A new method for atmospheric nitrogen dioxide measurements using the combination of a stripping coil and fluorescence detection.

A new stripping coil for the collection of nitrogen dioxide (NO2) has been developed to increase its versatility and efficiency. Nitrogen dioxide measurements based on quantitative collection through a reaction coil into an alkaline solution has been examined. Nitrogen dioxide is collected in a 0.1 N NaOH solution. This collection system has an efficiency of nearly 100%. The absorbed nitrogen dioxide has been measured by fluorescence detection with sub-ppbv detection limits. The excitation wavelength at 360 nm and the produced emission wavelength at 405 nm were suitable for nitrite ion measurements.     

Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine

Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.     

Improved preparation of racemic 2-amino-3-(heteroaryl)propanoic acids and related compounds containing a furan or thiophene nucleus

Racemic 2-amino-3-(heteroaryl)propanoic acids (1), mostly with a furan or thiophene nucleus as a heteroaryl group, were synthesized in 48-94% yield by the reduction of 3-(heteroaryl)-2-(hydroxyimino)propanoic acids (5) with zinc dust and formic acid in the presence of a catalytic amount of iron dust at 60 degrees C for 2 h. Under these conditions, unfavorable hydrogenolysis of bromine on the thiophene nucleus does not occur. Traditional N-formylation of the prepared 3-(heteroaryl)alanine (1) with a mixture of formic acid and acetic anhydride afforded 2-(formylamino)-3-(heteroaryl)propanoic acids (6) in 51-95% yield.     

Hydrogen analysis in solid samples by utilizing He metastable atoms induced by TEA CO2 laser plasma in He gas at 1 atm

A TEA CO₂ laser (350 mJ–1.5 J, 10.6 μm, 200 ns, 10 Hz) was focused onto a metal sub-target under He as host gas at 1 atmospheric pressure with a small amount of impurity gas, such as water and ethanol vapors. It was found that the TEA CO₂ laser with the help of the metal sub-target is favorable for generating a strong, large volume helium gas breakdown plasma at 1 atmospheric pressure, in which the helium metastable-excited state was then produced overwhelmingly. While the metal sub-target itself was never ablated. The helium metastable-excited state produced after the strong helium gas breakdown plasma was considered to play an important role in exciting the atoms. This was confirmed by the specific characteristics of the detected H emission, namely the strong intensity with low background, narrow spectral width, and the long lifetime. This technique can be used for gas and solid samples analysis. For nonmetal solid analysis, a metal mesh was introduced in front of the nonmetal sample surface to help initiation of the helium gas breakdown plasma. For metal sample, analysis can be carried out by combining the TEA CO₂ laser and an Nd–YAG laser where the Nd–YAG laser is used to ablate the metal sample. The ablated atoms from the metal sample are then sent into the region of helium gas breakdown plasma induced by the TEA CO₂ laser to be excited through the helium metastable-excited state. This technique can be extended to the analysis of other elements, not limited only to hydrogen, such as halogens.     

An intramolecular diels-alder approach to quassinoids—a stereoselective construction of a-aromatic klaineanone

Thermolysis of a benzocyclobutene derivative ($\text{20}$) prepared from norcamphor produced stereoselectively a tetracyclic compound ($\text{2}$), which was converted to a lactone ($\text{21}$) having correct stereochemistry at C₇, C₈, C₉, C₁₁, C₁₃, and C₁₄ positions of (±)-klaineanone.     

A comparison of supercritical carbon dioxide and organic solvents for the intercalation of 4-phenylazoaniline into a pillared clay mineral

The intercalation of 4-phenylazoaniline (PAA) in supercritical carbon dioxide (SC-CO(2)) into montmorillonite (TMA-Mnt) pillared with tetramethylammonium ions at 313 K and 15 MPa was investigated. The adsorption rate and equilibrium PAA uptake were compared with those in n-hexane, CCl(4) and benzene solutions at 313 K. The XRD and N(2) adsorption/desorption analyses showed that TMA-Mnt after adsorption of PAA in SC-CO(2) had the same pore structure as after adsorption of PAA in normal solvents. SC-CO(2) was found to be a good medium for PAA adsorption owing to its having a relatively high adsorption rate and the highest adsorptivity at the same PAA concentration. The properties of PAA adsorption on TMA-Mnt could be well elucidated by the difference in solubility parameters between liquid and solid phases.     

Ruthenium-catalyzed carbonylative cycloaddition of alpha-keto lactones with alkenes or alkynes: the participation of an ester-carbonyl group in cycloaddition reactions as the two-atom assembling unit

The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction.     

Synthesis of Six-Membered Compounds by Environmentally Friendly Cyclization Using Indirect Electrolysis

[Ni(cyclam)](ClO(4))(2)-catalyzed indirect electroreduction of olefinic bromides produced six-membered compounds in low to high yields. The synthetic intermediate 49 of Ipecac and Corynanthe alkaloids was obtained in 88% yield in a highly stereoselective manner. Lactam 66, the synthetic precursor of tacamonine, was prepared in 49% yield as a mixture of two diastereoisomers. The electrolysis of the bromoacetates gave the debrominated compounds in good yields.