Title Studies on Saligenin Cyclic Phosphorus Esters with Insecticidal
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Studies on Saligenin Cyclic Phosphorus Esters with Title Insecticidal Activity : Part X. Synergism of Malathion against Susceptible and Resistant Insects ETO, Morifusa; OSHIMA, Yasuyoshi; KITAKATA, Setuo; Author(s) TANAKA, Fumikazu; KOJIMA, Ken'ichi Citation 防虫科学 (1966), 31(1): 33-38 Issue Date 1966-02-28 URL http://hdl.handle.net/2433/158466 Right Type Departmental Bulletin Paper Textversion publisher Kyoto University m m fl ~ in 31 ~-I ~Wrff1lJ'Il:ar1tl-f-~ 24n~mO~0)~¥E~~l2;.R~t.:. c z hl2 Summary Bliss 0) probit r.tI~ t...t.:t.I~., -cmJ.1nt.... -( zcr:»: 1 iiJi Exploratory studies have been made with ~ I) O)rf:t~~r~rln1lt7Ja.Frf1~~3'Er!ftl:l2;J<~t.:. substituted benzyl esters of chrysanthemic acid M* :~~O)M*l2;U~'r Q c Table 1. sos 2 0) in search for effective insecticides. Of many benzyl tm< '"C"<b:Q. chrysanthemates synthesized, 4-allylbenzyl chry santhemate was found to show a high insecticidal activity and was designated as "Benathrin". 1) Chen, Y. L., Barthel. W. F. : U. 5. Dept. Agri., Benathrin was as 1.7 times toxic in knock·down ARS 23 (1956). and 9.2 times toxic in mortality as a-til-trans 2) Piquett, P. G.. Gersdorff, W. A.: J. Econ, allethrin to adult house fly, Musca domestica Entomol.• 51. 791 (1958). vicina Maq., when applied topically in acetone 3) Buei, K.: Boiyu-kagaku, 30, 37 (1965). solution. Studies on Saligenin Cyclic Phosphorus Esters with .Insecticidal Activity. Part X. Synergism of Malathion against Susceptible and Resistant Insects. Morifusa ETO, Yasuyoshi Osmsr», Setuo KITAKATA*. Fumikazu TANAKA* and Ken'ichi KOJIMA* (Department of Agricultural Chemistry. Kyushu University, Fukuoka and*Institute of Agricultural Chemicals, Toa Noyaku Co. Ltd., Odawara) Received November 30, 1965. Boiyu-Kagaku, 31, 33. 1965. 6. ~!llt1ofj' IJ If= ~iJ~ ~ AJM:r. A 7' )J,0)ii]f~ (t!HO¥fD r®~l!E.:i,;J: v:m;j/Ll!Emr1H~*{'rQ"7 :77'.i";; c 0)~l;1Jf'ffl] rrjJj'iT~' *tbm~ . ~t1J1m7-:::* • rnrf:15c-* • IN'M.l!-* (1L1H#J: n~mn1~ {t~~1. *mjffin~~~~fl:n~li1f~iYD 40. 11. 30 )'l:l]! ~ :7 :r:t ;;0)J1j1J 1l'm~ ~ -II 1.> L t 't'91l i; tt -CP 7.> tri-e-tolyl phosphate O)±~mt'J:{~;;qlPn~1l' ~tJ" HllO) -l} 9 7' =- ;;ro~ ~ A~:r. A 7"It-IC "?~,"(. ~:7:r:t;; t O)~~IJ{tm H~~tt;fd J: o:m;tlcfl 0) -1 x:»: :r.t ';1 ~ ~. P 3 ::J r«-11l' m p "(~JH L t..:. ll,l~:r. A 7"It-O) 7 9 1t-:m'.t;U= Ii. L t Icm;j;i:f'Jl IC~Jvnpti'it'J:1l'ff-v tz: 7 1t-4'- 1t-lt15'!;U=li:f1£Vtfililr.~vjJgp~~1JrFm ~~v tz: ll.tJtti v t":l~fr~ I1t, m:::rrWJt.. ~l;1JJi!Hi 7-methyl-2-phenyl-4H-l, 3, 2-benzodioxaphosphorin-2-oxide 't' a).,tz, LO) f, O)li:f1£Vtt'J:-1 :r./'{:r.IC~Jv, propyl paraoxon ~ Dibrom O)J: ? tJret?nj~IJJi!lJ: ~ f, lIWJ't' ih., tz: Certain organophosphorus compounds increase oitroi», it is metabolized in vivo to active anti the toxicity of malathion (O,O-dimethyl 5-(1.2 esterase agents. 1. e., saligenin cyclic phosphates biscarboethoxyethyl) phosphorodithioate) to marn 11,\2). A series of saligenin cyclic phosphorus esters mals!', EPN (ethyl p-nitrophenyl phenylphos have been synthetically preparedt3,!4landexamimed phonothionate)!' and TOCP(tri-c-tolyl phosphate)!' for biological activities. Aryl derivatives were are well known examples. For insects, particularly selective inhibitors of ali-eaterase!" and appeared resistant strains. several synergists of malathion to be synergistic with malathtonw, whereas small have been reported: propyl paraoxon (dipropyl alkyl derivatives were highly Insectlcidalr", p-nitrophenyl phosphate)4>, EPN and its oxoana Results of investigations on the synergistic loga> for house fly; tributyl phosphorotrithioate activities of some saligenin cyclic phosphorus and its some related substances for house fly and esters against resistant insects are presented in mosquitos-P ; EPN for mosquitov: Dibrom (1,2 this papar, It was observed that 7-methyl dibromo-2,2-dichloroethyl dimethyl phosphate) 2-phenyl-4H-l, 3. 2-benzodioxaphosphorin-2-oxide for green rice leafhopper!', Allofthesephosphorus (VII) was a quite effective synergist of malathion. compounds are known as inhibititors of ali-esterase or related hydrolases at least in vivo condition. Materials and Methods Although TOCP itself is not the inhibitor in Chemicals: Samples except Compound III were 33 Table 1. Joint action of saligenin cyclic phosphorus esters (I-VII) and some other phosphoric esters with malathion against susceptible house flies. Y,/"jO"f. I II f- R '\,/" /0 CH2 Compound' LDGO (pg/!f ) with Cotoxicity No. R X Y alone malathion coefficient (1 : 1) Malathion 0.46 I OMe H 0.02 0.06 0.6 II OEt ° H 0.16 0.14 1.7 III OEt °S H 0.11 0:22 0.8 IV OPh H c. 10 (30%) 0.38 2.3 V O-o-Tol ° H c. 10 (40%) 0.26 3.4 VI Ph ° H c. 10 (6096) 0.36 2.5 VII Ph ° Me c. 10 (70%) 0.26 3.4 TOCP ° >10 ( 096) 0.90 1.0 Dibrom 0.03 0.008 7.1 Propyl paraoxon O. 10 0.11 1.5 Isopropyl paraoxon 0.22 0.06 4.9 Abbreviations for designating structures: Me=methyl; Et=ethyl ; Ph=phenyl ; Tol=tolyl, Numbers in parentheses are mortality percentage at 10 pg dose per insect. purified through column chromatography, distil They were kept at 25'. Mortality counts were lation or recrystallization. Materials included were made 24 hours after treatment. malathion, Dibrom, proply paraoxon, isopropyl Joint toxic action was tested by applying the paraoxon (diisopropyl p-nitrophenyl phosphate), mixture of malathion and synergist at a 1:1 ratio. TOCP and seven' derivatives of saligenin cyclic The joint action was evaluated by the cotoxicity phosphorus esters. The cyclic esters were prepared coefficient2o,211 of the mixture. The coefficient was by a reported method. 13,14> Their structures are calculated by the following equation (1). shown in Table 1 (I-VII). Cotoxicity coefficient=Actual toxicity index of Insects: Oriental house fly (Musca domestica a mixture/Theoretical toxicity index of a mixture vicina Macquart) and green rice leafhopper .................................................................. (1) tNephotettix cincticeps Uhler) were used. The For some practically non-toxic compounds, a strains of house fly were: (1) Sapporo, a suscep modified simple equation (2) could be applied. tible strain and (2) Hokota, a diazinon-resistant Cotoxicity coefficiente-Llr., of malathion alone/ strain showing cross-resistance to malathion. LDGO of malathion in a mixture........·.... ·......· ( 2 ) The strains of leafhopper were: (1) Odawara, a The cotoxicity coefficient is the number of times susceptible strain and (2) Koti, a malathion-re of increase (or decrease) in toxicity. sistant strain caught in a field of Koti prefecturew. In some experiments, this was used after further Results selection with malathion for several generations. The activity of saligenin cyclic phosphorus esters Test method: Acetone solution of test chemicals in joint action with malathion was examined in was topically applied to female adult insects. comparison with some phosphoric esters which For green rice leafhopper, a previously reported have been reported as synergists of malathion. micro techniquewwas used. Five replicate samples Results with susceptible house flies are shown in each of ten insects were used for each treatment. Table 1. Aryl derivatives of saligenin cyclic esters 34 IW J1l ft ~ til 31 ),J-I Table 2. Synergistic effect of saligenin cyclic phosphorus esters (I-VII) with malathion against resistant house flies in comparison with other phosphate synergists. LOo• (flg/ ~) Cotoxicity Compound with alone malathion coefficient (1 : 1) Malathion 2.54 I 0.15 0.06 4.7 II 0.40 0.22 3. 1 III 0.20 0.10 3.6 IV >10 (10%) 0.55 9.2 V >10 (1096) 0.65 7.8 VI >10 (2596) 0.57 8.0 VII c. 10 (40%) 0.29 14.0 TOCP >10 ( 096) 3.44 1.5 Dibrorn 0.07 0.07 2.0 Propyl paraoxon 0.73 0.46 2.5 Isopropyl paraoxon 0.43 0.36 2.2 Numbers in parentheses are mortality percentage at 10/1g dose per insect. are synergistic with malathion. They increase 2-oxide (VII). Phenyl phosphate (IV) and phenyl the toxicity of malathion 2.3 to 3.4 times at a phosphonate(VI) arealmost same in the synergistic 1:1 mixing ratio. Their activities are more than activity. Alkyl derivatives of saligenin cyclic propyl paraoxon and less than Dibrom and iso phosphorus esters are much less synergistic (II) propyl paraoxon. The most active compounds or even antagonistic (I, III). TOCP known to among the tested cyclic esters are 2-(o-tolyloxy) potentiate the toxicity of malathion in mamrnalstt' -4H-1, 3, 2-benzodioxaphosphorin-2-oxide (V) did not show any effect to house flies. which is the active metabolite of TOCplI,12) and Synergism of saligenin cyclic phosphorus esters 7-methyl-2-phenyl-4H-1, 3, 2-benzodioxaphorin- with malathion in a resistant strain of house fly Table 3. Joint action of saligenin cyclic phosphorus esters (I-VII) with malathion against malathion susceptible green rice leafhoppers in comparison with some phosphate synergists. LOo• (pg/ ~) Compound with Cotoxicity alone malathion coefficient (1 : 1) ---- Malathion 0.003 I 0.008 0.004 1.1 II 0.069 0.003 1.9 III 1.892 0.005 1.2 IV 0.240 0.003 2.0 V 0.464 0.008 0.8 VI 0.218 0.005 1.2 VII 3.120 0.003 2.0 TOCP >10 0.005 1.2 Dibrom 0.208 0.005 1.2 Propyl poraoxon .