Thiophene derivatives

Abstract

This invention relates to new thiophene derivatives and their use as fungicides in agriculture and horticulture.

Description

The new thiophene derivatives according to the present invention are represented by the general formula (I). ##STR1##

In the general formula: R is C.sub.1-4 -alkyl; R.sub.1 is ##STR2## wherein R.sub.3 is C.sub.1-4 -alkyl, halogen-substituted C.sub.1-4 -alkyl, C.sub.2-4 -alkenyl, C.sub.3-8 -cycloalkyl, C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, C.sub.1-4 -alkylthio-C.sub.1-4 -alkyl, C.sub.1-4 -alkoxycarbonyl-C.sub.1-4 -alkyl, C.sub.1-10 -alkoxy, C.sub.1-4 -alkynyloxy, styryl, .alpha.-phenoxyethyl, thienyl, furyl, 2,3-dibromopropyloxy, a group ##STR3## (wherein A and B individually are halogen, C.sub.1-4 -alkyl, methoxy or methylthio, and m and n individually are 0 or 1 with the proviso m+n cannot exceed 2), mono-C.sub.1-4 -alkylamino, di-C.sub.1-4 -alkylamino, mono-C.sub.3-8 -cycloalkylamino, monoaralkylamino, diphenylamino, a group ##STR4## which may be substituted with one or two C.sub.1-4 -alkyl; a group ##STR5## (wherein C is a halogen atom, D is C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -alkylcarboxy, nitro or cyano, k is 0, 1 or 2 and 1 is 0, 1, 2 or 3); C.sub.1-4 -alkylthio; C.sub.1-4 -alkenylthio; C.sub.1-4 -alkoxycarbonyl-C.sub.1-4 -alkylthio; aralkylthio or C.sub.1-4 -alkyl-substituted aralkylthio; aralkyl which phenyl portion may be

substituted with halogen or C.sub.1-4 -alkoxy; a group ##STR6## phenoxy-C.sub.1-4 -alkyl which phenyl portion may be substituted with halogen; pyridine-4-yl; or a group ##STR7## wherein R.sub.4 is C.sub.1-6 -alkyl, di-C.sub.1-4 -alkylamino or a group ##STR8## (in which E is halogen or C.sub.1-4 -alkyl and .mu. is 0 or 1); R.sub.2 is C.sub.1-4 -alkyl or C.sub.2-4 -alkenyl; provided that; (a) When R.sub.3 is mono-C.sub.3-8 -cycloalkylamino, R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, aralkyl, phenoxy-C.sub.1-4 -alkyl or C.sub.2-4 -alkynyl; (b) When R.sub.3 is ##STR9## R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl or aralkyl; (c) When R.sub.3 is ##STR10## R.sub.2 represents C.sub.3-8 -cycloalkyl; and (d) When R.sub.3 is C.sub.1-4 -alkylthio, R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, aralkyl or phenoxy-C.sub.1-4 -alkyl.

A number of thiophene derivatives have been synthesized by us for investigation of their utility as fungicides in agriculture and horticulture. Consequently, new compounds of the above general formula (I) are found effective against various plant diseases such as rice blast, rice brown spot, rice sheath blight, tomato late blight, haricot sclerotinia rot, rice `Bakanae` disease, cucumber Fusarium wilt, tomato leaf mold, grape ripe pot, pear black spot, Japanese apple canker, vegetable soft rot, rice bacterial blight, cucumber bacterial spot, cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, etc. They are further useful for controlling powdery mildew and root knot diseases of various crops, vegetables, flowers and fruit trees, as well as phytophthora rot of soybean, adzuki bean and broad bean, phytophthora blight of taro, phytophthora dampingoff of cucumber, phytophthora rot of oriental melon, netted melon and oriental pickling melon, brown rot of water melon, phytophthora rot of pumpkin, phytophthora rot of bottle gourd, brown rot of egg plant, phytophthora blight of sweet pepper, red stele of strawberry, phytophthora rot of onion, phytophthora blight of Welsh onion, pythium blight of wheat or barley.

The compounds of the general formula (I) can be prepared by the following reactions: ##STR11##

The reaction (1) can be carried out in an organic solvent such as alcohol, ether, hydrocarbon, dimethyl formamide, etc., in the presence of a deprotonating agent such as metal sodium, NaH, butyl lithium, alcoholate, etc., at a temperature of 0.degree.-100.degree. C. for 2-24 hours. The resulting reaction mixture is poured into ice water and then worked up with a mineral acid like hydrochloric or sulfuric acid.

The reaction (2) or (4) can be carried out in an inert solvent such as dioxane, acetone, benzene, dimethyl formamide, etc., in the presence of a dehydrohalogenating agent such as triethylamine, pyridine, potassium or sodium carbonate, etc., at a temperature of 0.degree.-100.degree. C. for 1-24 hours. The resulting reaction mixture is poured into water and then worked up as by filtration, extraction, etc.

The reaction (3) can be carried out in an inert organic solvent such as dioxane, ethylether, hydrocarbon, benzene, etc., in the presence of a catalyst such as triethylamine, pyridine, etc., at a temperature of 20.degree.-80.degree. C. for 1-5 days. The reaction mixture obtained is worked up by distillation to remove the solvent and recrystallization.

The following examples are given to show the typical procedures for the preparation of the compounds of the present invention, without limiting the scope of the invention thereto.

EXAMPLE 1

Di-isopropyl 3-methyl-4-hydroxy-2,5-thiophenedicarboxylate

Sodium hydride (132 g, 5.52 mol) was added gradually into isopropyl alcohol (2-3 l) with cooling. To the resulting solution was then added a mixture of isopropyl pyruvate (360 g, 2.76 mol) and di-isopropyl 2,2'-thiodiglycolate (648 g, 2.76 mol) over 20-30 minutes with ice-cooling so that the solution was kept at 60.degree.-80.degree. C. The solution was stirred further for 2 hours at a temperature of 60.degree.-40.degree. C. The solution was poured into an ice-cooled dilute hydrochloric acid solution to form a white crystalline mass, which was recovered by filtration and then washed with water. It was recrystallized from methanol (3 l) to give pure di-isopropyl 3-methyl-4-hydroxy-2,5-thiophene-dicarboxylate (270 g, 34%), m.p. 87.degree.-89.degree. C.

IR(nujol): 3280, 1700, 1660, 1560, 1355, 1210, 1155, 1090, 910, 760 cm.sup.-1. NMR(CDCl.sub.3): 1.40(d, J=7 Hz, 12H, ##STR12## , 2.43 (s, 3H, --CH.sub.3), 5.1-5.5(m, 2H, ##STR13## , 9.77 ppm (s, 1H, --OH).

EXAMPLE 2

Di-isopropyl 3-methyl-4-benzoyloxy-2,5-thiophene dicarboxylate (Compound No. 4)

A mixture of di-isopropyl 3-methyl-4-hydroxy-2,5-thiophene-dicarboxylate (656 g, 2.30 mol), triethylamine (297 g, 2.98 mol) and dioxane (2 l) was cooled with ice to about 10.degree. C. The solution was added, while stirring, with benzoyl chloride (351 g, 2.5 mol) over about 10 minutes, followed by further stirring for 30 minutes at room temperature. After removing the precipitate of triethylamine hydrochloride salt by filtration, the solution was distilled in vacuo to remove dioxane. Toluene was then added to the remaining residue, and the solution was washed with 5% aqueous sodium bicarbonate and water, and then dried over MgSO.sub.4. The solvent was removed by distillation to give almost pure di-isopropyl 3-methyl-4-benzoyloxy-2,5-thiophene dicarboxylate (851 g, 95%). n.sub.D.sup.10 1.5499.

IR(neat): 1750, 1700, 1600, 1010, 965, 910, 762, 700 cm.sup.-1. NMR(CDCl.sub.3): 1.15(d, J=7 Hz, 6H, ##STR14## 1.40(d, J=7 Hz, 6H, ##STR15## 2.42 (s, 3H, CH.sub.3), 5.0-5.4 (m, 2H, ##STR16## 7.3-8.4 ppm (m, 5H).

EXAMPLE 3

Di-isopropyl 3-methyl-4-(4-nitrobenzoyloxy)-2,5-thiophene-dicarboxylate (Compound No. 46)

1.1 g (4 mmol) of di-isopropyl 3-methyl-4-oxy-2,5-thiophene dicarboxylate and 1 g (10 mmol) of triethylamine were dissolved into 6 ml of dioxane, and the resulting solution was ice-cooled with stirring, and then added with 1.1 g (6 mmol) of 4-nitro benzoyl chloride. The mixture was allowed to stand overnight, then added with 30 ml of 5% aqueous NaHCO.sub.3, extracted with 30 ml of ethylether, and washed with water 2 or 3 times. The extract was dried over MgSO.sub.4, and distilled to remove the solvent. The crude product obtained was recrystallized from about 5 ml of methyl alcohol to give the Compound No. 46 (1.6 g, 92%) in the white crystalline form.

IR (nujol): 1760(C.dbd.O), 1715(C.dbd.O), 1523, 1370, 1350, 710 cm.sup.-1. NMR(CDCl.sub.3): .delta.1.20(d, J=7 Hz, 6H --CH(CH.sub.3).sub.2), 1.38(d, J=7 Hz, 6H, --CH(CH.sub.3).sub.2), 2.40(s, 3H, --CH.sub.3), 4.9-5.4(m, 2H, --CH(CH.sub.3).sub.2), 8.35(br, 4H, ring proton).

EXAMPLE 4

Dipropyl 3-methyl-4-(4-methoxybenzoyloxy)-2,5-thiophene-dicarboxylate (Compound No. 58)

1.1 g (4 mmol) of dipropyl 3-methyl-4-oxy-2,5-thiophene-dicarboxylate and 1 g (10 mmol) of triethylamine were dissolved into 6 ml of dioxane to obtain a solution, to which was added dropwise 1.0 g (6 mmol) of 4-methoxybenzoyl chloride while the solution was stirred with ice-cooling. Thereafter, the mixture was allowed to stand overnight at room temperature. Then the reaction mixture was added with 30 ml of 5% aqueous NaHCO.sub.3, extracted with 30 ml of ethylether, and washed with water 2 to 3 times. The extract was dried with MgSO.sub.4 and then distilled to remove the solvent. The Compound No. 58 is obtained as an almost pure yellowish viscous liquid (1.1 g, 65%).

IR(neat): 1740(C.dbd.O), 1710(C.dbd.O), 1605, 850, 770 cm.sup.-1. NMR(CDCl.sub.3): .delta.0.85(t, 3H, --CH.sub.2 CH.sub.2 CH.sub.3), 1.02 (t, 3H, --CH.sub.2 CH.sub.2 CH.sub.3), 1.4-2.0(m, 4H, --CH.sub.2 CH.sub.2 CH.sub.3), ##STR17## 3.85(s, 3H, OCH.sub.3), 4.10 (t, 2H, --CH.sub.2 CH.sub.2 CH.sub.3), 4.25(t, 2H, --CH.sub.2 CH.sub.2 CH.sub.3), 6.95(d, J=SHz, 2H, ring proton), 8.13(d, J=8 Hz, 2H, ring proton).

EXAMPLE 5

Dimethyl 3-methyl-4-butylthio-carbonyloxy-2,5-thiophene dicarboxylate (Compound No. 78)

1.8 g (8 mmol) of dimethyl 3-methyl-4-oxy-2,5-thiophene dicarboxylate and 4 g (40 mmol) of triethylamine were dissolved into 40 ml of dioxane, and 1.8 g (12 mmol) of S-butyl chloro-thioformate was added dropwise to the solution thus obtained, while it was ice-cooled with stirring. After the addition, the mixture was allowed to stand overnight at at room temperature, added with 50 ml of 5% aqueous NaHCO.sub.3, extracted with 50 ml of ethylether and then washed 2 to 3 times with water. The extract was dried with MgSO.sub.4, and distilled to remove the solvent. The compound No. 78 was obtained (2.2 g, 79%).

IR(neat): 1720(C.dbd.O), 1260, 1070, 770 cm.sup.-1. NMR(CDCl.sub.3): .delta.0.95(t, 3H, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), 1.1-1.8(m, 4H, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), ##STR18## 2.95 (t, 2H, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), 3.90(s, 6H, CO.dbd.CH.sub.3).

EXAMPLE 6

Di-isopropyl 3-methyl-4-(4-methylbenzylthiocarbonyloxy)-2,5-thiophene-dicarboxylate (Compound No. 94)

2.3 g (8 mmol) of di-isopropyl 3-methyl-4-oxy-2,5-thiophene-dicarboxylic and 2 g (20 mmol) of triethylamine were dissolved into 20 ml of dioxane to form a solution, to which was added dropwise, while stirring with cooling with ice, 2.4 g (12 mmol) of S-4-methyl-benzyl chloro-thioformate. After the addition, the mixture was allowed to stand overnight at room temperature, added 50 ml of 5% aqueous NaHCO.sub.3, extracted with 50 ml of ethylether, and then washed 2 to 3 times with water. The extract was dried over MgSO.sub.4 and distilled to remove the solvent thereby to give the compound No. 94 as an almost pure yellowish viscous liquid (3.2 g, 89%).

IR(neat): 1730(C.dbd.O), 1720(C.dbd.O), 1320, 1285, 1125, 800 cm.sup.-1. NMR(CDCl.sub.3): .delta.1.35(t, 12H, --CH(CH.sub.3).sub.2), ##STR19## 4.24(s, 2H, --SCH.sub.2), 5.1-5.5 (m, 2H, --CH(CH.sub.3).sub.2), 7.1-7.5(m, 4H, ring proton).

EXAMPLE 7

Di-ethyl 3-methyl-4-methylcarbamoyloxy-2,5-thiophene-dicarboxylate (Compound No. 99)

5.2 g (20 mmol) of diethyl 3-methyl-4-hydroxy-2,5-thiophene dicarboxylate was dissolved in 60 ml of dioxane to form a solution, to which was added dropwise 1.7 g (30 mmol) of methyl isocyanate. The mixture was allowed to stand overnight at room temperature, to which was then added n-hexane. The white crystalline mass separated was recovered by filtration and then washed with n-hexane. It was dried in vacuo to give 5.5 g (87%) of the desired carbamic acid ester.

IR(nujol): 3300(NH), 1710(C.dbd.O), 1290, 1250 cm.sup.-1. NMR(CDCl.sub.3): .delta.1.2-1.3(m, 6H, --CH.sub.2 CH.sub.3), ##STR20## 2.94(d, J=6 Hz, 3H, NHCH.sub.3), 4.2-4.5 (m, 4H, --CH.sub.2 CH.sub.3), 5.1-5.4(br, 1H, NH).

EXAMPLE 8

Diethyl 3-methyl-4-dimethylcarbamoyloxy-2,5-thiophene-dicarboxylate (Compound No. 116)

5.2 g (20 mmol) of diethyl 3-methyl-4-hydroxy-2,5-thiophene dicarboxylate was dissolved in a mixture of 40 ml of dioxane and 20 ml of pyridine to form a solution, to which was added dropwise 3.2 g (30 mmol) of dimethyl carbamoyl chloride. The reaction mixture was stirred overnight and then poured into cold water, acidified with hydrochloric acid, extracted with ethylether and then dried over anhydrous magnesium sulfate. The solvent was removed by distillation, and the crude product was recrystallized by use of a mixed solvent of ethanol and hexane to give 5.2 g (79%) of the desired carbamic acid ester.

IR(nujol): 1710(C.dbd.O), 1690(C.dbd.O), 1370, 1250, 1140, 1360, 765 cm.sup.-1. NMR(CDCl.sub.3): .delta.1.2-1.5(m, 6H, --CH.sub.2 --CH.sub.3), ##STR21## 3.05(s, 3H, N--CH.sub.3), 3.18(s, 3H, N--CH.sub.3), 4.2-4.5(m, 4H, CH.sub.2 --CH.sub.3).

EXAMPLE 9

Dimethyl 3-methyl-4-acetoxy-2,5-thiophenedicarboxylate (Compound No. 189)

1.2 g (5 mmol) of dimethyl 3-methyl-4-oxy-2,5-thiophene-dicarboxylate and 1.3 g of triethylamine were dissolved into 20 ml of dioxane to form a solution, to which was added 0.6 g (7.5 mmol) of acetyl chloride while stirring the solution with ice-cooling. Further, the mixture was stirred for 2 hours at room temperature, added with 30 ml of 5% aqueous NaHCO.sub.3, extracted with 30 ml of ethylether, and then washed 2 to 3 times with water. The extract was dried over anhydrous magnesium sulfate and then distilled to remove the solvent to give a crude product, which was recrystallized from about 5 ml of methyl alcohol to give as a crystalline white mass the compound No. 189. Yield 10 g (70%).

IR(nujol): 1765(C.dbd.O), 1710(C.dbd.O), 1690(C.dbd.O), 1300, 1255, 1180, 1055 cm.sup.-1. NMR(CDCl.sub.3): ##STR22## 3.80(s, 3H, --CO.sub.2 CH.sub.3), 3.83(s, 3H, --CO.sub.2 CH.sub.3).

EXAMPLE 10

Diethyl 3-methyl-4-(3-methylcrotonoyloxy)-2,5-thiophene dicarboxylate (Compound No. 219)

2.1 g (8 mmol) of diethyl 3-methyl-4-oxy-2,5-thiophene dicarboxylate and 2 g of triethylamine were dissolved in 30 ml of dioxane to give a solution, to which was added 1.4 g (12 mmol) of 3-methyl-crotonyl chloride while stirring and ice-cooling. Further, the mixture was stirred for 2 hours at room temperature, added with 30 ml of 5% aqueous NaHCO.sub.3, extracted with 30 ml of ethylether, and washed with water 2 to 3 times. The extract was dried over anhydrous magnessium sulfate and distilled to remove the solvent. The crude product obtained was purified by silica gel column chromatography (hexane/ethyl ether=10:1). Yield 2.1 g (77%).

IR(KBr): 1742(C.dbd.O), 1715(C.dbd.O), 1695(C.dbd.O), 1640(C.dbd.C), 1293, 1248, 1105, 1070 cm.sup.-1. NMR(CDCl.sub.3): .delta.1.2-1.5(m, 6H, --CH.sub.2 CH.sub.3), ##STR23## 2.40 (s, 3H, ring --CH.sub.3), 4.3-4.6(m, 4H, --CH.sub.2 CH.sub.3), ##STR24##

EXAMPLE 11

Di-isopropyl 3-methyl-4-butane sulfonyloxy-2,5-thiophene-dicarboxylate (Compound No. 315)

A mixture of 2.3 g (8 mmol) of di-isopropyl 3-methyl-4-hydroxy-2,5-thiophene-dicarboxylate, 30 ml of dioxane, 60 ml of acetone, 1.6 g (120 mmol) of anhydrous potassium carbonate and 1.6 g (10 mmol) of butane-sulfonyl chloride was refluxed for about 10 hours. The mixture was then freed from dioxane and acetone by distillation in vacuo and then added with ethylether, washed with water, and dried with anhydrous magnessium sulfate. The solvent was removed by distillation and then recrystallization was effected from methanol to give 2.8 g (86%) of the desired white crystalline compound. m.p. 59.degree.-61.degree. C.

IR(nujol): 1720(C.dbd.O), 1255, 1150, 1110 cm.sup.-1. NMR(CDCl.sub.3): .delta.1.00(t, 3H, --CH.sub.2 --CH.sub.3), 1.35(d, J=7 Hz, 12H), 1.5-2.2(m, 4H, --CH.sub.2 --CH.sub.2 --), ##STR25## 3.61(t, 2H, --SO.sub.2 --CH.sub.2 --), ##STR26##

EXAMPLE 12

Dipropyl 3-methyl-4-(4-bromobenzene-sulfonyloxy)-2,5-thiophene-dicarboxylate (Compound No. 332)

A mixture of 2.3 g (8 mmol) of dipropyl 3-methyl-4-hydroxy-2,5-thiophene-dicarboxylate, 20 ml of dioxane, 40 ml of acetone, 1.6 g (12 mmol) of anhydrous potassium carbonate and 2.3 g (10 mmol) of 4-bromobenzene-sulfonyl chloride was refluxed for about 10 hours, removed of dioxane and acetone by distillation, added with ethyl ether, washed with water, and dried with anhydrous magnessium sulfate. The solvent was removed by distillation, and recrystallization was effected with use of methanol to give 3.8 g (94%) of the desired white crystalline compound, m.p. 73.degree.-74.degree. C.

IR(nujol): 1700(C.dbd.O), 1570, 1290, 1185, 1060, 790, 770 cm.sup.-1. NMR(CDCl.sub.3): .delta.0.90-1.18(m, 6H, --CH.sub.2 CH.sub.2 CH.sub.3), 1.5-2.0(m 4H, --CH.sub.2 CH.sub.2 --), ##STR27## 7.58-7.90(m, 4H, ring proton).

Exemplified below in Tables 1a and 1b are the compounds of the present invention as prepared in accordance with the procedures described in the foregoing examples. The compound number assigned to each compounds in the tables will be referred to in the examples and test examples that follow.

TABLE 1a__________________________________________________________________________ ##STR28## Physicochemical data m.p. (.degree.C.)Compound or refractiveNo. R R.sub.3 R.sub.2 index n.sub.D__________________________________________________________________________1 CH.sub.3 ##STR29## CH.sub.3 m.p. 96-982 " " C.sub.2 H.sub.5 m.p. 78-803 " " nC.sub.3 H.sub.7 n.sub.D.sup.10 1.55824 " " iC.sub.3 H.sub.7 n.sub.D.sup.16 1.54995 " " nC.sub.4 H.sub.9 n.sub.D.sup.16 1.54686 " " iC.sub.4 H.sub.9 n.sub.D.sup.16 1.54417 " " CH.sub.2CHCH.sub.2 m.p. 54-558 " ##STR30## C.sub.2 H.sub.5 m.p. 98-1009 " " nC.sub.3 H.sub.7 m.p. 90-9110 " " iC.sub.3 H.sub.7 n.sub.D.sup.18 1.556611 " " nC.sub.4 H.sub.9 n.sub.D.sup.17 1.553212 " " iC.sub.4 H.sub.9 m.p. 99-10013 " ##STR31## nC.sub.3 H.sub.7 n.sub.D.sup.12 1.565214 " " iC.sub.3 H.sub.7 n.sub.D.sup.12 1.558915 " " nC.sub.4 H.sub.9 n.sub.D.sup.12 1.560516 " ##STR32## nC.sub.3 H.sub.7 n.sub.D.sup.12 1.562617 " " iC.sub.3 H.sub.7 n.sub.D.sup.12 1.559018 " " nC.sub.4 H.sub.9 n.sub.D.sup.15 1.557719 " ##STR33## C.sub.2 H.sub.5 m.p. 97-9920 " " nC.sub. 3 H.sub.7 m.p. 56-5821 " " iC.sub.3 H.sub.7 n.sub.D.sup.10 1.570122 " " nC.sub.4 H.sub.9 n.sub.D.sup.15 1.560523 " ##STR34## nC.sub.3 H.sub.7 m.p. 52-5524 " " iC.sub.3 H.sub.7 n.sub.D.sup.12 1.570525 " " nC.sub.4 H.sub.9 n.sub.D.sup.15 1.577826 C.sub.2 H.sub.5 ##STR35## iC.sub.3 H.sub.7 n.sub.D.sup.10 1.548927 nC.sub.3 H.sub.7 " iC.sub.3 H.sub.7 n.sub.D.sup.10 1.545928 CH.sub.3 ##STR36## " n.sub.D.sup.12 1.541829 " ##STR37## " m.p. 77-7930 " ##STR38## " n.sub.D.sup.12 1.567431 " ##STR39## C.sub.2 H.sub.5 m.p. 84-85.degree. C.32 " " n-C.sub.3 H.sub.7 m.p. 55-57.degree. C.33 " " i-C.sub.3 H.sub.7 n.sub.D.sup.16 1.549034 " " n-C.sub.4 H.sub.9 n.sub.D.sup.16 1.547035 " " i-C.sub.4 H.sub.9 m.p. 74-75.degree. C.36 " ##STR40## n-C.sub.3 H.sub.7 n.sub.D.sup.15 1.553637 " " i-C.sub.3 H.sub.7 m.p. 87.degree. C.38 " " n-C.sub.4 H.sub.9 n.sub.D.sup.15 1.547939 " ##STR41## n-C.sub.3 H.sub.7 n.sub.D.sup.15 1.554540 " " i-C.sub.3 H.sub.7 n.sub.D.sup.15 1.549441 " " n-C.sub.4 H.sub.9 n.sub.D.sup.15 1.548742 " ##STR42## n-C.sub.3 H.sub.7 n.sub.D.sup.12 1.548343 " " i-C.sub.3 H.sub.7 m.p. 96-98.degree. C.44 " " n-C.sub.4 H.sub.9 n.sub.D.sup.15 1.541745 " ##STR43## n-C.sub.3 H.sub.7 m.p. 90-91.degree. C.46 " " i-C.sub.3 H.sub.7 m.p. 134-135.degree. C.47 " " n-C.sub.4 H.sub.9 m.p. 63-65.degree. C.48 " ##STR44## n-C.sub.3 H.sub.7 n.sub.D.sup.12 1.565949 " " i-C.sub.3 H.sub.7 n.sub.D.sup.12 1.562650 " " n-C.sub.4 H.sub.9 m.p. 58-60.degree. C.51 " ##STR45## C.sub.2 H.sub.5 m.p. 100-101.degree. C.52 " ##STR46## n-C.sub.3 H.sub.7 m.p. 48-51.degree. C.53 " " i-C.sub.3 H.sub.7 m.p. 93-95.degree. C.54 " " n-C.sub.4 H.sub.9 n.sub.D.sup.15 1.560655 " ##STR47## n-C.sub.3 H.sub.7 m.p. 84-85.degree. C.56 " " i-C.sub.3 H.sub.7 m.p. 97-100.degree. C.57 " " n-C.sub.4 H.sub.9 m.p. 61-63.degree. C.58 " ##STR48## n-C.sub.3 H.sub.7 n.sub.D.sup.12 1.565059 " " i-C.sub.3 H.sub.7 n.sub.D.sup.12 1.560260 " " n-C.sub.4 H.sub.9 n.sub.D.sup.15 1.555161 " ##STR49## n-C.sub.3 H.sub.7 n.sub.D.sup.12 1.569262 " " i-C.sub.3 H.sub.7 n.sub.D.sup.12 1.563263 " ##STR50## " n.sub.D.sup.12 1.549264 " ##STR51## i-C.sub.3 H.sub.7 n.sub.D.sup.12 1.566665 " ##STR52## " n.sub.D.sup.12 1.548066 C.sub.2 H.sub.5 ##STR53## " n.sub.D.sup.10 1.549067 " ##STR54## " n.sub.D.sup.10 1.548268 CH.sub.3 n-C.sub.3 H.sub.7 S C.sub.2 H.sub.5 m.p. 45-4669 " " n-C.sub.3 H.sub.7 n.sub.D.sup.17 1.525770 " " i-C.sub.3 H.sub.7 n.sub.D.sup.17 1.519671 " " n-C.sub.4 H.sub.9 n.sub.D.sup.17 1.520272 " " i-C.sub.4 H.sub.9 n.sub.D.sup.17 1.518073 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.17 1.543174 " " C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 n.sub.D.sup.17 1.519575 " " ##STR55## m.p. 66-6976 " " ##STR56## n.sub.D.sup.16 1.585477 " " ##STR57## n.sub.D.sup.16 1.561078 " n-C.sub.4 H.sub.9 S CH.sub.3 n.sub.D.sup.11 1.539379 " " C.sub.2 H.sub.5 m.p. 42-4380 " " n-C.sub.3 H.sub.7 n.sub.D.sup.11 1.525881 " " i-C.sub.3 H.sub.7 n.sub.D.sup.11 1.514282 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.516083 " " i-C.sub.4 H.sub.9 n.sub.D.sup.22 1.512984 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.22 1.536585 " t-C.sub.4 H.sub.9 S C.sub.2 H.sub.5 m.p. 84-8586 " " n-C.sub.3 H.sub.7 n.sub.D.sup.22 1.519687 " CH.sub.2CHCH.sub.2 S CH.sub.3 m.p. 74-7588 " " C.sub.2 H.sub.5 m.p. 61-6389 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.522690 " ##STR58## C.sub.2 H.sub.5 n.sub.D.sup.27 1.526891 " ##STR59## " m.p. 57-5892 " ##STR60## CH.sub.3 m.p. 92-9393 " " n-C.sub.3 H.sub.7 n.sub.D.sup.22 1.569794 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.553995 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.553896 " " i-C.sub.4 H.sub.9 n.sub.D.sup.22 1.550997 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.22 1.576498 " CH.sub.3 NH CH.sub.3 m.p. 127-13099 " " C.sub.2 H.sub.5 m.p. 120-122100 " C.sub.2 H.sub.5 NH " m.p. 199-121101 " n-C.sub.3 H.sub.7 NH CH.sub.3 m.p. 101-103102 " " C.sub.2 H.sub.5 m.p. 101-102103 " " n-C.sub.3 H.sub.7 m.p. 77-79104 " " i-C.sub.3 H.sub.7 m.p. 78-80105 CH.sub.3 " n-C.sub.4 H.sub.9 m.p. 80-82106 " " i-C.sub.4 H.sub.9 m.p. 70-71107 " " CH.sub.2CHCH.sub.2 m.p. 75-77108 " n-C.sub.4 H.sub.9 NH CH.sub.3 m.p. 111-113109 " " C.sub.2 H.sub.5 m.p. 88-90110 " " n-C.sub.3 H.sub.7 m.p. 65-67111 " " i-C.sub.3 H.sub.7 m.p. 59-61112 " " n-C.sub.4 H.sub.9 m.p. 77-78113 " " i-C.sub.4 H.sub.9 m.p. 64-66114 " " CH.sub.2 CHCH m.p. 70-72115 " (CH.sub.3).sub.2 N CH.sub.3 m.p. 121-122116 " " C.sub.2 H.sub.5 m.p. 75117 " " n-C.sub.3 H.sub.7 n.sub.D.sup.22 1.5180118 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.5109119 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5119120 " " i-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5120121 " " CH.sub.2 CHCH.sub.2 n.sub.D.sup.22 1.5356122 " (C.sub.2 H.sub.5).sub.2 N CH.sub.3 n.sub.D.sup.21 1.5267123 " " C.sub.2 H.sub.5 m.p. 54-55124 " " n-C.sub.3 H.sub.7 n.sub.D.sup.22 1.5106125 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.5051126 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5065127 " " i-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5046128 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.22 1.5270129 " (n-C.sub.3 H.sub.7).sub.2 N CH.sub.3 n.sub.D.sup.21 1.5186130 " " C.sub.2 H.sub.5 n.sub.D.sup.25 1.5074131 " " n-C.sub.3 H.sub.7 n.sub.D.sup.23 1.5070132 " " i-C.sub.3 H.sub.7 n.sub.D.sup.23 1.5018133 " " n-C.sub.4 H.sub.9 n.sub.D.sup.23 1.5043134 " (n-C.sub.4 H.sub.9).sub.2 N CH.sub.3 n.sub.D.sup.21 1.5137135 " " C.sub.2 H.sub.5 n.sub.D.sup.25 1.5030136 " " n-C.sub.3 H.sub.7 n.sub.D.sup.23 1.4971137 " " i-C.sub.3 H.sub.7 n.sub.D.sup.23 1.4972138 " " n-C.sub.4 H.sub.9 n.sub.D.sup.23 1.5002139 " ##STR61## C.sub.2 H.sub.5 m.p. 72-74140 " ##STR62## CH.sub.3 m.p. 116-118141 " " C.sub.2 H.sub.5 m.p. 115-116142 " ##STR63## CH.sub.3 m.p. 110-111143 " " C.sub.2 H.sub.5 m.p. 119-121144 " " n-C.sub.3 H.sub.7 m.p. 75-77145 " " i-C.sub.3 H.sub.7 m.p. 99-100146 " " n-C.sub.4 H.sub.9 m.p. 89-91147 " " i-C.sub.4 H.sub.9 m.p. 86-88148 " " sec-C.sub.4 H.sub.9 m.p. 67-68149 " " CH.sub.2CHCH.sub.2 m.p. 88-90150 " " ##STR64## m.p. 140-142151 " " ##STR65## m.p. 70-72152 " " C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 m.p. 73-75153 " " ##STR66## m.p. 116-118154 " ##STR67## CH.sub.3 m.p. 140-141155 " " C.sub.2 H.sub.5 m.p. 130-132156 " " i-C.sub.3 H.sub.7 m.p. 96-97157 " " n-C.sub.4 H.sub.9 m.p. 94-96158 " " i-C.sub.4 H.sub.9 m.p. 82-83159 " " CH.sub.2CHCH.sub.2 m.p. 93-94160 " " CHCCH.sub.2 m.p. 145-147161 " " sec-C.sub.4 H.sub.9 m.p. 79-81162 " " n-C.sub.8 H.sub.17 m.p. 63-65163 " " ##STR68## m.p. 140-142164 " " ##STR69## m.p. 97-99165 " " C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 m.p. 86-87166 " " ##STR70## m.p. 120-122167 " " n-C.sub.3 H.sub.7 m.p. 90-94168 " ##STR71## C.sub.2 H.sub.5 m.p. 87-89169 " " i-C.sub.3 H.sub.7 m.p. 63-65170 " (CH.sub.2).sub.4 N CH.sub.3 m.p. 112-115171 " " C.sub.2 H.sub.5 m.p. 110-111172 " " n-C.sub.3 H.sub.7 n.sub.D.sup.26 1.5255173 " " i-C.sub.3 H.sub.7 m.p. 70-73174 " " n-C.sub.4 H.sub.9 n.sub.D.sup.26 1.5199175 " " i-C.sub.4 H.sub.9 n.sub.D.sup.26 1.5174176 " " CH.sub.2CHCH.sub.2 m.p. 62-65177 " " C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 n.sub.D.sup.26 1.5189178 " " ##STR72## m.p. 104-105179 " (CH.sub.2).sub.5 N CH.sub.3 m.p. 91-94180 " " C.sub.2 H.sub.5 m.p. 88-89181 " " n-C.sub.3 H.sub.7 n.sub.D.sup.26 1.5222182 " " i-C.sub.3 H.sub.7 m.p. 66-69183 " " n-C.sub.4 H.sub.9 n.sub.D.sup.26 1.5172184 " " i-C.sub.4 H.sub.9 n.sub.D.sup.26 1.5158185 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.26 1.5389186 " " ##STR73## m.p. 125-127187 " i-C.sub.3 H.sub.7 NH C.sub.2 H.sub.5188 " m.p. 90-92 ##STR74## n-Bu m.p. 70-72189 " CH.sub.3 CH.sub.3 m.p. 119-120190 " " n-C.sub.3 H.sub.7 n.sub.D.sup.10 1.5148191 " " i-C.sub. 3 H.sub.7 n.sub.D.sup.21 1.4976192 " C.sub.2 H.sub.5 CH.sub.3 m.p. 71-72193 " " C.sub.2 H.sub.5 m.p. 53-55194 " " n-C.sub.3 H.sub.9 n.sub.D.sup.10 1.5118195 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.4943196 " n-C.sub.3 H.sub.7 C.sub.2 H.sub.5 n.sub.D.sup.25 1.5072197 " n-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 n.sub.D.sup.11 1.5258198 " t-C.sub.4 H.sub.9 n-C.sub.3 H.sub.7 n.sub.D.sup.28 1.5027199 " i-C.sub.4 H.sub.9 " n.sub.D.sup.27 1.4971200 " CH.sub.2 Cl " m.p. 52-54201 " CH.sub.2 Br " m.p. 81-83202 " CH.sub.3 CHCl " m.p. 43-45203 " CH.sub.3 CHBr n-C.sub.3 H.sub.7 m.p. 64-66204 " CH.sub.3 CH.sub.2 CH.sub.2 CHBr " n.sub. D.sup.23 1.5130205 " CH.sub.2CH CH.sub.3 m.p. 67-69206 " " C.sub.2 H.sub.5 n.sub.D.sup.25 1.5031207 " " n-C.sub.3 H.sub.7 n.sub.D.sup.11 1.5251208 " " i-C.sub.3 H.sub.7 n.sub.D.sup.11 1.5107209 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5133210 " " i-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5086211 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.22 1.5352212 " CH.sub.3 CHCH C.sub.2 H.sub.5 n.sub.D.sup.27 1.5244213 " " n-C.sub.3 H.sub.7 n.sub.D.sup.10 1.5270214 " " i-C.sub.3 H.sub.7 n.sub.D.sup.20 1.5115215 " " n-C.sub.4 H.sub.9 n.sub.D.sup.27 1.5152216 " " i-C.sub.4 H.sub.9 n.sub.D.sup.27 1.5110217 " " CH.sub.2CHCH m.p. 76-48218 " C.sub.2 H.sub.5 CHCH CH.sub.3 m.p. 92-94219 " ##STR75## C.sub.2 H.sub.5 m.p. 77-78220 " " CH.sub.3 m.p. 95-96221 " " n-C.sub.3 H.sub.7 n.sub.D.sup.24 1.5222222 " " i-C.sub.3 H.sub.7 n.sub.D.sup.20 1.5190223 " " n-C.sub.4 H.sub.9 n.sub.D.sup.26 1.5177224 " " i-C.sub.4 H.sub.9 n.sub.D.sup.26 1.5130225 " " CH.sub.2CHCH.sub.2 m.p. 57-60226 " CH.sub.3 OCH.sub.2 CH.sub.3 m.p. 81-83227 " " C.sub.2 H.sub.5 n.sub.D.sup.10 1.5125228 " " n-C.sub.3 H.sub.7 n.sub.D.sup.10 1.5125229 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.4971230 " " n-C.sub.4 H.sub.9 n.sub.D.sup.23 1.5037231 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.23 1.5258232 " C.sub.2 H.sub.5 OCH.sub.2 C.sub.2 H.sub.5 n.sub.D.sup.25 1.5037233 " C.sub.2 H.sub.5 OC.sub.2 H.sub.4 CH.sub.3 n.sub.D.sup.24 1.5048234 " " C.sub.2 H.sub.5 n.sub.D.sup.28 1.4948235 " " n-C.sub.3 H.sub.7 n.sub.D.sup.10 1.5061236 " " i-C.sub.3 H.sub.7 n.sub.D.sup.23 1.4937237 " " n-C.sub.4 H.sub.9 n.sub.D.sup.24 1.4979238 " " i-C.sub.4 H.sub.9 n.sub.D.sup.24 1.4913239 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.24 1.5170240 " ##STR76## C.sub.2 H.sub.5 n.sub.D.sup.15 1.5339241 " CH.sub.3 SCH.sub.2 " m.p. 53-55242 " i-C.sub.3 H.sub.7 SCH.sub.2 " n.sub.D.sup.25 1.5261243 " ##STR77## " n.sub.D.sup.26 1.5049244 " ##STR78## " n.sub.D.sup.26 1.5037245 " ##STR79## n-C.sub.4 H.sub.9 n.sub.D.sup.15 1.5615246 " CH.sub.3 OCH.sub.2 i-C.sub.4 H.sub.7 n.sub.D.sup.23 1.4996247 " ##STR80## C.sub.2 H.sub.5 n.sub.D.sup.26 1.5163248 " ##STR81## " m.p. 77-79249 " " n-C.sub.3 H.sub.7 m.p. 40-41250 " " i-C.sub.3 H.sub.7 n.sub.D.sup.17 1.5132251 " " n-C.sub.4 H.sub.9 n.sub.D.sup.17 1.5148252 " " i-C.sub.4 H.sub.9 n.sub.D.sup.17 1.5124253 " ##STR82## CH.sub.3 m.p. 121-123254 " " C.sub.2 H.sub.5 n.sub.D.sup.27 1.5751255 " " n-C.sub.3 H.sub.7 n.sub.D.sup.11 1.5689256 " " i-C.sub.3 H.sub.7 n.sub.D.sup.11 1.5508257 " ##STR83## C.sub.2 H.sub.5 n.sub.D.sup.27 1.5450258 " CH.sub.3 O CH.sub.3 m.p. 80-81259 " " C.sub.2 H.sub.5 n.sub.D.sup.20 1.5065260 " " n-C.sub.3 H.sub.7 n.sub.D.sup.10 1.5122261 " " i-C.sub.3 H.sub.7 n.sub.D.sup.21 1.4944262 " C.sub.2 H.sub.5 O C.sub.2 H.sub.5 m.p. 50-52263 " i-C.sub.4 H.sub.9 O " n.sub.D.sup.23.5 1.4958264 " n-C.sub.5 H.sub.11 O " m.p. 47-48265 " n-C.sub.7 H.sub.5 O " n.sub.D.sup.21 1.4941266 " n-C.sub.8 H.sub.17 O " n.sub.D.sup.21 1.4928267 " n-C.sub.9 H.sub.19 O " n.sub.D.sup.21 1.4923268 " CH.sub.2 BrCHBrCH.sub.2 O " n.sub.D.sup.29 1.5376269 " CHCCH.sub.2 O " n.sub.D.sup.24 1.5101270 " ##STR84## CH.sub.3 m.p. 118-119271 " " C.sub.2 H.sub.5 m.p. 103-105272 " " n-C.sub.3 H.sub.7 m.p. 79-80273 " " i-C.sub.3 H.sub.7 m.p. 62-64274 " " n-C.sub.4 H.sub.9 n.sub.D.sup.24 1.5282275 " " i-C.sub.4 H.sub.9 n.sub.D.sup.20 1.5280276 " ##STR85## C.sub.2 H.sub.5 m.p. 95-97277 " ##STR86## " m.p. 93-95278 " ##STR87## " m.p. 76-77279 " ##STR88## CH.sub.2CHCH.sub.2 m.p. 92-93280 " ##STR89## i-C.sub.3 H.sub.7 n.sub.D.sup.26 1.5685281 " ##STR90## " n.sub.D.sup.26 1.5362282 " ##STR91## " n.sub.D.sup.26 1.5744283 " ##STR92## " m.p. 130-133284 " ##STR93## " m.p. 111-114285 " ##STR94## " m.p. 130-132286 " ##STR95## " n.sub.D.sup.26 1.5612287 " ##STR96## " n.sub.D.sup.26 1.5440288 " ##STR97## " m.p. 170-172289 CH.sub.3 ##STR98## " m.p. 89-90290 " ##STR99## " n.sub.D.sup.26 1.5462291 " ##STR100## " m.p. 114-115292 " ##STR101## " m.p. 124-126293 " ##STR102## " m.p. 89-91294 " ##STR103## " m.p. 137-139295 " ##STR104## " n.sub.D.sup.23 1.5404296 " ##STR105## " n.sub.D.sup.26 1.5406297 " ##STR106## " n.sub.D.sup.26 1.5426298 " ##STR107## " n.sub.D.sup.26 1.5327299 " ##STR108## " n.sub.D.sup.27 1.5609300 " ##STR109## " n.sub.D.sup.26 1.5324301 " ##STR110## " n.sub.D.sup.26 1.5378302 " ##STR111## " m.p. 90-92303 " ##STR112## " n.sub.D.sup.18 1.5173304 CH.sub.3 ##STR113## " n.sub.D.sup.18 1.5173305 " ##STR114## " n.sub.D.sup.18 1.5192306 " ##STR115## " n.sub.D.sup.20 1.5372__________________________________________________________________________ TABLE 1b______________________________________ ##STR116## Physico- chemical data m.p.Com- (.degree.C.) orpound refractiveNo. R R.sub.4 R.sub.2 index n.sub.D______________________________________307 CH.sub.3 CH.sub.3 CH.sub.3 m.p. 62-64.degree. C.308 " " C.sub.2 H.sub.5 m.p. 83-85.degree. C.309 " " n-C.sub.3 H.sub.7 n.sub.D.sup.19 1.5200310 " " i-C.sub.3 H.sub.7 m.p. 95-96.degree. C.311 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5141312 " " i-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5106313 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.22 1.5397314 " n-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 n.sub.D.sup.19 1.5127315 " " i-C.sub.4 H.sub.9 n.sub.D.sup.19 1.5049316 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.20 1.5302317 " i-C.sub.3 H.sub.7 C.sub.2 H.sub.5 n.sub.D.sup.22 1.5130318 " n-C.sub.4 H.sub.9 CH.sub.3 m.p. 51-54319 " " i-C.sub.3 H.sub.7 m.p. 59-61320 " " n-C.sub.4 H.sub.9 n.sub.D.sup.18 1.5089321 " " i-C.sub.4 H.sub.9 n.sub.D.sup.18 1.5022322 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.18 1.5293323 " n-C.sub.5 H.sub.11 C.sub.2 H.sub.5 n.sub.D.sup.28 1.5100324 " (CH.sub.3).sub.2 N C.sub.2 H.sub.5 n.sub.D.sup.22 1.5232325 " ##STR117## CH.sub.3 m.p. 153-154326 " " i-C.sub.3 H.sub.7 n.sub.D.sup.19 1.5437327 " " n-C.sub.4 H.sub.9 n.sub.D.sup.21 1.5414328 " " i-C.sub.4 H.sub.9 n.sub.D.sup.21 1.5359329 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.21 1.5667330 " " C.sub.2 H.sub.5 m.p. 90-91331 " ##STR118## i-C.sub.3 H.sub.7 m.p. 99-101332 " " i-C.sub.4 H.sub.9 n.sub.D.sup.19 1.5486333 " " CH.sub.2CHCH.sub.2 n.sub.D.sup.20 1.5646334 " ##STR119## CH.sub.3 m.p. 124-125335 " " C.sub.2 H.sub.5 m.p. 98-99336 " " n-C.sub.3 H.sub.7 m.p. 73-74337 " " i-C.sub.3 H.sub.7 m.p. 98-99338 " " n-C.sub.4 H.sub.9 n.sub.D.sup.22 1.5530339 " " i-C.sub.4 H.sub.9 n.sub.D.sup.16 1.5546340 " ##STR120## CH.sub.3 m.p. 115-117341 " " C.sub.2 H.sub.5342 " " n-C.sub.3 H.sub.7 m.p. 81-83343 " " i-C.sub.3 H.sub.7 m.p. 102-104344 " " n-C.sub.4 H.sub.9 n.sub.D.sup.20 1.5374345 " " CH.sub.2CHCH.sub.2 m.p. 48-50346 " i-C.sub.3 H.sub.7 CH.sub.3 m.p. 143-145347 " " i-C.sub.3 H.sub.7 n.sub.D.sup.22 1.5092______________________________________

When the compounds of the present invention are used as agricultural and horticultural fungicides, they can be applied as they are or by diluting them with a liquid carrier such as water or an organic solvent or with a solid dust or other suitable carrier or by formulating them into wettable powder, oil, liquid, emulsion, sol (flowable), dust, driftless dust, granule and microgranule by adding auxiliary agents such as a wetting agent, a spreading agent, a dispersing agent, an emulsifying agent and a fixing agent as any occasion arises. As liquid carriers to be used for formulating, for example, solvents such as water, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, esters, ketones, acid amides and dimethylsulfoxide are usable. Solid carriers include mineral dusts such as clay, talc, kaolin, bentonite, diatomaceous earth, calcium carbonate and silicic acid. As auxiliary agents, for example, nonionic, anionic, cationic and amphoteric surfactants, lignin-sulfonic acid or its salts, gummy substances, aliphatic hydrocarbon salts, methyl cellulose and the like thickening agents are usable.

The formulations such as wettable powders, liquids, sols (flowable) and emulsions may contain their active components within the range of from 1 to 95% by weight, usually from 2 to 75% by weight.

These formulations are diluted with water to 0.0001% to 10% by weight in general and are applied at a rate of from 50 to 500 l per 10 ares, preferably from 100 to 300 l. Dusts, driftless dusts, microgranules and granules may contain in general 0.1 to 10% by weight of active components and are used at a rate of from 1 to 10 kg per 10 ares, preferably from 3 to 5 kg. Concentrated liquids such as oils, emulsions and sols (flowable) are usable as fine spray as they are without diluting them. Further, wettable powders and dusts are usable as seed dressings for crop seeds, and wettable powders, sols and emulsions when diluted with water are usable for immersing crop seeds.

In using the compounds of the present invention as agricultural and horticultural fungicides, it is possible to broaden their applicability by mixing them with insecticides, fungicides, herbicides and plant growth regulants. Depending on the situation, it is also possible to expect any synergistic effects.

Some examples are given below to illustrate the use as agricultural and horticultural fungicides of the compounds of the present invention, but it should not be construed that the principal ingredients and additives are not limited to those exemplified in these examples.

EXAMPLE 13

(Dust)

A homogeneous mixture of 2 parts of the compound No. 2 and 98 parts of clay is pulverized to obtain a dust preparation containing 2% of the effective ingredient.

EXAMPLE 14

(Wettable powder)

A homogeneous mixture of 30 parts of the compound No. 17, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay is pulverized uniformly to obtain a wettable powder containing 30% of the finely powdered effective ingredient. This wettable powder when actually applied to plants, is diluted to 1000 to 8000 times with water and then sprayed over the plants.

EXAMPLE 15

(Emulsion)

By dissolving 30 parts of the compound No. 4 in 55 parts of methyl ethyl ketone and 15 parts of polyethylene nonylphenyl ether, an emulsion containing 30% of the effective ingredient is obtained. The emulsion when actually applied to plants is diluted to 1000 to 8000 times with water and then sprayed over the plants.

EXAMPLE 16

(Granule)

A mixture of 5 parts of the compound No. 24, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin-sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded by means of a kneading machine, followed granulation. The granules thus obtained are then dried by means of a fluid bed type drier to obtain a granular preparation containing 5% of the effective ingredient.

EXAMPLE 17

(Dust)

A homogeneous mixture of 2 parts of the compound No. 32 and 98 parts of clay is uniformly pluverized to obtain a dust preparation containing 2% of the effective ingredient.

EXAMPLE 18

(Wettable powder)

A homogeneous mixture of 30 parts of the compound No. 36, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay is pulverized to obtain a wettable powder containing 3% of the effective ingredient. The wettable powder thus obtained when actually applied to plants is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 19

(Emulsion)

By dissolving 30 parts of the compound No. 45 in 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the effective ingredient is obtained. The emulsion thus obtained, when actually used, is diluted 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 20

(Granule)

A mixture of 5 parts of the compound No. 62, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin-sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded by means of a kneading machine, followed by granulation. The granules thus obtained are then dried on a fluid bed type drier to obtain a granule preparation containing 5% of the effective ingredient.

EXAMPLE 21

(Dust)

A homogeneous mixture of 2 parts of the compound No. 69 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the effective ingredient.

EXAMPLE 22

(Wettable powder)

A homogeneous mixture of 30 parts of the compound No. 73, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder containing 3% of the effective ingredient.

Thus obtained wettable powder when it is actually applied to plants is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 23

(Emulsion)

By dissolving 30 parts of the compound No. 92 in 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the effective ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 24

(Granule)

A mixture of 5 parts of the compound No. 101, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin-sulfonate, 25 parts of bentonite, 67 parts of clay and 15 parts of water is kneaded by means of a kneading machine, followed by granulation. The granules thus obtained are dried on a fluid bed type drier to obtain a granule preparation containing 5% of the effective ingredient.

EXAMPLE 25

(Dust)

A homogeneous mixture of 2 parts of the compound No. 109 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the effective ingredient.

EXAMPLE 26

(Wettable powder)

A homogeneous mixture of 30 parts of the compound No. 124, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder containing 3% of the effective ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 27

(Emulsion)

By dissolving 30 parts of compound No. 131 in 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the effective ingredient is obtained. The emulsion when actually applied to plants is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 28

(Granule)

A mixture of 5 parts of the compound No. 183, 1.5 parts of laryl sulfate, 1.5 parts of calcium lignin-sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded by means of a kneading machine, followed by granulation. The granules thus obtained are dried on a fluid bed type drier to obtain a granule preparation containing 5% of the effective ingredient.

EXAMPLE 29

(Dust)

A homogeneous mixture of 2 parts of the compound No. 190 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the effective ingredient.

EXAMPLE 30

(Wettable powder)

A homogeneous mixture of 30 parts of compound No. 204, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder containing 3% of the effective ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 31

(Emulsion)

By dissolving 30 parts of the compound No. 256 in 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the effective ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 1,000 to 8,000 times with water and sprayed over the plants.

EXAMPLE 32

(Granule)

A mixture of 5 parts of the compound No. 274, 1.5 parts of lauryl sulfonate, 1.5 parts of calcium lignin-sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded by means of a kneading machine, followed by granulation. The granules thus obtained are dried on a fluidized bed drier to obtain a granule preparation containing 5% of the effective ingredient.

EXAMPLE 33

(Dust)

A homogeneous mixture of 2 parts of the compound No. 304 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the effective ingredient.

EXAMPLE 34

(Wettable powder)

A homogeneous mixture of 30 parts of the compound No. 308, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder of the finely powdered uniform composition containing 30% of the effective ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 1,000 to 8,000 times with water and then sprayed over the plants.

EXAMPLE 35

(Emulsion)

By dissolving 30 parts of the compound No. 306 in 55 parts of methyl ethyl ketone and 15 parts of polyethylene nonylphenyl ether, an emulsion containing 30% of the effective ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 1,000 to 8,000 times with water and sprayed over the plants.

EXAMPLE 36

(Granules)

A mixture of 5 parts of the compound No. 317, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin-sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded by means of a kneading machine, followed by granulation. The granules thus obtained are dried on a fluid bed type drier to obtain a granule preparation containing 5% of the effective ingredient.

Fungicidal activities of the compounds of the present invention are illustrated below with reference to test examples.

TEST EXAMPLE 1

Test for the control effect on paddy rice blast

Over the 3rd-leaf stage seedlings of paddy rice (variety: Asahi) soil-cultured in a biscuit pot of 9 cm in diameter in a greenhouse was sprayed a test liquid, which was prepared by diluting a wettable powder prepared according to the general procedure of Example 14 to a predetermined concentration, at an amount of 10 ml per each pot. One day after the spraying of test liquid, the seedlings were inoculated by atomization with a spore suspension of rice blast fungus (Pyricuralia oryzae). Upon completion of the inoculation, the seedlings were kept overnight under a wet house condition (at 95-100% relative humidity and 24.degree.-25.degree. C.). Five (5) days after the inoculation, the number of lesions per leaf of the third stage leaves was investigated and the control value (%) was calculated on the basis of the following expression. Furthermore, the phytotoxicity against the rice plant of the test compound was investigated according to a fixed numeral scale, the injury ratings of which are defined as mentioned below. The results obtained are as shown in Table 2. ##EQU1##

TABLE 2______________________________________(Paddy rice blast) Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________ 1 100 100 0 2 100 82 0 4 100 88 0 8 100 86 0 9 100 100 0 11 100 98 0 16 100 97 0 23 100 100 0 98 200 100 0 100 80 0108 200 100 0 100 100 0114 200 100 0 100 84 0116 200 100 0 100 100 0117 200 100 0 100 100 0118 200 100 0 100 85 0120 200 100 0 100 88 0122 200 100 0 100 86 0124 200 100 0 100 86 0125 200 100 0 100 95 0128 200 100 0 100 93 0139 200 100 0 100 95 0146 200 100 0 100 96 0147 200 100 0 100 93 0149 200 100 0 100 100 0156 200 100 0 100 81 0170 200 100 0 100 82 0173 200 100 0 100 80 0180 200 100 0 100 84 0198 100 91 0199 100 100 0201 100 100 0202 100 79 0212 100 100 0217 100 100 0219 100 100 0221 100 77 0225 100 79 0227 100 100 0228 100 95 0233 100 88 0234 100 100 0235 100 99 0238 100 76 0239 100 87 0242 100 100 0243 100 82 0244 100 100 0247 100 100 0248 100 100 0249 100 100 0250 100 100 0251 100 100 0253 100 85 0254 100 96 0256 100 88 0257 100 91 0262 100 91 0263 100 84 0271 100 70 0272 100 70 0276 100 100 0292 100 90 0303 100 87 0304 100 87 0305 100 100 0306 100 100 0308 200 100 0 100 100 0309 200 100 0 100 79 0320 200 100 0 100 86 0323 200 100 0 100 100 0324 200 100 0 100 100 0325 200 100 0 100 75 0331 200 100 0 100 76 0340 200 100 0 100 82 0342 200 100 0 100 74 0343 200 100 0 100 74 0345 200 100 0 100 85 0Comparative 200 100 0chemical 100 95(EDDP)Non-treated -- 0 --______________________________________ (Note) ##STR121##

TEST EXAMPLE 2

Test for the control effect on cucumber powdery mildew

Over the first-leaf stage seedlings of cucumber (variety: Sagami hanjiro) soil-cultured in a porcelain pot of 9 cm in diatmeter in a greenhouse was sprayed 10 ml of a test solution of the compound diluted to a predetermined concentration. Next day the seedlings were inoculated by atomization with a spore suspension of cucumber powdery mildew fungus (Erysiphe cichobrcearum). Ten (10) days after the inoculation, percent lesion area (%) was investigated and the control value (%) was calculated according to the following expression. ##EQU2##

The results obtained are as shown in Table 3.

TABLE 3______________________________________(Cucumber powdery mildew) Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 50 100 0 12.5 100 02 50 100 0 12.5 83 03 50 100 0 12.5 97 04 50 100 0 12.5 100 05 50 100 0 12.5 81 06 50 100 0 12.5 92 07 50 100 0 12.5 79 08 50 100 0 12.5 100 09 50 100 0 12.5 58 010 50 100 0 12.5 70 011 50 95 0 12.5 64 012 50 86 0 12.5 62 013 50 100 0 12.5 80 014 50 100 0 12.5 100 015 50 100 0 12.5 50 016 50 100 0 12.5 100 017 50 100 0 12.5 100 018 50 100 0 12.5 84 019 50 100 0 12.5 98 020 50 100 0 12.5 54 021 50 100 0 12.5 92 022 50 80 0 12.5 34 023 50 100 0 12.5 52 024 50 100 0 12.5 100 025 50 100 0 12.5 73 026 50 85 0 12.5 62 027 50 65 0 12.5 43 028 50 100 0 12.5 100 029 50 100 0 12.5 68 030 50 100 0 12.5 100 031 50 100 0 12.5 98 032 50 100 0 12.5 100 033 50 100 0 12.5 100 034 50 100 0 12.5 100 035 50 100 0 12.5 90 036 50 100 0 12.5 90 037 50 100 0 12.5 100 038 50 100 0 12.5 82 039 50 100 0 12.5 100 040 50 100 0 12.5 100 041 50 100 042 50 100 043 50 90 044 50 100 0 12.5 91 045 50 100 046 50 100 0 12.5 90 047 50 100 0 12.5 100 048 50 100 0 12.5 100 049 50 100 0 12.5 100 050 50 100 051 50 100 0 12.5 100 052 50 82 053 50 100 0 12.5 100 054 50 86 055 50 100 056 50 100 057 50 74 058 50 100 0 12.5 100 059 50 100 0 12.5 100 060 50 100 0 12.5 80 061 50 100 062 50 100 0 12.5 100 063 50 100 0 12.5 100 064 50 100 0 12.5 100 065 50 100 0 12.5 100 066 50 100 0 12.5 80 067 50 100 0 12.5 85 068 50 100 0 25 100 069 50 100 0 12.5 100 070 50 100 0 12.5 100 071 50 100 0 12.5 100 072 50 100 0 25 100 073 50 100 0 25 93 074 50 100 075 50 100 0 25 83 076 50 100 0 25 87 077 100 100 0 50 75 078 100 95 0 50 75 079 50 100 0 25 100 080 50 100 0 12.5 100 081 50 100 0 12.5 100 082 50 100 0 12.5 100 083 50 100 0 25 100 084 50 100 0 12.5 100 085 50 100 0 12.5 100 086 50 100 0 12.5 100 087 100 90 0 50 75 088 50 100 0 12.5 100 089 50 100 090 50 100 0 25 100 091 50 100 0 25 100 092 50 100 0 12.5 100 093 50 100 0 25 100 094 50 100 0 25 100 095 50 100 0 12.5 100 096 50 79 097 50 100 0 25 72 098 200 96 099 100 100 0 50 86 0100 200 97 0101 200 94 0102 50 100 0 25 93 0103 50 100 0 25 86 0104 100 100 0 50 94 0105 50 100 0 12.5 100 0106 50 100 0 25 100 0107 100 100 0 50 80 0108 200 100 0109 50 100 0 12.5 90 0110 50 100 0 25 100 0111 50 100 0 25 100 0 12.5 82 0112 50 100 0 12.5 100 0113 50 100 0 25 100 0 12.5 86 0114 50 100 0 25 100 0115 200 100 0 100 95 0116 200 96 0117 100 100 0118 100 100 0 50 95 0 12.5 97 0119 100 100 0120 100 95 0121 100 100 0 50 100 0122 200 93 0123 100 100 0 50 100 0 12.5 100 0124 50 100 0 12.5 100 0125 50 100 0 12.5 100 0126 50 100 0 12.5 100 0127 100 100 0 50 100 0 25 90 0128 50 100 0 12.5 100 0129 100 100 0130 50 100 0 12.5 100 0131 50 100 0 12.5 100 0132 50 100 0 12.5 100 0133 50 100 0 12.5 100 0134 100 100 0 50 96 0135 50 100 0 12.5 100 0136 50 100 0 12.5 100 0137 50 100 25 90138 50 100 0 25 100 0 12.5 93 0139 50 100 0 12.5 86 0140 100 100 0 50 90 0141 200 96 0142 200 100 0143 100 100 0 50 100 0144 100 100 0 50 100 0145 100 100 0 50 100 0146 50 100 0 12.5 100 0147 100 100 0 50 100 0148 100 100 0 50 100 0 25 94 0149 50 100 0 25 100 0150 200 100 0 100 100 0 50 94 0151 200 100 0 100 100 0 50 95 0152 200 96 0153 200 100 0154 200 95 0155 50 100 0 12.5 100 0156 50 100 0 12.5 100 0157 50 100 0 12.5 100 0158 50 100 0 12.5 100 0159 50 100 0 12.5 100 0160 200 100 0 100 95 0161 100 100 0 50 100 0162 200 94 0163 100 100 0 50 92 0164 200 100 0 100 100 0165 100 100 0166 200 97 0167 50 100 0 12.5 100 0168 50 100 0 25 95 0169 50 100 0 12.5 82 0170 200 97 0171 50 100 0 12.5 100 0172 100 100 0 50 100 0173 100 100 0 50 100 0174 100 100 0 50 100 0175 100 100 0176 200 100 0 100 100 0177 200 100 0178 200 100 0 100 100 0179 200 100 0180 100 100 0 50 100 0181 50 100 0 25 90 0 12.5 82 0182 50 100 0 12.5 94 0183 50 100 0 12.5 100 0184 100 100 0 50 100 0185 50 100 0 25 90 0186 100 100 0 50 100 0 12.5 100 0187 50 100 0 12.5 100 0188 50 100 0 25 91 0189 200 100 0190 200 100 0191 200 100 0192 200 100 0193 100 100 0 50 91 0194 200 100 0195 200 100 0196 100 100 0 50 88 0197 50 100 0 12.5 100 0198 100 100 0 50 73 0199 100 100 0 50 96 0200 200 100 0 100 78 0201 200 100 0 100 83 0202 200 100 0 100 95 0203 100 100 0 50 90 0204 100 100 0 50 93 0205 200 100 0206 200 100 0 100 91 0207 200 100 0208 200 100 0209 200 100 0210 200 100 0 100 90 0211 200 100 0212 100 100 0 50 93 0213 100 100 0 50 82 0 12.5 70 0214 100 100 0 50 90 0215 50 100 0 12.5 84 0216 50 100 0217 100 100 0 50 96 0218 200 100 0219 50 100 0 12.5 100 0220 200 100 0 100 95 0221 50 100 0 12.5 100 0222 100 100 0 50 80 0223 50 100 0 12.5 100 0224 100 100 0 50 83 0225 50 100 0 12.5 90 0226 200 100 0227 200 100 0228 200 100 0229 200 100 0230 200 100 0231 100 100 0 50 93 0 12.5 78 0232 100 100 0 50 87 0233 200 100 0234 100 100 0 50 75 0235 200 100 0 100 91 0236 200 100 0 100 77 0237 50 100 0 12.5 85 0238 100 100 0 50 89 0239 100 100 0 50 84 0240 200 100 0241 200 100 0 100 90 0242 100 100 0 50 96 0243 200 100 0 100 90 0244 100 100 0 50 83 0245 50 100 0246 50 100 0 12.5 100 0247 50 100 0 12.5 97 0248 50 100 0 12.5 70 0249 50 100 0 12.5 88 0250 50 100 0 12.5 80 0251 50 100 0 12.5 100 0252 50 100 0 12.5 70 0253 100 100 0 50 86 0254 50 100 0 12.5 100 0255 50 100 0 12.5 100 0256 50 100 0 12.5 100 0257 100 100 0 50 84 0258 200 100 0259 200 100 0260 100 100 0 50 81 0261 200 100 0262 100 100 0 50 100 0263 50 100 0 12.5 100 0264 200 100 0265 200 100 0 100 100 0266 200 100 0 100 90 0267 200 100 0 100 76 0268 50 100 0 12.5 96 0269 100 100 0 50 96 0270 100 100 0 50 85 0271 50 100 0 12.5 84 0272 100 100 0 50 100 0273 100 100 0 50 100 0274 100 100 0275 200 100 0 100 94 0276 100 100 0 50 82 0277 100 100 0 50 90 0278 100 100 0 50 81 0279 100 100 0 50 80 0280 50 100 0 12.5 100 0281 50 100 0 12.5 100 0282 50 100 0 12.5 100 0283 50 100 0 12.5 100 0284 50 100 0 12.5 100 0285 100 100 0286 50 100 0 12.5 82 0287 50 100 0 12.5 100 0288 50 100 0 12.5 100 0289 50 100 0 12.5 100 0290 50 100 0 12.5 100 0291 50 100 0 12.5 100 0292 50 100 0 12.5 96 0293 50 100 0 12.5 100 0294 50 100 0 12.5 100 0295 50 100 0 12.5 100 0296 50 100 0 12.5 100 0297 50 100 0 12.5 100 0298 100 100 0 50 80 0299 50 100 0 12.5 100 0300 200 100 0 100 91 0301 100 100 0 50 84 0302 50 100 0 12.5 100 0303 50 100 0304 50 100 0305 50 100 0306 50 100 0308 50 100 0 12.5 100 0309 100 100 0310 100 86 0311 100 100 0312 100 80 0313 100 78 0314 50 100 0 25 91 0315 100 100 0 50 70 0316 100 100 0317 50 100 0 25 76 0318 100 100 0319 50 100 0 25 73 0320 50 100 0 12.5 90 0321 100 100 0322 100 100 0323 50 100 0 12.5 82 0324 100 100 0325 100 100 0326 100 100 0327 50 100 0 12.5 100 0328 100 100 0329 100 100 0330 50 100 0 12.5 70 0331 50 100 0 12.5 86 0332 100 100 0 50 94 0 12.5 84 0333 100 100 0334 100 100 0335 100 100 0 50 94 0 25 83 0336 100 100 0 50 91 0 25 76 0337 50 100 0 12.5 91 0338 50 100 0 12.5 76 0339 50 100 0 12.5 81 0340 100 100 0341 50 100 0 12.5 100 0342 50 100 0 12.5 100 0343 50 100 0 12.5 70 0344 50 100 0 12.5 74 0345 100 100 0346 100 100 0347 100 100 0Comparative 50 100 0chemical(Buthiobate) 25 100 0 12.5 95 0Non-treated -- 0 --______________________________________ (Note) Buthiobate ##STR122##

TEST EXAMPLE 3

Test for the control effect on barley powdery mildew

Over the first-leaf stage seedlings of barley (variety: Azuma golden) soil-cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed a solution of a wettable powder diluted to a predetermined concentration at a rate of 10 ml per 2 pots. Next day, the spore of powdery mildew preliminarily outbroken on the leaf of barley was inoculated by scattering over the leaf of barley. Seven days after the inoculation, the number of lesions was investigated and the control value (%) was calculated by the below-defined expression. Phytotoxicity against the barley plant was at the same time investigated by the same fixed numeral scale as used in the Test Example 1. ##EQU3##

The results thus obtained are as shown in Table 4.

TABLE 4______________________________________(Barley powdery mildew) Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 20 100 0 5 100 02 20 100 0 5 91 03 20 100 0 5 100 04 20 100 0 5 100 05 20 100 0 5 90 06 20 100 0 5 100 07 20 100 0 5 82 08 20 100 0 5 100 09 20 100 0 5 75 010 20 100 0 5 93 011 20 100 0 5 70 012 20 98 0 5 69 013 20 100 0 5 98 014 20 100 0 5 100 015 20 100 0 5 70 016 20 100 0 5 100 017 20 100 0 5 100 018 20 100 0 5 95 019 20 100 0 5 100 020 20 100 0 5 65 021 20 100 0 5 100 022 20 90 0 5 72 023 20 100 0 5 65 024 20 100 0 5 100 025 20 100 0 5 82 026 20 90 0 5 75 027 20 80 0 5 51 028 20 100 0 5 90 029 20 100 0 5 82 030 20 100 0 5 100 031 20 100 0 5 95 032 20 100 0 5 100 033 20 100 0 5 100 034 20 100 0 5 100 035 20 100 0 5 90 036 20 100 0 5 100 037 20 100 0 5 100 038 20 100 0 5 98 039 20 100 0 5 100 040 20 100 0 5 100 041 20 90 0 5 71 042 20 100 0 5 98 043 20 90 0 5 78 044 20 100 0 5 95 045 20 100 0 5 75 046 20 100 0 5 90 047 20 100 0 5 100 048 20 100 0 5 100 049 20 100 0 5 100 050 20 100 0 5 75 051 20 90 052 20 95 0 5 80 053 20 100 0 5 98 054 20 90 055 20 100 056 20 100 0 5 80 057 20 80 058 20 100 0 5 100 059 20 100 0 5 100 060 20 100 0 5 91 061 20 100 0 5 70 062 20 100 0 5 100 063 20 100 064 20 90 065 20 100 0 5 100 066 20 80 067 20 100 0 5 82 0280 20 100 0 5 100 0281 20 100 0 5 100 0282 20 100 0 5 100 0283 20 100 0 5 100 0284 20 100 0 5 93 0285 20 85 0286 20 100 0 5 85 0287 20 100 0 5 100 0288 20 100 0 5 100 0289 20 100 0 5 99 0290 20 100 0 5 100 0291 20 100 0 5 100 0292 20 100 0 5 98 0Comparative 20 100 0chemical 5 100 0(Buthiobate)Non-treated -- 0 --______________________________________

TEST EXAMPLE 4

Test for the control effect on apple powdery mildew

Over the third-leaf stage of seedlings from seed of apple (variety: Kogyoku) soil-cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed a test solution of the emulsion, which was prepared according the procedure of Example 5, by diluting to a predetermined concentration, at a rate of 30 ml per 4 pots. Next day, the seedlings were inoculated by atomizing with a spore suspension of apple powdery mildew fungus. Ten days after the inoculation, percent lesion area was investigated and the control value (%) was calculated according to the following expression. ##EQU4##

The results obtained are as shown in Table 5.

TABLE 5______________________________________(Apple powdery mildew) Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 50 100 0 12.5 100 02 50 100 0 12.5 95 03 50 100 0 12.5 100 04 50 100 0 12.5 100 05 50 100 0 12.5 100 06 50 100 0 12.5 100 07 50 100 0 12.5 92 08 50 100 0 12.5 100 09 50 100 0 12.5 85 010 50 100 0 12.5 93 011 50 100 0 12.5 73 012 50 98 0 12.5 79 013 50 100 0 12.5 100 014 50 100 0 12.5 100 015 50 100 0 12.5 92 016 50 100 0 12.5 100 017 50 100 0 12.5 100 018 50 100 0 12.5 98 019 50 100 0 12.5 100 020 50 100 0 12.5 78 021 50 100 0 12.5 100 022 50 97 0 12.5 70 023 50 100 0 12.5 80 024 50 100 0 12.5 100 025 50 100 0 12.5 95 026 50 97 0 12.5 75 027 50 81 0 12.5 65 028 50 100 0 12.5 98 029 50 100 0 12.5 92 030 50 100 0 12.5 100 031 50 100 0 12.5 98 032 50 100 0 12.5 100 033 50 100 0 12.5 100 034 50 100 0 12.5 100 035 50 100 0 12.5 95 036 50 100 0 12.5 100 037 50 100 0 12.5 100 038 50 100 0 12.5 95 039 50 100 0 12.5 100 040 50 100 0 12.5 98 041 50 93 0 12.5 80 042 50 100 0 12.5 100 043 50 95 0 12.5 80 044 50 100 0 12.5 98 045 50 100 046 50 100 0 12.5 92 047 50 100 0 12.5 100 048 50 100 0 12.5 100 049 50 100 0 12.5 100 050 50 100 0 12.5 81 051 50 93 052 50 98 0 12.5 83 053 50 100 0 12.5 100 054 50 95 055 50 95 056 50 100 0 12.5 85 057 50 87 058 50 100 0 12.5 95 059 50 100 0 12.5 100 060 50 100 0 12.5 88 061 50 100 062 50 100 0 12.5 100 063 50 100 064 50 95 065 50 100 0 12.5 100 066 50 83 067 50 100 0 12.5 91 0280 50 100 0 12.5 95 0281 50 100 0 12.5 97 0282 50 100 0 12.5 100 0283 50 100 0 12.5 89 0284 50 100 0 12.5 96 0285 50 93 0286 50 100 0 12.5 92 0287 50 100 0 12.5 100 0288 50 100 0 12.5 100 0289 50 100 0 12.5 100 0290 50 100 0 12.5 100 0291 50 100 0 12.5 99 0292 50 100 0 12.5 93 0294 50 100 0 12.5 97 0297 50 100 0 12.5 95 0299 50 100 0 12.5 100 0Comparative 50 100 0chemical 12.5 95 0(Buthiobate)Non-treated -- 0 --______________________________________

TEST EXAMPLE 5

Test for the control of Chinese cabbage root knot disease

A porcelain pot of 9 cm in diameter was filled with a soil infected naturally by Chinese cabbage root knot disease. To the soil was inoculated a Chinese cabbage root knot suspension prepared by grinding the refrigerated root knot and diluting same with water, in order to accelerate the outbreak of disease. Then the wettable powder prepared by the procedures of Example 4 was poured as a solution in water to the surface of the soil at the rate of 3 l/m.sup.2. Three hours later, 4 (four) seedlings of Chinese cabbage (variety: Sengoku Hakusai) were transplanted to one pot and then cultivated for 40 days. The degree of infection was investigated according to the below-mentioned standard, and the control value (%) was calculated by the below-defined expression. ##EQU5## Index by degree: 4: Outbreak of root knots was observed in the overall portion of the root and enlargement of the roots was visible

3: Outbreak of root knots was observed in more than 50% of roots 2: Outbreak of root knots was observed in not more than 50% of roots 1: Outbreak of root knots was observed in not more than 10% of roots 0: None ##EQU6##

The phytotoxicity against Chinese cabbage plants also was investigated by the same procedures as in Test Example 1.

The results are as shown in Table 6.

TABLE 6______________________________________(Chinese cabbage root knot disease) Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 1 92 02 1 90 03 1 100 04 1 100 05 1 93 06 1 98 07 1 95 08 1 91 09 1 90 010 1 99 011 1 97 012 1 92 013 1 90 014 1 100 015 1 96 016 1 90 017 1 100 018 1 97 019 1 97 020 1 93 021 1 100 022 1 94 023 1 98 024 1 99 025 1 95 026 1 100 027 1 100 028 1 100 029 1 100 030 1 100 031 1 97 032 1 92 033 1 100 034 1 91 035 1 93 036 1 100 037 1 100 038 1 100 039 1 100 040 1 100 041 1 98 042 1 100 043 1 100 044 1 100 066 1 100 067 1 100 0280 1 100 0281 1 100 0282 1 100 0283 1 100 0284 1 100 0287 1 100 0Comparative 5 88 0chemical 1 5 0(PCNB)Non-treated -- 0 --______________________________________ (Note) PCNB ##STR123##

Claims

1. A thiophene compound of the general formula (I) ##STR124## In the general formula: R is C.sub.1-4 -alkyl; R.sub.1 is ##STR125## wherein R.sub.3 is C.sub.1-4 -alkyl, halogen-substituted C.sub.1-4 -alkyl, C.sub.2-4 -alkenyl, C.sub.3-8 -cycloalkyl, C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, C.sub.1-4 -alkylthio-C.sub.1-4 -alkyl, C.sub.1-4 -alkoxycarbonyl-C.sub.1-4 -alkyl, C.sub.1-10 -alkoxy, C.sub.1-4 -alkynyloxy, styryl, .alpha.-phenoxyethyl, thienyl, furyl, 2,3-dibromopropyloxy,

a group ##STR126## (wherein A and B individually are halogen, C.sub.1-4 -alkyl, methoxy or methylthio, and m and n individually are 0 or 1 with the proviso m+n cannot exceed (2), mono-C.sub.1-4 -alkylamino, di-C.sub.1-4 -alkylamino, mono-C.sub.3-8 -cycloalkylamino, monoaralkylamino, diphenylamino,

a group ##STR127## which may be substituted with one or two C.sub.1-4 -alkyl; a group ##STR128## (wherein C is a halogen atom, D is C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -alkylcarboxy, nitro or cyano, k is 0, 1 or 2 and 1 is 0, 1, 2 or 3);

C.sub.1-4 -alkylthio; C.sub.1-4 -alkenylthio; C.sub.1-4 -alkoxycarbonyl-C.sub.1-4 -alkylthio; aralkylthio or C.sub.1-4 -alkyl-substituted aralkylthio; aralkyl which phenyl portion may be substituted with halogen or C.sub.1-4 -alkoxy;

a group ##STR129## phenoxy-C.sub.1-4 -alkyl which phenyl portion may be substituted with halogen; pyridine-4-yl; or

a group ##STR130## wherein R.sub.4 is C.sub.1-6 -alkyl, di-C.sub.1-4 -alkylamino or a group ##STR131## (in which E is halogen or C.sub.1-4 -alkyl and u is 0 or 1); R.sub.2 is C.sub.1-4 -alkyl or C.sub.2-4 -alkenyl; provided that:

(a) when R.sub.3 is mono-C.sub.3-8 -cycloalkylamino, R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, aralkyl, phenoxy-C.sub.1-4 -alkyl or C.sub.2-4 -alkynyl;

(b) when R.sub.3 is ##STR132## R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl or aralkyl; (c) when R.sub.3 is ##STR133## R.sub.2 represents C.sub.3-8 -cycloalkyl; and (d) when R.sub.3 is C.sub.1-4 -alkylthio, R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, aralkyl or phenoxy-C.sub.1-4 -alkyl.

2. A fungicidal composition which comprises in association with a carrier or diluent a fungicidally active amount of a compound of the general formula (I) ##STR134## In the general formula: R is C.sub.1-4 -alkyl;

R.sub.1 is ##STR135## wherein R.sub.3 is C.sub.1-4 -alkyl, halogen-substituted C.sub.1-4 -alkyl, C.sub.2-4 -alkenyl, C.sub.3-8 -cycloalkyl, C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, C.sub.1-4 -alkylthio-C.sub.1-4 -alkyl, C.sub.1-4 -alkoxycarbonyl-C.sub.1-4 -alkyl, C.sub.1-10 -alkoxy, C.sub.1-4 -alkynyloxy, styryl, .alpha.-phenoxyethyl, thienyl, furyl, 2,3-dibromopropyloxy,

a group ##STR136## (wherein A and B individually are halogen, C.sub.1-4 -alkyl, methoxy or methylthio, and m and n individually are 0 or 1 with the proviso m+n cannot exceed 2), mono-C.sub.1-4 -alkylamino, di-C.sub.1-4 -alkylamino, mono-C.sub.3-8 -cycloalkylamino, monoaralkylamino, diphenylamino,

a group ##STR137## which may be substituted with one or two C.sub.1-4 -alkyl; a group ##STR138## (wherein C is a halogen atom, D is C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -alkylcarboxy, nitro or cyano, k is 0, 1 or 2 and 1 is 0, 1, 2 or 3);

C.sub.1-4 -alkylthio; C.sub.1-4 -alkenylthio; C.sub.1-4 -alkoxycarbonyl-C.sub.1-4 -alkylthio; aralkylthio or C.sub.1-4 -alkyl-substituted aralkylthio; aralkyl which phenyl portion may be substituted with halogen or C.sub.1-4 -alkoxy;

a group ##STR139## phenoxy-C.sub.1-4 -alkyl which phenyl portion may be substituted with halogen; pyridine-4-yl; or

a group ##STR140## wherein R.sub.4 is C.sub.1-6 -alkyl, di-C.sub.1-4 -alkylamino or a group ##STR141##

(in which E is halogen or C.sub.1-4 -alkyl and u is 0 or 1);

R.sub.2 is C.sub.1-4 -alkyl or C.sub.2-4 -alkenyl; provided that:

(a) when R.sub.3 is mono-C.sub.3-8 -cycloalkylamino, R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, aralkyl, phenoxy-C.sub.1-4 -alkyl or C.sub.2-4 -alkynyl;

(b) when R.sub.3 is ##STR142## R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl or aralkyl; (c) when R.sub.3 is ##STR143## R.sub.2 represents C.sub.3-8 -cycloalkyl; and (d) when R.sub.3 is C.sub.1-4 -alkylthio, R.sub.2 represents C.sub.1-4 -alkoxy-C.sub.1-4 -alkyl, aralkyl or phenoxy-C.sub.1-4 -alkyl.