Thallium silver chalcogenides of the orderedanti-PbCl2-structure type

TlAgS, TlAgSe and TlAgTe crystallize with the orderedanti-PbCl₂-structure type, space group Pnma,Z=4. The lattice constants are: TlAgS:a=722.8(3).b=446.6(1),c=833.1(2)pm. TlAgSe:a=747.56(3),b=463.75(2),c=869.0(1) pm. TlAgTe:a=775.9(1),b=486.8(1),c=877.3(2) pm. The crystal structure of TlAgSe was refined from single crystal diffractometer data to a conventionalR-factor of 0.045. The relationship with the BaCu₂S₂-structure type is discussed.On leave from Institute of Inorganic Chemistry, University of Vienna A-1090, Wien, Austria     

Synthesis of isomeric 2-oxazolidinones from (1<Emphasis Type="Italic">R</Emphasis>,2<Emphasis Type="Italic">R</Emphasis>)-and (1<Emphasis Type="Italic">S</Emphasis>,2<Emphasis Type="Italic">S</Emphasis>)-2-amino-1-(4-nitrophenyl)-1,3-propanediols

A synthesis is reported for (4R,5R)-and (4S,5S)-4-hydroxymethyl-5-(4-nitrophenyl)oxazolidin-2-ones and (1′R,4R)-and (1′S,4S)-4-[hydroxy(4-nitrophenyl)methyl]oxazolidin-2-ones from (1R,2R)-and (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediols. The effect of the experimental conditions on the formation of these compounds was studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1562–1570, October, 2007.     

Effect of copper and manganese ions on activities of laccase and peroxidases in three Pleurotus species grown on agricultural wastes

Copper (Cu²⁺) and manganese (Mn²⁺) ions influenced laccase (Lac) and peroxidase production in Pleurotus eryngii, Pleurotus ostreatus, and Pleurotus pulmonarius. In P. eryngii, the optimum Cu²⁺ concentration for Lac production was 1 mM and for peroxidases 10mM, and Mn²⁺ concentration of 5mM led to peaks of Lac and peroxidase activity. In P. ostreatus HAI 493, the highest level of Lac activity was at Cu²⁺ concentrations of 1 and 10 mM and Mn²⁺ concentration of 1mM, respectively. The absence of Cu²⁺ and Mn²⁺ caused the highest levels of peroxidase production. In P. ostreatus HAI 494, the highest level of Lac activity was at a Cu²⁺ concentration of 5 mM and at Mn²⁺ concentration of 1 mM, respectively. High levels of peroxidase activity were found in the medium without and with 1mM Cu²⁺, and at 1 and 5 mM Mn²⁺, respectively. In P. pulmonarius, the highest Lac activity was found in the presence of 5 mM Cu²⁺ and 5 mM Mn²⁺, respectively. The absence of Cu²⁺ and Mn²⁺ as well as their presence at a concentration of 1 mM led to the peaks of peroxidase activities.     

Schiff base complexes of dioxouranium(VI). VII. Dioxouranium(VI) acetate complexes with monobasic bidentate and bibasic tridentateSchiff bases

11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC₆H₄CH=NR oro-HOC₁₀H₆CH=NR (R=C₂H₅,n-C₃H₇,n-C₄H₉ or C₆H₅) and bibasic tridentateSchiff bases,o-HOC₆H₄CH=NR(OH) oro-HOC₁₀H₆CH=NR(OH) (R=–CH₂CH(CH₃)- or —CH₂CH₂CH₂–) have been studied and derivates of the type UO₂(OAc)₂(SBH), UO₂(OAc)₂(SBH)₂, UO₂(OAc)₂(SBH ₂) and UO₂(OAc)₂(SBH ₂)₂ (whereSBH andSBH ₂ represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.

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UO₂ ²⁺-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen

Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO₂(OAc)₂·2H₂O mitSchiff-Basen (L) Komplexe des Typs UO₂(OAc)₂ L bzw. UO₂(OAc)₂ L ₂ isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.

     

Study of the transmetallation of silicon derivatives ofo-carboranes on treatment with BunLi

Silyl-substitutedo-carboranes 1-R-2-Me₃Si(CH₂) _n -1,2-C₂B₁₀H₁₀ (R=Me, Ph;n=0, 1) undergo transmetallation on treatment with BuⁿLi to form lithium derivatives ofo-carboranes, 1-R-2-Li(CH₂) _n -1,2-C₂B₁₀H₁₀, wheren=0, 1. A silicon derivative ofo-carborane, 1-Ph-2-(Me₃SiCHPh)-1,2-C₂B₁₀H₁₀, undergoes neither transmetallation nor metallation at the benzyl CH-group on treatment with BuⁿLi due to significant steric hindrance. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 492–494, March, 1998.     

Determination of cadmium in mixtures with metal ions

A method for the determination of cadmium microamounts in mixtures with metallic ions withE _1/2 near toE _1/2 of cadmium is discussed. For higher selectivity cadmium was extracted in the form of the pyridin-thiocyanate complexes prior to polarography.

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Bestimmung von Cadmium(II) neben anderen Metallionen

Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Cd(II) neben anderen Metallionen mitE _1/2 naheE _1/2(Cd) diskutiert. Zur Erhöhung der Selektivität und Genauigkeit wird eine Pyridin-Thiocyanat-Extraktion vorgeschalten.

     

Prins-Reaktionen mit Arylaldehyden, 5. Mitt.: Zur Umsetzung mit 2-Buten und mit Cyclohexen

By reaction of 2-[(1RS, 2RS)-2-hydroxy-1-methyl-propyl]-2-phenyl-1,3-dithiane (1 a) withcis-2-butene oxide, subsequent reduction and acetalizationc-4,t-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 a) andt-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 b) were synthesized as model compounds. For the same purpose by aldol reaction of cyclohexanone and reduction (1RS, 2SR)-2[(RS)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (7 a), (1RS, 2RS)-2[(SR)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (8 a), and (1RS, 2RS)-2[(RS)-hydroxy-(4-nitrophenyl)methyl]cyclohexanol (8 b) and by acetalization (2 , 4 , 4 a, 8 a)-2,4-bis(4-methoxyphenyl)hexahydro-4H-1,3-benzodioxin (9 a) and (2 , 4 , 4 a, 8 a)-2,4-bis(4-nitrophenyl)hexahydro-4H-1,3-benzodioxin (10 b) were obtained. FromPrins reactions, starting with 2-butene3 a,c-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 c),r-4,t-5-dimethyl-c-6-phenyl-1,3,2-dioxathiane-2,2-dioxide (4), and (2Z, 4E)-1,5-diphenyl-4-methyl-2,4-pentadien-1-on (5), and starting with cyclohexene (E)-3-(4-methoxybenzylidene)cyclohexenyl-4-methoxyphenyl ketone (11) have been isolated in low yields.

4. Mitt.:Griengl, H., Nowak, P., Mh. Chem.109, 11 (1978).     

A convenient synthesis of linear pyranocoumarins. Xanthyletin and 3-Phenylxanthyletin

A convenient synthesis of linear pyranocoumarins, viz., 8,8-dimethyl-2H,8H-benzo[1,2-b; 5,4-b]dipyran-2-one (xanthyletin,1) and 8,8-dimethyl-3-phenyl-2H,8H-benzo[1,2-b; 5,4-b]dipyran-2-one (3-phenylxanthyletin,2) is described. The key steps are blocking the 8-position of appropriate 7-hydroxy-2H-1-benzopyran-2-one derivatives with iodine and 1,1-dimethyl-2-propynylation followed by cyclisation.

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Ein einfacher Syntheseweg zu linearen Pyranocumarinen. Xanthyletin und 3-Phenylxanthyletin

Zusammenfassung Es wird ein vorteilhafter Weg zur Synthese von linearen Pyranocumarinen am Beispiel von Xanthyletin und 3-Phenylxanthyletin gezeigt. Das Syntheseprinzip besteht in einer Blockierung der 8-Position des entsprechenden 7-Hydroxy-2H-1-benzopyran-2-ons mit Jod und einer 1,1-Dimethyl-2-propinylierung mit nachfolgender Cyclisierung.

     

Synthesis and structural studies of Co(II) and Ni(II) complexes of glutaric- and adipic dihydrazides

Glutaric dihydrazide (GDH) and adipic dihydrazide (ADH) have been found to react with Co(II) chloride and Ni(II) chloride and nitrate in ethanolic solution to form complexes of the general empirical compositionsMLCl₂,ML ₂Cl₂ and [NiL ₂(H₂O)₂] (NO₃)₂ whereM=Co(II), Ni(II) andL=GDH,ADH. Tetrahedral geometry has been proposed for 11 complexes of Co(II) and octahedral geometry for the remaining complexes based on measurements of molar conductance, magnetic susceptibility, electronic and ir spectra.

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Synthese und Struktur von Co(II)- und Ni(II)-Komplexen von Glutarsäure- und Adipinsäuredihydraziden

Zusammenfassung Glutarsäuredihydrazid (GDH) und Adipinsäuredihydrazid (ADH) bilden mit Co(II)-Chlorid und Ni(II)-Chlorid bzw.-Nitrat in ethanolischer Lösung Komplexe der generellen ZusammensetzungenMLCl₂,ML ₂Cl₂ und [NiL(H₂O)₂] (NO₃)₂, mitM=Co(II), Ni(II) undL=GDH,ADH. Für 11-Komplexe von Co(II) wird eine tetragonale Geometrie, für alle anderen Komplexe eine oktaedrische Geometrie vorgeschlagen. Die Basis dazu lieferten Messungen der molaren Leitfähigkeit, der magnetischen Suszeptibilität und der UV- bzw. IR-Spektren.

     

Reaktivität der Pyrrolpigmente, 2. Mitt.: Deprotonierung von 3-Pyrrolin-2-onen

Deprotonation of 3,4-dimethyl-3-pyrrolin-2-on (1) int-butyl alcohol/potassiumt-butoxide solutions takes place on the N atom, as shown by¹H/²H exchange andpK _a determinations of1 (pK=17.1), 1,3,4-trimethyl-3-pyrrolin-2-one (pK _a =17.6), and 3,4-dimethyl-5-methoxy-2_H-pyrrole (pK _a =16.7). The SCF-MO approximation MINDO/3 indicates, however, that in the gas phase deprotonation of1 should occur at the C atom.

1.Mitt.:Ribó, J. M., Trull, F., Mh. Chem.110, 201 (1979).     

Supramolecular isomerism in the hydrogen-bonded network of (5<Emphasis Type="Italic">R</Emphasis>,10<Emphasis Type="Italic">R</Emphasis>)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-<Emphasis Type="Italic">cde</Emphasis>]chromene monohydrate

A new compound (5R, 10R)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-cde]chromene monohydrate was obtained from 3,4-dihydroxybenzaldehyde in aerobic basic aqueous ethanol solution in the presence of manganese chloride and triethylamine and crystallized in orthorhombic P2₁2₁2₁ space group (denoted as 1). When 1 was recrystallized from aqueous methanol, it was transformed to another crystal (2) with the same composition but in P2₁/n space group. The drastic difference in the extensive hydrogen bond network makes 1 a 3D and 2 a 2D infinite supramolecular structure, respectively.     

Cis- and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper（Ⅱ） and Silver（Ⅰ）

After the preparation of 1,4-bis（4,5-dihydro-lH-imidazol-2-yl）benzene（bdib）, a nitrogen heterocycle with potential coordination manners of both cis- and trans-configuration forms, three complexes, including cis-[Cuz（bdib ）2（/L-OCH3）2]Cl2·2MeOH（1）, trans-[Cu（bdib）（AcO）2]n（2）, and cis-[Ag2（bdib）2]（NO3）2.2H20（3）, were successfully self-assembled. Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with P1 space group.     

The vibrational spectra of linear and branched perchlorosilanes Si n Cl2n+2 and their simulation using a local symmetry force field

Infrared andRaman vibrational spectra ofn-Si₄Cl₁₀,n-Si₅Cl₁₂,neo-Si₅Cl₁₂ and [(SiCl₃)₃Si]₂ have been measured and assigned. A local symmetry force field has been developed to simulate vibrational spectra of all (noncyclic) perchlorosilanes Si _n Cl_2n+2 known today (n=2, 3, 4, 5, 8). The observed spectra are reproduced satisfactorily

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Die Vibrationsspektren linearer und verzweigter PerchlorsilaneSi _n Cl _2n+2 und deren Simulierung mittels eines lokalen Symmetrie-Kraftfeldes

Zusammenfassung Infrarot- undRaman-Spektren vonn-Si₄Cl₁₀,n-Si₅Cl₁₂,neo-Si₅Cl₁₂ und [(SiCl₃)₃Si]₂ wurden aufgenommen und zugeordnet. Ein lokales Symmetrie-Kraftfeld zur Simulation der Spektren aller bisher bekannten (nicht cyclischen) Perchlorsilane Si _n Cl_2n+2 (n=2, 3, 4, 5, 8) wird angegeben. Die beobachteten Spektren werden zufriedenstellend reproduziert

     

Studies on mixed complexes of Cd(II) with propylenediamine and trimethylenediamine at the dropping mercury electrode

Propylenediamine and trimethylenediamine have been found to form mixed complexes with Cd(II) in aqueous medium with stoichiometries 1:1:1 and 1:1:2. The overall formation constants of these mixed complexes have been evaluated usingSchaap andMcMaster's method. The tendency of the complexes (simple and mixed) to add and substitute another ligand is discussed.

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Polarographische Untersuchungen an gemischten Komplexen von Cd(II) mit Propylendiamin und Trimethylendiamin

Zusammenfassung Propylendiamin und Trimethylendiamin bilden in wäßr. Lösung gemischte Komplexe mit Cd(II) in den stöchiometrischen Zusammensetzungen 1:1:1, 1:1:2 und 1:2:1., Die Bildungskonstanten dieser Komplexe wurden mit der Methode nachSchaap undMcMaster bestimmt. Die Tendenz der (einfachen und gemischten) Komplexe, mit anderen Liganden Addition oder Substitution einzugehen, wird diskutiert.

     

Dipyrrolo[1,2-a:2',1'-c]pyrazines. 8. Electrophilic Substitution in Dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-Dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines. Acylation of Dipyrrolo[1,2-a:2',1'-c]pyrazines

Esters, nitriles, and amides of dipyrrolo[1,2-a:2',1'-c]pyrazines have been synthesized by the acylation of dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines with trichloroacetic acid chloride, p-tosyl isocyanate, and isocyanatophosphoric acid dichloride (Kirsanov isocyanate).     

Conformational Analysis,Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Summary. Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

金属离子导向自组装的磺酰化对氨基苯甲酸配合物的合成与表征

用普通溶液法合成了4个配合物:[Cu(Ts-p-aba)2(phen)(H2O)]n(1)、[Zn(Ts-p-aba)2(phen)(H2O)]·H2O(2)、[Pb(Ts-p-aba)2(phen)]2(3)和{[Pb(Ts-p-aba)(phen)(NO3)](DMF)}n(4)(Ts-p-aba=N-对甲苯磺酰对氨基苯甲酸,phen=菲咯啉,DMF=N,N-二甲基甲酰胺)。X-射线单晶衍射结果表明:配合物1和2均为三斜晶系,P1空间群。配合物1的中心铜离子处于变形的八面体配位环境,并通过配体N-对甲苯磺酰对氨基苯甲酸扩展为一维直线链结构;配合物2是个单核分子,锌离子的配位多面体为四角锥体。配合物3和4均为单斜晶系,P21/c空间群。配合物3由配体N-对甲苯磺酰对氨基苯甲酸桥联成二聚体,铅离子处于变形的八面体配位环境;配合物4是具有一维链状结构的配位聚合物,铅离子处于变形的一面心八面体配位环境。另外,对4个配合物的热稳定性、电化学性能和荧光性质也进行了研究。     

Cloning, characterization, and expression of a new cry2Ab gene from Bacillus thuringiensis strain 14-1

Bacillus thuringiensis is the major source for transfer of genes to impart insect resistance in transgenic plants. Cry2A proteins of B. thuringiensis are promising candidates for management of resistance development in insects owing to their difference from the currently used Cry1A proteins, in structure and insecticidal mechanism. The cry2Ab gene was found to lack a functional promoter and, hence, is cryptic in nature. The cry2Ab7 gene was cloned from a new indigenous B. thuringiensis strain, 14-1. Nucleotide sequencing of the cry2Ab gene cloned from B. thuringiensis strain 14-1 revealed an open reading frame of 1902 bp. The deduced amino acid sequence of Cry2Ab of B. thuringiensis strain 14-1 showed a variation in three amino acid residues in comparison to the holotype sequence, Cry2Ab1. Expression of the newly cloned cry2Ab gene was studied in an acrystalliferous strain of B. thuringiensis (4Q7) by fusing the cry2Ab gene downstream of cry2Aa promoter and orf1+orf2 sequences. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis of a spore-crystal mixture obtained from transformants of B. thuringiensis strain 4Q7 showed production of Cry2Ab protein of about 65 kDa. Alkali solubilized Cry2Ab7 protein showed toxicity against Helicoverpa armigera neonates.     

麝香草的新单萜配糖物的分离与合成

从麝香草(Thymus vulgaris L)的甲醇萃取物中分离出三个单萜配糖物. 用核磁共振光谱确定了它们的结构为对伞花-9-基-β-D-葡糖苷(1), 5-β-D-葡糖苷百里氢醌(2)和2-β-D-葡糖苷百里氢醌(3). 其中1是新化合物, 用以对伞花-9-醇为原料的对映体选择性合成方法确定了化合物1的8位的立体化学为R型.     

Synthesis and some transformation ofN-allyl-N′-methoxy-andN-allyl-N′-tosyloxydiazeneN-oxides

The first representatives ofN-2-alkenyl-N′-alkoxydiazeneN-oxides andN-2-alkenyl-N′-sulphonyloxydiazeneN-oxides have been synthesized. Some reactions of the double bond in these compounds have been studied. The possibility of isomerization ofN-2-alkenyl-N′-alkoxydiazeneN-oxides toN-alk-1-enyl derivatives has been discovered. See Ref. 1 and the references therein. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2262–2265, November, 1998.