Successive Jahn-Teller transitions and the canted pseudospin state in K2PbCu(NO2)6

The successive phase transitions in K₂PbCu(NO₂)₆ has been studied by precise X-ray measurements. The unit cell in Phase III is doubled along each of the cubic principal axes. The experimental results can be interpreted as sequencial cooperative Jahn-Teller transitions where the higher transition is due to the coupling with the uniform distortion, while the lower transition is caused by the coupling with the uniform distortion, while the lower transition is caused by the coupling with the zone boundary phonon mode with $\text{k}{}_0\text{= (}\text{1}\text{2}\text{,}\text{1}\text{2}\text{,}\text{1}\text{2}$. The electronic state in Phase III is characterized as the “canted pseudospin” state.     

Chromatographic preconcentration of copper in environmental and biological samples using 2,4,6-tri(2-pyridyl)-1,3,5-triazine-tetraphenylborate-naphthalene adsorbent

A method was established for the determination of trace amounts of copper using chromatographic preconcentration of copper(I) with 2,4,6-tri(2-pyridyl)-1,3,5-triazine and tetraphenylborate. Copper is quantitatively adsorbed on this adsorbent in the pH range 1.8–10.5 and at flow-rates of 0.2–10 ml/min. The solid mass consisting of copper complex along with naphthalene is dissolved from the column with 5 ml of dimethylformamide. A calibration curve is obeyed over the concentration range 0.2–10.0 g of copper in 5 ml of dimethylformamide. Eight replicate determinations of 3 g of copper gave a mean absorbance of 0.185 with a relative standard deviation of 1.4%. The characteristic concentration for 1% absorption is 0.0143 g/ml (0.103 gmg/ml for direct AAS in aqueous medium). The interference of various ion and salts has been studied and the proposed method has been employed to the determination of copper in biological and water samples.     

Laser Stark and laser-microwave double-resonance spectroscopy of the ν2 band of CD3I

The ν₂ fundamental band of CD₃I was investigated by means of the laser Stark spectroscopy using a 10.6 μm CO₂ laser and an N₂O laser as infrared radiation sources. The assignment was established for about 150 Stakr resonances. Laser-microwave double resonance was used to confirm the assignment. A least-squares analysis of the Stark spectrum gave the molecular constants: μ″ = 1.6504 ± 0.0004 D; μ′ = 1.6479 ± 0.0005 D; ν₀ = 28 461 093.8 ± 3.6 MHz; A′ - A″ = 234.0 ± 1.1 MHz; D_K′ - D_K″ = 0.121 ± 0.085 MHz. The uncertainties are 2.5 times the standard deviations. The single and the double primes refer to the ν₂ and the ground vibrational states, respectively.     

The reactions of evonine and neoevonine alkaloids obtained from Euonymus Sieboldiana blume

The reactions of evonine (1), neoevonine (2), alkaloids of Euonymus Sieboldiana Blume, and their derivatives are described. The structural proofs of some derivatives are included.     

Synthesis of rac-(1R,4aR,9aR)-2-methyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2,3-c]pyridin-6-ol. An unusual double rearrangement leading to the ortho- and para-f oxide-bridged phenylmorphan isomers

In an attempt to obtain the para-f isomer, rac-(1R,4aR,9aR)-2-methyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2,3-c]pyridin-6-ol, via mesylation of an intermediate 9[small alpha]-hydroxyphenylmorphan, we obtained, instead, a rearranged chloro compound with a 5-membered nitrogen ring, 7-chloro-3a-(2,5-dimethoxyphenyl)-1-methyl-octahydroindole. This indole underwent a second rearrangement to give us the desired para-f isomer. The structures of the intermediate indole and the final product were unequivocally established by X-ray crystallography. A resynthesis of the known rac-(1R,4aR,9aR)-2-methyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2,3-c]pyridin-8-ol, the ortho-f isomer, was achieved using the reaction conditions for the para-f isomer, as well as under Mitsunobu reaction conditions where, unusually, the oxide-bridge ring in the 5-phenylmorphan was closed to obtain the desired product. The synthesis of the para-f isomer adds an additional compound to those oxide-bridged phenylmorphans that were initially visualized and synthesized; the establishment of the structure and configuration of 8 of the theoretically possible 12 racemates has now been achieved. The X-ray crystallographic structure analysis of the para-f isomer provides essential data that will be needed to establish the configuration of a ligand necessary to interact with an opioid receptor.