Journal of Pesticide Science

Syntheses of Isocoumarins and Isocarbostyrils and their Biological Activities

Hiromichi YOSHIKAWA, Eiji TANIGUCHI, Kazuyuki MAEKAWA

1980 Volume 5 Issue 1 Pages 1-10
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.1

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From substituted homophthalic acid derivatives and various phenols, fifty 3-(hydroxyphenyl) isocoumarins and twenty-five isocarbostyrils were prepared. From the shift of λ_max value in the UV region of 3-(hydroxyphenyl) isocarbostyrils which were obtained by the conversion of the isocoumarins, the position of the phenols acylated by homophthalic acids was elucidated. Some isocoumarins such as 3-(2′-hydroxy-3′, 5′-dimethylphenyl) isocoumarin, 7-methyl-3-(2′-hydroxy-4′-methylphenyl) isocoumarin, 5-methyl-3-(4′-hydroxyphenyl) isocoumarin and 8-hydroxy-3-(2′-hydroxy-4′, 6′-dimethylphenyl)-5, 6-dimethylisocoumarin showed fairly strong phytotoxicity on radishes, but they were weakly phytotoxic on rice and barnyard grass.

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Bioaccumulation and Biodegradation of the (S)-Acid Isomer of Fenvalerate (Sumicidin^®) in an Aquatic Model Ecosystem

Hideo OHKAWA, Ryoichi KIKUCHI, Junshi MIYAMOTO

1980 Volume 5 Issue 1 Pages 11-22
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.11

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The degree of bioaccumulation and biodegradation of the (S)-acid isomer of fenvalerate [(RS)-α-cyano-3-phenoxybenzyl-(2S)-2-(4-chlorophenyl) isovalerate], S-fenvalerate, was examined in comparison with DDT. When carp were held in static water containing nominal initial concentration of 0.8ppb of either ¹⁴CN-S-fenvalerate or ¹⁴C-ring-DDT, S-fenvalerate was taken up into fish more slowly as compared with DDT. S-Fenvalerate residues in fish were readily excreted with a half-life of about 5 days during a clearing period, but DDT residues were hardly eliminated from the fish body. In an aquatic model ecosystem, bioaccumulation ratios (BR) for S-fenvalerate ranged from 69 to 117 in fish with three different labeled compounds, and were lower in fish than in snails, daphnids and algae. The BR values for DDT and DDT-R (sum of DDT, DDE and DDD) in fish were about 10 times and 20 times, respectively, larger than that of S-fenvalerate. Metabolism of S-fenvalerate proceeded through hydroxylation at the phenoxy group, hydrolysis of the CN group and cleavage of the ester linkage in four species of aquatic organisms in the ecosystem. It appears that fish is most active in the metabolism of S-fenvalerate among four species. The S-fenvalerate metabolites did not tend to accumulate to high degrees in these aquatic organisms.

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The Influence of Soil Properties on the Adsorption and the Phytotoxicity of Piperophos

Yoshiro HATA, Yukinobu ISOZAKI

1980 Volume 5 Issue 1 Pages 23-27
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.23

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The adsorption of piperophos by paddy field soils was studied by the slurry method. The equilibrium concentrations were determined by gas chromatography (FPD). The amounts of the herbicide adsorbed varied from 15.2 to 78.0μg/g depending on soil properties with the initial concentration of 2.5μg/ml. The extent of adsorption was correlated with C. E. C., phosphate absorption coefficient, and hygroscopic water content, but not with total carbon content, clay content and pH. The lack of correlation between the amount of piperophos adsorbed and the contents of soil colloids may indicate that the quality of colloid affect the adsorption. The phytotoxicity of piperophos to young rice seedlings was measured by pot test under extreme conditions. When piperophos granules were applied at the rate of 40kg/ha, the dry weight of seedlings as % of control changed from 50 to 106 according to soil properties and was highly correlated with the amount of piperophos adsorbed. Significant correlations were observed between the phytotoxicity and the hygroscopic water content and phosphate absorption coefficient.

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Absorption, Translocation and Metabolism of Fluoroimide in Inu-apple Trees, Malus prunifolia BORKHOUSEN

Fate of Fluoroimide, N-(4-Fluorophenyl)-2, 3-dichloromaleimide (Part 1)

Kunihiko OGAWA, Hiroyasu AIZAWA, Fumio YAMAUCHI

1980 Volume 5 Issue 1 Pages 29-36
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.29

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Fate of Fluoroimide, N-(4-fluorophenyl)-2, 3-dichloromaleimide, on/in Inu-apple trees (Males prunifolia BORKHOUSEN) was investigated using two ¹⁴C-labeled compounds at either benzene ring or carbonyl group. Half lives of Fluoroimide applied on the leaves and fruits were about 20 days and 30 days, respectively. It remained mainly unchanged on the applied surface and was slowly absorbed by the plant. Only 2% of applied Fluoroimide was translocated into the leaves 9 days after treatment, and 9% and 18% of applied radioactivity were absorbed and translocated into the leaves and fruits, respectively, after 93 days. A main metabolite of Fluoroimide was sodium 4-fluorodichloromaleanilate, a hydrolyzed compound of imide ring, that was identified by MS, IR, NMR and FX. Other four metabolites, such as 4-fluoroaniline, (E)-2, 3-dichloro-N-(4-fluorophenyl) acrylamide, N-(4-fluorophenyl) maleimide and N-(4-fluorophenyl) succinimide, were identified by cochromatography on tlc and MS, but residual amounts of these metabolites were quite low both in the leaves and fruits. It is considered that succinimide moiety of a reduced metabolite was derived from dichloromaleic acid portion of Fluoroimide, but not from the plant component.

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Metabolism of 3, 3′-Dimethyl-4-Methoxybenzophenone (Methoxyphenone, NK-049) in Paddy Soils and by Soil Microorganisms

Akira KUROZUMI, Takashi KUROKAWA, Isamu YAMAGUCHI, Tomomasa MISATO

1980 Volume 5 Issue 1 Pages 37-43
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.37

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The fate of 3, 3′-dimethyl-4-methoxybenzophenone (methoxyphenone, NK-049) in paddy soils and its metabolism by soil microorganisms were investigated by using ¹⁴C-NK-049 labeled at carbonyl carbon. NK-049 disappeared rapidly under static (“anaerobic”) flooded conditions with half-life of about 10 days. Main products obtained were 3, 3′-dimethyl-4-hydroxybenzophenone (NK-049-OH) and ¹⁴CO₂. Oxidized products of 3- or 3′-methyl group and reduced form at carbonyl group of NK-049 were also detected by thin layer chromatography (tlc). After 2 weeks of incubation, radioactivity of NK-049-OH reached 43.0 and 70.8% of the applied radioactivity in Mito soil and Konosu soil, respectively. Significant liberation of ¹⁴CO₂ (55.0%) was observed in Konosu soil after 6 weeks of incubation, but it was only 0.7% in Mito soil. NK-049-OH was also degraded to yield almost the same amount of ¹⁴CO₂ in Konosu soil as in the case of NK-049. Under shaking (“aerobic”) flooded conditions, ¹⁴CO₂ was liberated from Konosu soil treated with ¹⁴C-NK-049 as under static conditions but little accumulation of NK-049-OH was observed. Microbial metabolites obtained by an isolated microorganism were common with those found in the soil except 3, 3′-dimethyl-4-methoxybenzhydrol.

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Alkylation of Cellular Macromolecules by Reactive Metabolic Intermediate of DBCP

Yasuhiro KATO, Kiyoshi SATO, Osami MATANO, Shinko GOTO

1980 Volume 5 Issue 1 Pages 45-53
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.45

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Alkylating potential of DBCP on cellular macromolecules in vitro and in vivo was investigated using ¹⁴C-DBCP and male Wistar rats. In studies in vitro with rat-liver-microsome system, incorporation of DBCP-radiocarbon into TCA- and organic-solvents unextractable microsomal proteins was determined. The incorporation was dependent on incubation time, ¹⁴C-DBCP concentration, enzymatically active microsomes, NADPH, and oxygen, but it was not affected by sufficient puromycin to inhibit protein synthesis. Addition of SKF-525A, diethyldithiocarbamic acid, cysteine, or glutathione prevented the incorporation, and low concentration of 1, 1, 1-trichloropropane-2, 3-oxide, an inhibitor of epoxide hydrase stimulated the incorporation. When ¹⁴C-DBCP (20mg/kg) was orally administered to rats, TCA- and organic-solvents unextractable macromolecular residues were formed in rat tissues in parallel to the depletion of hepatic glutathione. Gel-fitration, protease digestion, and 2, 4-dinitrofluorobenzene treating of the liver homogenate showed an existence of radioactive proteins of which primary structure was radiolabeled. DNA isolated from the liver was also radiolabeled. From these results it was concluded that DBCP is oxidatively metabolized to reactive metabolic intermediate (s) by microsomal cytochrome p-450 system and covalently bind with nucleophilic sites of the cellular macromolecules in vitro and also in vivo. And epoxide was proposed as one of the reactive metabolic intermediate (s) responsible for protein alkylation by DBCP.

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Fate of Propaphos (Kayaphos^®) in Rice Plants

Yasuo FUJII, Shiro ASAKA, Tomomasa MISATO

1980 Volume 5 Issue 1 Pages 55-62
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.55

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¹⁴C-Propaphos was rapidly absorbed via leaf surface by foliar application and translocated mostly to the upper part of the plant body. By root application, ¹⁴C-propaphos was readily absorbed and rapidly translocated to the shoots and levaes, but the radiocarbon was released to the culture solution from the roots when they were transferred to propaphos free solution. The released radioactive compounds consisted of propaphos and propaphos-SO of nearly equal amount. Metabolic reactions included oxidation of the methylthio sulfur to sulfoxide and sulfone, hydrolysis of the phosphorus-O-phenyl ester, and four of the metabolites were identified. Recovery of radoicarbon from 4 and a half month old rice plant and the soil treated with ¹⁴C-propaphos at 3g/are were estimated to be 3.7% (roots), 20% (shoots and leaves), 0.14% (hulls), 0.07% (hulled rice) and 58.2% (soil), respectively. Radioactive residue in hulled rice treated with ¹⁴C-propaphos was 0.02ppm; it is below enough compared with the residue limit of 0.05ppm, and no intact propaphos was detected in it.

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Mass Spectrometry of the Insecticide Salithion and Related Cyclic Phosphorus Esters

Studies on Saligenin Cyalic Phosphorus Esters with Insecticidal Activity (Part 14)

Nobuhiro FUKUHARA, Morifusa ETO

1980 Volume 5 Issue 1 Pages 63-67
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.63

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Mass spectrometry of fifteen benzodioxaphosphorins and dioxaphosphoranes including the insecticide salithion was studied. The mass fragmentation of saligenin cyclic phosphorus esters is characteristic as follows: 1) β-Cleavage of an exocyclic ester bond occurs with charge retention on the phosphorus moiety in the phosphate and phosphorothionate esters, whereas α-cleavage is dominant in the thiolate esters. 2) The thiono type esters lose SH. 3) Thionothiolo rearrangement occurs particularly in the aryl phosphorothionates. 4) No proton rearrangement occurs in the process of ester cleavage. 5) Fragmentation of non-phosphorus containing moiety is similar with that of saligenin.

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Comparison of Tridemorph with Buthiobate in Antifungal Mode of Action

Toshiro KATO, Masako SHOAMI, Yasuo KAWASE

1980 Volume 5 Issue 1 Pages 69-79
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.69

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Tridemorph, at a concentration of 10μM, hardly inhibited spore germination of Botrytis cinerea but caused multiple emergence of the germ tubes and their excessive branching, inhibiting hyphal extension. The morphological abnormality was similar to that caused by buthiobate. In addition, tridemorph at the above concentration inhibited ergosterol biosynthesis in B. cinerea as strongly as buthiobate. However, the site of inhibition during the sterol biosynthetic pathway was distinct from that of buthiobate. The analysis of sterols in the control and treated cultures indicated that tridemorph possibly blocked the Δ⁸→Δ⁷ isomerization, i. e. the conversion of fecosterol to episterol, but buthiobate inhibited the demethylation at the C-14 position of sterol nucleus. A higher concentration (100μM) of tridemorph inhibited spore germination of B. cinerea, caused a prominent leakage of the cellular constituents, and suppressed the incorporations of glucose-U-¹⁴C, leucine-U-¹⁴C and uracil-U-¹⁴C. But, such effects were not detected at lower fungitoxic concentrations (10 and 30μM). Thus, a high antifungal activity of tridemorph at low concentrations can be possibly attributed to the inhibition of ergosterol biosynthesis.

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Correlation between Macromolecular Binding of DBCP-Metabolite and Pathogenicity of Necrosis

Metabolic Fate of DBCP in Rats (Part 3)

Yasuhiro KATO, Kiyoshi SATO, Takanori HARADA, Shin-ichi MAKI, Osami MA ...

1980 Volume 5 Issue 1 Pages 81-88
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.81

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Correlation of macromolecular binding and cellular necrosis caused by DBCP was investigated in male Wistar rats orally treated with 20 to 400mg/kg (lethal dose) of ¹⁴C-DBCP. Radiocarbon was located mainly in the liver and kidney (proximal tubules). In these target organs, bound radiocarbon with macromolecules was the predominant chemical form of the tissue-radioactive substances and dose-dependently increased in parallel to the depletion of hepatic glutathione content. Residue level of DBCP also increased dose-dependently, however, it constituted only a part of the tissue-radiocarbon in either doses. Phenobarbital pretreatment potentiated the DBCP-induced mortality, radioactive elimination into the urine, severity of the necrosis, macromolecular binding, depletion of glutathione in the liver and kidney without any significant effect on the non-bound radiocarbon content in these target organs. SKF-525A pretreatment reduced these indices with a slight increase of the non-bound radiocarbon content in the kidney. Concomitant administration of glutathione also reduced the mortality and macromolecular binding. From these results it is consdiered that the macromolecular binding in vivo is caused by an activated metabolic intermediate formed on microsome as previously reported in the experiments in vitro and it causes a cellular necrosis leading to mortality. A sulfhydryl compound, glutathione was considered to possess a protective role for the incidence of necrosis by inactivating the reactive metabolic intermediate of DBCP in target organs.

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Determination of Rotenoids in Soil and Crops by High-performance Liquid Chromatography

Hiroko KOBAYASHI, Osami MATANO, Shinko GOTO

1980 Volume 5 Issue 1 Pages 89-92
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.89

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Using high-performance liquid chromatography, a method for the determination of seven rotenoids (rotenone, O-demethylrotenone, dehydrorotenone, 8′-hydroxy-6aα, 12aα-rotenolone, 6aβ, 12aβ-rotenolone, 6aβ, 12aα-rotenolone and 8′-hydroxyrotenone) in soil and crops has been investigated. Successful separation was achieved by reversed-phase chromatography (column packed with JASCO, SC-02). The limits of detection were 0.02-0.08ppm for all seven rotenoids. The mean recoveries of rotenone added to apples, tomatoes and soil were greater than 95% in all samples and those with the other six rotenoids were also satisfactory for quantitative residue analysis.

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Anaerobic Degradation of Tetra-, Penta-, and Hexa-chlorocyclohexene Isomers by Rat Liver Microsomal P-450

Norio KURIHARA, Kazue YAMAKAWA, Toshio FUJITA, Minoru NAKAJIMA

1980 Volume 5 Issue 1 Pages 93-100
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.93

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In the presence of rat liver microsomes and NADPH, tetra-, penta- and hexachloro-cyclohexene isomers were anaerobically metabolized. The reaction rate was dependent on the amount of cytochrome P-450, but not on the amount of protein. Major products from the hexa- and pentachlorocyclohexene isomers were 1, 2, 4-trichlorobenzene and 1, 4-dichlorobenzene, respectively. The results suggest that the reaction was 1, 2- or 1, 4-dechlorination followed by dehydrochlorination. Polarography in dimethyl sulfoxide showed the most positive half-wave potential for (36/45)-hexachlorocyclohexene and the most negative one for (35/46)-tetrachlorocyclohexene. The trend which shows the relative redox potential of the compounds seems to reflect the reductive susceptibility of the allylic chlorine substituent, depending on its conformation and the other chemical environments. Partition coefficients in octanol/water increased about three fold on each introduction of a chlorine atom into the vinylic positions among the analogs of the same chlorine configurations. Reactivity in the anaerobic biochemical reaction was shown to relate not only with the half-wave potential but also with the hydrophobicity expressed in terms of the partition coefficient, although some exceptions were observed. Thus, the biochemical reaction seems to proceed at a hydrophobic milieu of microsomes via the rate-determining dechlorination step, the mechanism of which is similar to electrochemical reduction.

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Utility of Basic Lead Acetate Treatment for Analysis of Pesticides Residues in Tea Infusion

Yasuhisa ONODA, Masako IMAMURA

1980 Volume 5 Issue 1 Pages 101-105
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.101

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The procedures on the residual analysis of pesticides, DMTP (methidathion), isoxathion, methomyl, PAP (phenthoate), phosalone and TPN (chlorothalonil) were simplified by some modifications. Basic lead acetate solutions added to tea infusion to precipitate polyphenols and saponins as lead complexes. These lead complexes were filtered through a filter paper piled with some celite, and washed with 50ml of acetone and then 100ml of n-hexane. In case of methomyl, the remnant was washed with 50ml of ethanol.
From the resulting aqueous layer, chemicals except methomyl were extracted with n-hexane and cleaned up by column chromatography. In Florisil column chromatography, the first eluate with ether containing 50% of n-hexane contained isoxathion, and the next eluate with ether containing 50% of benzene contained DMTP and phosalone. PAP and TPN were eluted with n-hexane containing 20% of ether in silica-gel column chromatography. Methomyl was extracted with ethyl acetate from solution alkalified with sodium hydroxide and superheated for over 30min.
The recovery ranged between 87 and 100% in DMTP, isoxathion, PAP, phosalone and TPN, and 86% in methomyl.
Using 6g of the tea sample, the lower limits of detection of each chemical were 0.003ppm (TPN), 0.03ppm (methomyl, PAP), 0.04ppm (DMTP) and 0.05ppm (isoxathion, phosalone) in the obtained tea infusion each 360ml of which had been subjected to the analysis.

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Identification of S-Benzyl N, N-Diethylthiocarbamate in Paddy Field Soil Applied with Benthiocarb Herbicide

Kanji ISHIKAWA, Rokuro SHINOHARA, Akira YAGI, Shoji SHIGEMATSU, Ichiro ...

1980 Volume 5 Issue 1 Pages 107-109
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.107

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Insecticidal Control for Insects of Medical Importance in Japan

Kazuo YASUTOMI

1980 Volume 5 Issue 1 Pages 111-117
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.111

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[title in Japanese]

[in Japanese], [in Japanese], [in Japanese], [in Japanese], [in Japane ...

1980 Volume 5 Issue 1 Pages 119-136
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.119

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[title in Japanese]

[in Japanese]

1980 Volume 5 Issue 1 Pages 137-138
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.137

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[title in Japanese]

[in Japanese]

1980 Volume 5 Issue 1 Pages 139-140
Published: February 20, 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.139

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Erratum to : Behavior of 1-Methylthiosemicarbazide in Rice Plants under Submerged Application

1980 Volume 5 Issue 1 Pages 151
Published: 1980
Released on J-STAGE: August 05, 2010

DOIhttps://doi.org/10.1584/jpestics.5.1_151

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