Kazuo Komatsu

The alkylamination of naphthazarin

Abstract The alkylamination of naphthazarin ( 1 ) was investigated. TLC of the reaction product of 1 with n-butylamine under refluxing conditions showed the presence of at least 16 coloured spots. 2-Butylaminonaphthazarin ( 2 ) and leuco-5-butylamino-8-hydroxynaphthoquinone ( 3 ) in trace amounts and 4,8-bis(butylamino)-1,5-naphthoquinone ( 4 , 9·9%) and 3,5-bis(butylamino)-8-hydroxynaphthoquinone ( 5 , 25·6%) were isolated. The alkylamination largely depends on the reaction temperature and the molar ratio of the amine. At low temperature (0°C), 2 was obtained in 73·7% yield and the optimum conditions were using a 10–15 molar ratio of amine with respect to 1. The reactivity of 2 with amines depends on the reaction temperature. Compounds 5 was obtained in 82·3% yield by the reaction of 2 with the amine under refluxing conditions. A novel leuco-compound of 5 was synthesized and its structure was shown to be 3,5-bis(butylamino)-6,7-dihydro-1-hydroxy-naphthalene-4,8-dione. The amination mechanism is also discussed.

Development of Semimicro LC/NMR and Its Applications in Cosmetic Ingredients Analysis

セミミクロLCに, 内径3mmのプローブを組み込んだ400MHzのNMRを接続し, セミミクロLC/NMR装置を開発した。セミミクロカラムには内径1.5mm長さ25cmのカラムを用い, 移動相に重水と重アセトニトリルの混液を流量100-125μL/minで用いて種々の検討を行った。本装置は, 1時間あたりわずか6-7.5mLの移動相しか必要とせず, その優れたコストパフォーマンスにより, 高価な重水素化溶媒を移動相に使用できるので, 容易に移動相信号を極小化することが可能となった。また, セミミクロLCの濃縮効果による感度の向上が得られ, セミミクロLC/NMRの優れた性能が示された。本法の, p-ヒドロキシ安息香酸エチルを試料としたときの解析限界は, ON-FLOW法でμgオーダー, STOP & FLOW法でサブμgオーダーであった。また, 化粧品原料分析への応用として, 生薬エキス末中の成分分析へ適用したところ, 分取することなく含有成分をモニターできたことにより, 本システムが迅速な有効成分の探索に有用であることが実証された。

Rapid Analysis of Clay minerals (Talc, Kaolin etc.) by Fluorescent X-ray spectrometry

Rapid analysis of cosmetic clay minerals such as Talc, Kaolin etc. was studied by fluorescent X-ray spectrometry. It was said to effect much the differences of samples composition and partical size in this study. In order to reduce these effects, a fusing technique was introduced as a pretreatment.Several standard mixtures were made similar to the composition of Talc and Kaolin, the calibration curves of every composition were determined. They were found linear. Using these curves, practical samples ware analyzed. The analytical results of the present method coincided well with those of chemical wet analysis.The present method was found to be of great advantage in time and procedure to the chemical wet analysis.