Recent progress in environmental catalytic technology

Recent progress and trends in environmental catalytic technology in Japan are described with emphasis on the catalysts having hybridized functions. In addition to automobile exhaust cleaning, use of environmental catalysts such as titanium oxide photocatalysts is rapidly growing for the control of residential environments, e.g., antimicrobial activity and odor control, as life styles change gradually and the living environment is deteriorating considerably. Many new catalysts are evolving through hybridization of functions. The market of environmental catalyst products in 2005 is estimated 2,000 billion yen/year (photocatalyst: 1,100 billion yen/year).     

Pyrolysis of amines: Infrared spectrum of 1-aminopropene

The infrared absorption spectrum of 1-aminopropene was observed for the first time in the gas phase. This molecule was produced by the thermal decomposition of cyclopropylamine. Two rotational isomers, cis and trans around the C=C double bond, occur. The relative yield of the conformers depends on the experimental conditions. The main conformer could not be identified experimentally, but an ab initio MO calculation suggests that the trans conformer is a little more stable form than the cis. These empirical assignments of the vibrational modes are supported by the ab initio MO calculation.     

Vibrational analysis and conformational studies of allylamine

Infrared absorption spectra of allylamine and its amino-deuterated species were observed in the gas phase and in the low-temperature Ar matrix. An analysis of the spectra showed that there exist mainly three rotational conformers, and possibly one other conformer as a minor component. At room temperature, the skew forms around the CC bond populate about 70%, while the rest are assigned to the cis form(s). On the other hand, two forms around the CN bond, gauche and trans, exist with about equal populations.     

Planarity recognition of large polycyclic aromatic hydrocarbons by various octadecylsilica stationary phases in non-aqueous reversed-phase liquid chromatography

Summary Planarity recognition of polycyclic aromatic hydrocarbons has been investigated using bonded octadecyl stationary phases synthesized in different ways. Retention results indicate apparent differences among the functionalities of the stationary phases, a fact found useful for identifying the functionality of commercially available octadecylsilica (ODS) phases. Retention behevior can be explained by the slit-like structures of polymeric oDS phases, as evidenced by suspension¹³C NMR measurements.     

Synthesis and spectrophotometric study of 2-[2-(3,5-dibromopyridyl,)azo] -5-dimethylaminobenzoic acid as an analytical reagent: Determination of nickel

2-[2-(3,5-Dibrornopyridyl)azo]-5-dimethyIam;nobenzoic acid (3,5-diBr-PAMB) has been synthesized and its potential for the spectrophotometric determination of metals studied. It reacts sensitively with nickel, cobalt, iron and copper, and is particularly useful for nickel. The apparent molar absorptivity in chloroform is 1.50 × 10⁵ l mol^-1 cm^-1 and the Sandell sensitivity is 0.4 ng Ni cm^-2. Nickel reacts with 3.5-diBr-PAMB at pH 4–10; at pH 4–7 the complex can be extracted into chloroform to give a stable purple solution. The optimal calibration range is 0.04–0.4 ppm Ni. Only Cu, Co, Fe, Pd and V interfere seriously but Pd, Cu and V can be masked by thiourea.     

Selective preparation of pyridines, pyridones, and iminopyridines from two different alkynes via azazirconacycles

Selective preparation of pyridine derivatives from two different alkynes and a nitrile was achieved by a novel procedure in which an alkyne and a nitrile couple first to give an azazirconacyclopentadiene followed by reaction with the second alkyne in the presence of 1 equiv of NiCl(2)(PPh(3))(2). This procedure gives only single products of pyridine derivatives from two different symmetrical alkynes and a nitrile. Our novel procedure can be used even with two similar alkyl-substituted alkynes such as 3-hexyne and 4-octyne. Two possible pyridine isomers from 3-hexyne, 4-octyne, and acetonitrile could be completely and independently prepared as single products by this method. The origin of the selectivity comes from the addition order of two different alkynes. This method was applied for the formation of pyridones and iminopyridines using isocyanate and carbodiimide derivatives instead of nitriles, respectively. Reaction of an alkyne with Cp(2)ZrEt(2) and an isocyanate or a carbodiimide gives an azazirconacycle. Treatment of the azazirconacycle with the second alkyne in the presence of 1 equiv of NiCl(2)(PPh(3))(2) gave a pyridone or an iminopyridine derivative. The use of two different unsymmetrical alkynes afforded the pyridine with five different substituents when the first alkyne has a trialkylsilyl group and the second alkyne has a phenyl group as functional groups. On the other hand, azazirconacyclopentadienes reacted with propargyl bromide in the presence of CuCl with excellent regioselectivity to give tetrasubstituted pyridine derivatives as single products. With the assistance of the trialkylsilyl groups, pyridines with all different substituents including H were also prepared.