US005703064A United States Patent (19) 11 Patent Number: 5,703,064 Yokoi et al. 45) Date of Patent: Dec. 30, 1997 54 PESTICIDAL COMBINATIONS FOREIGN PATENT DOCUMENTS 75 Inventors: Shinji Yokoi; Akira Nishida, both of 0 196524 10/1986 European Pat. Of.. Shiga-ken; Tokio Obata; Kouichi Golka, both of Ube, all of Japan OTHER PUBLICATIONS 73) Assignees: Sankyo Company, Limited, Tokyo; Worthing et al, The Pesticide Manual, 9th Ed. (1991), pp. Ube industries Ltd., Ube, both of 747 and 748. Japan L.C. Gaughan et al., "Pesticide interactions: effects of orga nophosphorus pesticides on the metabolism, toxicity, and 21 Appl. No.: 405,795 persistence of selected pyrethroid insecticides". Chemical Abstracts, vol. 94, No. 9, 1981, No. 59740k of Pestic. 22 Filed: Mar 16, 1995 Biochem. Physio., vol. 14, No. 1, 1980, pp. 81-85. 30 Foreign Application Priority Data I. Ishaaya et al., "Cypermethrin synergism by pyrethroid esterase inhibitors in adults of the whitefly Bemisia tabaci". Mar 16, 1994 JP Japan ............................ HE6045.405 Chemical Abstracts, vol. 107, No. 9, 1987, No. 72818y of (51) Int. Cl................. A01N 43/54; A01N 57/00 Pestic Biochem. Physiol., vol. 28, No. 2, 1987, pp. 155-162. 52 U.S. C. ......................................... 51480; 514/256 (58) Field of Search ..................................... 514/80, 256 Primary Examiner Allen J. Robinson Attorney, Agent, or Firm-Frishauf, Holtz, Goodman, 56 References Cited Langer & Chick, P.C. U.S. PATENT DOCUMENTS 57 ABSTRACT 4,374,833 2/1983 Badmin et al. ...................... 424/225 Combinations of the known compound pyrimidifen with 4,845,097 7/1989 Matsumoto et al... 514/234.2 phosphorus-containing pesticides have a synergistic pesti 4,935,516 6/1990 Ataka et al. ............................ 544,319 4,982,008 1/1991 Ataka et al. ........................... 568/592 cidal effect, especially against mites. 4,985,596 1/1991 Ataka et al. ... ... 564/258 5,120,721 6/1992 Morimoto et al. ...................... 514/03 3 Claims, No Drawings 5,703,064 1. 2 PESTCDAL COMBINATIONS R represents an alkoxy group having from one to eight carbon atoms, an alkylthio group having from one to eight BACKGROUND OF THE INVENTION carbon atoms, an alkylcarbonylamino group having from one to four carbon atoms or a phenyl group; and The present invention relates to combinations of the R represents an alkyl group having from one to eight known pesticide pyrimidifen with other phosphorus carbon atoms, an alkenyl group having from two to six containing pesticides. carbon atoms, an amino group, a phenyl group or a het EP-A-196524 discloses a large number of phenoxyalky eroaryl group, and is unsubstituted or is substituted with one, laminopyrimidine derivatives in the context of insecticides two or three substituents which may be the same or different and acaricides. One of these compounds, 5-chloro-N-2-2, O and which are selected from the group (A) consisting of: 3-dimethyl-4-(2-ethoxyethyl)phenoxy-ethyl-6-ethyl-4- halogen atoms, phenyl groups, nitro groups, cyano pyrimidinamine, also known as pyrimidifen (compound no. groups, oxo groups, alkyl groups having from one to 75 in Table 1 of EP-A-196,524), is demonstrated as having eight carbon atoms, alkoxy groups having from one to good insecticidal and acaricidal activity. The formula of eight carbon atoms, aliphatic acyl groups having from pyrimidifen is as follows: 15 one to six carbon atoms, alkoxycarbonyl groups having from one to six carbon atoms, alkylthio groups having CH CH from one to six carbon atoms, alkylamino groups having from one to six carbon atoms, dialkylamino NHCHCHO CHCHOCHCH groups wherein each alkyl is the same or different and each has from one to six carbon atoms, heteroaryl C 21 N. groups, carbamoyl groups, alkylcarbamoyl groups wherein the alkyl part has one to six carbon atoms, and heterocyclyl groups which are unsubstituted or are CHCH1 N y substituted with one, two or three substituents selected from group A, other than heterocyclyl groups, Phosphorus-containing pesticides are well known in the or R represents a group of formula art, and the art also provides well known methods for the production of further such compounds where they ar not R-O X NI known perse. EP-A-196,524 also discloses a lengthy list of P possible insecticides and fungicides which may be used in 30 M combination with the claimed R2 phenoxyalkylaminopyrimidines, and states that "in some cases, a synergistic effect may be expected", but fails to provide any justification for this statement. wherein R, R and X are respectively selected Spider mites are a significant crop pest, worldwide. To 35 from the groups defined above for R', R and XI for use this end, many groups have attempted to find suitable pest in agriculture or horticulture. control agents. Many agents have been found, but the DETALED DESCRIPTION OF INVENTION efficacy of such agents tends to be rather short-lived, owing to the development of resistance to newly introduced cidal Preferred compounds of formula (I) for use in the formu agents. In areas of heavy cultivation, it is often the case that lations of the present invention are those compounds known the mite population is resistant to a large number of chemi as isoxathion, diazinon, prothiofos, methidathion, cals. In this respect, some mites are even developing resis thiometon, malathion, quinallphos, dimethoate, chlorpyrifos, tance to pyrimidifen, one of the newest miticidal agents. profenofos, monocrotophos and ethion, the systematic names of which are given hereinunder. Of the above BRIEFSUMMARY OF INVENTON 45 compounds, dimethoate, chlorpyrifos, profenofos, monocro Surprisingly, we have now discovered that a combination tophos and ethion are particularly preferred. of pyrimidifen with one or more phosphorus-containing In an alternative aspect, the present invention provides a pesticides has a surprisingly potent synergistic effect, espe pesticidal composition comprising pyrimidifen and at least cially against spider mites, even where resistance to pyrim one of profenofos, monocrotophos and ethion. idifen has developed. The present invention further provides vegetative repro Thus, in a first aspect, the present invention provides a ductive material, especially seeds, treated with the compo pesticidal composition comprising 5-chloro-N-2-2,3- sitions of the invention; and methods of treating such dimethyl-4-(2-ethoxyethyl)phenoxy-ethyl-6-ethyl-4- material with the compositions of the present invention. pyrimidinamine (hereinafter referred to as pyrimidifen) 55 The present invention further provides a method for the together with one or more compounds having the general treatment of an agricultural or horticultural area against formula: non-mammalian, non-arian and non-reptilian pests compris ing the administration thereto of an effective amount of a Rl-O X (I) composition comprising pyrimidifen and one or more com P-Y-3 60 pounds of formula (). It will be appreciated that the compositions of the present R2 invention do not necessarily have to be administered as a wherein X represents an oxygen atom or a sulfur atom; combination, and that they may be provided as separate Y represents an oxygen atom, a sulfur atom or a single ingredients and even administered separately, provided that bond; 65 the active ingredients are present together in situ. R" represents an alkyl group having from one to six While it is possible to use two or more compounds of carbon atoms; formula () in the compositions of the present invention, it 5,703,064 3 4 is generally preferred to use only one compound of formula pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3- (I), generally for reasons of convenience and cost. pentenyl, 2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-4- It will be appreciated that the term "pesticidal", as used pentenyl, 2-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, herein, is used in the context of non-mammalian, non 3-hexenyl, 4-hexenyl and 5-hexenyl groups, particularly the reptilian and non-arian pests. Pests against which the com vinyl and allyl groups. positions of this invention are particularly useful are mites, In the definitions of R and substituent group A in general especially spider mites, but those skilled in the art will formula (I), heteroaryl groups may suitably be selected from appreciate that the compositions of the present invention 5- to 8-membered mono-, bi- or tricyclicheterocyclic groups may also be used as insecticides and cidal agents for having from one to five hetero-atoms which may be the same crustacea and the like. It is a particular advantage of the O or different and selected from oxygen, sulfur and nitrogen present invention that the compositions which are provided atoms. Suitable examples of heteroaryl groups include; the are useful against spider mite populations insensitive to furanyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, pyrimidifen. thianyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazolyl, In the definitions of R' and R' in the compounds of imidazolyl, triazinyl, thiadiazolyl, imidazothiazolyl, general formula (I), alkyl groups having from one to six 15 benzisoxazolyl, chromenyl, quinolinyl, benzothianyl, qui carbon atoms may suitably be selected from straight or noxalinyl and benzotriazinyl groups. branched chain alkyl groups such as, for example; the In the definition of substituent group A in general formula methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, (I), aliphatic acyl groups may suitably be selected from tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, neopentyl, straight or branched chain aliphatic acyl groups such as, for 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, example; the formyl, acetyl, propionyl, butyryl and valleryl 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2- groups. dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- In the definition of substituent group Ain general formula dimethylbutyl, 2,3-dimethylbutyl and 2-ethylbutyl groups, (I), alkoxycarbonyl groups having from one to six carbon particularly the methyl and ethyl groups.