Yasuyoshi Oshima

Syntheses and Degradation of Cyclic Phosphorus Esters Derived from Saligenin and Its Analogues

Some cyclic phosphorus esters were prepared from o-hydroxybenzyl alcohol and its analogues. They reacted with nucleophilic agents to open their heterocyclic ring at P-O-C (aryl) bond. Phosphate ion catalyzed the hydrolysis of the cyclic phosphorus esters under a mild condition. An intermediate hydrolysate was separated by paper electrophoresis.

Metabolic Formation of Saligenin Cyclic Phosphates from o -Tolyl Phosphates in House Flies, Musca domestica

The toxicological effects on house flies of several tri-esters of phosphoric acid and a di-ester of phosphsphonic acid were examined. Certain esters were converted to biologically active metabolites. At least one o-tolyl group and another aryl substituent were necessary for the ester to show any distinctive biological effects. The active metabolites were confirmed by chromatography to be saligenin cyclic phosphates.

Saligenin Cyclic Alkyl Phosphates and Phosphorothionates with Insecticidal Activity

Several saligenin cyclic alkyl phosphates and phosphorothionates were prepared and their insecticidal activities were examined. 2-Methoxy-4H-1,3,2-benzodioxaphosphoran-2-one and its thiono analog are strong insecticides, the toxicities of which to a number of insects are almost equal to or superior to parathion. They are less toxic to mouse than parathion. When the length of alkyl radical was increased, the insecticidal activity decreased.

Pesticidal Activities of Some Cyclic Phosphorus Esters

Preliminary tests for pesticidal activities of some cyclic phosphorus esters derived from o-hydroxybenzyl alcohol or its analogues were undertaken. 2-Ethoxy-4H-l,3,2-benzodioxa-phosphoran-2-one has strong insecticidal activity. Some other esters have weak or no insecti-cidal activity by themselves but strong synergistic action with malathion to houseflies and silkworms. Some cyclic esters show nematocidal activity and phytotoxicity.

The Reaction of Cyclic Phosphorus Esters with Some Oximes

Some oximes reacted with cyclic phosphorus esters derived from o-hydroxybenzyl alcohol and its analogues to give phenolic and acidic products. The phenolic products were O-o-hydroxybenzyl derivatives of the oximes and the acidic products were phosphoric-oximinic anhydrides. The rate of reaction decreased in the order; phcnylphosphonate>phenyl phos-phate>alkyl phosphate. Phosphoramide ester was not reactive. Three of eight tested oximes, monoisonitrosoacetone, pyridine-2-aldoxime mcthiodidc and salicylaldoximc, were reactive. The reaction mechanism was discussed.

Studies on Saligenin Cyclic Phosphorus Esters with Insecticidal Activity Part IX:Derivatives of Phosphonic and Phosphonothionic Acids

A number of saligenin cyclic phosphonates and phosphonothionates were prepared and their insecticidal activity and stability were examined. They were less stable than corresponding phosphate esters. 2-Ethyl-4H-l, 3, 2-benzodioxaphosphorin-2-sulfide was the most effective against house flies.

Studies on the Tannin of Japanese Persimmon ( Diospyros Kaki L.):Part I. Isolation of Leucoanthocyanin from Kaki Fruit

Kaki tannin was isolated from methanol extracts of unripe kaki fruit (Japanese persimmon) and it was found that a main constituent composing kaki tannin was a leucoanthocyanin. Its acetate and methyl ether were prepared and their properties and reactions were studied. From the results of these experiments, kaki tannin was presumed to be a (+) leucodelphinidin-3-glucoside (5,7,3′,4′,5′-pentahydroxyflavan-3,4-diol-3-g1ucoside).

Paper Chromatography of Tannins

タンニンのpaper chromatographyに影響を及ぼす種種の因子について検討を行つた結果 i. タンニンのスポットの検出には紫外線及び0.5% FeCl3メタノール溶液が用いられる. ii. 濾紙を塩酸で前処理することによりタンニンのスポットのtailingを減少せしめることが出来た. iii. 多数の溶媒系について検討した結果NaHSO3の添加が有効であることより次の溶媒が比較的良好なchromatogramを与える事を知つた. n-BuOH: AcOH: 1% NaHSO3水溶液=4:1:5 (溶比)の上層(I)及び下層(II)並びに1% NaHSO3水溶液飽和フェノール(III)及びフェノール飽和1% NaHSO3水溶液(IV). Fig. 3にみられるようにタンニンのpaper chromatographyは1次元展開のみでは尚不充分であるが上記の4溶媒を適宜組合せて2次元展開を行えば更に良好なchromatogramがえられることは当然予想される処であるので,著者等は本実験で得られた成果に基づいてタンニンの2次元paper chromatographyを行い,ほぼ所期の目的を達することができた.この点については次報に於て述べる.

Studies on the Black Tea Tannin

By the oxidation of tea catechins on the black tea fermentation, black tea tannin is red and weekly astringent. On the two dimensional paper chromatogram of black tea tannin, some catechins, which have not been oxidized, and oxidized tannin are detected (Fig. 1), and it is, therefore. supposed that the black tea tannin contains not only oxidized tannin but also some unoxidized catechins. By the method of the counter current distribution, the black tea tannin is fractionated as follows; ether soluble (I) (unoxidized catechins) and ether insoluble but ethyl acetate soluble (II) (oxidized catechins) and ethyl acetate insoluble fraction (III) (polymerized tannin) (Fig. 2, 3). Of these three fractions, I and II are dialyzable but III is not (Fig, 4, 5). Several qualities of these fractions are detailed in Table 1 and fraction II has good color and taste. From the results of this experiments, it is supposed that the formation of black tea tannin is as follows: Tea catechins oxidation→ Primary products oxidation and→condensation Secondary products↓polymerization Polymers

Studies on_??_-Aminoisobutyric Acid by Paper Chromatography

カゼインを加水分解して〓-アミノイソ酪酸の分離確認をペーパークロマトグラフィーで研究して次の結果を得た. (1) ブタノール・酢酸・水(4・1:1.5重量)混液で他の殆んどのアミノ酸からイソの部分を分離できるがノルマルとは分離できない. (2) エタノール・水混液(9 1)が両異性体をよく分離展開する. (3) サリチルアルデハイドによるアセトン呈色によつて上記の経過で展開分離したアミィ酸がイソであることを傍証した. (4) 故に第一次にブタノール酢酸水混液で,第二次にてエタノール水混液で展開すればイソを純粋に分離確認し得る.この方法でガゼイン水解物中にイソの存在を確認した.