinander verglichen. Das älteste, von Brodie beschriebene Oxydationsverfahren liefert fast weißes, sehr stabiles Graphitoxyd, das sich im Verpuffungspunkt, im Schichtabstand und in seiner spezifischen Oberfläche von den auf andere Weise hergestellten Präparaten unterscheidet.
Die gezielte Synthese von Catena‐Verbindungen, IV1). Einwirkung von Salpetersäure auf 2.5‐disubstituierte Hydrochinonäther
Authors: Schill Gottfried
Published: July 2007

Hydrochinonäther, die in 2.5‐Stellung Alkyl‐ oder substituierte Alkylgruppen tragen, liefern bei der Umsetzung mit Salpetersäure im allgemeinen die entsprechenden Benzochinone. Ausnahmen bilden 2.5‐Bis‐methoxymethyl‐hydrochinonäther (11) und Tetrahydro‐benzo‐[1.2‐b:4.5‐b']dipyran (14), die ebenso wie 2.5‐Dicyan‐hydrochino‐dimethyläther Nitroderivate ergeben. Eine mögliche theoretische Deutung des Reaktionsverlaufes unter Einbeziehung der Ausnahmen wird diskutiert.
Über das Vorkommen von Pro‐anthocyanidinen in schwedischen Farnen
Authors: Fredga Arne , Bendz Gerd
Published: July 2007

Die in Schweden einheimischen Farne (33 Arten) wurden auf Pro‐anthocyanidine untersucht. Bei 26 Arten entstand mit Salzsäure Cyanidin und meistens auch Delphinidin.
Isolierung und Konstitution einer strukturisomeren Chlorogensäure aus den Hülsen von Gleditschia triacanthos
Authors: Weinges Klaus , Seiler Dieter
Published: July 2007

Neben dem schon früher beschriebenen kondensierten Proanthocyanidin wurde aus den Hülsen von Gleditschia triacanthos eine farblose, kristalline Säure C16H18O9 erhalten, die bei alkalischer Verseifung Kaffeesäure (2 und (–)‐Chinasäure (3) liefert und damit die Zusammensetzung einer Chlorogensäure besitzt. Der physikalische Vergleich mit den bekannten strukturisomeren Chlorogensäuren zeigt, daß es sich um 5‐[3.4‐Dihydroxy‐cinnamoyl]‐(–)‐chinsäure (5) handelt.
Anwendung des Freudenbergschen Verschiebungssatzes bei der Konstellationsanalyse
Authors: Fodor Gábor , Ötvös László
Published: July 2007

Die optische Drehwertverschiebung im Laufe der Acetalisierung von vicinalen Diolen, z. B. der Zuckerreihe, wird zur Bestimmung der Konstellationen herangezogen.
Ein neuer Weg in die Bicyclo[3.3.1]nonan‐ und Bicyclo[3.2.1]octan‐Reihe
Authors: Buchta Emil , Billenstein Siegfried
Published: July 2007

Natrium‐malonsäurediäthylester und ein cis,trans‐Isomerengemisch des Ditosylats von 1.3‐Bis‐hydroxymethyl‐cyclohexan liefern beim Kochen in Xylol in 45‐proz. Ausbeute Bicyclo[3.3.1]nonan‐dicarbonsäure‐(3.3)‐diäthylester (5a) neben 10% 1.3‐Bis‐[β.β‐diäthoxycarbonyl‐äthyl]‐cyclohexan (6a) (cis,trans‐Gemisch). Bei Verwendung des cis‐Ditosylats steigt die Ausbeute an 5a auf 60%, diejenige an 6a fällt auf 6%. Zum Strukturbeweis wird 6a in 5 Stufen in 1.3‐Bis‐[2‐carboxy‐äthyl]‐benzol (7b) übergeführt. Aus 5a wird über die Monocarbonsäure 5c und das Brom‐Derivat 5f Bicyclo[3.3.1]nonan (5g) dargestellt. — Aus dem Ditosylat des cis‐1.3‐Bis‐hydroxymethyl‐cyclopentans und Natrium‐malonsäurediäthylester wird auf analogem Weg Bicyclo[3.2.1]octan (8g) erhalten.
Umlagerungen vinyloger Carbonsäurechloride, III. Über 3H‐Tetrachlor‐pentadien‐(1.3)‐al‐(5) und Ketonsynthesen mit 3H‐Tetrachlor‐pentadien‐(1.3)‐säure‐(5)‐chlorid
Authors: Roedig Alfred , Kleppe Hans‐Georg , Märkl Gottfried
Published: July 2007

3H‐Tetrachlor‐pentadien‐(1.3)‐al‐(5) (5a) läßt sich im Gegensatz zum Perchlor‐pentadien‐(1.3)‐al‐(5) (1) nicht in ein Carbonsäurechlorid umlagern. Der Aldehyd 5a gibt mit Carbonyl‐reagenzien normale Derivate und ist mit aktiven Methylenverbindungen kondensierbar. Das entsprechende Säurechlorid 5c liefert bei der Friedel‐Crafts‐ und Grignard‐Reaktion Ketone. Für die Unterschiede gegenüber dem Verhalten der perchlorierten Analoga werden sterische Gründe in Betracht gezogen.
Reaktionen mit Diazocarbonylverbindungen, XXIII. Über p‐Chinon‐trisaminophosphazine
Authors: Ried Walter , Trummlitz Helga
Published: July 2007

p‐Chinondiazide reagieren mit Trisaminophosphinen zu gefärbten, thermisch und hydrolytisch stabilen p‐Chinon‐trisaminophosphazinen, die mit Säuren in Wasser teilweise schwer lösliche Salze bilden. Mit Alkalien können die Phosphazine daraus wieder freigesetzt werden.
Notiz über Alkylen‐trisamino‐phosphazine
Authors: Ried Walter , Hersek Sükran , Trummlitz Helga
Published: July 2007

Diazoalkane kuppeln mit Trisaminophosphinen zu Alkylen‐trisamino‐phosphazinen.
Über die Oxydationsprodukte von Thiocarbonsäureamiden, X. Oxydationsreaktionen an Thiocarbamidsäure‐O‐estern und Dithiocarbamidsäureestern
Authors: Walter Wolfgang , Bode Klaus‐Dieter
Published: July 2007

Die Oxydation von Thiocarbamidsäure‐ und Phenylthiocarbamidsäure‐O‐estern sowie von Dithiocarbamidsäureestern mit Wasserstoffperoxid führt zu den entsprechenden S‐Oxiden. Sterisch wirksame Substituenten erhöhen die Stabilität der S‐Oxide, so daß sie sich isolieren lassen. Substituenten mit —I‐Effekt, jedoch ohne sterische Wirkung, vermögen die Stabilität der S‐Oxide nicht zu erhöhen.
Untersuchungen über Pyrimidine, II. Darstellung und Eigenschaften von 2.6‐Dichlor‐5‐chlormethyl‐pyrimidin
Authors: Brossmer Reinhard , Röhm Erich
Published: July 2007

Aus 5‐Hydroxymethyl‐uracil (1) entsteht bei der Chlorierung mit einer Mischung von Phosphoroxidchlorid und Phosphorpentachlorid in guter Ausbeute 2.6‐Dichlor‐5‐chlormethyl‐pyrimidin (2). Dieses reagiert mit den verschiedensten Verbindungen, die nucleophile Gruppen enthalten. Die drei Chlor‐Atome besitzen eine deutlich abgestufte Reaktionsfähigkeit: Cl‐aliphatisch (allylständig) > Cl an C‐6 > Cl an C‐2. So lassen sich gezielt mono‐, di‐ und trisubstituierte Derivate, z. B. Alkyläther, Phenoläther, Thioäther, Amine und Azide darstellen. Einige dieser Verbindungen besitzen beträchtliche bakteriostatische und fungistatische Wirksamkeit. Die Glykolyse von Tumorzellen wird gehemmt, die Transplantierbarkeit gewisser Tumorarten aufgehoben.