Palladium-catalyzed cycloheptatriene formation by [3+2+2] cocyclization of 2-substituted allylic alcohols and alkynes

Cycloheptatrienes were obtained by the reaction of 2-substituted allylic alcohols with alkynes in the presence of catalytic amounts of palladium complexes and p-toluenesulfonic acid.     

Reactions of substituted furo[3,2-<Emphasis Type="Italic">b</Emphasis>]pyrrole-5-carboxhydrazides and their biological activity

The reactions of substituted furo[3,2-b]pyrrole-5-carboxhydrazides 1 with 5-arylfuran-2-carboxaldehydes 2, 4,5-disubstituted furan-2-carboxaldehydes 3 and thiophene-2-carboxaldehyde 4 has been studied. The advantage of microwave irradiation on some of these reactions was reflected in the reduced reaction time and increased yields. Reactions of 1 with 4-substituted 1,3-oxazol-5(4H)-ones 11 led to diacylhydrazines 13 or to imidazole derivatives 14 depending on the temperature. 1,2,4-Triazole-3-thione 17 was synthesized by two-step reaction of 1 with phenylisothiocyanate and subsequent base-catalyzed cyclization of thiosemicarbazide 16. The effects of hydrazones 5–10 on inhibition of photosynthetic electron transport in spinach chloroplasts and chlorophyll content in the antialgal suspensions of Chlorella vulgaris were investigated.     

Theoretical study and rate constant calculation for the reactions of SH (SD) with Cl2, Br2, and BrCl

The mechanisms of the SH (SD) radicals with Cl2 (R1), Br2 (R2), and BrCl (R3) are investigated theoretically, and the rate constants are calculated using a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the MP2/6-311G(d,p) and MPW1K/6-311G(d,p) levels. Higher-level energies are obtained at the approximate QCISD(T)/6-311++G(3df, 2pd) level using the MP2 geometries as well as by the multicoefficient correlation method based on QCISD (MC-QCISD) using the MPW1K geometries. Complexes with energies less than those of the reactants or products are located at the entrance or the exit channels of these reactions, which indicate that the reactions may proceed via an indirect mechanism. The enthalpies of formation for the species XSH/XSD (X = Cl and Br) are evaluated using hydrogenation working reactions method. By canonical variational transition-state theory (CVT), the rate constants of SH and SD radicals with Cl2, Br2, and BrCl are calculated over a wide temperature range of 200-2000 K at the a-QCISD(T)/6-311++G(3df, 2pd)//MP2/6-311G(d, p) level. Good agreement between the calculated and experimental rate constants is obtained in the measured temperature range. Our calculations show that for SH (SD) + BrCl reaction bromine abstraction (R3a or R3a') leading to the formation of BrSH (BrSD) + Cl in a barrierless process dominants the reaction with the branching ratios for channels 3a and 3a' of 99% at 298 K, which is quite different from the experimental result of k3a'/k3' = 54 +/- 10%. Negative activation energies are found at the higher level for the SH + Br2 and SH + BrCl (Br-abstraction) reactions; as a result, the rate constants show a slightly negative temperature dependence, which is consistent with the determination in the literature. The kinetic isotope effects for the three reactions are "inverse". The values of kH/kD are 0.88, 0.91, and 0.69 at room temperature, respectively, and they increase as the temperature increases.     

Silica nanoparticles for separation of biologically active amines by capillary electrophoresis with laser-induced native fluorescence detection

This paper describes the analysis of biologically active amines by capillary electrophoresis (CE) in conjunction with laser-induced native fluorescence detection. In order to simultaneously analyze amines and acids as well as to achieve high sensitivity, 10 mM formic acid solutions (pH < 4.0) containing silica nanoparticles (SiNPs) were chosen as the background electrolytes. With increasing SiNP concentration, the migration times for seven analytes decrease as a result of increase in electroosmotic flow (EOF) and decrease in their electrophoretic mobilities against EOF. A small EOF generated at pH 3.0 reveals adsorption of SiNPs on the deactivated capillary wall. The decreases in electrophoretic mobilities with increasing SiNP concentration up to 0.3x indicate the interactions between the analytes and the SiNPs. Having a great sensitivity (the limits of detection at a signal-to-noise ratio (S/N) = 3 of 0.09 nM for tryptamine (TA)), high efficiency, and excellent reproducibility (less than 2.4% of the migration times), this developed method has been applied to the analysis of urinal samples with the concentrations of 0.50 +/- 0.02 microM, 0.49 +/- 0.04 microM, and 74 +/- 2 microM for TA, 5-hydroxytryptamine, and tryptophan, respectively. The successful examples demonstrated in this study open up a possibility of using functional nanoparticles for the separation of different analytes by CE.     

Identification (GC and GC-MS) of unsaturated acetates in Elasmopalpus lignosellus and their biological activity (GC-EAD and EAG)

Two insect colonies of Elasmopalpus lignosellus were reared in our laboratory, the first being initiated from pupae obtained from a cornfield in the region of Sete Lagoas, Minas Gerais and the second from a cornfield in the region of Goiania, Goiás. From the two colonies, two extracts were prepared from the pheromone glands of virgin E. lignosellus females. The extract obtained from the first colony was designated as extract 1 while the extract obtained from the second colony was designated as extract 2. Extract 1 was analyzed by gas chromatography-mass spectrometry (GC-MS) with (Z)-9-hexadecenyl acetate [(Z)-9-HDA] and (Z)-11-hexadecenyl acetate [(Z)-11-HDA] being identified and confirmed by the formation of DMDS derivatives. In addition, a third acetate, which could be either (E)-8-hexadecenyl acetate [(E)-8-HDA] or (E)-9-hexadecenyl acetate [(E)-9-HDA] was detected by GC-MS. Extract 2 was analyzed by gas chromatography (GC) and gas chromatography-electroannetography (GC-EAD) revealing the presence of (Z)-11-HDA and (Z)-9-TDA. In addition, the same compounds elicited a response with the E. lignosellus male antenna obtained from the second insect colony. Electroantennography (EAG) screening with the male E. lignosellus antenna (obtained from the second insect colony) was conducted with the 23 possible tetradecenyl acetates (TDA) and 22 hexadecenyl acetates (HDA) as standards. Out of the 23 TDA isomers evaluated, only (Z)-9-TDA elicited a response and out of the 22 HDA [(Z) and (E) isomers gamma2 to delta13] evaluated only (Z)-11-HDA elicited a response. The acetate compositions of two extracts obtained from insects originating from the two states (Minas Gerais and Goiás) of Brazil were different from one another as well as from that obtained from insects in Tifton, GA, USA. The bioactivity data (GC-EAD) of the extract 2 differed from those reported for the Tifton, GA, USA population. These data suggest polymorphism in relation to the insect populations found in Brazil and in the USA. The possibility of the existence of an E. lignosellus sub-species cannot be ruled out.     

Metathesis of hex-1-ene in ionic liquids catalyzed by WCl6

Metathesis of hex-1-ene in ionic liquids catalyzed by WCl₆ was studied. The metathesis is preceded by isomerization of hex-1-ene to hex-2-ene, from which the main reaction product, viz., oct-4-ene, is derived. The WCl₆-1-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF₄) system efficiently catalyzes metathesis of linear olefin, the ionic liquid serving as the reaction medium by forming a stable homogeneous catalytic system with WCl₆. The yields of the metathesis products increase with increasing reaction temperature. The addition of tin-containing promoters leads to a substantial increase in the reaction rate. In the WCl₆-BMIM·BF₄-SnBu₄ system, the selectivity of the formation of oct-4-ene is significantly enhanced.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2094–2097, October, 2004.     

Kinetic resolution of heterocyclic amines by reaction with optically active acid chlorides. The effect of reaction conditions on the diastereoselectivity of acylation of (±)-3-methyl-2,3-dihydro-4H-1,4-benzoxazine

The influence of the reaction conditions (solvent, base) on the diastereoselectivity of acylation of (±)-3-methyl-2,3-dihydro-4H-1,4-benzoxazine with (S)-naproxen and N-tosyl-(S)-proline chlorides was studied. The highest diastereoselectivity was observed for the reaction carried out in benzene in the presence of aliphatic tertiary amines.     

Zur Kenntnis des Natrium-tetrahydroxoaluminat-chlorids Na2[Al(OH)4]Cl

On the Sodium Tetrahydroxoaluminate Chloride Na₂[Al(OH)₄]Cl The hitherto unknown compound Na₂[Al(OH)₄]Cl was prepared by crystallisation from a NaCl containing sodium aluminate solution. According to the X-ray single crystal investigation (tetragonal, space group P4/nmm, a = 7.541 Å, c = 5.059 Å, Z = 2) the compound represents the first example of a crystalline hydroxoaluminate with monomeric [Al(OH)₄]^? anions. Cl^? shows a quadratic anti prismatic coordination to 4 Na⁺ and over hydrogen bonds to 4 O^2? while Na⁺ is octahedrally coordinated by 4 O^2? and 2 Cl^? (axial). The results of the crystal structure analysis are confirmed by ²⁷Al and ²³Na MAS NMR investigations. Na₂[Al(OH)₄]Cl decomposes at about 200°C without intermediates under formation of β-NaAlO₂ and NaCl.     

Synthesen und Reaktionen von Pyridazinderivaten, 11. Mitt.: 5-Acyl-4-pyridazincarbonsäurrester als „key intermediates” für 4-Acylpyridazine und 4-Alkyl-bzw. 4-Arylpyridazino[4,5-d]pyridazin-1 (2H) one

A convenient general method of preparing 4-acylpyridazines (4) is reported. It involves homolytic acylation of ethyl-4-pyridazinecarboxylate yielding ethyl-5-acyl-4-pyridazinecarboxylates (2) which easily can be converted to4 by alkaline hydrolysis followed by decarboxylation. The hitherto unknown pyridazino[4,5-d]pyridazine-1 (2H) ones bearing an alkyl- or arylsubstituent on C-4 (5a-g) were prepared in quantitative yields by reaction of2 with hydrazine.

10. Mitt.:G. Heinisch, A. Jentzsch undI. Kirchner, Tetrahedron Lett.1978, 619.     

Thermal analysis of phenylethynyl end-capped fluorinated imide oligomer afr-pepa-4

Thermal analysis of phenylethynyl end-capped imide oligomer AFR-PEPA-4 was performed to characterize cure reaction, thermal stabilities and semicrystalline behavior of AFR-PEPA-4 oligomer and its cured polyimide. Cured AFR-PEPA-4 polyimide showed high T _gs up to 418°C. Both AFR-PEPA-4 oligomer and polyimide exhibit excellent thermal stabilities comparable to PETI-5 polyimides. AFR-PEPA-4 imide oligomer has a T _m of 330°C and exhibits spherulite crystalline morphology in the film. The crystallinity in AFR-PEPA-4 films could not be regenerated under any annealing conditions after the initial melt.