Nitrogen-containing heterocyclic compounds and compositions for controlling and/or preventing pests and blights (diseases)

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel nitrogen-containing heterocyclic compounds, insecticidal, acaricidal, nematicidal compositions and fungicidal compositions for agricultural and horticultural uses, said compositions containing said compounds as an active ingredient.
2. Description of the Prior Art
Hitherto, many insecticidal and acaricidal agents as well as fungicidal agents for agricultural and horticultural uses have been developed, and some of them have been put into practical use. These drugs have contributed to saving works for controlling and preventing pests and blights (or diseases); increasing productivity of agricultural and horticultural crops, domestic cattles and domestic fowls, as well as for improving environments to prevent epidemics.
However, pests and blights (diseases) have become resistant to these drugs and, thus, the effects thereof have not fully been exhibited.
From this viewpoint, there has been a demand for developing novel drugs having superior insecticidal and fungicidal properties.
Compounds which are similar to those of the invention are described in the publications given below. Representatives thereof are illustrated below: ##STR9##
(1) Japanese Pat. Laid-open Publication No. Sho 51-118768 discloses Compound A and the analogues thereof as intermediates for synthesizing medical drugs, wherein the substituent at 4-position of the 2(1H)-pyridone is restricted to an alkylamino group.
(2) European Pat. Laid-open Publication No. 216541 and Japanese Pat. Laid-open Publication No. Sho 61-72754 disclose that Compounds B and the analogues thereof are useful as an active ingredient of insecticides, wherein the substituent at 1-position of 2(1H)-pyridone is restricted to benzene ring and the substituent at 4-position thereof is restricted to CF.sub.3 group. Thus, these compounds are different in chemical structure from those of the present invention.
(3) West German Pat. Laid-open Publication Nos. 3439363 and 3605002 disclose that Compounds C are useful as an active ingredient of insecticidal and acaricidal agents, wherein the substituent at 6-position of the 4(3H)-pyridazinone is phosphate radical. Thus, compositions containing same are classified into so-called organophosphorous insecticides, and the compounds described therein are different from those of the present invention with respect to chemical structure and mechanism of insecticidal action.
(4) Japanese Pat. Laid-open Publication No. Sho 54-5995 discloses that Compounds D are useful as an active ingredient of herbicides. Therefore, the compounds described therein are different from those of the invention with respect to uses. Moreover, the substituent at 6-position of thienopyridiminone in the structure of the Compounds D is restricted to an alkyl group.
(5) U.S. Pat. No. 4634690 discloses that Compounds E are useful as an active ingredient of insecticidal, acaricidal and nematicidal compositions. These compounds, however, are different in chemical structure from those of the present invention because the substituent at 6-position of the 4(3H)-pyrimidinone ring of Compound E is restricted to an alkyl group.
(6) Japanese Pat. Laid-open Publication No. Sho 63-41466 discloses that Compounds F are useful as an active ingredient of herbicides. These compounds are different from those of the invention with respect to both their uses and chemical structure.
(7) Japanese Pat. Laid-open Publication No. Sho 61-145167 discloses that Compound G have an anti-tumor activity. These compounds are different from those of the present invention also in chemical structure.
(8) West German Pat. Laid-open Publication No. 3522805 discloses that Compounds H are useful as an active ingredient of herbicides. Therefore, the compounds described therein are different from those of the present invention in their uses. Moreover, the former compounds are different from the latter in chemical structure because the radical R" in the substituent (SR") at 4-position of the 2(1H)-pyrimidinone of the Compounds H is restricted to an alkyl, an alkenyl or an alkynyl group.
(9) U.S. Pat. No. 3,585,197 discloses that Compounds I are useful as an intermediate for synthesizing a herbicide. These is no description therein as to the biological action of the intermediate. These compounds are different also in chemical structure from those of the invention because the sbustituent at 4-position of the Compounds I is restricted to SCH.sub.2 C.sub.6 H.sub.5 radical.
(10) U.S. Pat. No. 4,500,345 discloses that Compounds J are useful as an active ingredient of herbicides. The compounds described therein are different from those of the present invention with respect to both their uses and chemical structure.
(11) European Pat. Laid-open Publication No. 35333 discloses that Compounds K are useful as an intermediate for synthesizing a herbicide. There is no description therein as to the biological action of the intermediate itself. The Compounds K are differnet in chemical structure from those of the present invention because the substituent at 5-position of the former compounds is restricted to SCH.sub.2 C.sub.6 H.sub.5 radical.
SUMMARY OF THE INVENTION
An object of the present invention is to provide novel nitrogen-containing heterocyclic compounds which have activities for controlling and/or preventing pests and blights (diseases).
Another object of the present invention is to provide an insecticidal, acaricidal and nematicidal compositions and fungicidal compositions for agricultural and horticultural uses, said compositions containing the above compounds as an active ingredient.
Other objects of the present invention will become apparent from the description given below.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to novel nitrogen-containing heterocyclic compounds and compositions for controlling and/or preventing pests and blights (diseases), said compositions comprising said compounds as an active ingredient.
Namely, the present invention relates to a nitrogen-containing heterocyclic compound of the following formula: ##STR10## wherein D represents --N.dbd. or ##STR11## E represents .dbd.N--, ##STR12## G represents --N.dbd., ##STR13## with proviso that when G represents --N.dbd. or ##STR14## the bond of G and E is double bond, and when G represents ##STR15## the bond thereof is a single bond, but the case that D represents ##STR16## E represents ##STR17## and G represents --N.dbd. is omitted; R.sup.1 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms;
R.sup.2 represents hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, an alkylsulfinyl group having 1 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms, a phenyl unsubstituted or substituted by halogen atom or an alkyl group, and,
R.sup.1 and R.sup.2 together form a ring of the formula: ##STR18## wherein, p represents 2 or 3, B.sup.1 represents sulfur atom, oxygen atom or CH.sub.2, and B.sup.2 represents nitrogen atom or CH:
X represents halogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl unsubstituted or substituted by halogen atom or an alkyl group, benzyl group, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, nitro group, cyano group, a haloalkyl group having 1 to 5 carbon atoms, or an alkylcarbonyl group having 1 to 5 carbon atoms;
Y represents an oxygen or sulfur atom;
A represents ##STR19## (wherein, R.sup.3 to R.sup.8 each independently represent hydrogen atom or an alkyl group having 1 to 5 carbon atoms);
Q represents a phenyl gorup having substituents or a pyridine which may have substituents wherein said substituents are selected from the group consisting of halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an alkynyloxy group having 2 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, a cyanoalkyl group having 1 to 5 carbon atoms, a haloalkyloxy group having 1 to 5 carbon atoms, a haloalkylthio group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, ##STR20## (wherein, W represents halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms or a haloalkylthio group having 1 to 5 carbon atoms; and m represents zero or an integer of from 1 to 4, said W being the same or different when m is an integer of 2 to 4), the number of the substituents being from 1 to 4 and said substituents being the same or different when the number thereof is 2, 3 or 4;
R.sup.9 represents hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a halogen atom; and
R.sup.10 represents hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more specifically the compound represented by any one of the following formulae [I]and [VII]: ##STR21## wherein R.sup.1, R.sup.2, R.sup.9, R.sup.10, X, Y, A and Q respectively represent the meaning defined above, as well as compositions for controlling and/or preventing pests and blights (or diseases), said compositions containing one or two or more of said compounds as an active ingredient.
the present inventors have found that the compounds of the present invention represented by one of the general formulae [I] through [VII] have excellent insecticidal, acaricidal, nematicidal actions and fungicidal actions for agricultural and horticultural uses. More specifically, the present inventors have found that the compounds of the invention are very useful for insecticidal, acaricidal and nematicidal compositions and fungicidal compositions for agricultural and horticultural uses; excellent compositions for sanitary and veterinary pest such as ticks, flies and mosquitoes (compositions for prevention of epidemics; and excellent compositions for ectoparasites on animals (e.g., ticks and flies). The present inventors have also found excellent these compounds exhibit excellent insecticidal, nematicidal activities against those pests which are resistant to conventional pesticidal compositions, as well as a long term persistency and/or residual activity to have completed the present invention.
Among the compounds of the present invention, those which have excellent activities for controlling and/or preventing blights (diseases) and pests are described below referring to the compound No. shown in Tables 1 and 2.
Compounds Nos. 54, 68, 72, 73, 74, 75, 118, 119, 122, 123, 125, 139, 140, 141, 144, 145, 146, 147, 149, 150, 154, 155, 156, 159, 161, 196, 218, 219, 220, 221, and 249.
The following compounds exhibit more remarkable effects. Compound Nos. 149, 154, 156 and 161
The compounds of the present invention can be prepared by any one of the following synthetic processes [A] through [C]. ##STR22##
In the above formulae (in Processes A through C), R.sup.1, R.sup.2, X, A, Q, R.sup.9 and R.sup.10 each have the same meanings as defined above, Y' represents SH group or halogen atom; M represents halogen atom, methanesulfonate, an arylsulfonate, OH or SH; R.sup.11 represents hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R.sup.12 represents an alkyl group having 1 to 5 carbon atoms.
In the above reaction (in Processes A through B), it is preferable to conduct the reactions in a solvent which does not affect the reaction in the presence of an appropriate base. As such solvents can be used lower alcohols (such as methanol and ethanols, etc.), ketones (such as acetone, methylethylketone, etc.), hydrocarbons (such as benzene, toluene, etc.), ethers (such as isopropylether, tetrahydrofuran, 1,4-dioxane, etc.), amides (such as N,N-dimethylformamine, hexamethylphosphoric triamide, etc.), and halogenated hydrocarbons (such as dichloromethane, dichloroethane). As necessary, it is possible to use mixtures of these solvents or mixtures of the solvent with water.
As the base can be used inorganic bases (such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate) and organic bases (such as sodium methoxide, sodium ethoxide, triethylamine, pyridine, etc.). As necessary, can be added the reaction system a tetraammonium salt (such as triethylbenzylammonium chloride or the like) as a catalyst. The reaction temperature ranges from -20.degree. C. to the boiling point of the solvent used in the reaction system, and is preferably in the range of from -5.degree. C. to the boiling point of the solvent used therein. Molar ratio of the starting materials can be optionally selected. However, it is advantageous to use the materials in an equimolar ration or near such ratio.
In Process A, a nitrogen-containing heterocyclic compound of the present invention represented by one of the formulae [I] through [VII] can be produced by reacting a compound represented by one of the formulae [Ia] through [VIIa] with a compound of the formula [VIII].
More specifically, in Process A, M in the formula [VIII] represents halogen atom, methanesulfonate or an arylsulfonate, preferably halogen atom and more preferably chloride or bromine atom, when Y' in the formulae [Ia] through [VIIa] is SH group. On the other hand, when Y' in the formulae [Ia] through [VIIa] is halogen atom, M in the formulae [VIII] represents OH or SH group. The solvents preferably used for the reaction include methanol, dioxane, N,N-dimethylformamide, hexamethylphosphoric triamide, toluene, etc. The bases preferably used include inorganic bases, especially sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, etc. The reaction temperature is preferably in the range of from 10.degree. C. to 80.degree. C.
In the case where purification of the compound of the present invention is required, conventional purification technics such as recrystallization, column chromatography, etc. can be used for separation and purification of the compound.
In Process B, a nitrogen-containing heterocyclic compound of the present invention represented by one of the formulae [I] through [III] can be produced by reacting a compound represented by one of the formulae [Ib] through [IIIb] with a compound of the formula [VIII], wherein M represents halogen atom, methanesulfonate or an arylsulfonate.
In Process B, there may be produced C-alkylated substances of the following formula [Ic], [IIc] or [IIIc] as by-products. ##STR23##
In such case, it is necessary to separate these by-products from the compound of the invention to purify the latter compound. Conventional purification technics such as recrystallization, column chromatography, etc. can be used for such separation and purification.
Process C utilizes a cyclization reaction to produce the compounds of the present invention.
In Process C-1, a compound [V] of the present invention can be produced by heating an isothiourea of the formula [IX] and an ortho-ester of the formula [X] in the presence of an organic acid or an inorganic acid.
In Process C-2, a compound [VI] of the present invention can be produced by reacting an isothiourea of the formula [XI] with a carbonylating agent (such as phosgene or the like).
In Process C-3, a compound [VI] of the present invention can be produced by heating an isothiourea of the formula [XII] in the presence of an inorganic base or an organic base.
The compounds according to the present invention are specifically illustrated, for example, by the compounds listed in Tables 1 and 2 below.
Incidentally, it should be understood that the compounds shown in Tables 1 and 2 are only illustrated and that the present invention is not restricted to these compounds.
In the tables below, t represents tertiary, i represents iso, s represents secondary, c represents cyclo, Me represents methyl group, Et represents ethyl group, Pr represents propyl group, Bu represents butyl group, Pen represents pentyl group, Hex represents hexyl group and Ph represents phenyl group.
TABLE 1__________________________________________________________________________ In the compounds of the formula: ##STR24##No. R.sup.1 R.sup.2 X Y A Zn__________________________________________________________________________1 Me H Br S CH.sub.2 4-Cl2 Et H Br S CH.sub.2 4-Cl3 i-Pr H Br S CH.sub.2 4-Cl4 t-Bu H Br S CH.sub.2 4-Cl5 Me H Br O CH.sub.2 4-Cl6 Me H Br S CH.sub.2 4-Me7 Et H Br S CH.sub.2 4-Me8 Me H Br S CH.sub.2 4-i-Pr9 Et H Br S CH.sub.2 4-i-Pr10 Me H Br S CH.sub.2 4-t-Bu11 Et H Br S CH.sub.2 4-t-Bu12 t-Bu H Br S CH.sub.2 4-t-Bu13 Me H Br O CH.sub.2 4-t-Bu14 Me H Br S CH.sub.2 4-Hex15 Et H Br S CH.sub.2 4-Hex16 t-Bu H Br S CH.sub.2 4-c-Hex17 Me H Br O CH.sub.2 4-CF.sub.318 Me H Br S CH.sub.2 4-C.sub.6 H.sub.519 Et H Br S CH.sub.2 4-C.sub.6 H.sub.520 Et H Br S CH.sub.2 4-Q121 t-Bu H Br O CH.sub.2 4-Q122 Me H Br O CH.sub.2 4-Q223 Et H Br O CH.sub.2 4-Q224 Pr H Br O CH.sub.2 4-Q225 t-Bu H Br S CH.sub.2 4-Q426 Me H Br O CH.sub.2 4-Q427 Et H Br O CH.sub.2 4-Q428 Pr H Br O CH.sub.2 4-Q429 Et H Br S CH.sub.2 4-OPr30 t-Bu H Br S CH.sub.2 4-OPr31 t-Bu H Br S CHMe 4-t-Bu32 Et H Cl S CH.sub.2 4-t-Bu33 t-Bu H Cl O CH.sub.2 4-t-Bu34 Et H Me S CH.sub.2 4-t-Bu35 t-Bu H Me O CH.sub.2 4-t-Bu36 t-Bu H Me S CH.sub.2 4-c-Hex37 Me Me Br S CH.sub.2 4-Cl38 t-Bu Me Br S CH.sub.2 4-Cl39 Me Me Br O CH.sub.2 4-Cl40 Me Me Br S CH.sub.2 4-Me41 Pr Me Br O CH.sub.2 4-i-Pr42 Me Me Br S CH.sub.2 4-t-Bu43 t-Bu Me Br S CH.sub.2 4-t-Bu44 Me Me Br O CH.sub.2 4-t-Bu45 Pr Me Br O CH.sub.2 4-t-Bu46 t-Bu Me Br O CH.sub.2 4-t-Bu47 Me Me Br S CH.sub.2 4-Hex48 t-Bu Me Br S CH.sub.2 4-Hex49 t-Bu Me Br S CH.sub.2 4-c-Hex50 Me Me Br O CH.sub.2 4-CF.sub.351 t-Bu Me Br S CH.sub.2 4-C.sub.6 H.sub.552 t-Bu Me Br S CH.sub.2 4-Q153 Me Me Br O CH.sub.2 4-Q254 Et Me Br O CH.sub.2 4-Q255 Pr Me Br O CH.sub.2 4-Q256 t-Bu Me Br S CH.sub.2 4-Q457 Me Me Br O CH.sub.2 4-Q458 Et Me Br O CH.sub.2 4-Q459 t-Bu Me Br O CH.sub.2 4-OPr60 t-Bu Me Br S CHMe 4-t-Bu61 t-Bu Me Cl O Ch.sub.2 4-t-Bu62 t-Bu Me Cl S CH.sub.2 4-c-Hex63 t-Bu Me Cl S CH.sub.2 4-Q164 t-Bu Me Cl O CH.sub. 2 4-Q265 Et Me Me S CH.sub.2 4-t-Bu66 t-Bu Me Me S CH.sub.2 4-t-Bu67 t-Bu Me Me S CH.sub.2 4-c-Hex68 Et Me Me O CH.sub.2 4-Q269 Et Me Me S CHMe 4-t-Bu70 Et Et Br S CH.sub.2 4-Cl71 Et Et Cl S CH.sub.2 4-t-Bu72 Et Et Me O CH.sub.2 4-t-Bu73 Et Et Me O CH.sub.2 4-c-Hex74 Et Et Me O CH.sub.2 4-Q175 Et Et Me O CH.sub.2 4-Q276 Et i-Pr Br S CH.sub.2 4-t-Bu77 Et i-Pr Br S CH.sub.2 4-c-Hex78 Me i-Pr Br O CH.sub.2 4-Q279 Et i-Pr Br S CH.sub.2 4-OPr80 Et i-Pr Cl S CH.sub.2 4-t-Bu81 Me t-Bu Br S CH.sub.2 4-t-Bu82 Et t-Br Br S CH.sub.2 4-OPr83 Me t-Bu Cl S CH.sub.2 4-t-Bu84 Me t-Bu Me S CH.sub.2 4-t-Bu85 Me C.sub.6 H.sub.5 Br O CH.sub.2 4-t-Bu86 Me C.sub.6 H.sub.5 Br O CH.sub.2 4-Q287 Me C.sub.6 H.sub.5 Cl S CH.sub.2 4-t-Bu88 Et MeO Br S CH.sub.2 4-Cl89 Et MeO Br S CH.sub.2 4-t-Bu90 t-Bu MeO Br S CH.sub.2 4-t-Bu91 Et MeO Br O CH.sub.2 4-t-Bu92 Et MeO Br S CH.sub.2 4-c-Hex93 Me MeO Br S CH.sub.2 4-Q194 Et MeO Br O CH.sub.2 4-Q295 Et MeO Br S CH.sub.2 4-OPr96 t-Bu MeO Br S CH.sub.2 4-OPr97 Et MeO Br S CHMe 4-t-Bu98 Et MeO Cl S CH.sub.2 4-t-Bu99 t-Bu MeO Cl S CH.sub.2 4-t-Bu100 Et MeO Cl S CH.sub.2 4-c-Hex101 Et MeO Cl S CH.sub.2 4-Q1102 Et MeO Cl S CH.sub.2 4-Q2103 t-Bu MeO Me S CH.sub.2 4-t-Bu104 Et MeO Me O CH.sub.2 4-t-Bu105 Et MeO Me S CH.sub.2 4-Q1106 Et MeO Me S CH.sub.2 4-Q2107 t-Bu MeO Me S CH.sub.2 4-Q2108 Me EtO Br S CH.sub.2 4-t-Bu109 Et EtO Me S CH.sub.2 4-t-Bu110 t-Bu CH.sub.2 CHCH.sub.2 O Br S CH.sub.2 4-t-Bu111 Et CH.sub.2 CHCH.sub.2 O Me S CH.sub.2 4-Q1112 t-Bu CH CCH.sub.2 O Me O CH.sub.2 4-t-Bu113 Me MeS Br O CH.sub.2 4-Cl114 Et MeS Br O CH.sub.2 4-Cl115 i-Pr MeS Br O CH.sub.2 4-Cl116 Me MeS Br O CH.sub.2 4-i-Pr117 Et MeS Br O CH.sub.2 4-i-Pr118 Me MeS Br O CH.sub.2 4-t-Bu119 Et MeS Br O Ch.sub.2 4-t-Bu120 i-Pr MeS Br O CH.sub.2 4-t-Bu121 t-Bu MeS Br O CH.sub.2 4-t-Bu122 Me MeS Br O CH.sub.2 4-c-Hex123 Et MeS Br O CH.sub.2 4-c-Hex124 i-Pr MeS Br O CH.sub.2 4-c-Hex125 Me MeS Br O CH.sub.2 4-Hex126 Me MeS Br O CH.sub.2 4-C.sub.6 H.sub.5127 Me MeS Br O CH.sub.2 4-OPr128 Et MeS Br O CH.sub.2 4-Q1129 i-Pr MeS Br O CH.sub.2 4-Q1130 Me MeS Br O CH.sub.2 4-Q2131 Et MeS Br O CH.sub.2 4-Q2132 i-Pr MeS Br O CH.sub.2 4-Q2133 Me MeS Br O CHMe 4-t-Bu134 Et MeS Br S CMe.sub.2 4-t-Bu135 Et MeS Cl O CH.sub.2 4-Q1136 Et MeS Me S CH.sub.2 4-Cl137 Me MeS Me O CH.sub.2 4-Cl138 Me MeS Me O CH.sub.2 4-i-Pr139 Et MeS Me S CH.sub.2 4-t-Bu140 Me MeS Me O CH.sub.2 4-t-Bu141 Et MeS Me O CH.sub.2 4-t-Bu142 Pr MeS Me O CH.sub.2 4-t-Bu143 t-Bu MeS Me O CH.sub.2 4-t-Bu144 Me MeS Me O CH.sub.2 4-c-Hex145 Et MeS Me O CH.sub.2 4-c-Hex146 Pr MeS Me O CH.sub.2 4-c-Hex147 Et MeS Me O CH.sub.2 4-Bu148 Et MeS Me S CH.sub.2 4-CF.sub.3149 Et MeS Me S CH.sub.2 4-OPr150 Et MeS Me O CH.sub.2 4-OPr151 Me MeS Me O CH.sub.2 3,4-Cl.sub.2152 Pr MeS Me O CH.sub.2 3,4-Cl.sub.2153 Me MeS Me O CH.sub.2 2,4-Cl.sub.2154 Et MeS Me S CH.sub.2 4-Q1155 Me MeS Me O CH.sub.2 4-Q1156 Et MeS Me O CH.sub.2 4-Q1157 Pr MeS Me O CH.sub.2 4-Q1158 t-Bu MeS Me O CH.sub.2 4-Q1159 Et MeS Me S CH.sub.2 4-Q2160 Me MeS Me O CH.sub.2 4-Q2161 Et MeS Me O CH.sub.2 4-Q2162 Pr MeS Me O CH.sub.2 4-Q2163 Me MeS Me O CH.sub.2 4-Q3164 Et MeS Me O CH.sub.2 4-CMe.sub.2 CN165 t-Bu MeS Me S CH.sub.2 4-OCH.sub.2 CF.sub.3166 Et MeS Et O CH.sub.2 4-t-Bu167 Et MeS Et O CH.sub.2 4-c-Hex168 Et MeS Et O CH.sub.2 4-Q1169 Et MeS Et O CH.sub.2 4-Q2170 Et MeS i-Pr O CH.sub.2 4-Q1171 c-Hex MeS Me S CH.sub.2 4-t-Bu172 Et MeS MeS(O) S CH.sub.2 4-t-Bu173 Et MeS EtS(O) S CH.sub.2 4-OPr174 Et MeS MeSO.sub.2 S CH.sub.2 4-Cl175 Me 4-ClC.sub.6 H.sub.4 Br O CH.sub.2 4-t-Bu176 Me 4-MeC.sub.6 H.sub.4 Br O CH.sub.2 4-Q1177 Et MeS Me S CH.sub.2 4-OCH.sub.2 CHCH.sub.2178 Et MeS Me S CH.sub.2 4-OCH.sub.2 CCH179 Et MeS Me S CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-OPh180 Et MeS Me S CH.sub.2 CH.sub.2 O 2,6-Me.sub. 2 4-(OC.sub.6 H.sub.4 Me4)181 Et MeS Me S CH.sub.2 4-OCHF.sub.2182 Et MeS Me S CH.sub.2 4-COOMe183 Me MeS Me S CH.sub.2 4-COOBut184 Et MeS Me S CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-Q5185 Et MeS Me S CH.sub.2 4-Q6186 Et MeS Me O CH.sub.2 4-(C.sub.6 H.sub.4 OCHF.sub.2 4)187 Et MeS Me O CH.sub.2 4-(C.sub.6 H.sub.4 SCHF.sub.2 4)188 Et MeS Me S CH.sub.2 4-CO(C.sub.6 H.sub.4 SMe4)189 Et EtS Br O CH.sub.2 4-t-Bu190 Et EtS Br O CH.sub.2 4-c-Hex191 Et EtS Br O CH.sub.2 4-Q2192 Et EtS Br O CH.sub.2 4-F193 Et EtS Br O CH.sub.2 3,4-Cl.sub.2194 Et EtS Me O CH.sub.2 4-t-Bu195 Et EtS Me O CH.sub.2 4-c-Hex196 Et EtS Me O CH.sub.2 4-Q1197 Et EtS Me O CH.sub.2 4-O(CH.sub.2).sub.4 OMe198 Et i-PrS Me O CH.sub.2 4-t-Bu199 Et i-PrS Me O CH.sub.2 4-c-Hex200 Et i-PrS Me O CH.sub.2 4-Q1201 Et i-PrS Me O CH.sub.2 4-Q2202 Et PrS Br O CH.sub.2 4-t-Bu203 Et PrS Br O CH.sub.2 4-c-Hex204 Et PrS Br O CH.sub.2 4-Q1205 Et PrS Br O CH.sub.2 4-Q2206 Et PrS Br O CH.sub.2 4-F207 Et PrS Br O CH.sub.2 3,4-Cl.sub.2208 t-Bu PrS Me S CH.sub.2 4-t-Bu209 Et CH.sub.2 CHCH.sub.2 S Br S CH.sub.2 4-Q1210 Et CH.sub.2 CHCH.sub.2 S Me S CH.sub.2 4-Q1211 Et CHCCH.sub.2 S Me S CH.sub.2 4-Q1212 Et Me.sub.2 N Me S CH.sub.2 4-t-Bu213 Me MeS Br O CH.sub.2 CMeCH 4-Br214 Me MeS Br O CH.sub.2 CMeCH 2,4-Cl.sub.2215 Me MeS Me O CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-Pen216 Et MeS Me O CH.sub.2 CH.sub.2 4-Cl217 Et MeS Br S CH.sub.2 CH.sub.2 CH.sub.2 4-OPr218 CH.sub.2 CHCH.sub.2 MeS Me O CH.sub.2 4-t-Bu219 CH.sub.2 CHCH.sub.2 MeS Me O CH.sub.2 4-c-Hex220 CH.sub.2 CHCH.sub.2 MeS Me O CH.sub.2 4-Q1221 CH.sub.2 CHCH.sub.2 MeS Me O CH.sub.2 4-Q2222 CHCCH.sub.2 MeS Me O CH.sub.2 4-Q1223 Et MeS Ph O CH.sub.2 4-t-Bu224 Et MeS Ph O CH.sub.2 4-c-Hex225 Et MeS Ph O CH.sub.2 4-Q1226 Et MeS Ph O CH.sub.2 4-Q2227 Et MeS MeO O CH.sub.2 4-t-Bu228 Et MeS MeO O CH.sub.2 4-Q1229 Et MeS MeS O CH.sub.2 4-t-Bu230 Et MeS NO.sub.2 O CH.sub.2 4-Q1231 Et MeS CF.sub.3 S CH.sub.2 4-t-Bu232 Et MeS CF.sub.3 S CH.sub.2 4-Q1233 Et Et Me O CH.sub.2 4-F234 Et MeS Et O CH.sub.2 3,4-Cl.sub.2235 Et MeS Et O CH.sub.2 4-i-Pr236 Et EtS Me O CH.sub.2 3,4-Cl.sub.2237 Et MeS Et O CH.sub.2 4-F238 Et EtS Me O CH.sub.2 4-F239 Pr MeS Me O CH.sub.2 4-F240 Et Et Me O CH.sub.2 4-Bu241 Et Et Me O CH.sub.2 4-i-Pr242 CH.sub.2 CHCH.sub.2 MeS Me O CH.sub.2 4-F243 CH.sub.2ad,4 CHCH.sub.2 MeS Me O CH.sub.2 3,4-Cl.sub.2244 Et i-PrS Me O CH.sub.2 4-F245 Et i-PrS Me O CH.sub.2 3,4-Cl.sub.2246 Et MeS Ph O CH.sub.2 4-F247 Et MeS Ph O CH.sub.2 3,4-Cl.sub.2248 Et MeS Ph O CH.sub.2 CMeCH 2,4-Cl.sub.2249 CH.sub.2CHCH.sub.2 MeS Me O CH.sub.2 4-OPr250 Et EtS Me O CH.sub.2 4-OPr251 Et MeS Me O CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-Q7252 Et MeS Me O CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-Q8253 Et MeS Me O CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-Q9254 Et MeS Me O CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-I255 Et MeS Me O CH.sub.2 CH.sub.2 O 2,6-Me.sub.2 4-OMe256 Et MeS Cl O CH.sub.2 4-F257 Et MeS OMe O CH.sub.2 4-F258 Et MeS CH.sub.2 Ph O CH.sub.2 4-Q1259 Et MeS CH.sub.2 Ph O CH.sub.2 4-Q2260 Et MeS CH.sub.2 Ph O CH.sub.2 4-c-Hex261 Et MeS CH.sub.2 Ph O CH.sub.2 4-F262 Et MeS CH.sub.2 Ph O CHMe 4-t-Bu263 Et MeS i-Pr O CH.sub.2 4-F__________________________________________________________________________
TABLE 2______________________________________ ##STR25## ##STR26## ##STR27## ##STR28## ##STR29## ##STR30## ##STR31## ##STR32## ##STR33## ##STR34## ##STR35## ##STR36## ##STR37## ##STR38## ##STR39## ##STR40## ##STR41## ##STR42## ##STR43## ##STR44## ##STR45## ##STR46## ##STR47## ##STR48## ##STR49## ##STR50## ##STR51## ##STR52## ##STR53## ##STR54## ##STR55## ##STR56## ##STR57## ##STR58## ##STR59## ##STR60## ##STR61## ##STR62## ##STR63## ##STR64## ##STR65## ##STR66## ##STR67## ##STR68## ##STR69## ##STR70## ##STR71## ##STR72## ##STR73##______________________________________
Incidentally, in case that a compound of the present invention has asymmetric carbon atoms, the optically active (+) isomer and (-) isomer thereof are also included in the present invention.
Moreover, in case that a compound of the present invention has stereoisomers, all the isomers are included in the present invention.
In Tables 1 and 2 above, Q1 through Q9 represents the following groups; ##STR74##
The compound numbers described in Tables 1 and 2 above are referred to in the following preparation examples, formulation examples and test examples.
The preparation of the present compounds is explained in detail by way of the following working examples which are not to restrict the present invention.

PREPARATION EXAMPLE 1
Synthesis of 5-bromo-6-(4'-t-butylbenzylthio)-3-ethyl-4(3H)-pyrimidinone (Synthesis of Compound No. 11)
In 10 ml of methanol were dissolved 0.48 g of 5-bromo-6-chloro-3-ethyl-4(3H)-pyrimidinone and 0.36 g of 4-t-buthylbenzyl-mercaptan. The resulting solution was incorporated with 0.25 g of sodium carbonate and then stirred for 3 hours at room temperature. The solution was poured into water and then extracted with benzene. The extract was washed with water and dried over anhydrous sodium sulfate. Solvent was distilled off under reduced pressure. The oil thus obtained was purified by means of column chromatography (on silica gel, eluting with benzene) to give 0.73 g of the intended product as a colorless oil.
.sup.1 H-NMR(CDCl.sub.3, .delta., TMS) 1.29 (s, 9H), 1.37 (t, 3H, J=7 Hz), 3.95 (q, 2H, J=7 Hz), 4.31 (s, 2H), 7.22 (s, 4H), 7.90 (s, 1H).
PREPARATION EXAMPLE 2
Synthesis of 5-bromo-6-(4'-trifluoromethylbenzyloxy)-3-methyl-4(3H)-pyrimidinone (Synthesis of Compound No. 17)
Sodium hydride (55% in mineral oil) (0.22 g) was suspended in 10 ml of dioxane, and then 0.88 g of 4-trifluoromethylbenzyl alcohol was added thereto. The resulting mixture was stirred for one hour at room temperature, then incorporated with 1.12 g of 5-bromo-6-chloro-3-methyl-4(3H)-pyrimidinone and stirred for 15 hours. The resulting solution was poured into water, and the resulting crystals were filtered off and then recrystallized from a benzene-hexane mixture to give 1.60 g of the intended product.
Melting point (m.p.): 171.9.degree.-172.9.degree. C.
PREPARATION EXAMPLE 3
Synthesis of 5bromo-6-(4'-methylbenzylthio)-2,3-dimethyl-4(3H)-pyrimidinone (Synthesis of Compound No. 40)
In 10 ml of methanol were dissolved 0.59 g of 5-bromo-6-chloro-2,3-dimethyl-4(3H)-pyrimidinone and 0.35 g of 4-methylbenzyl mercaptan and then 0.25 g of sodium carbonate was added thereto. The resulting mixture was stirred for 3 hours at room temperature. The solution thus obtained was poured into water and extracted with benzene. The extract was washed with water and dried over anhydrous sodium sulfate. Solvent was distilled off therefrom under reduced pressure to give an oil. The oil thus obtained was purified by means of column chromatography (on silica gel, eluting with benzene) to give 0.72 g of the intended product.
M.p.: 73.0.degree.-74.0.degree. C.
PREPARATION EXAMPLE 4
Synthesis of 2,5-dimethyl-3-ethyl-6-[4'-(4"-fluoro-benzyloxy)benzyloxy]-4(3H)-pyrimidinone (Synthesis of Compound No. 68)
Sodium hydride (55% in mineral oil) (0.23 g) was suspended in 10 ml of dioxane, and then 1.24 g of 4-(4'-fluorobenzyloxy)benzyl alcohol was added thereto. The resulting mixture was stirred for one hour at room temperature, then incorporated with 1.00 g of 6-chloro-2,5-dimethyl-3-ethyl-4(3H)-pyrimidinone and stirred for 15 hours. The resulting solution was poured into water, and the resulting crystals were filtered off and recrystallized from a benzene-hexane mixture to give 1.83 g of the intended product.
M.p.: 81.0.degree.-82.3.degree. C.
PREPARATION EXAMPLE 5
Synthesis of 2,3-diethyl-5-methyl-6-[4'-(4"-trifluoromethyl-phenoxy)benzyloxy]-4(3H)-pyrimidinone (Synthesis of Compound No. 74)
In 15 ml of N,N-dimethylformamide were dissolved 0.91 g of 2,3-diethyl-6-hydroxy-5-methyl-4(3H)-pyrimidinone and 1.66 g of 4-(4'-trifluoromethylphenoxy)benzyl bromide, and then 0.69 g of potassium carbonate was added thereto. The mixture was stirred for 18 hours at room temperature. The resulting solution was poured into water and extracted with benzene. The extract was washed with water, dried over anhydrous sodium sulfate and freed of solvent by distillation under reduced pressure. The oil thus obtained was purified by means of column chromatography (on silica gel, eluting with benzene) to give 1.35 g of the intended product.
M.p.: 93.8.degree.-95.7.degree. C.
PREPARATION EXAMPLE 6
Synthesis of 5-bromo-6-(4'-chlorobenzyloxy)-2-methylthio-3-i-propyl-4(3H)-pyrimidinone (Synthesis of Compound No. 115)
In 20 ml of N,N-dimethylformamide were dissolved 1.0 g of 5-bromo-6-hydroxy-2-methylthio-3-i-propyl-4(3H)-pyrimidinone and 0.74 g of 4-chlorobenzylbromide, and then 1 g of potassium carbonate was added thereto. The mixture was subjected to a reaction at 80.degree. C. for 3 hours. After allowing to cool in air, the resulting solution was poured into 50 ml of water and then extracted twice with 30 ml of ethyl ether. The ethyl ether layer was washed with water, dried over anhydrous sodium sulfate and freed of solvent by distillation under reduced pressure to give 1.25 g of a crude product. The product was purified by means of column chromatography (on silica gel, eluting with benzene) to give 0.8 g of the intended product as an oil.
n.m.r. (CDCl.sub.3, .delta., TMS) 1.58 (d, 6H, J=7 Hz), 2.48 (s, 3H), 4.60 (dq, 1H, J=7 Hz), 5.39 (s, 2H), 7.30 (s, 4H).
PREPARATION EXAMPLE 7
Synthesis of 5-bromo-6-(4'-cyclohexylbenzyloxy)-3-ethyl-2-methylthio-4(3H)-pyrimidinone (Synthesis of Compound No. 123)
In 20 ml of N,N-dimethylformamide were dissolved 1 g of 5-bromo-3-ethyl-6-hydroxy-2-methylthio-4(3H)-pyrimidinone and 0.8 g of 4-cyclohexylbenzyl chloride, and then 1 g of anhydrous potassium carbonate was added thereto. The mixture was subjected to a reaction at 80.degree. C. for 3 hours. After allowing to cool in air, the resulting solution was poured into 50 ml of water and extracted twice with 30 ml of ethyl ether. The ethyl ether layer was washed with water, dried over anhydrous sodium sulfate and then freed of solvent by distillation under reduced pressure to give 1.65 g of a crude product.
The product was purified by means of column chromatography (on silica gel, eluting with benzene) to give 0.7 g of the intended product as an oil.
n.m.r. (CDCl.sub.3, .delta., TMS) 1.31 (t, 3H, J=7 Hz), 1.2-2.1 (m, 10H), 2.53 (s, 3H), 2.3-2.7 (m, 1H), 4.10 (q, 2H, J=7 Hz), 5.41 (s, 2H), 7.05-7.45 (m, 4H).
PREPARATION EXAMPLE 8
Synthesis of 6-(4'-t-butylbenzyloxy)-3,5-dimethyl-2-methylthio-4(3H)-pyrimidinone (Synthesis of Compound No. 140)
In 10 ml of hexamethyl phosphoric triamide were dissolved 1 g of 3,5-dimethyl-6-hydroxy-2-methylthio-4(3H)-pyrimidinone and 1 g of 4-t-butylbenzyl chloride, and thereto was added 0.3 g of sodium hydride (55% in mineral oil). The mixture was stirred for 15 hours at room temperature. The resulting solution was poured into 50 ml of water and then extracted twice with 30 ml of ethyl ether. The ethyl ether layer was dried over anhydrous sodium sulfate and freed of solvent by distillation under reduced pressure to give 1.9 g of a crude product. The product was purified by means of column chromatography (on silica gel, eluting with benzene) and then washed with a mixture of hexane and ethyl ether (10:1) to give 0.8 g of the intended product.
M.p.: 91.0.degree.-96.6.degree. C.
PREPARATION EXAMPLE 9
Synthesis of 3-ethyl-5-methyl-2-methylthio-6-[4'-(4"-trifluoromethylphenoxy)benzyloxy]-4(3H)-pyrimidinone (Synthesis of Compound No. 156)
In 10 ml of hexamethylphosphoric triamide were dissolved 1 g of 6-hydroxy-3-ethyl-5-methyl-2-methylthio-4(3H)-pyrimidinone and 1.66 g of 4-(4'-trifluoromethylphenoxy)benzyl bromide and thereto was added 0.3 g of sodium hydride (55% in mineral oil). The mixture was stirred for 15 hours at room temperature. The resulting solution was poured into 50 ml of water and then extracted twice with 30 ml of ethyl ether. The ethyl ether layer was washed with water, dried over anhydrous sodium sulfate and freed of solvent by distillation under reduced pressure to give 2.1 g of crystals. The crystals were recrystallized from a mixture of hexane and ethyl ether (3:1 ) to give 0.6 g of the intended product.
M.p.: 96.5.degree.-98.0.degree. C.
PREPARATION EXAMPLE 10
Synthesis of 3-ethyl-6-[2'-(4"-fluorobenzyloxy)-5'-pyridylmethyloxy]-5methyl-2-methylthio-4(3H)-pyrimidinone (Synthesis of Compound No. 301)
In 20 ml of N,N-dimethylformamide were dissolved 1 g of 3-ethyl-6-hydroxy-5-methyl-2-methylthio-4(3H)-pyrimidinone and 1.25 g of 2-(4'-fluorobenzyloxy)-5-pyridylmethyl chloride, and thereto was added 1 g of anhydrous potassium carbonate. The mixture was subjected to a reaction at 80.degree. C. for 3 hours.
After allowing to cool in air, the resulting solution was poured into water and then extracted twice with 30 ml of ethyl ether. The ethyl ether layer was washed with water, dried over anhydrous sodium sulfate and freed of solvent by distillation under reduced pressure to give 2.1 g of a crude product.
The product was purified by means of column chromatography (on silica gel, eluting with benzene) and the resulting crystals were washed with a mixture of hexane and ethyl ether (3:1) to give 1.0 g of the intended product.
M.p.: 91.0.degree.-92.2.degree. C.
PREPARATION EXAMPLE 11
Synthesis of 5-bromo-6-(3',4'-dichlorobenzyloxy)-3-ethyl-2-ethylthio-4(3H)-pyrimidinone (Synthesis of Compound No. 193)
In 20 ml of N,N-dimethylformamide were dissolved 1 g of 5-bromo-3-ethyl-2-ethylthio-6-hydroxy-4(3H)-pyrimidinone and 0.7 g of 3,4-dichlorobenzyl chloride, and thereto was added 1 g of potassium carbonate. The mixture was subjected to a reaction at 80.degree. C. for 3 hours.
After allowing to cool in air, the resulting solution was poured into 50 ml of water and then extracted twice with 30 ml of ethyl ether. The ethyl ether layer was washed with water, dried over anhydrous sodium sulfate and freed of solvent by distillation under reduced pressure to give 1.4 g of a crude product.
The product was purified by means of column chromatography (on silica gel, eluting with benzene) to give 0.8 g of the intended product.
M.p.: 93.4.degree.-95.0.degree. C.
PREPARATION EXAMPLE 12
Synthesis of 5-methyl-6-(4'-propyloxybenzylthio)-2-methylthio-3-ethyl-4(3H)-pyrimidinone (Synthesis of Compound No. 149)
Sodium hydride (55% in mineral oil) (0.70 g) was suspended in 20 ml of hexamethyl phosphoric triamide, and then 3.0 g of 4-propyloxybenzyl mercaptan was added thereto. The mixture was stirred for one hour at room temperature and then incorporated with 3.0 g of 6-chloro-5-methyl-2-methylthio-3-ethyl-4(3H)-pyrimidinone. After stirring at room temperature, resulting mixture was heated to 80.degree. C. under stirring for 3 hours. The resulting solution was poured into water and then extracted with benzene. The extract was washed with an aqueous sodium hydroxide solution and then with water, dried over anhydrous sodium sulfate and freed of solvent by distillation udner reduced pressure. The oil thus obtained was purified by means of column chromatography (on silica gel, eluting with chloroform) to give 2.6 g of the intended product.
M.p.: 91.0.degree.-93.0.degree. C.
PREPARATION EXAMPLE 13
Synthesis of 3-cyclohexyl-6-(4'-t-butylbenzylthio)-2,4-(1H, 3H)-triazinedione (Synthesis of Compound No. 344)
A mixture of 1.9 g of N-cyclohexylaminocarbonyl-N'-methoxycarbonyl-S-(4-t-butylbenzyl) isothiourea, 0.3 g of sodium methoxide and 30 ml of methanol was heated under reflux for one hour. After cooling, the resulting crystals were filtered off, washed sufficiently with 0.1N hydrochloric acid and then dried to give 0.9 g of the intended product.
.sup.1 H-NMR (CDCl.sub.3, .delta., TMS) 1.0-2.1 (m, 10H), 1.28 (s, 9H), 2.2-2.8 (m, 1H), 4.34 (s, 2H), 6.25 (bs, 1H), 7.27 (s, 4H).
REFERENCE EXAMPLE 1
Synthesis of ##STR75##
In 30 ml of 50% aqueous solution of methanol was dissolved 9.1 g of S-(4-t-butyl-benzyl) isothiourea.hydrobromide, and thereto was added dropwise 2.6 g of 50% aqueous solution of sodium hydroxide under ice-cooling. After stirring for 15 minutes udner ice-cooling, 10 ml of a tetrahydrofuran solution containing 3.0 g of t-butylisocyanate was added dropwise thereto. The mixture was stirred for 3 hours at room temperature. The reaction solution was incorporated with 100 ml of chloroform, washed with water, dried over anhydrous sodium sulfate, and then freed of solvent by distillation under reduced pressure to give 6.9 g of the intended product as a pale yellow solid.
.sup.1 H-NMR(CDCl.sub.3, .delta., TMS) 1.27 (s, 9H), 1.31 (s, 9H), 3.65 (bs, 2H), 4.05 (s, 2H), 5.20 (bs, 1H), 7.23 (s, 4H).
According to any one of Preparation Examples 1 through 13, compounds of the present invention were prepared, and the melting points and .sup.1 H-NMR data of the compounds are shown in Table 3. Compound Nos. therein correspond to those shown in Tables 1 and 2.
TABLE 3______________________________________No. m.p. (.degree.C.) .sup.1 H--NMR data (CDCl.sub.3, .delta.,______________________________________ TMS)1 133.1.about.133.82 109.4.about.110.75 170.2.about.173.46 146.2.about.148.37 127.4.about.129.08 127.3.about.128.99 108.7.about.110.110 183.6.about.187.411 oil 1.29(s,9H) 1.37(t,3H) 3.95 (q,2H,J=7Hz) 4.31(s,2H) 7.22(s,4H) 7.90(s,1H)13 141.1.about.147.314 81.5.about.84.815 124.8.about.125.117 171.9.about.172.918 194.1.about.196.619 154.9.about.157.922 123.8.about.125.523 146.2.about.147.624 149.9.about.152.026 162.1.about.164.227 175.9.about.176.628 171.5.about.174.637 106.5.about.108.339 112.2.about.114.040 73.0.about.74.041 oil 0.98(t,3H,J=7Hz) 1.23(d,6H, J=7Hz) 1.63.about.1.90(m,2H) 2.50(s,3H) 2.76.about.2.92(m,1H) 3.95(t,2H,J=7Hz) 5.37(s,2H) 7.23(s,4H)42 152.0.about.153.944 176.2.about.177.545 100.2.about.100.847 149.5.about.150.450 137.5.about.138.353 151.9.about.154.154 110.6.about.111.655 104.3.about.106.757 98.1.about.100.358 95.0.about.98.068 81.0.about.82.372 oil 1.27(t,3H,J=7Hz) 1.30(s,9H) 1.33(t,3H,J=7Hz) 1.97(s,3H) 2.77(q,2H,J=7Hz) 4.03(q,2H, J=7Hz) 5.37(s,2H) 7.37(s,4H)73 oil 1.17.about.2.00(m,10H) 1.28(t,3H, J=7Hz) 1.33(t,3H,J=7Hz) 1.95(s,3H) 2.16.about.2.50(m,1H) 2.70(q,2H,J=7Hz) 4.03(q,2H, J=7Hz) 5.31(s,2H) 7.20(bs,4H)74 93.8.about.95.775 oil 1.20(t,3H,J=7Hz) 1.27(t,3H, J=7Hz) 1.92(s,3H) 2.64(q, 2H,J=7Hz) 3.93(q,2H,J=7Hz) 4.87(s,2H) 5.25(s,2H) 6.73.about. 7.33(m,8H)78 78.0.about.80.685 85.1.about.87.386 168.3.about.169.6113 151.1.about.153.3114 119.6.about.121.1115 oil 1.58(d,6H,J=7Hz) 2.48(s,3H) 4.60(dq,1H,J=7Hz) 5.39(s, 2H) 7.30(s,4H)116 oil 1.23(d,6H,J=7Hz) 2.50(s,3H) 2.88(dq,1H,J=7Hz) 3.45(s, 3H) 5.38(s,2H) 7.05.about.7.40 (m,4H)117 oil 1.24(d,6H,J=7Hz) 1.30(t,3H, J=7Hz) 2.54(s,3H) 2.90(dq, 1H,J=7Hz) 4.10(q,2H,J=7Hz) 5.41(s,2H) 7.05.about.7.45(m,4H)118 118.5.about.120.0119 106.1.about.107.0120 oil 1.31(s,9H) 1.61(d,6H,J=7Hz) 2.50(s,3H) 4.60(dq,1H, J=7Hz) 5.41(s,2H) 7.32(s,4H)122 142.0.about.145.0123 oil 1.31(t,3H,J=7Hz) 1.20.about.2.10 (m,10H) 2.53(s,3H) 2.30.about. 2.70(m,1H) 4.10(q,2H,J=7Hz) 5.41(s,2H) 7.05.about.7.45(m,4H)124 oil 1.10.about.2.10(m,10H) 1.60(d, 6H,J=7Hz) 2.25.about.2.80(m,1H) 2.49(s,3H) 4.60(dq,1H, J=7Hz) 5.39(s,2H) 7.00.about. 7.40(m,4H)125 35.0.about.42.0126 137.3.about.143.5127 101.7.about.105.0128 142.6.about.143.7129 171.9.about.174.1130 159.8.about.160.2131 162.0.about.164.4132 142.0.about.145.0133 160.3.about.160.9137 106.0.about.110.0138 oil 1.25(d,6H,J=7Hz) 1.97(s,3H) 2.50(s,3H) 2.90(dq,1H, J=7Hz) 3.46(s,3H) 5.36(s, 2H) 7.15.about.7.40(m,4H)140 91.0.about.96.6141 70.0.about.72.5142 oil 0.98(t,3H,J=7Hz) 1.35(s,9H) 1.52.about.2.19(m,2H) 1.96(s,3H) 2.51(s,3H) 3.97(t,2H,J=7Hz) 5.38(s,2H) 7.32(s,4H)144 oil 1.10.about.2.10(m,10H) 1.97(s, 3H) 2.25.about.2.80(m,1H) 2.47 (s,3H) 3.40(s,3H) 5.42(s, 2H) 7.10.about.7.40(m,4H)145 oil 1.30(t,3H,J=7Hz) 1.20.about.2.10 (m,10H) 1.97(s,3H) 2.20.about. 2.70(m,1H) 2.49(s,3H) 4.07 (q,2H,J=7Hz) 5.37(s,2H) 7.20.about. 7.40(m,4H)146 oil 0.95(t,3H,J=7Hz) 1.20.about.2.80 (m,13H) 1.95(s,3H) 2.50(s, 3H) 3.97(t,2H,J=7Hz) 5.35 (s,2H) 7.25(s,4H)147 oil 0.92(t,3H,J=7Hz) 1.20.about.1.80 (m.4H) 1.30(t,3H,J=7Hz) 1.96(s,3H) 2.50(s,3H) 2.45.about. 2.70(m,2H) 4.07(q,2H, J=7Hz) 5.37(s,2H) 7.10.about. 7.35(m,4H)151 121.8.about.122.3152 66.5.about.67.0153 160.0.about.161.1155 109.6.about.110.8156 96.5.about.98.0157 88.5.about.88.9160 131.3.about.132.7161 127.0.about.129.5162 109.6.about.110.0163 158.0.about.164.0301 91.0.about.92.2164 111.3.about.113.2166 oil 1.08(t,3H,J=7Hz) 1.30(t,3H, J=7Hz) 1.30(s,9H) 2.50(s, 3H) 2.52(q,2H,J=7Hz) 4.05 (q,2H,J=7Hz) 5.38(s,2H) 7.31(s,4H)167 oil 1.04(t,3H,J=7Hz) 1.29(t,3H, J=7Hz) 1.10.about.2.20(m.10H) 2.20.about.2.80(m,3H) 2.48(s,3H) 4.02(q,2H,J=7Hz) 5.31(s,2H) 7.18(s,4H)168 79.0.about.80.0169 99.5.about.101.0189 oil 1.30(t,3H,J=7Hz) 1.30(s,9H) 1.35(t,3H,J=7Hz) 3.14(q,2H, J=7Hz) 4.09(q,2H,J=7Hz) 5.40(s,2H) 7.32(s,4H)190 oil 1.30(t,3H,J=7Hz) 1.33(t,3H, J=7Hz) 1.20.about.1.99(m,10H) 2.20.about.2.80(m,1H) 3.13(q,2H, J=7Hz) 4.07(q,2H,J=7Hz) 5.38(s,2H) 7.20(s,4H)191 123.0.about.124.0192 86.5.about.87.0193 93.4.about.95.0194 oil 1.28(t,3H,J=7Hz) 1.30(s,9H) 1.33(t,3H,J=7Hz) 1.96(s,3H) 3.12(q,2H,J=7Hz) 4.05(q,2H, J=7Hz) 5.32(s,2H) 7.27(s,4H)195 oil 1.28(t,3H,J=7Hz) 1.32(t,3H, J=7Hz) 1.00.about.2.10(m,10H) 1.95(s,3H) 2.20.about.2.80(m,1H) 3.10(q,2H,J=7Hz) 4.03(q,2H, J=7Hz) 5.31(s,2H) 7.21(s,4H)196 110.0.about.111.1197 oil 1.30(t,3H,J=7Hz) 1.39(t,3H, J=7Hz), 1.70.about.2.10(m,4H) 1.95(s,3H) 3.15(q,2H,J=7Hz) 3.31(s,3H) 3.41(t,2H,J=7Hz) 4.00(t,2H,J=7Hz) 4.05(q,2H, J=7Hz) 5.30(s,2H) 6.87(d, 2H,J=9Hz) 7.29(d,2H,J=9Hz)198 oil 1.30(t,3H,J=7Hz) 1.35(s,9H) 1.40(d,6H,J=7Hz) 1.98(s,3H) 3.60.about.4.00(m,1H) 4.07(q,2H, J=7Hz) 5.32(s,2H) 7.31(s,4H)199 oil 1.30(t,3H,J=7Hz) 1.38(d,6H, J=7Hz) 1.15.about.2.05(m,10H) 1.95(s,3H) 2.20.about.2.70(m,1H) 3.60.about.4.20(m,1H) 4.05(q,2H, J=7Hz) 5.31(s,2H) 7.22(s,4H)200 74.0.about.75.7201 94.0.about.96.0202 oil 1.00(t,3H,J=7Hz) 1.31(s,9H) 1.31(t,3H,J=7Hz) 1.55.about.1.92 (m,2H) 3.10(t,2H,J=7Hz) 4.11(q,2H,J=7Hz) 5.40(s,2H) 7.33(s,4H)203 oil 1.00(t,3H,J=7Hz) 1.29(t,3H, J=7Hz) 0.81.about.2.08(m,12H) 2.16.about.2.75(m,1H) 3.06(t,2H, J=7Hz) 4.09(q,2H,J=7Hz) 5.48(s,2H) 7.22(s,4H)204 122.0.about.123.1205 oil 1.02(t,3H,J=7Hz) 1.3(t,3H, J=7Hz) 1.60.about.1.84(m,2H) 3.11(t,2H,J=7Hz) 4.10(q,2H, J=7Hz) 5.00(s,2H) 5.36(s, 2H) 6.85.about.7.51(m,8H)206 96.7.about.97.8207 101.6.about.102.5213 152.7.about.154.3214 160.0.about.164.1215 82.0.about.85.0218 oil 1.31(s,9H) 1.96(s,3H) 2.51 (s,3H) 4.62(d,2H,J=5Hz) 5.00.about.6.10(m,3H) 5.37(s,2H) 7.33(s,4H)219 oil 1.09.about.2.80(m,11H) 1.96(s, 3H) 2.50(s,3H) 4.63(d,2H, J=5Hz) 5.00.about.6.30(m,3H) 5.36(s,2H) 7.22(s,4H)220 91.0.about.92.0221 98.0.about.99.1223 oil 1.30(s,9H) 1.32(t,3H,J=7Hz) 2.53(s,3H) 4.10(q,2H,J=7Hz) 5.38(s,2H) 7.01.about.7.69(m,9H)224 oil 1.10.about.2.22(m,10H) 1.35(t, 3H,J=7Hz) 2.30.about.2.80(m,1H) 2.55(s,3H) 4.12(q,2H,J=7Hz) 5.38(s,2H) 7.18.about.7.70(m,9H)225 107.2.about.109.0226 125.0.about.128.0135 105.1.about.106.2136 103.0.about.105.0139 oil 1.29(s,9H), 1.31(t,3H), 2.00 (s,3H), 2.52(s,3H), 4.08(q,2H), 4.40(s,2H), 7.28(bs,4H)148 122.0.about.124.0149 91.0.about.93.0150 47.0.about.48.0154 109.0.about.111.0159 154.0.about.158.0170 oil 1.25(d,6H), 1.30(t,3H), 2.50 (s,3H), 3.30(dq,1H), 4.03(q,2H) 5.32(s,2H), 6.9.about.7.6(m,8H)228 79.6.about.81.5305 122.0.about.124.0306 141.7.about.143.6307 95.4.about.113.3308 101.9.about.103.1309 133.8.about.134.9233 192.1.about.193.4234 oil 1.08(t,3H), 1.30(t,3H), 2.50 (s,3H), 2.45(q,2H), 4.05(q,2H), 5.33(s,2H), 7.1.about.7.5(m,3H)235 oil 1.08(t,3H), 1.25(d,6H), 1.30 (t,3H), 2.45(q,2H), 2.49(s,3H), 2.85(dq,1H), 4.05(q,2H), 5.35(s,2H), 8.22(bs,4H)236 130.0.about.130.2237 80.0.about.81.3238 79.5.about.80.4239 oil 0.98(t,3H), 1.5.about.1.9(m,2H), 1.95 (s,3H), 2.48(s,3H), 3.95(t,3H), 5.32(s,2H), 6.9.about.7.4 (m,4H)240 oil 0.9.about.1.6(m,13H), 1.96(s,3H), 2.5.about.2.9(m,4H), 4.05(q,2H), 5.31(s,2H), 6.9.about.7.4(m,4H)241 oil 1.0.about.1.4(m,12H), 1.95(s,3H), 2.5.about.3.2(m,3H), 4.01(q,2H), 5.32(s,2H), 7.0.about.7.3(m,4H)242 oil 1.92(s,3H), 2.49(s,3H), 4.60 (d,2H), 5.0.about.6.1(m,3H), 5.30 (s,2H), 6.8.about.7.4(m,4H)243 93.4.about.94.5244 84.6.about.85.8245 120.0.about.121.0246 111.0.about.113.0247 119.6.about.122.4248 124.7.about.125.8249 60.6.about.62.5250 69.2.about.70.5251 129.4.about.130.2252 98.0.about.100.0253 131.0.about.132.0254 93.0.about.94.5255 106.9.about.107.8256 131.6.about.132.7257 oil 1.30(t,3H), 2.49(s,3H), 3.79 (s,3H), 4.50(q,2H), 5.40(s,2H), 6.9.about.7.4(m,4H)258 oil 1.30(t,3H), 2.30(s,3H), 3.62 (s,2H), 3.85(q,2H), 5.13(s,2H), 6.7.about.7.4(m,13H)259 oil 1.28(t,3H), 2.43(s,3H), 3.72 (s,2H), 4.02(q,2H), 4.96(s,2H), 5.30(s,2H), 6.8.about.7.4(m,13H)260 oil 1.27(t,3H), 1.3.about.2.0(m,11H), 2.42(s,3H), 3.78(s,2H), 4.03(q,2H), 5.31(s,2H), 8.0.about.8.3(m,9H)261 oil 1.26(t,3H), 2.40(s,3H), 3.78(s,2H), 4.00(q,2H), 5.28(s,2H), 6.8.about.7.3(m,9H)262 oil 1.25(t,3H), 1.29(s,9H), 1.59(d,3H), 2.36(s,3H), 3.80(s,2H), 4.00(q,2H), 6.05(q,1H), 7.1.about.7.4(m,9H)263 oil 1.23(d,3H), 1.29(t,3H), 2.48(s,3H), 3.35(dp,1H), 4.03(q,2H), 5.33(s,2H), 6.9.about.7.5(m,4H)310 161.0.about.163.0311 131.0.about.131.7344 white crystal 1.0.about.2.1(m,10H), 1.28(s,9H), 2.2.about.2.8(m,1H), 4.34(s,2H), 6.25(bs,1H), 7.27(s,4H),______________________________________
When the compounds of the present invention are used for insecticidal, acaricidal, nematicidal and/or fungicidal agents for agricultural and horticultural uses, sanitary and veterinary insect pest-controlling agents and for expellents of ectoparasites on animals, they are generally mixed with suitable carriers such as solid carriers, e.g., clay, talc, bentonite or diatomaceous earth, or liquid carriers, e.g., water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethyl formamide etc.), or the like. If desired, these mixtures may be incorporated with an emulsifier, dispersing agent, suspending agent, penetrating agent, spreader, and/or stabilizing agent to form liquid preparations, emulsifiable concentrates, wettable powders, dusts, granules, flowables, poison baits, solutions, atomizing agents, smoking agents or the like for practical uses. The above-mentioned solution means a preparation wherein an active ingredient is added to a paraffin oil, corn oil or rapeseed oil for the use of controlling ectoparasites on animals, especially by painting and/or spraying. If necessary, the resulting mixtures may be incorporated with other herbicides, various insecticides, fungicides, plant-growth regulating agents, synergists, sanitary and veterinary insect pest-controlling agents and/or animals drugs during preparation or application thereof. The kinds of the compounds to be added are described, for example, in Farm Chemicals Handbook, 73 edition (1987).
The amount of the compounds of the invention to be used as an active ingredient is generally in the range of 0.005 to 5 Kg per hectare (diluted with water to give a diluted solution containing an active ingredient in a concentration of 2 to 50,000 ppm) although it varies depending upon the place and the season where the compounds are applied, manner of application, blights (diseases) and pests to be applied, cultivated crops to be protected, animals to be applied and the like.
In the following, there are shown formulation examples of compositions for controlling and/or preventing pests and blights (diseases), said compositions containing the compounds of the present invention as an active ingredient. These examples are merely illustrative and not to restrict the present invention. Incidentally, in the following examples, "part" means "part by weight".
______________________________________Formulation Example 1 Emulsifiable concentrates______________________________________Compound No. 156 20 partsXylene 50 partsN,N--dimethylformamide 20 partsSolpol 2680 (trade name, 10 partsa mixture of a non-ionicsurfactant and an anionicsurfactant supplied byToho Chemical IndustriesCo., Ltd., Japan)______________________________________
The above components are mixed intimately together to form an emulsifiable concentrate. Upon use, the emulsifiable concentrate is diluted with water up to one fifth to one two thousandth in concentration and applied at a rate of 0.005 to 5 Kg of the active ingredient per hectare.
______________________________________Formulation Example 2: Wettable powders______________________________________Compound No. 118 25 partsZeeklite PFP (trade name, 67 partskaolinite clay supplied byZeeklite Industries Co., Ltd.)Solpol 5039 (trade name, 5 partsa mixture of a non-ionicsurfactant and an anionicsurfactant supplied by TohoChemical Industries Co., Ltd.,Japan)Carplex (anticoagulant) 3 parts(trade name, a mixture of asurfactant and white carbonsupplied by Shionogi SeiyakuK.K., Japan)______________________________________
The above components are homogenously mixed together and ground to form a wettable powder. Upon use, the wettable powder is diluted with water up to one five hundredth to one twenty thousandth and applied at a rate of 0.005 to 5 Kg of the active ingredient per hectare.
______________________________________Formulation Example 3: Oil solutions______________________________________Compound No. 141 20 partsMethylcellosolve 80 parts______________________________________
The above components are homogeneously mixed together to form an oil solution. Upon use, the oil solution is applied at a rate of 0.005 to 5 Kg of the active ingredient per hectare.
______________________________________Formulation Example 4: Dusts______________________________________Compound No. 145 3.0 partsCarplex (anticoagulant) 0.5 part(trade name, a mixture of asurfactant and white carbonsupplied by Shionogi K.K.,Japan)Clay 95 partsdi-isopropyl phosphate 1.5 parts______________________________________
The above components are homogeneously mixed together and ground to form a dust. Upon use, the dust is applied at a rate of 0.005 to 5 Kg of the active ingredient per hectare.
______________________________________Formulation Example 5: Granules______________________________________Compound No. 147 5 partsBentonite 54 partsTalc 40 partsCalcium lignin sulfonate 1 part______________________________________
The above components are mixed intimately together and ground, incorporated with a small amount of water and mixed together under stirring. The resulting mixture is granulated by means of extrusion-granulator and dried to form granules. Upon use, the granule is applied at a rate of 0.005 to 5 Kg of the active ingredient per hectare.
______________________________________Formulation Example 6: Flowable______________________________________Compound No. 138 25 partsSolpol 3353 (trade name, 10 partsa non-ionic surfactantsupplied by Toho ChemicalIndustries Co., Ltd.,Japan)Runox l000C (trade name, 0.5 partan anionic surfactantsupplied by Toho ChemicalIndustries, Ltd., Japan)1% aqueous solution of 20 partsXanthan gum (naturalhigh-molecular compound)Water 44.5 parts______________________________________
The above components except the active ingredient are homogeneously mixed together to form a solution, and thereto is added Compound No. 138. The resulting mixture is throughly stirred, wet-ground by means of sand mill to form a flowable. Upon use, the flowable is diluted to one fifth to one two thousandth with water and applied at a rate of 0.005 to 10 Kg of the active ingredient per hectare.
The compounds according to the present invention not only exhibit superior insecticidal action on Hemipterous insect such as green rice leafhopper (Nephotettix cincticeps), Lepidopterous insect such as diamondback moth (Plutella xylostella), Coleoptera and sanitary and veterinary insect pests such as Dipterous insect pests (e.g., mosquitoes, flies, sand flies, horseflies), Blattariae insect pests, Pulicidae insect pests, and Ixodidae insect pests, but are also useful for expelling mites parasitic on fruits and vegetables such as two-spotted spider mite (Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai), carmine mite (Tetranychus cinnabarinus), citrus red mite (Panonychus citri) and European red mite (Panonychus ulmi); ticks parasitic on animals such as southern cattle tick (Boophilus microplus), cattle tick (Boophilus annulatus), galf coast tick (Amblyomma maculatum), brown-ear tick (Rhipicephalus appendiculatus) and Haemaphysalis longicornis; as well as flies parasitic on animals such as Dipterous insect pests (e.g., Lucilia sericata). Moreover, the compounds of the present invention are also useful for controlling various nematoda parasitic on fruits and vegetables such as root knot nematode, root lesion nematode, cist nematode, etc. The main features of the compounds according to the present invention resides in that the compounds are useful for the prevention or control of blight (or disease) of fruits and vegetables such as powdery mildew, downy mildew, etc. in addition to having the above mentioned insecticidal, acaricidal and nematicidal actions. Moreover, they are excellent as an expellent for ticks and flies parasitic on animals such as domestic animals (e.g., cattle, horse, sheep and pig), domestic fowls, and other animals such as dog, cat, rabbit and the like.
The present invention is explained in detail by way of the following test examples.
TEST EXAMPLE 1
Insecticidal Test on Green Rice Leafhopper (Nephotettix cincticeps)
An emulsifiable concentrate containing each of the present compounds was diluted with water to give a 1000 ppm aqueous solution. Stems and leaves by rice-plant were immersed in this solution for 10 seconds and then placed in a glass cylinder. Ten second instar green rice leafhopper larvae which are resistant to organic phosphorous insecticides were released in the cylinder. Then the cylinder was covered with a plastic cap provided with pores and placed in a thermostatic chamber kept at 25.degree. C. Mortality of the larvae after 96 hours was calculated according to the following equation. Incidentally, the test was repeated twice for each compound. ##EQU1##
As the results, the following compounds showed a mortality of 100%.
Compound Nos.: 74, 85, 116, 117, 119, 123, 125, 128, 140, 141, 142, 144, 145, 146, 147, 152, 155, 156, 157, 162, 194, 195, 197, 218, 219, 220, 135, 139, 148, 149, 150, 154, 308, 249, 250.
TEST EXAMPLE 2
Contact Insecticidal Test on 28-Spotted Lady Beetle (Henosepilachna viginitioctopunctata)
Leaves of tomato were immersed for 10 seconds in a 1000 ppm aqueous solution of a compound of the present invention which had been prepared by diluting with water an emulsifiable concentrate of the compound, and then air-dried. The leaves thus treated were placed in a laboratory dish, into which 10 second instar 28-spotted lady beetle larvae were released. The dish was covered with a cap provided with pores and then placed in a thermostatic chamber kept at 25.degree. C. Mortality of the larvae after 96 hours was calculated according to the equation described in Test Example 1. Incidentally, the test was repeated twice for each compound.
As the results, the following compounds showed a mortality of 100%.
Compound Nos.: 54, 57, 68, 73, 75, 123, 128, 131, 132, 141, 144, 145, 146, 147, 155, 156, 157, 160, 161, 162, 301, 194, 195, 197, 218, 219, 220, 221, 135, 136, 139, 148, 149, 150, 154, 159, 308, 309, 249, 250, 254.
TEST EXAMPLE 3
Acaricidal Test on Kanzawa Spider Mite (T. Kanzawai)
A leaf of kideny bean was cut into a round piece of 1.5 cm in diameter by a leaf punch, and then placed on a moistened filter paper on a styrol cup of 7 cm in diameter. Each piece of the leaf was inoculated with 10 Kanzawa spider mite nymphs. Half a day after the inoculation, to each styrol cup was applied 2 ml of an aqueous solution containing 1000 ppm of a compound of the present invention which had been prepared by diluting an emulsifiable concentrate of the compound with water containing an extender by means of a rotary spray tower. After 96 hours, mortality of the nymph was calculated according to the equation described in Test Example 1. Incidentally, the test was repeated twice for each compound.
As the results, the following compounds showed a mortality of 100%.
Compound Nos.: 2, 11, 28, 55, 68, 72, 73, 74, 75, 113, 116, 118, 119, 122, 123, 125, 128, 138, 140, 141, 142, 144, 145, 146, 147, 155, 156, 157, 194, 195, 196, 197, 218, 219, 220, 221, 135, 136, 139, 149, 150, 154, 159, 307, 308, 240, 241, 242, 256.
Test Example 4
Test for Controlling Downy Mildew of Cucumber
To cucumbers (variety: Sagamihanjiro) which had been grown in pots for 2 weeks was sprayed at a rate of 20 ml per pot a 500 ppm aqueous solution of a compound of the present invention which had been prepared by diluting with water an emulsifiable concentrate of the compound. Each pot was placed in a green house for one day, and then thereto was sprayed a suspension of spores of Pseudoperonospora cubensis (the concentration of the suspension being such that 15 spores can be observed by a 150 magnification microscope) to inoculate the cucumber with the spores. The cucumbers inoculated therewith were placed in a room at 25.degree. C. with a relative humidity of 100% for 24 hours and then in a green house for observation of disease appearance.
As the results, no disease appearance was observed at all when the following compounds were used.
Compound Nos.: 53, 54, 55, 57, 68, 75, 128, 131, 132, 141, 144, 145, 156, 160, 161, 301, 149, 154, 238, 242, 255.
TEST EXAMPLE 5
Test for Controlling Powdery Mildew of Cucumber
To cucumbers (variety: Sagamihanjiro) which had been grown in pots for 2 weeks was sprayed, at a rate of 20 ml per pot, a 1000 ppm solution of a compound of the present invention which had been prepared by diluting an emulsifiable concentrate of the compound with water. After each pot was placed for one day in a green house, a suspension of spores of Sphaerotheca fuliginea (the concentration of the spore being such that 25 spores can be observed by a 150 magnification microscope) was sprayed to the cucumbers for inoculation. The cucumbers thus treated were placed in a green house at 25.degree.-30.degree. C. for observation of disease appearance. Ten days after the inoculation, percentage of the disease appearance was evaluated. As the results, no disease appearance was observed at all when the following compounds were used.
Compound Nos.: 135, 150, 238.

Number	Name	Date
3853900	Shone	Dec 1974
3855219	Fuchs et al.	Dec 1974
3914224	Jewell	Oct 1975
3985735	Powell	Oct 1976
4540698	Ishikawa et al.	Sep 1985

Number	Date	Country
0035333	Sep 1981	EPX
0088384	Sep 1983	EPX
0134439	Mar 1985	EPX
018212	Jun 1986	EPX
0193853	Sep 1986	EPX
0199281	Oct 1986	EPX
0232825	Aug 1987	EPX

Nitrogen-containing heterocyclic compounds and compositions for controlling and/or preventing pests and blights (diseases)

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US Referenced Citations (5)

Foreign Referenced Citations (7)

Non-Patent Literature Citations (5)

Entry
Prystas et al., Chemical Abstracts, vol. 65, 15969e, (1966).
Mizuno et al., Chemical Abstracts, vol. 82, entry 112039u, (1975).
Fourrey et al., Chemical Abstracts, vol. 86, entry 55382g, (1977).
Rothe et al., Chemical Abstracts, vol. 93, entry 204580u, (1980).
Koshiba et al., Chemical Abstracts, vol. 108, entry 56721b, (1988).