Oxadiazole derivative

Description

DESCRIPTION
1. Technical Field
The present invention relates to new oxa(thia)diazole derivatives having an excellent acaricidal activity, their manufacturing processes and the acaricides made therefrom.
2. Background Art
To control acaricides, organophosphorous compounds, dinitrotype compounds or a variety of other compounds have been used. In recent years, however, there have emerged mites resistant to these chemicals, and as a result the advent of a new type of acaricides has been desired.
The following compound is known as a compound having an acaricidal activity and the oxadiazole skeleton similar to the compounds of this invention. ##STR9##
The purpose of this invention is to offer agricultural chemicals which can be advantageously synthesized on a commercial basis and which are capable of safe use with positive effects.
DISCLOSURE OF INVENTION
The present invention relates to the compounds having the following formula, their manufacturing methods and the acaricides containing said compound(s) as active ingredients: ##STR10## (wherein R.sub.1 denotes a phenyl radical (which may be substituted by halogen atoms, C.sub.1-6 alkyl radicals, C.sub.1-6 alkoxy radicals (which may be substituted by C.sub.1-6 alkoxy radicals,) C.sub.2-6 alkynyloxy radicals, amino radicals, nitro radicals, phenyl radicals, phenoxy radicals or C.sub.1-6 alkylthio radicals), a five or six menbered heterocyclic radical (which may be substituted by halogen atoms C.sub.1-6 alkyl radicals), a C.sub.1-6 alkyl radical (which may be substituted by aryl radicals) or ##STR11## (wherein each of r.sup.1 and r.sup.2 denotes a C.sub.1-6 alkyl radical or a phenyl radical)
X denotes oxygen atom or sulfur atom;
A denotes ##STR12##
B denotes ##STR13##
D denotes ##STR14## n, m and 1 each denote 0 or 1, (wherein r.sup.3, r.sup.4, r.sup.6, r.sup.7, r.sup.9 and r.sup.10, respectively, denotes hydrogen atom, halogen atom, C.sub.1-6 alkyl radical, the radical expressed by the formula --Y--r.sup.12 (wherein r.sup.12 denotes hydrogen atom, cyano radical, C.sub.1-6 alkyl radical (which may be substituted by C.sub.1-6 alkoxycarbonyl radicals,) cycloalkyl radical, C.sub.1-6 alkoxycarbonyl radical, C.sub.1-6 alkylcarbamoyl radical, C.sub.1-6 alkylthiocarbamoyl radical, phenylcarbamoyl radical (which may be substituted by halogen atom), phenylthiocarbamoyl radical (which may be substituted by halogen atoms), or C.sub.1-6 alkylcarbonyl radical (which may be substituted by halogen atoms); Y denotes oxygen atom, sulfur atom, --SO--, --SO.sub.2 --, or the radical expressed by the formula ##STR15## (r.sup.13 hydrogen atom, C.sub.1-6 alkyl radical)), or oxo-radicals or the radical expressed by the formula NOr.sup.14 where r.sup.3 and 4.sup.4 ; r.sup.6 and r.sup.7 or r.sup.9 and r.sup.10 are combined (wherein r.sup.14 denotes hydrogen atom, C.sub.1-6 alkyl radical, C.sub.1-6 alkylcarbonyl radical, or C.sub.1-6 alkylcarbamoyl radical), provided, however, that r.sup.6 may form a double bond in combination with r.sup.3 or r.sup.9 ; k, k' and k" denote 0, 1 or 2, respectively;
r.sup.5, r.sup.8 and r.sup.11 each denote hydrogen atom or C.sub.1-6 alkyl radical;
When A is ##STR16## however, m denotes 1. Further, A and B, or B and D do not simultaneously denote oxygen atoms or sulfur atoms.)
R.sub.2 denotes a phenyl radical (which may be substituted by --Z--r.sup.15 (wherein r.sup.15 denotes hydrogen atom, C.sub.1-6 alkyl radical (which may be substituted by C.sub.1-6 alkoxycarbonyl radicals or halogen atoms), phenyl radicals, cycloalkyl radicals, the pyridyl radicals (which may be substituted by halogen atoms or C.sub.1-6 haloalkyl radicals), C.sub.1-6 alkylcarbamoyl radicals, or C.sub.1-6 alkylcarbonyl radicals; Z denotes oxygen atom, sulfur atom or the radicals expressed by the formula ##STR17## (wherein r.sup.16 denotes hydrogen atom or C.sub.1-6 alkyl radical), C.sub.1-6 alkyl radicals, halogen atoms or nitro radicals), a cycloalkyl radical, a naphthyl radical, a benzthiazolyl radical (which may be substituted by C.sub.1-6 alkoxy radicals or a C.sub.1-6 alkylamino radicals or halophenylamino radicals), or C.sub.1-6 alkyl radical which may be substituted by halogen atoms).
The compounds of the invention are effective against desert spider mite, two-spotted spider mite, citrus red mite and a variety of other phytophagous mites on plants. At the ovular, larval and nymphal stages of a variety of mites, in particular, these compounds exhibit excellent ovicidal, larvicidal and nymphocidal activities. Their toxicity to warmblooded animals is low and their safety high.
BEST MODE FOR CARRYING OUT THE INVENTION The compounds of the invention can be manufactured in compliance with the following reaction schemes.
(1) Manufacturing method ##STR18## Reactions are allowed to proceed for 30 minutes to 5 hours at 50.degree. C.-200.degree. C. in an organic solvent. For the solvent, DMF, xylene, dichlorobenzene, etc. can be used.
(2) Manufacturing method ##STR19## (where E denotes halogen atoms or C.sub.1-6 alkoxy radicals) Reactions are allowed to go in an organic solvent for 1 hour to several tens of hours at a temperature of 0.degree. C. to boiling point of the solvent used, in the presence, if desired, of a base. For the solvent, benzene, toluene, etc. may be used. For the base, pyridine, toluene, etc. may be used.
(3) Manufacturing method ##STR20## Reactions are allowed to go in methanol or any other suitable organic solvent for 1 hour to 10 hours at a temperature of 50.degree. C. to the boiling point of the solvent used.
(4) Manufacturing method ##STR21## Reactions are allowed to go in DMF or any other suitable organic solvent for 30 minutes to 5 hours at a temperature of -20.degree. C. to 50.degree. C. and in the presence of a base. For the base, triethylamine, pyridine, etc. may be used. It is also possible to use sodium hydride etc. to produce beforehand a sodium salt of the compound having the formula (VII) and after this to allow this sodium salt to react with the compound having the formula (VIII).
(5) Manufacturing method (5) (A=A') ##STR22## Condensation reactions are allowed to go in acetonitrile or any other suitable organic solvent, at a temperature of 0.degree. C. to the boiling point of the solvent used and in the presence of a base. When this ends, if desired, the reaction solution is allowed to undergo cyclization reaction under heat. In the cyclization reaction are used acetonitrile, DMF, xylene, dichlorobenzene or other solvent.
(6) Manufacturing method (6) (A=A", B=B") ##STR23## Reactions are allowed to go in diethyl ether or any one of other suitable organic solvents, in the presence of a base, such as triethyleneamine for a period of 1 hour to several tens of hours, at a temperature of -20.degree. C. to 50.degree. C.
(7) Further, depending on the type of substituents of R.sub.1, A, B, D and R.sub.2, the compounds of this invention can also be manufactured by following the reaction scheme below or by suitably choosing known and similar reactions. ##STR24##
In whichever methods these reactions are allowed to proceed, normal after-treatments on completion of the reactions produce specified substance in good yields. The structure of the compounds of this invention has been determined by IR, NMR, MASS, etc. Depending on the type of substituents, some of the compounds of this invention have isomers, which this invention shall invariably cover.
The following examples illustrate the present invention.

EXAMPLE1
3-(2,6-dichlorophenyl)-5-(4-isopropoxybenzyl)-1,2,4-oxadiazole (Compound No. 10) ##STR25##
A solution of 102.5 g of N'-(4-isopropoxyphenylacetoxy)-2,6-dichlorobenzamidine in 500 ml of DMF was heated at 140.degree. C. for 1.5 hours.
After cooling, the solution was poured into 2 kg of ice, and extracted several times with ethyl acetate. The collected extracts were washed with water, dried over anhydrous magnesium colorised with chacoal and evaporated under reduced pressure.
The residue was washed with ligroin, then with cold absolute methanol to give 64.7 g of Compound No. 10. m.p. 67.degree.-68.degree. C.
EXAMPLE 2
3-(2,6-dichlorophenyl)-5-(4-t-butylanilinomethyl)-1,2,4-oxadiazole (Compound No. 68) ##STR26##
To a solution of 1 g of 3-(2,6-dichlorophenyl)-5-chloromethyl-1,2,4-oxadiazole in 10 ml of toluene, 1,13 g of 4-t-butylaniline and 2 ml of DMF were added, and the mixture was heated under reflux over night.
After cooling, the reaction mixture was poured into water, extracted with ethyl acetate and the extract was dried over anhydrous magnesium sulfate, evaporated under reduced pressure.
The residue obtained was purified by silica gel column chromatography to give 1.1 g of Compound No. 68. m.p. 104-106.degree. C.
EXAMPLE 3
3-(2,6-dichlorophenyl)-5-cyclohexylcarbamoyl-1,2,4-oxadiazole (Compound No. 114) ##STR27##
To a solution of 1 g of 3-(2,6-dichlorophenyl)-5-methoxycarbonyl-1,2,4-oxadiazole in 5 ml of toluene, was added 0.4 g of cyclohexylamine at room temperature.
After 3 hours, the reaction mixture was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography to give 1.1 g of Compound No. 114. m.p. 153-155.degree. C.
EXAMPLE 4
3-(2,6-dichlorophenyl)-5-(4-chlorobenzylamine)-1,2,4-oxadiazole (Compound No. 66) ##STR28##
To a solution of 1 g of 3-(2,6-dichlorophenyl)-5-trichloromethyl-1,2,4-oxadiazole in 10 ml of absolute methanol was added 0.5 g of 4-chlorobenzylamine at room temperature, and the mixture was heated under reflux for 10 hours.
The reaction mixture was then evaporated under reduced pressure and the residue was purified by column chromatography on silica gel to give 0.55 g of Compound No. 66. m.p. 148-150.degree. C.
EXAMPLE 5
3-(2,6-dichlorophenyl)-5-(4-t-butylbenzylthio)-1,2,4-oxadiazole (Compound No. 64) ##STR29##
To a solution of 0.6 g of 3-(2,6-dichlorophenyl)-5-mercapto-1,2,4-oxadiazole in 10 ml of DMF was added 0.11 g of 60% sodium hydride under cooling.
After one hour of stirring at room temperature, 0.5 g of 4-t-butylbenzyl chloride was added to the reaction mixture under cooling.
After 3 hours of stirring at room temperature, the reaction mixture was poured into ice-water, extracted with ethyl acetate and the extracted was washed with water, dried over anhydrous magnesium sulfate and evaporated under reduced pressure.
The residue obtained was purified by silica gel column chromatography to give 0.5 g of Compound No. 64. N.sub.D .sup.25 1.5893.
EXAMPLE 6
3-phenyl-5-benzoyl-1,2,4-oxadiazole (Compound No. 76) ##STR30##
To a solution of 2,5 g of N-hydroxybenzamidine in 20 ml of acetonitrile, 3.41 g of phenylglyoxyl chloride was added under cooling, and then 1.6 g of pyridine was added.
After 2 hours of stirring at room temperature, acetonitrile was distilled off under reduced pressure. The residue was extracted with ethyl acetate and the extract was washed with water, dried over anhydrous magnesium sulfate and after filtration ethyl acetate was evaporated under reduced pressure.
The residue obtained was purified by silica gel column chromatography to give 2,3 g of Compound No. 76. n.sub.D.sup.24.5 1 6119.
EXAMPLE 7
3-(2,6-dichlorophenyl)-5-(.alpha.-methyl-4-isopropoxybenzyl)-1,2,4-oxadiazole (Compound No. 61) ##STR31##
To a solution of 3 g of 3-(2,6-dichlorophenyl)-5-(4-isopropoxybenzyl)-1,2,4-oxadiazole in 20 ml of DMF was added 0.33 g of 60% sodium hydride below -5.degree. C.
After 2 hours of stirring at the same temperature, 1,2 g of methyl iodide was added to the solution, followed by stirring for 4 hours at room temperature.
The reaction mixture was then poured into ice-water, extracted with ethyl acetate and the extract was washed with water, dried over anhydrous magnesium sulfate and after filtration ethyl acetate was evaporated under reduced pressure.
The residue was purified by silica gel column chromatography to give 2.3 g of Compound No. 61. m.p. 84-86.degree. C.
EXAMPLE 8
3-(2,6-dichlorophenyl)-5-(4-(1-ethoxycarbonylethoxy) benzyl)-1,2,4-oxadiazole (Compound No. 33) ##STR32##
To a solution of 0.7 g of 3-(2,6 dichlorophenyl)-5-(4-hydroxybenzyl)-1,2,4-oxadiazole in 10 ml of acetonitrile, 0.31 g of anhydrous potassium carbonate and 0.45 g of ethyl 2-bromopropionate were added at room temperature.
The suspension solution was then heated under reflux over night.
After cooling, the reaction mixture was poured into water, extracted with ethyl acetate and the extract was washed with water, dried over anhydrous magnesium sulfate and after filtration ethyl acetate was evaporated under reduced pressure.
The residue obtained was purified by silica gel column chromatography to give 0.9 g of Compound No. 33. m.p. 90-92.degree. C.
EXAMPLE 9
3-(2,6-dichlorophenyl)-5-(.alpha.-hydroxyimino)-4-isopropoxybenzyl)-1,2,4-oxadiazole (Compound Nos. 106, 107) ##STR33##
To a suspension of 8 g of 3-(2,6-dichlorophenyl)-5-4-isopropoxybenzyl)-1,2,4-oxadiazole in 80 ml of absolute ethanol was added dropwise a solution of 5.2 g of isobutylnitrite in 5 ml of absolute ethanol with bubbling gaseous hydrogen chloride at room temperature.
After the addition of isobutylnitrite was completed, gaseous hydrogen chloride passed into the suspension for an additional 6 hours at the same temperature. The reaction mixture was then evaporated under reduced pressure, extracted with ethyl acetate and the extract was washed with water, dried over anhydrous magnesium sulfate and after filtration ethyl acetate was evaporated under reduced pressure.
The residue obtained was purified by silica gel column chromatography to give 1.6 g of Compound No. 106. m.p. 191-194 and 0.4 g of Compound No. 107. m.p. 146-149.degree. C.
EXAMPLE 10
3-(2,6-dichlorophenyl)-5-(-(N methylcarbamoyloximino)-4-isopropoxybenzyl)-1,2,4-oxadiazole (Compound No. 110) ##STR34##
To a solution of 0.7 g of 3-(2,6-dichlorophenyl)-5-(4-isopropoxy-.alpha.-hydroxyiminobenzyl)-1,2,4-oxadiazole in 10 ml of benzene, 0.12 g of methyl isocyanate and one drop of DBU were added at room temperature.
After 3 hours, the reaction mixture was evaporated under reduced pressure and the residue was purified by silica gel column chromatography to give 0.5 g of Compound No. 110. m.p 123-125.degree. C.
EXAMPLE 11
3-(2,6-dichlorophenyl)-5-(.alpha.-chloro-4-isopropoxybenzyl)-1,2,4-oxadiazole (Compound No. 101) ##STR35##
To a solution of 4 g of 3-(2,6-dichlorophenyl)-3-(4-isopropoxy-.alpha.-hydroxybenzyl)1,2,4oxadiazole in 12 ml of chloroform, 2.51 g of thionyl chloride and one drop of pyridine were added at room temperature.
After 1 hour of stirring the reaction mixture was heated under reflux for 30 minute and then evaporated under reduced pressure.
The residue was purified by column chromatography on silica gel to give 3.62 g of Compound No. 101. m.p 124-126.degree. C.
EXAMPLE 12
3-(2,6-dichlorophenyl)-5-(4-t-butylbenzylthio)-1,2,4-thiadiazole (Compound No. 127) ##STR36##
To a solution of 0.5 g of 3-(2,6-dichlorophenyl)-5-5-mercapto-1,2,4-thiadiazole in 5 ml of DMF was added 0.08 g of 60% sodium hydride at 0.degree. C.
After 30 minutes of stirring at room temperature, 0.35 g of 4-t-butylbenzyl chloride was added dropwise to the suspension at 0.degree. C.
After 2 hours of stirring at room temperature, the reaction mixture was poured into ice-water, extracted with ethyl acetate and the extract was washed with water, dried over anhydrous magnesium sulfate and evaporated under reduced pressure.
The residue obtained was purified by silica gel column chromatography to give 0.6 g of Compound No. 127. n.sub.D.sup.26 1 6132.
Inclusive the above, each compound with the scope of the present invention which can be prepared in analogous method is tabulated in Table 1.
TABLE 1 Structural Formula Compound ##STR37## Physical No. R.sub.1 X (A)n(B)m(D)l R.sub.2 Properties ( ) m.p. 1 ##STR38## O CH.sub.2 ##STR39## (30-31) 2 ##STR40## " " " (67-68) 3 ##STR41## " " " n.sub.D.sup.26 1.3935 4 ##STR42## " " " n.sub.D.sup.26 1.5717 5 ##STR43## " " " (48-50) 6 ##STR44## " " " (49-50) 7 ##STR45## " " " (83-85) 8 ##STR46## " " " (114-116) 9 ##STR47## " " " n.sub.D.sup.22 1.3320 10 ##STR48## " " " (67-68) 11 ##STR49## O CH.sub.2 ##STR50## n.sub.D.sup.26 1.5915 12 ##STR51## " " " (128-130) 13 ##STR52## " " " n.sub.D.sup.26 1.5511 14 ##STR53## " " " (42-44) 15 ##STR54## " " " n.sub.D.sup.27 1.5988 16 ##STR55## " " " (82-84) 17 ##STR56## " " " n.sub.D.sup.26 1.5469 18 ##STR57## " " " n.sub.D.sup.26 1.5610 19 ##STR58## " " " n.sub.D.sup.26 1.5618 20 ##STR59## O CH.sub.2 ##STR60## n.sub.D.sup.26 1.5836 21 ##STR61## " " " n.sub.D.sup.26 1.5923 22 ##STR62## " " " n.sub.D.sup.26 1.5593 23 ##STR63## " " " n.sub.D.sup.26 1.5640 24 ##STR64## " " ##STR65## (77-80) 25 " " " ##STR66## n.sub.D.sup.26 1.5669 26 " " " ##STR67## n.sub.D.sup.26 1.5611 27 " " " ##STR68## n.sub.D.sup.25 1.5997 28 " " " ##STR69## (108-111) 29 ##STR70## O CH.sub.2 ##STR71## (97-99) 30 " " " ##STR72## (74-75) 31 " " " ##STR73## (84-85) 32 " " " ##STR74## (127-128) 33 " " " ##STR75## (90-92) 34 " " " ##STR76## (133-135) 35 " " " ##STR77## (124-126) 36 ##STR78## " "" n.sub.D.sup.26 1.6176 37 ##STR79## " " " (75-77) 38 ##STR80## " " ##STR81## (117-119) 39 ##STR82## O CH.sub.2 ##STR83## (122-125) 40 " " " ##STR84## n.sub.D.sup.25 1.5744 41 " " " ##STR85## (79-80) 42 " " " ##STR86## (82-84) 43 " " " ##STR87## (93-95) 44 " " " ##STR88## (130-132) 45 " " " ##STR89## n.sub.D.sup.26 1.5727 46 " " " ##STR90## n.sub.D.sup.26 1.5622 47 " " " ##STR91## n.sub.D.sup.26 1.5641 48 " " " ##STR92## (68-70) 49 " " " ##STR93## (47-50) 50 ##STR94## O CH.sub.2 CH.sub.2 ##STR95## n.sub.D.sup.27 1.5625 51 ##STR96## " " " n.sub.D.sup.25 1.4365 52 ##STR97## " " " n.sub.D.sup.25 1.3145 53 ##STR98## " " " (78-80) 54 ##STR99## " " " (61-62) 55 ##STR100## " (n = m = 1 = O) " (90-92) 56 ##STR101## " " " (84-86) 57 ##STR102## " " " (105-107) 58 ##STR103## " " " (55-58) 59 ##STR104## " " " (115-118) 60 ##STR105## O (n = m = 1 = O) ##STR106## (122-124) 61 " " ##STR107## ##STR108## (84-86) 62 " " ##STR109## " (103-105) 63 " " ##STR110## " (95-96) 64 " " SCH.sub.2 ##STR111## n.sub.D.sup.25 1.5893 65 " " " ##STR112## (95-98) 66 " " NHCH.sub.2 " (148-150) 67 " " CH.sub.2 NH " (116-118) 68 " " " ##STR113## (104-106) 69 " " " ##STR114## (105-107) 70 " " " ##STR115## (101-103) 71 ##STR116## O CH.sub.2 NH ##STR117## (100-101) 72 " " " ##STR118## (67-69) 73 " " " ##STR119## (134-136) 74 " " " ##STR120## (110-111) 75 ##STR121## " ##STR122## ##STR123## (98-101) 76 ##STR124## " " " n.sub.D.sup.24.5 1.6119 77 ##STR125## " " " (107-108) 78 ##STR126## " " " (101-102) 79 ##STR127## " CHCH " (138-139) 80 " " " ##STR128## (170-173) 81 " " " ##STR129## (116-118) 82 ##STR130## O CHCH ##STR131## (92-94) 83 ##STR132## " " " (108-110) 84 ##STR133## " " " (135-136) 85 ##STR134## " " ##STR135## (116-118) 86 " " " ##STR136## (94-96) 87 ##STR137## " " " (120-122) 88 ##STR138## " ##STR139## ##STR140## (102-103.5) 89 " " ##STR141## " (117-117.5) 90 ##STR142## " " " (102-104) 91 ##STR143## " " " (121-124) 92 ##STR144## " " " (109-111) 93 ##STR145## O ##STR146## ##STR147## (206-208) 94 " " ##STR148## " (66-68) 95 ##STR149## " " " (78-80) 96 ##STR150## " ##STR151## ##STR152## (100-104) 97 " " ##STR153## " (112-114) 98 " " ##STR154## " (116-118) 99 " " ##STR155## ##STR156## (92-96) 100 " " ##STR157## " (112-114) 101 " " ##STR158## " (124-126) 102 " " ##STR159## " n.sub.D.sup.21.5 1.5651 103 " " ##STR160## " n.sub.D.sup.23 1.5519 104 ##STR161## O ##STR162## ##STR163## n.sub.D.sup.22.5 1.5525 105 " " ##STR164## " (86-89) 106 " " ##STR165## " (191-194) 107 " " " " (146-149) isomer 108 " " ##STR166## " (95-97) 109 " " ##STR167## " (110-115) 110 " " ##STR168## " (123-125) 111 " " CH.sub.2 ##STR169## (90-91) 112 " " " ##STR170## n.sub.D.sup.25 1.5541 113 " " (n = m = l = O) CH.sub.3 n.sub.D.sup.25 1.4711 114 " " ##STR171## ##STR172## (153-155) 115 ##STR173## O ##STR174## ##STR175## (148-149) 116 ##STR176## " ##STR177## CH.sub.3 (72-74) 117 ##STR178## " " " (112-114) 118 ##STR179## " CH.sub.2 ##STR180## (106-108) 119 " " " ##STR181## (82-84) 120 ##STR182## " " ##STR183## (61-64) 121 ##STR184## " " " (61-63) 122 ##STR185## " " " (45-47) 123 CH.sub.3 " " " n.sub.D.sup.25 1.5153 124 C.sub.2 H.sub.5 " " " n.sub.D.sup.26 1.5628 125 ##STR186## " " " n.sub.D.sup.26 1.5239 126 .sup.t C.sub.4 H.sub.9 O CH.sub.2 ##STR187## n.sub.D.sup.27 1.6574 127 ##STR188## S SCH.sub.2 ##STR189## n.sub.D.sup.26 1.6132 128 " " " ##STR190## (72-75) 129 " O ##STR191## ##STR192## (103-106) 130 " " ##STR193## " (63-66) 131 " " ##STR194## " n.sub.D.sup.30 1.5692 132 " " ##STR195## " (147-149) 133 " " ##STR196## " (192-194) 134 " " ##STR197## " n.sub.D.sup.25.5 1.5993 135 " " ##STR198## " (130-132) 136 " " ##STR199## " (85.5-87.5) 137 ##STR200## O CH.sub.2 ##STR201## n.sub.D.sup.24 1.5665 138 ##STR202## " " " (77-79) 139 ##STR203## " (n = m = 1 = O) ##STR204## (87-89) 140 ##STR205## " CH.sub.2 " (88-90) 141 ##STR206## " " ##STR207## (67-68) 142 ##STR208## " " " n.sub.D.sup.25 l.5609 143 ##STR209## " " " n.sub.D.sup.25 1.5755 144 ##STR210## " " ##STR211## (68-69) 145 ##STR212## O CH.sub.2 ##STR213## (74-75) 146 ##STR214## " ##STR215## ##STR216## (117-119) 147 " " ##STR217## " (125.5-127.5) 148 " " ##STR218## " (103.5-105.5) 149 " " ##STR219## " (66-67.5) 150 " " ##STR220## " (89-92.5) 151 " " ##STR221## " n.sub.D.sup.23.5 1.5425 152 " " ##STR222## " (119-120) 153 " " ##STR223## " n.sub.D.sup.23 1.5855 154 " " ##STR224## " n.sub.D.sup.26 1.5662 155 ##STR225## O ##STR226## ##STR227## (119-121) 156 " " ##STR228## " (183-186.5) 157 " " ##STR229## " (114-116.3) 158 " " ##STR230## " (173-175.5) 159 ##STR231## " ##STR232## " n.sub.D.sup.24 1.5810 160 ##STR233## " ##STR234## ##STR235## n.sub.D.sup.22 1.5698 161 " " ##STR236## " n.sub.D.sup.23 1.5609 162 " " ##STR237## " (68-71.5) 163 " " ##STR238## " (127-130) 164 " " ##STR239## " n.sub.D.sup.21 1.5708 165 ##STR240## O ##STR241## ##STR242## n.sub.D.sup.23 1.5812 166 " " ##STR243## " n.sub.D.sup.23 1.5851 167 " " ##STR244## " n.sub.D.sup.21 1.5471 168 " " O " (86-88) 169 " " S ##STR245## (147-151) 170 " " ##STR246## ##STR247## (146-148) 171 ##STR248## " ##STR249## " (vis oil) 172 " " ##STR250## " (vis oil) 173 ##STR251## " S " (76-80) 174 " " CF.sub.2 " n.sub.D.sup.27 1.5438 175 ##STR252## O ##STR253## ##STR254## (106-109) 176 ##STR255## " " " (143-145) 177 ##STR256## " ##STR257## " (127-131) 178 ##STR258## " " " 179 " " CF.sub.2 ##STR259## n.sub.D.sup.22 1.5471 180 ##STR260## " ##STR261## " (113-115) 181 ##STR262## " ##STR263## " (104-107) 182 " " ##STR264## " (97-100) 183 " " " " (182-184) isomer 184 " " ##STR265## " (51-55) 185 ##STR266## O ##STR267## ##STR268## n.sub.D.sup.20 1.5927 186 " " ##STR269## " (79-83) 187 ##STR270## " " " n.sub.D.sup.24 1.5910 188 " " (n = m = l = O) CCl.sub.3 (35-37) 189 ##STR271## " " " (91-93) 190 ##STR272## " " ##STR273## (62-64) 191 ##STR274## " " ##STR275## (184-187) 192 ##STR276## " " " (170-171) 193 ##STR277## " " ##STR278## (195-197) 194 ##STR279## " " ##STR280## (192-193) 195 ##STR281## S " ##STR282## (80-83) 196 " " " ##STR283## (79-81) 197 ##STR284## " " ##STR285## n.sub.D.sup.21 1.6022 198 " " " ##STR286## (65-68) 199 ##STR287## O CH.sub.2 ##STR288## (46-48) 200 " " " ##STR289## (90-92) 201 ##STR290## " " ##STR291## (52-53.5) 202 " " " ##STR292## (58-60) 203 ##STR293## S (n = m = l = O) ##STR294## (70-72) 204 ##STR295## O CH.sub.2 ##STR296## (41-42) 205 " " " ##STR297## (95.5-97) 206 ##STR298## " " " (76-78) 207 " " " ##STR299## n.sub.D.sup.21 1.5562 208 ##STR300## " " " (94-96) 209 " " " ##STR301## n.sub.D.sup.22.5 1.5646 210 ##STR302## " " " (109-110) 211 " " " ##STR303## n.sub.D.sup.31.5 1.5719
The acaricides covered by this invention contain as active ingredients one or more types of the compounds as expressed by the general formula (1). These active ingredients, which the compounds are, may be used as-produced but normally they are used in any of the forms which ordinary agricultural chemicals can take, namely wettable powder, dust, emulsifiable concentrate, suspension concentrates or other formulations. For additives and carriers are used soybean flour, wheat flour or other vegetable flours, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, clay or other fine mineral powders, when solid formulations are intended.
When liquid formulations are intended, then for solvents are used kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, water, etc. A surface active agent may, if necessary, be added in order to give a homogeneous and suitable formulation. The wettable powder, emulsifiable concentrates, flowables, etc. thus obtained are diluted with water into suspensions or emulsions of a prescribed concentration, before they are actually sprayed on plants in the field. In the case of dusts or granules, they are directly applied without further processing.
The concentration of the active ingredient in an pesticidal composition may very according to type of formulation, and is, for example, in the range of 5-70 weight percent, preferably 10-30 weight percent, in wettable powder; 5-30 weight percent, preferably 10-20 weight percent, in emulsifiable concentrate; 1-10 weight percent, preferably 2-5 weight percent in dust; 5-40 weight percent, preferably 10-30 weight percent in suspension concentrate; 1-10 weight percent, preferably 2-5 weight percent in granular formulation.
Needless to say, the compounds which this invention covers are sufficiently effective even if they are applied singly. Since these compounds are weak in adulticidal activity, however, their application in combination with one of more types of compounds having adulticidal activity against phytophagous mites, proves to be remarkably effective. In addition to adultcidally active compounds, one or more types of other agricultural chemicals may also be used in combination with the compounds of this invention.
Typical examples of acaricides or insecticides that can be used together with the compounds of this invention are as follows.
Acaricides (fungicides): BCPE chlorobenzilate, chloropropylate, proclonol, phenisobromolate, dicofol, dinobuton, binapacryl, chlorophenamidine, amitraz, BPPS, PPPS, benzomate, cyhexatin, fenbutatin-oxide, polynactin, chinomethionate, thioquinox, CPCBS, tetradifon, tetrasul, cycloprate, kayacidc, kayahope, 3-n-dodecyl-1,4-naphthoquinon-2-yl-acetate, calcium polysulfide.
Organophosphorus insecticides (acaricides): fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, vamidothion, phenthoate, dimethoate, formothion, malathion, dipterex, thiometon, phosmet, menazon, dichlorvos, acephate, EPBP, dialifor, methyl parathion, oxydemethon-methyl, ethion, aldicarb, propoxur.
Pyrethroid-type insecticides (acaricides): permethrin, cypermethrin, decamethrin, fenvalerate, fenpropathrin, pyrethrin, allethrin, tetramethrine, resmethrin, pallethrin, dimethrin, proparthrin, prothrin, 3-phenoxybenzyl-2,2-dichloro-1-(4-ethoxyphenyl)-1-cyclopropanecarboxylate .alpha.-cyano-3-phenoxybenzyl-2,2-dichloro-1-(4-ethoxyphenyl)-1-cyclopropanecarboxylate
(RS)-.alpha.-cyano-3-phenoxybenzyl(RS)-2-(4-trichlormethoxypenyl)-3-methylbutylate
(RS)-.alpha.-cyano-3-phenoxybenzyl(RS)-2-(2-chloro-4-trichloromethylanilino)3-methylbutylate
Machine oils
Some examples of the formulations are given below. The carriers, surface-active agents, etc. that are added, however, are not limited to these examples.
EXAMPLE 13
Emulsifiable concentrate
______________________________________The compound of this invention 10 partsAlkylphenyl polyoxyethylene 5 partsDimethyl formamide 50 partsXylene 35 parts______________________________________
These components are mixed and dissolved and, for use in spraying, the liquid mixture is water-diluted into an emulsion.
EXAMPLE 14
Wettable powder
______________________________________The compound of this invention 20 partsHigher alcohol sulfuric ester 5 partsDiatomaceous earth 70 partsWhite carbon 5 parts______________________________________
These components are mixed and ground to fine powders, which for use in spraying, are water-diluted into a suspension.
EXAMPLE 15
Dust
______________________________________The compound of this invention 5 partsTalc 94.6 partsSilica 0.3 partAlkylphenyl polyoxyethylene 0.1 part______________________________________
These are mixed and ground and used as-ground in spraying.
Industrial Applicability
The tests below show the acaricidal activity of the compounds of this invention.
Test 1
Control effect on desert spider mite
After being sowed in a 6 cm diameter pot, kidney beans sprouted and 7 to 10 days elapsed, their first leaves were inoculated with 30 female adults of desert spider mite resistant to organophosphorus chemicals. In the procedures of the Example 13 above, an emulsifiable concentrate of the compound of the present invention was then water-diluted to an emulsion at a concentration of 500 ppm and was sprayed on the inoculated leaves. Three days after spraying, the adults were removed. Concerning the eggs which the adults had deposited during these 3 days, an examination was conducted on the 11th day to see whether they had grown to adults. Thus the control efficacy of the acaricide was determined. The result are as shown in the following Table 2.
The control efficacy was obtained by the following formula. ##EQU1##
TABLE 2______________________________________Compound No. Control Efficacy (%)______________________________________4 1009 10010 10011 10012 10013 10014 10016 10018 10024 10026 10027 10028 10029 10030 10034 10035 10041 10043 10045 10046 10047 10048 10049 10050 10051 10052 10061 10063 10096 10097 10098 10099 100100 100101 100102 100105 100106 100110 100119 100135 100136 100146 100147 100148 100149 100150 100151 100152 100153 100154 100155 100156 100157 100158 100160 100161 100162 100163 100164 100165 100170 100174 100180 100185 100186 100190 100195 100197 100198 100199 100200 100201 100203 100204 100206 100207 100Comparative Compound* 48______________________________________ ##STR304##

Claims

1. A compound selected from the group consisting of:
(1) 3-(2,6-difluorophenyl)-5-(4-isopropoxybenzyl)-1,2,4-oxadiazole;
(2) 3-(2,6-dichlorophenyl)-5-)4-isopropoxybenzyl)-1,2,4-oxadiazole;
(3) 3-(2,6-dibromophenyl)-5-(4-isopropoxybenzyl)-1,2,4-oxadiazole;
(4) 3-(2,6-dichlorophenyl)-5-(4-cyclopentyloxybenzyl)-1,2,4,-oxadiazole;
(5) 3-(2,6-dichlorophenyl)-5(4-cyclohexyloxybenzyl)-1,2,4-oxadiazole;
(6) 3-(2,6-dichlorophenyl)-5-(4-sec-butyloxybenzyl)-1,2,4-oxadiazole;
(7) 3-(2,6-dichlorophenyl)-5(4-isopropylthiobenzyl)-1,2,4-oxadiazole;
(8) 3-(2,6-dichlorophenyl)-5-(.alpha.-acetoxy-4-cyclopentyl oxybenzyl)-1,2,4-oxadiazole;
(9) 3-(2,6-dichlorophenyl)-5-(.alpha.-hydroxy-4-cyclopentyl oxybenzyl)-1,2,4-oxadiazole;
(10) 3-(2,6-dichlorophenyl)-5-(.alpha.-chloro-4-cyclopentyl oxybenzyl)-1,2,4-oxadiazole;
(11) 3-(2,6-dichlorophenyl)-5-(.alpha.-acetoxy-4-isopropoxy benzyl)-1,2,4-oxadiazole;
(12) 3-(2,6-dichlorophenyl)-5-(.alpha.-hydroxy-4-isopropoxy benzyl)-1,2,4-oxadiazole;
(13) 3-(2,6-dichlorophenyl)-5-(.alpha.-dichloro-4isopropoxy benzyl)-1,2,4-oxadiazole;
(14) 3-(2,6-dichlorophenyl)5-(4-isopropoxybenzoyl)-1,2,4-oxadiazole;
(15) 3-(2,6-dichlorophenyl)-5-(.alpha.-hydroxyimino-4-isopropoxybenzyl)-1,2,4-oxadiazole;
(16) 3-(2,6-dichlorophenyl-5[(N-methylcarbamoyloxy imino)-4isopropoxybenzyl]-1,2,4oxadiazole;
(17) 3-(2,6-dichlorophenyl)5-(.alpha.-ethoxycarbonyloxy-4isopropoxybenzyl)-1,2,4-oxadiazole;
(18) 3-(2,6-dichlorophenyl)-5-(.alpha.-dichloroacetoxy-4isopropoxybenzyl)-1,2,4-oxadiazole;
(19) 3-(2,6-dichlorophenyl)-5(.alpha.-amino-4-isopropoxybenzyl)-1,2,4-oxadiazole; and,
(20) 3-(4-cyclopentyloxybenzyl)-5-(2,6-dichlorophenyl)-1,2,4-oxadiazole.
2. A compound selected from the group consisting of:
(1) 3-(2,6-dichlorophenyl)-5-(4-isopropoxybenzyl)-1,2,4-oxadiazole;
(2) 3-(2,6-difluorophenyl)-5-(4-isopropoxybenzyl)-1,2,4-oxadiazole;
(3) 3-(2,6-dibromophenyl-5-(4-1,2,4,-oxadiazole;
(4) 3-(2,6-dichlorophenyl)-5[(.alpha.-hydroxyimino)-4-isopropoxybenzyl]-1,2,4-oxadiazole; and,
(5) 3-(2,6-dichlorophenyl)-5-[(N-methylcarbamoyloxy imino)-4-isopropoxybenzyl]-1,2,4-oxadiazole.
3. The compound 3-(2,6-dichlorophenyl)-5-(4-isopropoxylbenzyl)-1,2,4-oxadiazole.
4. As a compound of claim 1, the compound being 3-(2,6-difluorophenyl)-5(4-isopropoxtbenzyl)-1,2,4oxadiazole.
5. As a compound of claim 1, the compound being 3-(2,6-dibromophenyl)-5-(4-isopropoxylbenzyl)-1,2,4-oxadiazole.
6. As a compound of claim 1, the compound being 3-(2,6-dichlorophenyl)-5(.alpha.-hydroxyimino)-4-isopropoxybenzyl)-1,2,4-oxadiazole.
7. 3-(2,6-dichlorophenyl-5[(N-methylcarbamoyloxy imino)-4-isopropoxybenzyl]-1,2,4-oxadiazole.
8. An acaricidal composition comprising as active ingredient the compound of claim 3.
9. An acaricidal composition comprising as active ingredient the compound of claim 4.
10. An acaricidal composition comprising as active ingredient the compound of claim 5.
11. An acaricidal composition comprising as active ingredient the compound of claim 6.
12. An acaricidal composition comprising as active ingredient the compound of claim 7.

Priority Claims (1)

Number	Date	Country	Kind
61-310145	Dec 1986	JPX

US Referenced Citations (1)

Number	Name	Date	Kind
4632983	Lamm	Dec 1980

Foreign Referenced Citations (1)

Number	Date	Country
713052	Jul 1965	CAX

Continuations (1)

	Number	Date	Country
Parent	136190	Dec 1987

Oxadiazole derivative

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