Thiophene derivatives

This invention relates to novel thiophene derivatives and to fungicides for agricultural and horticultural purposes which are characterized by containing as their active ingredients said derivatives. The novel thiophene derivatives prepared according to the present invention are represented by the general formula (I) ##STR2## wherein X represents hydrogen atom, alkali metal, NH.sub.4, COR.sub.1 (in which R.sub.1 represents phenyl, halophenyl, lower alkyl, lower alkenyl, lower alkoxy lower alkyl, lower alkylthio lower alkyl, lower haloalkyl, ##STR3## cycloalkyl or lower alkylthio), --CO-lower alkyl-R.sub.2 (in which R.sub.2 represents lower alkylcarbonyloxy or lower alkoxycarbonyl), ##STR4## (in which n represents an integer of 4 to 6 inclusive), di-lower alkylcarbamoyl, mono-lower alkylcarbamoyl, cycloalkylcarbamoyl, --COOR.sub.3 (in which R.sub.3 represents lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxy lower alkyl, lower alkoxycarbonyl lower alkyl, phenyl, substituted phenyl or benzyl), --SO.sub.2 R.sub.4 (in which R.sub.4 represents lower alkyl, lower alkyl-substituted phenyl or di-lower alkylamino) or ##STR5## (in which R.sub.5 represents lower alkyl); Y represents --COOR.sub.6 (in which R.sub.6 represents alkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl or benzyl), hydrogen atom or ##STR6## (in which p represents hydrogen atom, halogen atom or lower alkyl); and Z represents COOR.sub.6 (in which R.sub.6 is as defined above), cyano or ##STR7## (in which p is as defined above), provided that both Y and Z are not --COOR.sub.6 (in which R.sub.6 represents alkyl, lower alkenyl or lower alkynyl) when X represents hydrogen atom, alkali metal or NH.sub.4.
The term "lower", as used herein in connection with any alkyl, alkenyl or alkynyl portion is to mean that said portion as referred to contains one to four carbon atoms.
A sub-generic group of the particularly useful compounds of the invention can cover the compounds of the general formula (I), wherein X is a group --COR.sub.1 (in which R.sub.1 is lower alkyl, lower alkoxy lower alkyl, lower alkylthio lower alkyl), a group --COOR.sub.3 (in which R.sub.3 is lower alkyl) or mono-lower alkylcarbamoyl; Y is a group --COOR.sub.6 (in which R.sub.6 is lower alkyl, lower alkenyl or lower alkynyl) or a group ##STR8## (in which p is hydrogen or halogen); and Z is a group --COOR.sub.6 as defined above.
The present inventors prepared by synthesis a large number of thiophene derivatives and extensively studied and invenstigated on practical usefulness of these thiophene derivatives as fungicides for agricultural and horticultural purposes. As a result, it has been found that novel compounds represented by the aforesaid general formula (I) are broadly and divergently usable as fungicides for agricultural and horticultural purposes, exhibiting their controlling activity against various plant deseases 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 rot, pear black spot, Japanese apple canker, vegetable soft rot, rice bacterial blight, cucumber bacterial spot, cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, etc.
The compounds of the general formula (I) of the present invention can be prepared according to processes represented by the following reaction formulas, respectively. ##STR9## wherein A is alkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl or benzyl; and Y and Z are individually defined as previously.
The instant reaction can be carried out in an organic solvent such as alcohol, ether, hydrocarbon, DMF (dimethylformamide), etc., in the presence of a deprotonating reagent such as metallic sodium, sodium hydride, butyl lithium, alkali metal alcoholate, etc., at a temperature of 0.degree.-100.degree. C. for 2-24 hours. The reaction mixture can be worked up by pouring it into ice water and then acidifying the resulting mixture with hydrochloric acid, sulfuric acid or the like mineral acid, thereby to have the desired 3,4-dihydroxythiophene derivative separated out. ##STR10## wherein X, Y and Z are individually as defined previously provided that X is not hydrogen, and Hal represents halogen atom.
The above reaction can be carried out in an inert solvent such as dioxane, acetone, benzene, DMF, etc., in the presence of a dehydrohalogenating agent such as triethylamine, pyridine, potassium carbonate, sodium carbonate, etc., at a temperature of 0.degree. to 150.degree. C. for 1-24 hours. After the reaction, the resulting mixture is poured into water and then worked up by filtration, extraction or the like procedures to obtain the intended thiophene derivative.
(2') The compounds of the above formula (I) wherein X is COR.sub.1 (in which R.sub.1 is lower alkyl) can be prepared by the following reaction: ##STR11## The above reaction can be achieved at a temperature of 30.degree. to 140.degree. C. for 2-16 hours, with or without using a solvent, e.g. benzene, acetic acid, chloroform, ether, etc. by removing an acid formed during the reaction.
(2") The compounds of the formula (I) wherein X is mono-lower alkylcarbamoyl can be prepared by the following reaction: ##STR12## The above reaction is carried out in an inert solvent such as dioxane, benzene, DMF, etc., in the presence of a catalytic amount of triethylamine or the like organic base at a temperature of from room temperature to 80.degree. C. for 2-24 hours. The resulting reaction mixture can be worked up in the similar manner as mentioned above.

Illustrative of the synthesis of the compounds of the present invention are mentioned below with reference to examples.
EXAMPLE 1
3,4-Diacethoxy-2,5-di-n-propoxycarbonylthiopene
(Compound No. 3)
A mixture comprising 57.6 g (0.2 mol) of 3,4-dihydroxy-2,5-di-n-propoxycarbonyl-thiophene, 60 ml of acetic anhydride and 1 g of sodium acetate is stirred at about 40.degree. C. to undergo reaction, whereupon the reaction liquid shows pale brown. The reaction is continued at 60.degree.-80.degree. C. for additional 2 hours. Into the reaction liquid having been allowed to cool is poured 500 ml of ice-cooled water, whereby crystals are deposited. The crystal collected by filtration and washed with water are then recrystallized from 60 ml of methanol to give 59 g of the title compound as colorless prisms, m.p. 46.degree.-48.degree. C.
EXAMPLE 2
3,4-Bis(N-methylcarbamoyloxy)-2,5-dicarbethoxy-thiophene
(Compound No. 50)
To a solution of 100 g (0.384 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene in 350 ml of dioxane are added 55 g (0.96 mol) of methyl isocyanate and 10 drops of triethylamine, and the resulting mixture is stirred, whereupon an exothermic reaction occurs and the internal temperature rises to 50.degree.-60.degree. C. The reaction is continued, as it is, for 8 hours (in this case the reaction may be carried out by warming the reaction liquid). After the reaction liquid is allowed to cool, the deposited crystals were collected by filtration and washed with n-hexane, whereupon the title compound is obtained as colorless crystals, m.p. 152.degree.-153.degree. C. The yield 117 g.
EXAMPLE 3
3,4-Dimethoxycarbonyloxy-2,5-dicarbethoxy-thiophene
(Compound No. 22)
To a solution of 7.8 g (0.03 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene in a mixture of 10 g (0.1 mol) of pyridine and 100 ml of benzene is added dropwise while cooling with ice 14.5 g (0.066 mol) of methyl chlorocarbonate in a period of 1.5 hours. The reaction liquid is brought back to room temperature and then stirred for additional 2 hours to terminate the reaction. The reaction liquid is washed with water, dilute solution of sodium hydroxide, dilute hydrochloric acid, and water in that order, dried over sodium sulfate and then concentrated. The concentrate is charged with n-hexane and cooled with ice to deposit crystals. On collecting the deposited crystals by filtration, the title compound is obtained as colorless prisms, m.p. 87.degree.-88.degree. C. The yield 6.5 g.
EXAMPLE 4
3,4-Bis(diethoxythiophophoryloxy)-2,5-dicarbethoxy-thiophene
(Compound No. 108)
In a solution of 2.6 g (0.01 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene in 60 ml of acetone is suspended with stirring 2.8 g (0.02 mol) of sodium carbonate. The suspension was charged with 4.2 g (0.022 mol) of diethyl chlorothiophosphate, and the mixture is heated under reflux for 3 hours. After allowing the reaction liquid to cool, the solvent is distilled off, and the residue is dissolved in benzene. On distilling off the solvent, the title compound is obtained as colorless glass-like flakes, m.p. 105.6.degree. C. The yield 1.7 g.
EXAMPLE 5
3,4-Dihydroxy-2,5-di-2'-ethoxyethoxycarbonylthiophene
(Compound No. 159)
Into a mixture of 150 ml of 2-ethoxyethanol and 100 ml of DMF is added with ice-cooling 18 g (0.45 mol) of NaH (60%) powder, and thereto is then added dropwise at room temperature to 80.degree. C. a mixed liquid of 54 g (0.2 mol) of diethoxyethyl ester of thiodiglycolic acid and 63 g (0.3 mol) of diethoxyethyl ester of oxalic acid, followed by stirring at 60.degree.-80.degree. C. for additional 1 hour. The reaction liquid is poured into 50 ml (0.5 mol) of concentrated hydrochloric acid and 500 ml of water, and the deposited crystals are separated by filtration. Recrystallization from aqueous methanol to give 33.2 g (48% yield) as yellow powder, m.p. 79.degree.-80.degree. C.
Elemental analysis (for C.sub.14 H.sub.20 O.sub.8 S): Calculated (%): C 48.27; H 5.79. Found (%): C 50.00; H 5.90.
EXAMPLE 6
3,4-Di-methylcarbamoyloxy-2,5-di-2'-ethoxyethoxycarbonylthiophene
(Compound No. 161)
To a solution of 3.5 g (0.01 mol) of 3,4-dihydroxy-2,5-di-2'-ethoxyethoxycarbonylthiophene and 1.2 g (0.02 mol) of methyl isocyanate is added 0.1 ml of triethylamine, and the mixture is stirred at room temperature for 7 hours. The reaction liquid is then poured into 100 ml of water, and the deposited crystals were separated by filtration. Recrystallization from a mixed solvent of n-hexane and benzene gives 2.1 g (46% yield) of the title compound as white needles, m.p. 87.5.degree. C.
Elemental analysis (for C.sub.18 H.sub.26 N.sub.2 O.sub.10 S): Calculated (%): C 46.75; H 5.63; N 6.06. Found (%): C 46.90; H, 5.65; N 5.70.
EXAMPLE 7
3,4-Di-methoxymethylcarbonyloxy-2,5-di-2'-methoxyethoxycarbonylthiophene
(Compound No. 170)
To a solution of 3.2 g (0.01 mol) of 3,4-dihydroxy-2,5-di-2'-methoxyethoxycarbonylthiophene and 3.0 g (0.028 mol) of methoxyacetyl chloride in 50 ml of dioxane is added dropwisw with ice-cooling 10 ml of triethylamine, and the mixture, after being stirred for 30 minutes, is allowed to undergo reaction at room temperature for additional 1 hour. The reaction liquid is poured into 200 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol to give 1.6 g (35% yield) of the title compound as white needles, m.p. 81.2.degree. C.
Elemental analysis (for C.sub.18 H.sub.24 O.sub.12 S): Calculated (%): C 46.55; H 5.17. Found (%): C 46.55; H 5.10.
EXAMPLE 8
3,4-Di-methoxycarbonyloxy-2,5-dibenzyloxycarbonylthiophene
(Compound No. 179)
To a solution of 3.8 g (0.01 mol) of 3,4-dihydroxy-2,5-di-benzyloxycarbonylthiophene and 2.2 g (0.023 mol) of methyl chloroformate in 20 ml of dioxane is added 5 ml of pyridine, and the mixture is heated with stirring at 60.degree. C. for 2 hours. After completion of the reaction, the reaction liquid is poured into 150 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol gives 3.2 g (64% yield) of the title compound as white plate-like flakes, m.p. 103.4.degree. C.
Elemental analysis (for C.sub.24 H.sub.20 O.sub.10 S): Calculated (%): C 57.60; H 4.00. Found (%): C 57.60; H 4.00.
EXAMPLE 9
3,4-Dihydroxy-2-cyano-5-carbethoxythiophene
(Compound No. 210)
A solution of 18.5 g (0.126 mol) of ethyl ester of oxalic acid and 20 g (0.126 mol) of ethyl ester of cyanomethylthioglycolic acid in 50 ml of ethanol is maintained on an ice bath at 2.degree. C. Subsequently, to the solution is gradually added dropwise a sodium ethylate solution prepared by treating 7.3 g (0.315 mol) of metallic sodium with 120 ml of dry ethanol, and the mixture is allowed to undergo reaction for 30 minutes. During that period of time, the reaction temperature is maintained at 2.degree.-5.degree. C. After completion of the reaction, the reaction liquid is allowed to stand in a refrigerator for 2 days, whereupon Na salt is deposited as crystals. The crystals collected is dissolved in 50 ml of water and acidified with hydrochloric acid. Recrystallization from acetic acid to give 14.0 g of the title compound as colorless crystals, m.p. 177.degree.-180.degree. C. (decomposition).
Elemental analysis (for C.sub.8 H.sub.7 O.sub.4 NS): Calculated (%): C 45.06; H 3.31; N 6.57. Found (%): C 44.80; H 3.26; N 6.51.
______________________________________H.sup.1 --NMR: .delta. (ppm) 1.4 (C--CH.sub.3) 3H .delta. (ppm) 4.4 (O--CH.sub.2 --) 2H .delta. (ppm) 11.1 (--OH) 2H______________________________________
EXAMPLE 10
3,4-Di(N-ethylcarbamoxyloxy)-2-cyano-5-methoxycarbonylthiophene
(Compound No. 208)
One (1) drop of triethylamine is added to a solution in 20 ml of DMF of 1 g (0.005 mol) of 3,4-dihydroxy-2-cyano-5-methoxycarbonylthiophene which has been synthesized in the same manner as in Example 1, and thereot is added dropwise at room temperature 1.5 g of (0.02 mol) of ethyl isocyanate and thereby to effect reaction. The reaction system is warmed for 20 minutes to terminate the reaction, and the reaction liquid is poured into water, whereupon crystals are deposited. Recrystallization from ethanol give 0.4 g of the title compound as colorless crystals, m.p. 118.degree.-121.degree. C.
______________________________________H'NMR: .delta. (ppm) 1.2 (CCH.sub.3) 6H .delta. (ppm) 3.3 (NCH.sub.2) 4H .delta. (ppm) 3.9 (OCH.sub.3) 3H .delta. (ppm) 5.5 ##STR13## 2H______________________________________
EXAMPLE 11
3,4-Di-acethoxy-2-cyano-5-carbethoxythiophene
(Compound No. 212)
In 10 ml of acetic anhydride, 1.5 g (0.007 mol) of 3,4-dihydroxy-2-cyano-5-carbethoxythiophene is refluxed for 2 hours. After allowing to cool, the reaction liquid is poured into water, whereupon crystals are deposited which are then separated by filtration. Recrystallization from ethanol-water to give 1.4 g of the title compound as colorless crystals, m.p. 92.degree.-94.degree. C.
______________________________________H'NMR: .delta. (ppm) 1.3 (CCH.sub.3) 3H .delta. (ppm) 2.4 ##STR14## 6H .delta. (ppm) 4.4 (OCH.sub.2) 2H______________________________________
EXAMPLE 12
3,4-Di-(ethylcarbonyldioxy)-2-cyano-5-carbethoxythiophene
(Compound No. 216)
To a solution in 30 ml of dioxane of 2 g (0.0094 mol) of 3,4-dihydroxy-2-cyano-5-carbethoxythiophene is added 10 ml of pyridine, and thereto is added dropwise with cooling 3.1 g (0.028 mol) of ethyl chloroformate, whereupon pyridine hydrochloride is immediately deposited. The reaction liquid is stirred, as it is, for 2 hours and then allowed to stand overnight.
The reaction liquid is poured into 200 ml of cold water and then acidified with hydrochloric acid, whereupon crystals are desposited which are then separated by filtration. Recrystallization from ethanol-water to give 2.3 of the title compound as colorless needles, m.p. 53.degree.-54.degree. C.
______________________________________H'--NMR: .delta. (ppm) 1.3-1.5 (C--CH.sub.3) 9H .delta. (ppm) 4.3-4.6 (O--CH.sub.2 --) 6H______________________________________
EXAMPLE 13
3,4-Dihydroxy-2-carbomethoxy-5-benzoylthiophene
(Compound No. 246)
To an ice-cold solution of 130 g (0.30 mol) of normal butyl lithium (a 15% n-hexane solution) in 400 ml of dry ether is added dropwise with stirring a mixed solution of 27 g (0.12 mol) of methyl ester of phenacylthioglycolic acid and 28 g (0.24 mol) of dimethyl oxalate in 50 ml of dry dioxane and 100 ml of dry ether in a period of about 1 hour. After completion of the addition, the reaction liquid is stirred with ice-cooling for additional 1 hour and then brought back to room temperature, followed by standing for one day. The precipitate thus formed is separated by filtration, washed with a small amount of ether and then dissolved in a possible small amount of acetone. The solution is diluted with water to 5 to 6 times, acidified with dilute hydrochloric acid, salted out with sodium chloride and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer formed is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is crystallized from a mixed solvent of benzene and n-hexane to obtain 6.2 g (26% yield) of the title compound as yellow fine powder, m.p. 136.degree.-138.degree. C.
______________________________________NMR: .delta. (ppm) 8.2-8.4 Aromatic 2H .delta. (ppm) 7.7-8.0 Aromatic 3H .delta. (ppm) 4.1 O--CH.sub.3 .delta. (ppm) 9.6 OH .delta. (ppm) 12.3 OH______________________________________
EXAMPLE 14
3,4-Dihydroxy-2-carbethoxy-5-benzoylthiophene
(Compound No. 247)
To an ice-cold solution of 53 g (0.13 mol) of normal butyl lithium (a 15% n-hexane solution) in 200 ml of dry ether is gradually added dropwise with stirring a mixed solution of 12 g (0.05 mol) of ethyl ester of phenacylthioglycolic acid and 15 g (0.10 mol) of diethyl oxalate in 50 ml of dry ether in a period of about 1 hour. After completion of the addition, the reaction liquid is stirred with ice-cooling for additional 30 minutes and then brough back to room temperature, followed by standing for one day. The deposited precipitate is separated by filtration, washed with a small amount of ether and then dissolved in a possible small amount of acetone. The solution is diluted with water to 5 to 6 times, acidified with dilute hydrochloric acid, salted out with sodium chloride and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer formed is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is crystallized from a mixed solvent of benzene and n-hexane to obtain 3.2 g (23% yield) of the title compound as yellow microcrystals, m.p. 147.degree.-148.degree. C.
______________________________________IR (cm.sup.-1) .degree.3300 cm.sup.-1 Enolic OH .degree.1680 cm.sup.-1 COOEt .degree.1600 cm.sup.-1 ##STR15##______________________________________
______________________________________NMR: .delta. (ppm) 8.0-8.2 Aromatic 2H .delta. (ppm) 7.5-7.9 Aromatic 3H .delta. (ppm) 4.4-4.6 O--CH.sub.2 -- .delta. (ppm) 1.3-1.6 C--CH.sub.3 .delta. (ppm) 9.45 OH .delta. (ppm) 11.8 OH______________________________________
EXAMPLE 15
3,4-Dihydroxy-2-benzoylthiophene
(Compound No. 250)
To an ice-cold sodium ethoxide solution prepared from 3.8 g (0.17 mol) of metallic sodium and 200 ml of ethanol is added dropwise with stirring in a period of about 1 hour a mixed solution of 13 g (0.055 mol) of ethyl ester of phenacylthioglycolic acid and 16 g (0.11 mol) of diethyl oxalate in 50 ml of ethanol. After completion of the addition, the ice bath is withdrawn and the reaction liquid is stirred at room temperature for 2 hours. Thereafter, the reaction liquid is poured into saline water, acidified with dilute hydrochloric acid and then extracted with a mixed solvent of benzene and ethyl acetate. The organic layer separated is extracted twice with a dilute aqueous sodium hydroxide solution. The alkaline layer thus formed is acidified with dilute hydrochloric acid and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer obtained is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom, and the residue obtained is crystallized from a small amount of a mixed solvent of benzene and n-hexane to obtain 1.0 g (9% yield) of the title compound as brown powder, m.p. 152.degree.-154.degree. C. (decomp.).
______________________________________NMR: .delta. (ppm) 8.2-8.3 Aromatic 2H .delta. (ppm) 7.5-8.0 Aromatic 3H .delta. (ppm) 7.4 H .delta. (ppm) 9.5-11.4 2OH______________________________________
EXAMPLE 16
3,4-Dihydroxy-2,5-dibenzoylthiophene
(Compound No. 265)
To an ice-cold solution of 55 g (0.13 mol) of normal butyl lithium (a 15% n-hexane solution) in 200 ml of dry ether is gradually added dropwise with stirring in a period of about 1 hour a mixed solution of 13.5 g (0.05 mol) of diphenacyl sulfide and 15 g (0.12 mol) of diethyl oxalate in 50 ml of dry ether. After completion of the addition, the reaction liquid is stirred for 30 minutes, brought back to room temperature and allowed to stand overnight. The reaction liquid is charged with 200 ml of n-hexane and thoroughly stirred, and the precipitate deposited is separated by filtration, washed with a small amount of ether and dissolved in a possible small amount of acetone. The solution is diluted to 5 to 6 times with water, acidified with dilute hydrochloric acid, salted out with sodium chloride and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer obtained is then extracted with a dilute aqueous sodium hydroxide solution. The alkaline layer thus obtained is acidified with dilute hydrochloric acid and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer obtained is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is crystallized with a small amount of a mixed solvent of benzene and n-hexane to obtain 1.6 g (10% yield) of the title compound as yellow microgranules, m.p. 179.degree.-181.degree. C.
______________________________________NMR: .delta. (ppm) 8.2-8.4 Aromatic 4H .delta. (ppm) 7.6-8.1 Aromatic 6H .delta. (ppm) 12.15 2OH______________________________________
EXAMPLE 17
3,4-Diacetoxy-2-carbethoxy-5-benzoylthiophene
(Compound No. 249)
To an ice-cold solution of 1.3 g (0.0045 mol) of 3,4-dihydroxy-2-carbethoxy-5-benzoylthiophene in a mixture of 10 ml of pyridine and 20 ml of dioxane is added dropwise with stirring 1.8 g (0.023 mol) of acetyl chloride. The mixture is stirred, as it is, for 30 minutes and thereafter at room temperature for 1 hour. The reaction liquid is poured into ice-cold water and extracted with benzene. The extract is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel column chromatography with a mixed solvent of benzene and ethyl acetate to give 0.6 g (36% yield) of the title compound as a viscous reddish brown liquid, n.sub.d.sup.22 1.5710.
______________________________________NMR: .delta. (ppm) 7.8-7.9 Aromatic 2H .delta. (ppm) 7.4-7.7 Aromatic 3H .delta. (ppm) 4.3-4.5 OCH.sub.2 .delta. (ppm) 1.2-1.5 CHCH.sub.3 .delta. (ppm) 2.0 ##STR16## .delta. (ppm) 2.3 ##STR17##______________________________________
EXAMPLE 18
3,4-Di(methylcarbonyldioxy)-2-carbethoxy-5-benzoylthiophene
(Compound No. 252)
To a solution of 0.5 g (0.0017 mol) of 3,4-dihydroxy-2-carbethoxy-5-benzoylthiophene in 20 ml of dioxane is added 0.6 g (0.006 mol) of triethylamine, and the mixture is ice-cooled. To the ice-cooled mixture is added with stirring 0.6 g (0.0063 mol) of methyl chloroformate, and the mixture is stirred, as it is, for 10 minutes and thereafter at room temperature for additional 1 hour. The reaction liquid is then poured into ice-cold water and extracted with chloroform, and the extract is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel column chromatography with a mixed solvent of benzene and ethyl acetate to give 0.6 g (90% yield) of the title compound as a pale brown viscous liquid n.sub.D.sup.21 1.5510.
______________________________________NMR: .delta. (ppm) 8.0-8.2 Aromatic 2H .delta. (ppm) 7.6-7.9 Aromatic 3H .delta. (ppm) 4.4-4.7 COOCH.sub.2 .delta. (ppm) 1.3-1.5 COOCH.sub.2CH.sub.3 .delta. (ppm) 3.9 ##STR18## .delta. (ppm) 4.1 ##STR19##______________________________________
EXAMPLE 19
3,4-Di(N,N-dimethylcarbamoyloxy)-2-carbethoxy-5-(p-methylbenzoyl)-thiophene
(Compound No. 287)
To a solution of 1 g (0.0033 mol) of 3,4-dihydroxy-2-carbethoxy-5-(p-methylbenzoyl)thiophene in 30 ml of benzene are added 1 g (0.01 mol) of triethylamine and 0.9 g (0.008 mol) of N,N-dimethylcarbamoyl chloride, and the mixture is heated with stirring at 50.degree.-70.degree. C. for 3 hours. The reaction liquid is then washed with water, dried over anhydrous sodium sulfate, and distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel chromatography with a mixed solvent of benzene and ethyl acetate to give 1.2 g (82% yield) of the title compound as a reddish brown liquid, n.sub.D.sup.25 1.5382.
______________________________________NMR: .delta. (ppm) 2.45 ##STR20## .delta. (ppm) 7.8-7.9 Aromatic 2H .delta. (ppm) 7.3-7.4 Aromatic 2H .delta. (ppm) 4.3-4.5 COOCH.sub.2 .delta. (ppm) 1.3-1.4 COOCH.sub.2CH.sub.3 .delta. (ppm) 2.8 ##STR21## .delta. (ppm) 3.1-3.2______________________________________
EXAMPLE 20
3,4-Di(methanesulfonyloxy)-2-carbethoxy-5-benzoylthiophene
(Compound No. 290)
To a solution of 0.6 g (0.0020 mol) of 3,4-dihydroxy-2-carbethoxy-5-benzoylthiophene in 50 ml of benzene are added 0.8 g of triethylamine and 0.8 g (0.007 mol) of methanesulfonyl chloride, and the mixture is stirred for 2 hours while warming at 50.degree.-70.degree. C. to undergo reaction. The reaction liquid is then washed successively with a dilute aqueous sodium hydroxide solution and then with water. The benzene layer separated is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel chromatography with a mixed solvent of benzene and ethyl acetate to give 0.4 g (45% yield) of the title compound as a brown liquid, n.sub.D.sup.25 1.5439.
______________________________________Mass spectrum (m/e) 448 Parent peak (P) 369 P-79 (CH.sub.3 SO.sub.2) 323 P-125 (CH.sub.3 SO.sub.2 + C.sub.2 H.sub.5 OH) 105 ##STR22## 77 ##STR23##______________________________________
EXAMPLE 21
3,4-Di(2'-ethoxyethylcarbonyloxy)-2,5-dicarbethoxy-thiophene
(Compound No. 295)
To an ice-cold solution of 3.9 g (0.015 mol) of 3,4-dihydroxy-2,5-dicarbethoxythiophene and 5.0 g (0.037 mol) of 2-ethoxy-propionyl chloride in 50 ml of dioxane is added dropwise with stirring 15 ml of triethylamine. After completion of the addition, the mixture is heated at 60.degree. C. for 1 hour. The reaction liquid is then poured into 150 ml of water and extracted with 200 ml of benzene. The extract is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom, whereby 4.9 g of the title compound is obtained as a yellowish brown viscous liquid, n.sub.D.sup.25.5 1.4929.
Elemental analysis (for C.sub.18 H.sub.28 O.sub.8 S): Calculated (%): C 46.96; H 6.09. Found (%): C 46.91; H 6.07.
EXAMPLE 22
3,4-Di-(2'-furoyloxy)-2,5-dicarbethoxythiophene
(Compound No. 296)
To an ice-cold solution of 2.6 g (0.01 mol) of 3,4-dihydroxy-2,5-dicarbethoxythiophene and 3.1 g (0.024 mol) of furoyl chloride in 50 ml of dioxane is added dropwise with stirring 10 ml of triethylamine. After completion of the addition, the mixture is heated at 60.degree. C. for 1 hour. The reaction liquid is then poured into 200 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol gives 3.8 g (85% yield) of the title compound as white needles, m.p. 137.1.degree. C.
Elemental analysis (for C.sub.22 H.sub.18 O.sub.10 S): Calculated (%): C 58.93; H 4.02. Found (%): C 58.85; H 4.05.
EXAMPLE 23
3,4-Di-(2'-thenoyloxy)-2,5-dicarbethoxythiophene
(Compound No. 299)
To an ice-cold solution of 3.9 g (0.015 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene and 5.3 g (0.036 mol) of thenoyl chloride in 50 ml of dioxane is added dropwise with stirring 15 ml of triethylamine. After completion of the addition, the mixture is stirred at 60.degree. C. for 1 hour. The reaction liquid is then poured into 200 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol gives 5.3 g (74% yield) of the title compound as white columns, m.p. 132.8.degree. C.
Elemental analysis (for C.sub.22 H.sub.18 O.sub.8 S.sub.3): Calculated (%): C 55.23; H 3.77. Found (%): C 55.18; H 3.81.
Exemplified below in Tables 1a through 1e are the compounds of the present invention as prepared according to the procedures described in the foregoing examples. The compound number assigned to each compound in the tables will be referred to in examples and test examples that follow.
TABLE 1a__________________________________________________________________________ ##STR24## Physicochemical data [m.p. (.degree.C.) orCompound refractiveNo. OX COOR.sub.6 index n.sub.D ]__________________________________________________________________________1 OCOCH.sub.3 COOCH.sub.3 m.p. 106.82 " COOC.sub.2 H.sub.5 m.p. 82-833 " COOC.sub.3 H.sub.7n m.p. 46-484 " COOC.sub.3 H.sub.7i m.p. 87.15 " COOC.sub.4 H.sub.9n n.sub.D.sup.23 1.49916 " COOC.sub.4 H.sub.9i n.sub.D.sup.28 1.49457 " COOCH.sub.2 CHCH.sub.2 m.p. 67-688 OCOOCH.sub.3 COOCH.sub.2 CCH n.sub.D.sup.21 1.51919 OCOCH.sub.3 COOC.sub.6 H.sub.13n n.sub.D.sup.21 1.465810 OCOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 n.sub. D.sup.30 1.498511 OCOC.sub.3 H.sub.7i " n.sub.D.sup.29 1.493512 OCOC.sub.4 H.sub.9n COOC.sub.2 H.sub.5 n.sub.D.sup.26.5 1.494313 " COOC.sub.3 H.sub.7n n.sub.D.sup.27 1.488414 " COOC.sub.4 H.sub.9i n.sub.D.sup.27 1.474015 OCOCHCHCH.sub.3 COOC.sub.2 H.sub.5 n.sub.D.sup.29 1.523216 ##STR25## COOC.sub.2 H.sub.5 m.p. 74.017 OCOCH.sub.2 Cl " n.sub.D.sup.30 1.517418 OCOCH.sub.2 OCH.sub.3 " n.sub.D.sup.30 1.500419 OCOCH.sub.3 OC.sub.2 H.sub.5 " n.sub.D.sup.29 1.496020 OCOCH.sub.2 SCH.sub.3 " n.sub.D.sup.30 1.537021 OCOOCH.sub.3 COOCH.sub.3 m.p. 118.022 " COOC.sub.2 H.sub.5 m.p. 87-8823 " COOC.sub.3 H.sub.7n n.sub.D.sup.29 1.495024 " COOC.sub.3 H.sub.7i n.sub.D.sup.26 1.489225 " COOC.sub.4 H.sub.9n n.sub.D.sup.27.5 1.496326 " COOC.sub.4 H.sub.9i n.sub.D.sup.27 1.491127 " COOCH.sub.2 CHCH.sub.2 n.sub.D.sup.21 1.515828 " COOC.sub.6 H.sub.13n n.sub.D.sup.21 1.475029 OCOOC.sub.2 H.sub.5 COOCH.sub.3 m.p. 53.230 " COOC.sub.2 H.sub.5 m.p. 54.231 " COOC.sub.3 H.sub.7n n.sub.D.sup.28 1.488532 " COOC.sub.3 H.sub.7i n.sub.D.sup.26 1.482033 " COOC.sub.4 H.sub.9n n.sub.D.sup.28 1.486034 " COOC.sub.4 H.sub.9i n.sub.D.sup.27 1.475235 " COOCH.sub.2 CHCH.sub.2 n.sub.D.sup.21 1.505236 OCOOC.sub.3 H.sub.7n COOCH.sub.3 n.sub.D.sup.27.5 1.463137 OCOOC.sub.3 H.sub.7i " m.p. 81.838 " COOC.sub.3 H.sub.7i m.p. 59.839 " COOC.sub.4 H.sub.9n m.p. 69.640 OCOOC.sub.4 H.sub.9n COOCH.sub.3 n.sub.D.sup.27.5 1.485341 " COOC.sub.3 H.sub.7i m.p. 59.842 ##STR26## COOCH.sub.3 n.sub.D.sup.27.5 1.555843 " COOC.sub.3 H.sub.7i n.sub.D.sup.28 1.535644 ##STR27## COOCH.sub.3 m.p. 133-13445 OCOSC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 n.sub.D.sup.26.5 1.537046 OCOSC.sub.3 H.sub.7i COOCH.sub.3 m.p. 96-9847 " COOC.sub.2 H.sub.5 m.p. 47-4948 " COOC.sub.4 H.sub.9n n.sub.D.sup.27 1.516049 OCONHCH.sub.3 COOCH.sub.3 m.p. 172.450 " COOC.sub.2 H.sub.5 m.p. 152-15351 " COOC.sub.3 H.sub.7n m.p. 113.252 " COOC.sub.3 H.sub.7i m.p. 146.453 " COOC.sub.4 H.sub.9n m.p. 110.654 " COOC.sub.4 H.sub.9i m.p. 125-12755 " COOCH.sub.2 CHCH.sub.2 m.p. 120-12356 OCONHC.sub.2 H.sub.5 COOCH.sub.3 m.p. 129-13257 " COOC.sub.2 H.sub.5 m.p. 115-11658 " COOC.sub.3 H.sub.7n m.p. 100-10259 " COOC.sub.3 H.sub.7i m.p. 100.760 " COOC.sub.4 H.sub.9n m.p. 108.761 " COOC.sub.4 H.sub.9i m.p. 124-12562 OCONHC.sub.3 H.sub.7n COOCH.sub.3 m.p. 152-15463 " COOC.sub.2 H.sub.5 m.p. 98.464 " COOC.sub.3 H.sub.7n m.p. 115-11665 " COOC.sub.3 H.sub.7i m.p. 122.166 " COOC.sub.4 H.sub.9n m.p. 87.767 " COOC.sub.4 H.sub.9i m.p. 94-9668 OCONHC.sub.3 H.sub.7i COOCH.sub.3 m.p. 149-15169 " COOC.sub.2 H.sub.5 m.p. 125.970 " COOC.sub.3 H.sub.7n m.p. 112-11471 " COOC.sub.3 H.sub.7i m.p. 134.672 " COOC.sub.4 H.sub.9n m.p. 127.573 " COOC.sub.4 H.sub.9i m.p. 127-12974 OCONHC.sub.4 H.sub.9n COOCH.sub.3 m.p. 133-13775 " COOC.sub.2 H.sub.5 m.p. 120-12176 " COOC.sub.3 H.sub.7n m.p. 105-10677 " COOC.sub.3 H.sub.7i m.p. 90.478 " COOC.sub.4 H.sub.9n m.p. 78.779 " COOC.sub.4 H.sub.9i m.p. 89-9080 OCON(CH.sub.3).sub.2 COOC.sub.2 H.sub.5 m.p. 102.681 " COOC.sub.3 H.sub.7n n.sub.D.sup.26 1.515082 " COOC.sub.4 H.sub.9n m.p. 67-6983 ##STR28## COOCH.sub.3 m.p. 168-17184 " COOC.sub.2 H.sub.5 m.p. 169.985 " COOC.sub.3 H.sub.7n m.p. 163-16486 " COOC.sub.3 H.sub.7i m.p. 149.887 " COOC.sub.4 H.sub.9i m.p. 166-16788 OSO.sub.2 CH.sub.3 COOCH.sub.3 m.p. 131-13289 " COOC.sub.2 H.sub.5 n.sub.D.sup.28 1.522890 " COOC.sub.3 H.sub.7n n.sub.D.sup.30 1.513291 " COOC.sub.3 H.sub.7i n.sub.D.sup.27 1.51092 " COOC.sub.4 H.sub.9n n.sub.D.sup.28 1.510093 " COOC.sub.4 H.sub.9i n.sub.D.sup.28 1.508394 OSO.sub.2 C.sub.2 H.sub.5 COOC.sub.2 H.sub.5 n.sub.D.sup.30 1.516395 ##STR29## COOCH.sub.3 m.p. 158-16096 " COOC.sub.2 H.sub.5 m.p. 125-12797 " COOC.sub.3 H.sub.7n m.p. 83-8698 " COOC.sub.3 H.sub.7i m.p. 116-11799 " COOC.sub.4 H.sub.9n n.sub.D.sup.28 1.5435100 " COOC.sub.4 H.sub.9i n.sub.D.sup.26 1.5467101 " COOCH.sub.2CH CH.sub.2 m.p. 65-66102 " COOCH.sub.2 CCH n.sub.D.sup.21 1.5759103 OSO.sub.2 N(CH.sub.3).sub.2 COOC.sub.3 H.sub.7n n.sub.D.sup.30 1.4980104 OSO.sub.2 N(C.sub.2 H.sub.5).sub.2 COOC.sub.2 H.sub.5 n.sub.D.sup.30 1.5080105 ##STR30## " m.p. 96.2106 " COOC.sub.3 H.sub.7n n.sub.D.sup.29 1.5600107 " COOC.sub.4 H.sub.9i n.sub.D.sup.28 1.5500108 OP(S)(OC.sub.2 H.sub.5).sub.2 COOC.sub.2 H.sub.5 m.p. 105.6109 OP(S)(OCH.sub.3).sub.2 COOCH.sub.3 m.p. 89.9110 OCON(CH.sub.3).sub.2 COOC.sub.4 H.sub.9i m.p. 94-95111 OP(S)(OCH.sub.3).sub.2 COOC.sub.2 H.sub.5 m.p. 77.6112 " COOC.sub.3 H.sub.7n m.p. 52.2113 OCOCH.sub.2 Cl " n.sub.D.sup.22 1.5210114 OCOC.sub.2 H.sub.5 " n.sub.D.sup.22 1.4980115 OCOCH.sub.2 OCH.sub.3 " n.sub.D.sup.22 1.5017116 OCOCH.sub.2 SCH.sub.3 " n.sub.D.sup.20 1.5389117 OCOC.sub.3 H.sub.7n " n.sub.D.sup.21 1.4912118 OCOCH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.20 1.4972119 OCONHC.sub.2 H.sub.5 COOCH.sub.2 CHCH.sub.2 m.p. 113-114120 OCONHC.sub.3 H.sub.7n " m.p. 103-104121 OCOC.sub.3 H.sub.7n COOC.sub.4 H.sub.9n n.sub.D.sup.11 1.4887122 OCOC.sub.2 H.sub.5 " n.sub.D.sup.11 1.4991123 OCOCH.sub.2 Cl " n.sub.D.sup.11 1.5168124 OCOCH.sub.2 OCH.sub.3 " n.sub.D.sup.11 1.4992125 OCOCH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.11 1.4921126 OCOCH.sub.2 SCH.sub.3 " n.sub.D.sup.11 1.5340127 OCOC.sub.3 H.sub.7n COOC.sub.2 H.sub.5 n.sub.D.sup.17 1.4974128 OCOCH.sub.2 Cl COOCH.sub.2 CHCH.sub.2 n.sub.D.sup.19 1.5392129 OCOC.sub.2 H.sub.5 " n.sub.D.sup.17 1.5160130 OCOC.sub.3 H.sub.7n " n.sub.D.sup.16 1.5073131 OCOCH.sub.2 OCH.sub.3 " n.sub.D.sup.19 1.5231132 OCOCH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.20 1.5080133 OCOCH.sub.2 SCH.sub.3 " n.sub.D.sup.19 1.5542134 OCOCH.sub.2 OCH.sub.3 COOCH.sub.2 CCH m.p. 86-87135 OCOCH.sub.2 SCH.sub.3 " m.p. 88-89136 OCOCH.sub.2 OC.sub.2 H.sub.5 " m.p. 71-72137 OCOC.sub.2 H.sub.5 COOC.sub.3 H.sub.7i m.p. 62.6138 OCOC.sub.3 H.sub.7n " n.sub.D.sup.10.5 1.4858139 OCOCH.sub.2 OCH.sub.3 " n.sub.D.sup.10 1.500140 OCOCH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.10 1.4945141 OCOCH.sub.2 SCH.sub.3 " n.sub.D.sup.10 1.5378142 OCOCH.sub.2 Cl " n.sub.D.sup.10 1.5177143 OCOCH.sub.2 OC.sub.2 H.sub.5 COOCH.sub.3 m.p. 120.4144 OCOCHCH.sub.2 " n.sub.D.sup.22.5 1.5269145 " COOC.sub.3 H.sub.7n n.sub.D.sup.27 1.5165146 OCOCH.sub.2 Cl COOCH.sub.3 m.p. 95.0147 OCOCH.sub.2 OCH.sub.3 " m.p. 99.6148 OCOCHCH.sub.2 " m.p. 83.0149 OCOC.sub.2 H.sub.5 " m.p. 64.5150 OCOC.sub.4 H.sub.9t " m.p. 127.9151 OCOC.sub.3 H.sub.7n " m.p. 45.1152 OCOCHCHCH.sub.3 " m.p. 131.6153 OCOC.sub.3 H.sub.7i COOCH.sub.3 m.p. 66.7154 OCOCH.sub.3 COOCH.sub.2 CCH m.p. 113.5155 OCOCHCH.sub.2 COOCH.sub.2 CHCH.sub.2 n.sub.D.sup.23 1.5337156 " COOCH.sub.2 CCH m.p. 88.1157 OCOC.sub.2 H.sub.5 " m.p. 106.2158 OCOCH.sub.2 SCH.sub.3 COOCH.sub.3 m.p. 79-80__________________________________________________________________________
TABLE 1b______________________________________ ##STR31## Physicochemical dataCom- [m.p. (.degree.C.) orpound refractiveNo. X CH.sub.2 R index n.sub.D ]______________________________________159 H CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 m.p. 79-80160 COOCH.sub.3 " n.sub.D.sup.19 1.5040161 CONHCH.sub.3 " m.p. 87.5162 COCH.sub.3 " n.sub.D.sup.19 1.5021163 COCH.sub.2 Cl " n.sub.D.sup.27 1.5123164 COCH.sub.2 OCH.sub.3 " n.sub.D.sup.27 1.4902165 COCH.sub.2 SCH.sub.3 " n.sub.D.sup.27 1.5288166 COC.sub.2 H.sub.5 " n.sub.D.sup.27 1.4890167 ##STR32## " n.sub.D.sup.27 1.4976168 H CH.sub.2 CH.sub.2 OCH.sub.3 m.p. 126.5169 COCH.sub.3 " m.p. 67.7170 COCH.sub.2 OCH.sub.3 " m.p. 81.2171 COCH.sub.2 Cl " m.p. 83.8172 COCH.sub.2 SCH.sub.3 " n.sub.D.sup.27 1.5060173 ##STR33## " n.sub.D.sup.27 1.5190174 COCHCH.sub.2 " n.sub.D.sup.27 1.5190175 COC.sub.2 H.sub.5 " n.sub.D.sup.27 1.4897176 COOCH.sub.3 " m.p. 92.1177 H ##STR34## m.p. 153-154178 COCH.sub.3 " m.p. 95.7179 COOCH.sub.3 " m.p. 103.4180 COCH.sub.2 Cl " m.p. 102.9181 ##STR35## " ##STR36##182 ##STR37## " n.sub.D.sup.27 1.5366183 CONHC.sub.2 H.sub.5 " m.p. 158-159184 ##STR38## " m.p. 145-148185 CON(C.sub.2 H.sub.5).sub.2 " n.sub.D.sup.27 1.5145186 ##STR39## CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 n.sub.D.sup.25 1.5781187 ##STR40## " n.sub.D.sup.25 1.5088188 ##STR41## " m.p. 80-81189 ##STR42## " n.sub.D.sup.31 1.5333190 ##STR43## " n.sub.D.sup.30 1.4803191 COSC.sub.3 H.sub.7i " n.sub.D.sup.30 1.5126192 ##STR44## " n.sub.D.sup.25 1.5399193 ##STR45## " m.p. 67-68194 SO.sub.2 CH.sub.3 " n.sub.D.sup.21 1.5159195 SO.sub.2 N(CH.sub.3).sub.2 " n.sub.D.sup.21 1.5012196 ##STR46## " m.p. 129-130197 ##STR47## ##STR48## n.sub.D.sup.24 1.5770198 ##STR49## " n.sub.D.sup.24 1.5843199 SO.sub.2 C.sub.2 H.sub.5 " n.sub.D.sup.24 1.5585200 SO.sub.2 N(CH.sub.3).sub.2 " n.sub.D.sup.22 1.5664201 ##STR50## " n.sub.D.sup.21 1.5954202 COSC.sub.4 H.sub.9n " n.sub.D.sup.24 1.5624203 ##STR51## " n.sub.D.sup.24 1.5811204 ##STR52## " n.sub.D.sup.20 1.5448______________________________________
TABLE 1c______________________________________ ##STR53## Physicochemical data [m.p. (.degree.C.) orCompound refractiveNo. X R.sub.6 index n.sub.D ]______________________________________205 COCH.sub.3 CH.sub.3 m.p. 112-113206 H " m.p. 250207 CONHCH.sub.3 " m.p. 159-160208 CONHC.sub.2 H.sub.5 " m.p. 118-121209 CONHC.sub.4 H.sub.9n " m.p. 116-118210 H C.sub.2 H.sub.5 117-180 (dec.)211 Na " m.p. >280212 COCH.sub.3 " m.p. 92-94213 CONHCH.sub.3 " 144-146 (dec.)214 CONHC.sub.2 H.sub.5 " m.p. 92-94215 CON(CH.sub.3).sub.2 " n.sub.D.sup.27 1.5300216 COOC.sub.2 H.sub.5 " m.p. 53-54217 COOCH.sub.3 " m.p. 70.4218 CONHC.sub.3 H.sub.7n " m.p. 121-122219 CONHC.sub.3 H.sub.7i " m.p. 137-140220 CONHC.sub.4 H.sub.9n " m.p. 106-107221 ##STR54## " m.p. 131-133222 COOCH.sub.3 CH.sub.3 m.p. 78.5223 COOC.sub.2 H.sub.5 " m.p. 64.2224 COOC.sub.3 H.sub.7n " n.sub.D.sup.12.5 1.4981225 COC.sub.2 H.sub.5 C.sub.2 H.sub.5 n.sub.D.sup.10.5 1.5105226 COC.sub.3 H.sub.7n " n.sub.D.sup.10.5 1.5075227 COCH.sub.2 OCH.sub.3 " n.sub.D.sup.10 1.5220228 COCH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.10 1.5119229 COCH.sub.2 SCH.sub.3 " m.p. 70.4230 COCH.sub.2 Cl " n.sub.D.sup.21 1.5453231 COCH.sub.3 C.sub.3 H.sub.7n m.p. 52.8232 COOC.sub.2 H.sub.5 " n.sub.D.sup.21.5 1.4990233 COOC.sub.3 H.sub.7n " n.sub.D.sup.21.5 1.4913234 ##STR55## C.sub.2 H.sub.5 n.sub.D.sup.25 1.5295235 ##STR56## " m.p. 127-128236 ##STR57## " n.sub.D.sup.25 1.5060237 ##STR58## " n.sub.D.sup.27 1.5458238 ##STR59## " m.p. 98-101239 ##STR60## " n.sub.D.sup.27 1.5495240 COSC.sub.3 H.sub.7n " n.sub.D.sup.26 1.5386241 SO.sub.2 C.sub.2 H.sub.5 " m.p. 102-103242 ##STR61## " m.p. 117-120243 SO.sub.2 N(CH.sub.3).sub.2 " m.p. 93-95244 ##STR62## " n.sub.D.sup.25 1.5630245 ##STR63## " m.p. 81.4______________________________________
TABLE 1d__________________________________________________________________________ ##STR64## No.Compound X ##STR65## Z index n.sub.D ]refractive[m.p. (.degree.C.) ordataPhysicochemical__________________________________________________________________________246 H ##STR66## COOCH.sub.3 m.p. 136-138247 " " COOC.sub.2 H.sub.5 m.p. 147-148248 " ##STR67## " m.p. 140-142249 COCH.sub.3 ##STR68## " n.sub.D.sup.22 1.5710250 H " H m.p. 152-154 (dec.)251 OCOCH.sub.3 " " n.sub.D.sup.23 1.5380252 " " COOC.sub.2 H.sub.5 n.sub.D.sup.21 1.5510253 OCOC.sub.2 H.sub.5 " " n.sub.D.sup.20 1.5195254 COCH.sub.2 OCH.sub.3 " " n.sub.D.sup.20 1.5392255 OCOC.sub.2 H.sub.5 " H n.sub.D.sup.18 1.5132256 COCH.sub.3 " COOCH.sub.3 n.sub.D.sup.27 1.5595257 COC.sub.2 H.sub.5 " " n.sub.D.sup.27 1.5430258 OCOCH.sub.3 " " Rf(.phi.H) 0.3259 OCOC.sub.2 H.sub.5 " " n.sub.D.sup.25 1.5483260 COC.sub.2 H.sub.5 " COOC.sub.2 H.sub.5 n.sub.D.sup.26 1.5513261 SCOC.sub.3 H.sub.7n " " n.sub.D.sup.28 1.5694262 COCH.sub.2 OC.sub.2 H.sub.5 " " n.sub.D.sup.28 1.5328263 H " COOC.sub.3 H.sub.7i m.p. 130-132264 OCOCH.sub.3 " " Rf(.phi.) 0.37265 H " CO m.p. 179-181266 OCOC.sub.2 H.sub.5 " " n.sub.D.sup.26 1.5681267 COCH.sub.2 OCH.sub.3 " COOCH.sub.3 n.sub.D.sup.26 1.5670268 COCHCHCH.sub.3 " " n.sub.D.sup.28 1.5930269 ##STR69## " " n.sub.D.sup.27 1.5608270 COCH.sub.2 SCH.sub.3 " " n.sub.D.sup.27 1.6020271 COCH.sub.2 OC.sub.2 H.sub.5 " " n.sub.D.sup.27 1.5533272 COSC.sub.3 H.sub.7n " " n.sub.D.sup.25 1.5772273 ##STR70## " COOC.sub.2 H.sub.5 n.sub.D.sup.25 1.5645274 COCHCH.sub.2 " " n.sub.D.sup.25 1.5905275 COCH.sub.2 SCH.sub.3 " " n.sub.D.sup.27 1.5913276 COCH.sub.3 " COOC.sub.3 H.sub.7i n.sub.D.sup.26 1.5538277 COC.sub.2 H.sub.5 " ##STR71## m.p. 179-180278 OCOCH.sub.3 " " n.sub.D.sup.27 1.5762279 OCOC.sub.2 H.sub.5 ##STR72## COOC.sub.2 H.sub.5 n.sub.D.sup.25 1.4991280 COCH.sub.2 OCH.sub.3 " " n.sub.D.sup.28 1.5508281 COCHCH.sub.2 " " n.sub.D.sup.26 1.5822282 OCOCH.sub.3 " " n.sub.D.sup.29 1.5578283 COCH.sub.3 " " n.sub.D.sup.29 1.5605284 H ##STR73## " m.p. 139-141285 OCOC.sub.2 H.sub.5 " " n.sub.D.sup.26 1.5358286 OCOCH.sub.3 " " n.sub.D.sup.26 1.5470287 CON(CH.sub.3).sub.2 " " n.sub.D.sup.25 1.5382288 COCH.sub.3 " " m.p. 79-81289 COCHCH.sub.2 " " n.sub.D.sup.26 1.5748290 SO.sub.2 CH.sub.3 ##STR74## " n.sub.D.sup.25 1.5439__________________________________________________________________________
TABLE 1e__________________________________________________________________________ ##STR75## Physicochemical data [m.p. (.degree.C.) orCompound refractiveNo. X R.sub.6 index n.sub.D ]__________________________________________________________________________291 ##STR76## C.sub.2 H.sub.5 m.p. 96.4292 ##STR77## CH.sub.3 m.p. 161.2293 ##STR78## " m.p. 191.4294 ##STR79## C.sub.2 H.sub.5 n.sub.D.sup.25.5 1.5150295 COCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.25.5 1.4929296 ##STR80## " m.p. 137.1297 ##STR81## " n.sub.D.sup.25.5 1.5221298 ##STR82## " n.sub.D.sup.25.5 1.4916299 ##STR83## " m.p. 132.8300 COCH.sub.2 OCOCH.sub.3 " n.sub.D.sup.25.5 1.5042301 ##STR84## C.sub.3 H.sub.7n n.sub.D.sup.27 1.5050302 ##STR85## CH.sub.3 n.sub.D.sup.26 1.5204303 ##STR86## " m.p. 91304 COCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 " n.sub.D.sup.27 1.4970305 ##STR87## C.sub.2 H.sub.5 n.sub.D.sup.27 1.5270306 " C.sub.3 H.sub.7n n.sub.D.sup.27 1.5168307 COCH.sub.2 Br C.sub.2 H.sub.5 n.sub.D.sup.27 1.5392308 " C.sub.3 H.sub.7n n.sub.D.sup.27 1.5333309 ##STR88## CH.sub.2CHCH.sub.2 n.sub.D.sup.27 1.5260310 ##STR89## " n.sub.D.sup.27 1.5340311 ##STR90## C.sub.2 H.sub.5 n.sub.D.sup.28 1.4958312 COOCH.sub.2 CH.sub.2 Br " n.sub.D.sup.25 1.5252313 COOCH.sub.2 CH.sub.2 OCH.sub.3 " n.sub.D.sup.25 1.4949314 " CH.sub.3 n.sub.D.sup.25 1.5006315 ##STR91## C.sub.2 H.sub.5 n.sub.D.sup.25 1.4909316 COOCH.sub.2 CHCH.sub.2 " n.sub.D.sup.31 1.5031317 COOCH.sub.2 CCH " n.sub.D.sup.30 1.5058318 ##STR92## CH.sub.2 CHCH.sub.2 n.sub.D.sup.30 1.4990319 COOCH.sub.2 CH.sub.2 Cl CH.sub.3 m.p. 94-100320 ##STR93## " m.p. 90321 ##STR94## CH.sub.2 CCH m.p. 133-134322 ##STR95## " n.sub.D.sup.30 1.5012323 COOCH.sub.2 CH.sub.2 F CH.sub.3 m.p. 75-85324 ##STR96## CH.sub.2 CHCH.sub.2 m.p. 124-125325 ##STR97## CH.sub.2 CCH m.p. 86-87326 COCH.sub.2 OCH.sub.3 C.sub.5 H.sub.11n n.sub.D.sup.28 1.4859327 ##STR98## C.sub.2 H.sub.5 m.p. 131.0328 ##STR99## " m.p. 106.0329 COCH.sub.3 C.sub.5 H.sub.11n n.sub.D.sup.26 1.4892330 ##STR100## " n.sub.D.sup.25 1.5277331 ##STR101## " n.sub.D.sup.28 1.5410332 ##STR102## CH.sub.2 CCH m.p. 176-177333 COCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 C.sub. 5 H.sub.11n n.sub.D.sup.25 1.4885334 COCH.sub.2 SCH.sub.3 " n.sub.D.sup.19 1.5377335 SO.sub.2 CH.sub.3 " n.sub.D.sup.20 1.5072336 COCH.sub.2 OCOCH.sub.3 " n.sub.D.sup.25 1.4822337 ##STR103## " n.sub.D.sup.23 1.5056338 ##STR104## " n.sub.D.sup.24 1.5160339 CON(CH.sub.3).sub.2 " n.sub.D.sup.22 1.5082340 ##STR105## " n.sub.D.sup.22 1.5149341 COSC.sub.3 H.sub.7n " n.sub.D.sup.21 1.5179342 SO.sub.2 N(CH.sub.3).sub.2 " n.sub.D.sup.20 1.5123343 ##STR106## C.sub.6 H.sub.13n n.sub.D.sup.29 1.4870__________________________________________________________________________
The compounds of the present invention can be formulated, when they are intended to be used as agricultural and horticultural fungicides, into any forms conventionally adopted in the art for these purposes, for example, such compositions as dust, wettable powder, emulsion, granule, microgranule and the like. The carrier material, used for the uniform distribution of the present compounds in effective amounts, may be either a liquid or particulate solid material, and is not limited to specific materials. Suitably usable solid carrier materials include, for example, various kinds of kaolin, clay, diatomaceous earth, talc, silica and the like. Suitably usable liquid carrier materials may be those which are inert solvents for the present active ingredient compounds and those which are non-solvents therefor but capable of dispersing or dissolving said active ingredient compounds by the aid of appropriate adjuvants used in combination therewith. Such liquid carrier materials include, for example, benzene, xylene, toluene, kerosene, alcohols, ketones, dimethyl sulfoxide, dimethylformamide and the like. By using such liquid carriers in admixture with appropriate surface active agents and other formulation aids, for example, spreading agents, sticking agents and the like, the present active ingredient compounds can be formulated into, and used as, aqueous solution or emulsions.
Furthermore, the compounds of the present invention can be used in admixture with other fungicides, insecticides, herbicides, plant growth regulators, etc. for the purpose of lessening the labor and of ensuring the controlling effect of the present compounds.
When operating in accordance with the present invention, effective amounts of the compounds or compositions of this invention are applied to the plants in any convenient fashion. The application of liquid and particulate solid compositions to plants can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages.
The application of an effective amount of the compounds or compositions of this invention to the plant is essential for the practice of the present invention. The exact amount of active ingredient to be employed may vary depending on several factors including the response desired as well as the plant species to be treated and stage of development thereof, and the amount of rainfall as well as the specific type of compound used. Generally, however, the active ingredients are applied in amounts of from about 100 grams to about 1,000 grams per hectare.
Some examples are given below to illustrate the use as agricultural and horticultural fungicides of the compounds of the present invention in compositions of varied types, but it should be construed that both the active ingredient compounds of the present invention and additives usable in such compositions are not limited to those exemplified in these examples.
EXAMPLE 24
(Dust)
A homogeneous mixture of 2 parts of compound No. 7 and 98 parts of clay is pulverized to obtain a dust preparation containing 2% of the active ingredient.
EXAMPLE 25
(Wettable Powder)
A homogeneous mixture of 30 parts of compound No. 11, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is pulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the finely divided active ingredient. This wettable powder, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 26
(Emulsion)
By mixing 30 parts of compound No. 12 with, and dissolving in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion, when it is actually applied to plants, is diluted to 600 to 1000 time with water and then sprayed over the plants.
EXAMPLE 27
(Granule)
A mixture of 5 parts of compound No. 15, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded with a kneading machine, followed granulation. The granules thus obtained are then dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.
EXAMPLE 28
(Dust)
A homogeneous mixture of 2 parts of compound No. 162 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.
EXAMPLE 29
(Wettable Powder)
A homogeneous mixture of 30 parts of compound No. 163, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is pulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the active ingredient. The wettable powder thus obtained, when it is actually used, is diluted 600 to 1000 times with water and then sprayed over plants.
EXAMPLE 30
(Emulsion)
By mixing 30 parts of compound No. 165 with, and dissolved in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 31
(Granule)
A mixture of 5 parts of compound No. 173, 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 with a kneading machine, followed by granulation. The granules thus obtained are then dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.
EXAMPLE 32
(Dust)
A homogeneous mixture of 2 parts of compound No. 220 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.
EXAMPLE 33
(Wettable Powder)
A homogeneous mixture of 30 parts of compound No. 223, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is uniformly poulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the active ingredient. The thus obtained wettable powder, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 34
(Emulsion)
By mixing 30 parts of compound No. 225 with, and dissolved in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 35
(Granule)
A mixture of 5 parts of compound No. 232, 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 with a kneading machine, followed by granulation. The granules thus obtained are dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.
EXAMPLE 36
(Dust)
A homogeneous mixture of 2 parts of compound No. 252 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.
EXAMPLE 37
(Wettable Powder)
A homogeneous mixture of 30 parts of compound No. 253, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder having uniformly dispersed therein all the constituents including 30% of the finely divided active ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 38
(Emulsion)
By mixing 30 parts of compound No. 256 with, and dissolving in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 39
(Granule)
A mixture of 5 parts of compound No. 258, 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 with a kneading machine, followed by granulation. The granules thus obtained are dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.
EXAMPLE 40
(Dust)
A homogeneous mixture of 2 parts of compound No. 297 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.
Example 41
(Wettable Powder)
A homogeneous mixture of 30 parts of compound No. 301, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the active ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.
EXAMPLE 42
(Emulsion)
By mixing 30 parts of compound No. 302 with, and dissolving in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and sprayed over the plants.
EXAMPLE 43
(Granule)
A mixture of 5 parts of compound No. 305, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfonate, 67 parts of acid clay, 25 parts of bentonit and 15 parts of water is kneaded with a kneading machine, followed by granulation. The granules thus obtained are dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.
Control effects on various plant diseases of the compounds of the present invention, when they are used as agricultural and horticultural fungicides, are illustrated below with reference to test examples.
TEST EXAMPLE 1
Test for 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 prepared by diluting a wettable powder prepared according to the general procedure of Example 25 to a predetermined concentration with water. One day after the spraying of the test liquid, the seedings were inoculated by atomizing technique with a spore suspension of rice blast fungus (Pyricularia oryzae). Upon completion of the inoculation, the seedlings were kept overnight under humidified circumstances (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 preventive value was calculated on the basis of the following equation. Furthermore, the phytotoxic activity against the rice plant of the test compound was investigated according to a fixed numerical scale, the injury ratings of which are defined as mentioned below. The results obtained are as shown in Table 2. ##EQU1##
______________________________________Injury rating:______________________________________5: Very severe phototoxicity4: Severe phototoxicity3: Great phototoxicity2: Moderate phototoxicity1: Slight phototoxicity0: No phototoxicity______________________________________
TABLE 2______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 200 89 02 " 84 03 " 100 04 " 100 05 " 83 06 " 93 07 " 100 08 " 99 010 " 80 011 " 100 012 " 87 013 " 82 014 " 100 015 " 100 017 " 75 019 " 75 020 " 86 022 " 94 023 " 100 024 " 100 025 " 75 026 " 100 027 " 80 028 " 75 029 " 91 030 " 85 031 " 75 032 " 100 034 " 87 035 " 76 036 " 100 037 " 80 038 " 91 039 " 100 040 " 79 041 " 95 042 " 89 044 " 81 045 " 75 047 " 75 048 " 100 049 " 94 051 " 100 052 " 100 053 " 75 054 " 84 055 " 97 056 " 75 058 " 100 059 " 100 061 " 100 062 " 100 063 " 100 065 " 100 066 " 75 067 " 97 069 " 100 070 " 88 071 " 100 072 " 75 073 " 100 074 " 88 075 " 96 076 " 75 077 " 81 078 " 79 079 " 75 080 " 75 081 " 80 082 " 77 083 " 75 084 " 75 086 " 87 087 " 95 088 " 85 089 " 75 090 " 83 091 " 99 092 " 98 093 " 100 094 " 75 096 " 86 098 " 95 099 " 75 0100 " 83 0103 " 82 0104 " 75 0105 " 75 0107 " 93 0108 " 75 0109 " 82 0110 " 75 0111 " 75 0112 " 85 0113 " 96 0114 " 100 0115 " 100 0116 " 100 0117 " 100 0118 " 100 0119 " 93 0120 " 100 0121 " 75 0122 " 94 0123 " 100 0124 " 100 0125 " 100 0127 " 100 0128 " 100 0129 " 100 0130 " 90 0131 " 100 0132 " 100 0133 " 93 0134 " 86 0135 " 78 0136 " 75 0137 " 100 0138 " 75 0139 " 100 0140 " 100 0141 " 81 0142 " 100 0143 " 100 0144 " 100 0145 " 100 0146 " 100 0147 " 100 0148 " 100 0149 " 100 0151 " 100 0152 " 99 0153 " 100 0155 " 100 0156 " 100 0157 " 100 0158 " 100 0159 " 71 0160 " 82 0162 " 83 0164 " 97 0166 " 77 0167 " 93 0168 " 87 0169 " 78 0170 " 87 0171 " 98 0172 " 100 0173 " 100 0174 " 84 0175 " 80 0176 " 100 0177 " 83 0178 " 75 0179 " 75 0180 " 100 0181 " 100 0182 " 90 0183 " 95 0184 " 100 0185 " 100 0186 " 100 0187 " 95 0188 " 90 0189 " 100 0190 " 90 0191 " 99 0192 " 100 0193 " 100 0194 " 99 0195 " 100 0196 " 100 0197 " 100 0198 " 100 0199 " 100 0200 " 100 0201 " 100 0202 " 95 0203 " 100 0204 " 100 0216 " 75 0217 " 81 0218 " 84 0219 " 82 0220 " 100 0221 " 88 0222 " 100 0223 " 100 0224 " 100 0225 " 100 0226 " 75 0229 " 75 0232 " 100 0233 " 100 0234 " 100 0235 " 100 0236 " 96 0237 " 100 0238 " 95 0239 " 100 0240 " 89 0241 " 100 0242 " 100 0243 " 90 0244 " 100 0245 " 75 0246 " 100 0247 " 90 0248 " 80 0249 " 97 0250 " 80 0251 " 80 0252 " 100 0253 " 100 0254 " 100 0255 " 100 0256 " 100 0257 " 100 0258 " 85 0259 " 100 0260 " 100 0262 " 100 0263 " 100 0264 " 100 0265 " 100 0267 " 100 0268 " 80 0269 " 100 0270 " 100 0273 " 100 0274 " 100 0275 " 100 0276 " 100 0277 " 100 0278 " 100 0279 " 100 0280 " 100 0281 " 100 0282 " 100 0283 " 100 0284 " 100 0285 " 100 0288 " 100 0289 " 100 0290 " 100 0291 " 75 0292 " 75 0293 " 75 0294 " 99 0295 " 75 0296 " 75 0297 " 100 0298 " 100 0299 " 75 0300 " 92 0301 " 92 0302 " 100 0303 " 100 0304 " 100 0305 " 79 0306 " 75 0307 " 83 0308 " 75 0309 " 100 0310 " 90 0311 " 100 0312 " 95 0313 " 98 0314 " 100 0315 " 95 0316 " 100 0317 " 95 0318 " 92 0319 " 100 0320 " 100 0321 " 100 0322 " 92 0323 " 100 0324 " 90 0325 " 91 0326 " 100 0327 " 100 0328 " 88 0329 " 97 0330 " 100 0331 " 90 0332 " 93 0333 " 100 0334 " 94 0335 " 100 0336 " 91 0337 " 100 0338 " 100 0339 " 100 0340 " 91 0341 " 100 0342 " 99 0343 " 100 0Comparative " 95 0chemical(EDDP)Non-treated -- 0 --______________________________________ (Note) ##STR107##
TEST EXAMPLE 2
Test for Control Effect on Paddy Rice Brown Spot
Over the 4th-true leaf stage seedlings of paddy rice (variety: Asahi) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed a test liquid prepared by diluting the compound to a predetermined concentration with water. One day after completion of the spraying of the test liquid, the seedlings were inoculated with a spore suspension of rice brown spot fungus (Cochliobolus miyabeanus). Five (5) days after the inoculation, the number of lesions per leaf of the 4-stage true leaves was investigated and the preventive value was calculated on the basis of the following equation. Furthermore, the phytotoxic activity against the paddy rice plant of the test compound was investigated according to the same procedure as in Test Example 1. The results obtained are as shown in Table 3. ##EQU2##
TABLE 3______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________2 500 100 03 " 100 04 " 100 05 " 100 06 " 100 07 " 100 08 " 94 010 " 100 015 " 83 016 " 75 017 " 93 018 " 100 019 " 100 020 " 100 021 " 100 022 " 100 023 " 100 024 " 100 025 " 92 026 " 85 027 " 89 029 " 100 030 " 100 031 " 93 032 " 75 036 " 92 037 " 75 044 " 79 049 " 100 050 " 100 051 " 91 052 " 100 054 " 90 055 " 100 056 " 100 058 " 98 059 " 100 062 " 100 063 " 100 064 " 91 065 " 100 068 " 100 069 " 100 071 " 100 074 " 83 077 " 75 085 " 75 086 " 75 095 " 75 097 " 75 0103 " 88 0106 " 75 0113 " 100 0114 " 100 0115 " 100 0116 " 100 0118 " 100 0119 " 90 0120 " 100 0123 " 100 0124 " 100 0125 " 100 0126 " 100 0128 " 100 0129 " 100 0131 " 100 0132 " 100 0133 " 100 0134 " 100 0135 " 88 0136 " 92 0139 " 100 0140 " 100 0141 " 100 0142 " 100 0143 " 100 0144 " 100 0145 " 100 0146 " 100 0147 " 100 0148 " 100 0149 " 100 0155 " 100 0159 " 96 0160 " 96 0161 " 100 0162 " 99 0163 " 100 0164 " 100 0165 " 99 0167 " 73 0170 " 82 0171 " 80 0172 " 84 0181 " 85 0182 " 95 0183 " 100 0184 " 100 0185 " 100 0186 " 90 0187 " 100 0188 " 90 0189 " 100 0190 " 99 0191 " 100 0192 " 100 0193 " 100 0194 " 90 0195 " 100 0196 " 95 0197 " 90 0198 " 100 0199 " 100 0200 " 100 0201 " 100 0202 " 100 0203 " 100 0204 " 100 0205 " 93 0207 " 95 0208 " 97 0209 " 75 0210 " 75 0212 " 84 0213 " 91 0214 " 75 0215 " 96 0216 " 100 0217 " 92 0218 " 97 0211 " 88 0212 " 100 0213 " 100 0214 " 100 0215 " 100 0216 " 100 0217 " 75 0229 " 75 0231 " 100 0232 " 100 0233 " 100 0234 " 100 0235 " 100 0236 " 95 0237 " 100 0238 " 100 0239 " 100 0240 " 96 0241 " 98 0242 " 100 0243 " 98 0244 " 100 0246 " 100 0247 " 100 0248 " 100 0249 " 100 0250 " 100 0251 " 100 0252 " 95 0254 " 95 0255 " 100 0256 " 100 0257 " 90 0258 " 90 0262 " 100 0263 " 93 0267 " 100 0270 " 90 0271 " 90 0274 " 85 0275 " 90 0276 " 90 0279 " 90 0280 " 100 0281 " 90 0282 " 100 0283 " 100 0284 " 95 0288 " 100 0289 " 100 0291 " 100 0294 " 100 0295 " 100 0297 " 97 0298 " 100 0300 " 95 0301 " 100 0302 " 100 0303 " 86 0304 " 100 0305 " 100 0306 " 100 0307 " 100 0308 " 100 0309 " 100 0310 " 100 0311 " 100 0312 " 100 0313 " 100 0314 " 100 0315 " 100 0316 " 100 0317 " 100 0318 " 92 0319 " 94 0320 " 100 0321 " 100 0322 " 100 0323 " 93 0324 " 100 0325 " 100 0326 " 94 0327 " 100 0328 " 100 0329 " 91 0330 " 100 0331 " 97 0332 " 100 0333 " 100 0334 " 100 0335 " 100 0336 " 99 0337 " 100 0338 " 98 0339 " 100 0340 " 100 0341 " 100 0342 " 100 0343 " 100 0Comparative " 90 0chemical(Triazine)Non-treated -- 0 --______________________________________ (Note) ##STR108##
TEST EXAMPLE 3
Test for Control Effect of Paddy Rice Sheath Blight
Over the 6th-leaf stage seedlings of paddy rice soil cultured in a porcelain pot of 9 cm in diameter was sprayed 40 ml per 3 pots of a test liquid of the compound having a predetermined concentration, and the seedlings thus treated were allowed to stand in a highly humidified glass chamber for weathering. One day after the spraying of the test liquid, inoculation conducted by patching each seedling at the second leaf sheath position with an agar disc obtained by perforating by means of a cork borer of 5 mm in diameter the edge of a colony of the pathogenic fungus (Pellicularia sasakii), which had previously been cultured (at 27.degree. C. for 48 hours) on a potato sucrose agar medium, and the thus inoculated seedlings were kept in a moist chamber (at 95-100% relative humidity and 28.degree. C.). Four days after the inoculation, outbreak of the disease was observed by investigating the lesion length per seedling and the preventive value (%) was obtained in comparison with the blank plot, according to the following equation. ##EQU3##
The test results obtained are as shown in Table 4.
TABLE 4______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________4 500 100 06 " 100 07 " 100 08 " 83 017 " 75 024 " 100 027 " 100 029 " 75 032 " 100 034 " 75 035 " 100 037 " 78 038 " 100 043 " 100 045 " 100 047 " 75 048 " 75 052 " 96 054 " 75 055 " 90 059 " 99 065 " 75 067 " 80 073 " 75 087 " 75 089 " 75 093 " 75 0101 " 75 0102 " 75 0127 " 75 0129 " 75 0131 " 95 0133 " 75 0134 " 79 0135 " 94 0137 " 75 0140 " 75 0144 " 100 0145 " 75 0151 " 85 0153 " 92 0294 " 75 0295 " 94 0296 " 83 0Comparative 65 90 0chemical(Neoasozine)Non-treated -- 0 --______________________________________ (Note) Neoasozine: Ammonium iron methanearsonate
TEST EXAMPLE 4
Test for Control Effect on Tomato Late Blight
Over the young seedlings of tomato (variety: Sekai-ichi, the second true leaf stage seedlings) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed by means of a pressure sprayer a test liquid prepared by diluting to a predetermined concentration with water a wettable powder prepared according to the general procedure of Example 25. Three days after completion of the spraying of the test liquid, the leaves of treated seedlings were inoculated by dropping the zoosporangia suspension of pathogenic fungus (Phytophthora infestans) with a needle injector, said pathogenic fungus having previously been cultured on potato tubers at 20.degree. C. for 3 days. After completion of the inoculation, the thus treated seedlings were kept in a humidified chamber (at 95-98% relative humidity), and three days thereafter, outbreak of the disease was observed and the control value (%) was calculated according to the following equation. Furthermore, the phytotoxicity against the tomato plant of the test compound was investigated according to the same procedure as in Test Example 1. ##EQU4##
The results obtained are as shown in Table 5.
TABLE 5______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________2 500 100 03 " 93 04 " 100 05 " 100 07 " 100 08 " 100 010 " 100 013 " 92 015 " 84 017 " 78 018 " 100 019 " 100 020 " 100 021 " 100 022 " 100 023 " 100 024 " 100 027 " 100 029 " 100 030 " 100 032 " 75 041 " 75 042 " 92 045 " 81 052 " 100 053 " 96 054 " 100 055 " 100 056 " 84 058 " 100 059 " 100 061 " 88 063 " 100 064 " 96 065 " 100 066 " 85 067 " 75 069 " 86 071 " 100 072 " 98 075 " 100 076 " 100 077 " 100 081 " 100 082 " 91 0110 " 80 0113 " 100 0114 " 96 0115 " 100 0116 " 100 0117 " 100 0118 " 100 0119 " 100 0120 " 100 0125 " 100 0126 " 100 0128 " 100 0129 " 75 0131 " 100 0132 " 100 0133 " 100 0134 " 100 0135 " 100 0136 " 100 0139 " 75 0141 " 100 0142 " 75 0143 " 100 0144 " 100 0145 " 100 0146 " 100 0147 " 100 0148 " 100 0149 " 100 0157 " 90 0159 " 99 0160 " 75 0162 " 100 0163 " 80 0164 " 100 0165 " 100 0169 " 91 0171 " 75 0173 " 77 0174 " 75 0177 " 93 0178 " 83 0180 " 100 0181 " 100 0182 " 95 0183 " 100 0184 " 100 0185 " 100 0187 " 100 0188 " 100 0190 " 96 0191 " 100 0192 " 90 0193 " 100 0194 " 100 0196 " 96 0197 " 100 0198 " 100 0199 " 100 0200 " 100 0202 " 100 0203 " 100 0204 " 100 0205 " 75 0207 " 77 0208 " 75 0210 " 82 0211 " 75 0212 " 94 0214 " 98 0215 " 88 0216 " 99 0217 " 100 0218 " 77 0219 " 91 0220 " 100 0222 " 100 0223 " 75 0224 " 99 0225 " 89 0226 " 100 0227 " 75 0229 " 96 0231 " 100 0233 " 76 0234 " 95 0235 " 100 0236 " 100 0237 " 95 0238 " 90 0239 " 100 0240 " 100 0241 " 96 0242 " 100 0243 " 90 0244 " 100 0246 " 100 0247 " 100 0248 " 100 0249 " 100 0251 " 100 0252 " 100 0253 " 100 0254 " 100 0255 " 100 0256 " 90 0257 " 90 0258 " 95 0259 " 100 0262 " 90 0264 " 90 0265 " 100 0266 " 90 0267 " 100 0270 " 100 0271 " 100 0274 " 100 0275 " 100 0276 " 100 0280 " 100 0281 " 100 0282 " 100 0283 " 100 0284 " 100 0286 " 90 0288 " 100 0289 " 100 0291 " 90 0292 " 100 0294 " 100 0295 " 100 0297 " 100 0298 " 100 0301 " 100 0302 " 100 0303 " 100 0304 " 100 0305 " 100 0306 " 100 0307 " 100 0308 " 100 0309 " 95 0310 " 100 0311 " 95 0312 " 100 0314 " 100 0315 " 100 0316 " 100 0318 " 100 0320 " 100 0321 " 100 0322 " 100 0324 " 100 0326 " 100 0328 " 100 0329 " 100 0330 " 90 0331 " 95 0332 " 100 0333 " 100 0335 " 100 0336 " 100 0337 " 99 0338 " 100 0339 " 100 0340 " 100 0341 " 100 0342 " 100 0343 " 100 0Comparative " 95 0chemical(TPN)Non-treated -- 0 --______________________________________ ##STR109##
TEST EXAMPLE 5
Test for Control Effect on Haricot Sclerotinia Rot
Over the seedlings of haricot (variety: Taisho Kintoki) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed, when the first rue leaf completely developed, 15 ml each per pot of a test liquid of the compound diluted with water to a predetermined concentration. On the following day, the first trifoliate leaf was cut off and the each leaflet of trifoliate leaf were placed in a 15 cm petri dish kept under moist conditions by placeing a wet filter paper thereon and were inoculated on the center portion of each leaflet with a fungus-containing agar segment obtained by perforating by means of a cork borer of 8 mm in diameter an edge of a colony of a haricot sclerotinia rot (Sclerotinia sclerotiorum) cultured previously at 20.degree. C. for 2 days in PSA medium. Three days after inoculation, the lesion diameter formed was measured by means of slide calipers and the control value (%) was obtained according to the following equation. Furthermore, the phytotoxicity against the haricot plant of the test compound was investigated according to the same procedure as in Test Example 1.
Control value (%)=(1-B/A).times.100
A=Lesion length in blank plot--diameter of inoculation source (8 mm)
B=Lesion length in treated plot--diameter of inoculation source (8 mm)
The results obtained are as shown in Table 6.
TABLE 6______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 200 81 03 " 100 04 " 75 05 " 100 06 " 94 07 " 100 017 " 72 019 " 90 020 " 75 022 " 95 023 " 81 025 " 95 027 " 100 029 " 75 030 " 78 033 " 75 045 " 75 051 " 75 052 " 79 065 " 75 067 " 75 089 " 75 096 " 100 0103 " 79 0113 " 100 0114 " 93 0115 " 100 0116 " 100 0118 " 100 0119 " 75 0120 " 75 0123 " 100 0124 " 100 0125 " 100 0127 " 75 0128 " 100 0131 " 100 0132 " 100 0134 " 100 0135 " 100 0136 " 100 0139 " 100 0140 " 100 0142 " 100 0146 " 82 0205 " 75 0206 " 75 0216 " 75 0217 " 100 0218 " 84 0219 " 75 0220 " 100 0221 " 100 0223 " 86 0224 " 100 0225 " 75 0226 " 75 0234 " 80 0235 " 75 0241 " 75 0243 " 80 0244 " 80 0246 " 100 0247 " 100 0248 " 100 0249 " 100 0252 " 90 0254 " 90 0280 " 90 0287 " 90 0304 " 98 0Comparative " 70 0chemical(Thiophanate-methyl)Non-treated -- 0 --______________________________________ (Note)- ##STR110##
TEST EXAMPLE 6
Test for Control Effect on Cucumber Downy Mildew
The young seedlings of cucumber (variety: Sagami Hanjiro, the first true leaf stage seedlings) cultivated in a greenhouse were placed on a turn table, and thereover was sprayed by means of a spray gun a test liquid of a wettable powder prepared according to the general procedure of Example 25 and diluted with water to a predetermined concentration. On the following day, the seedlings were inoculated by atomizing technique with a suspension of spores of a cucumber downy mildew fungus (Pseudoperonospora cubensis) which had been sporulated on the affected leaves of cucumber were brushed away into deionized water containing 50 ppm of Tween 20 (polyoxyethylene sorbitan monolaurate), so that the spore concentration in the suspension became 20-30 spores per unit visible field under a microscope of 150 magnifications. After keeping in a fumidified chamber at 20.degree. C. for 24 hours, the inoculated seedlings were placed in a greenhouse to accelerate infection. Five days after the inoculation, percent lesion area of each leaf was investigated and the control value (%) in a treated plot was calculated in comparison with a blank plot, according to the following equation. ##EQU5##
The results obtained are as shown in Table 7.
TABLE 7______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________1 500 100 02 " 100 05 " 100 06 " 100 010 " 100 018 " 78 019 " 100 020 " 100 021 " 100 022 " 100 023 " 100 024 " 100 025 " 100 026 " 100 029 " 100 030 " 100 031 " 100 032 " 100 049 " 100 050 " 100 051 " 100 052 " 100 053 " 100 054 " 100 056 " 100 057 " 100 058 " 100 059 " 100 060 " 100 061 " 100 062 " 100 063 " 100 064 " 100 065 " 100 066 " 100 067 " 100 068 " 100 069 " 100 070 " 100 071 " 100 072 " 100 073 " 94 074 " 100 075 " 100 076 " 100 077 " 90 078 " 97 0114 " 100 0122 " 100 0129 " 100 0137 " 100 0143 " 100 0144 " 100 0145 " 100 0146 " 100 0147 " 100 0148 " 100 0149 " 100 0160 " 100 0163 " 100 0178 " 100 0179 " 100 0166 " 100 0169 " 85 0170 " 93 0174 " 87 0175 " 80 0205 " 100 0207 " 100 0208 " 100 0209 " 100 0211 " 100 0213 " 100 0214 " 90 0215 " 100 0217 " 100 0219 " 100 0221 " 100 0222 " 100 0223 " 100 0225 " 100 0227 " 100 0228 " 100 0229 " 100 0230 " 100 0231 " 100 0232 " 100 0233 " 100 0234 " 100 0236 " 100 0238 " 100 0240 " 100 0242 " 100 0244 " 100 0245 " 100 0252 " 100 0253 " 100 0254 " 100 0255 " 100 0256 " 100 0257 " 100 0258 " 100 0259 " 100 0260 " 100 0262 " 100 0263 " 100 0264 " 100 0265 " 90 0267 " 100 0268 " 100 0269 " 100 0270 " 100 0271 " 100 0272 " 100 0273 " 95 0274 " 90 0275 " 100 0276 " 100 0278 " 100 0279 " 100 0280 " 100 0281 " 100 0283 " 100 0284 " 90 0285 " 95 0286 " 100 0287 " 90 0288 " 100 0289 " 100 0290 " 100 0291 " 100 0292 " 100 0293 " 100 0294 " 100 0295 " 100 0296 " 100 0297 " 100 0298 " 100 0299 " 100 0300 " 100 0301 " 100 0302 " 100 0303 " 100 0304 " 100 0305 " 100 0306 " 100 0307 " 100 0308 " 100 0309 " 100 0310 " 100 0311 " 100 0312 " 100 0313 " 100 0314 " 100 0315 " 100 0316 " 100 0317 " 100 0318 " 100 0319 " 100 0320 " 100 0321 " 100 0322 " 100 0323 " 100 0324 " 100 0325 " 100 0326 " 100 0327 " 100 0328 " 100 0329 " 100 0330 " 100 0331 " 100 0332 " 100 0333 " 100 0334 " 100 0335 " 100 0336 " 100 0337 " 100 0338 " 100 0339 " 100 0340 " 100 0341 " 100 0342 " 100 0343 " 100 0Comparative " 100 0chemical(TPN)Non-treated -- 0 --______________________________________
TEST EXAMPLE 7
Test for 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 diameter in a greenhouse was sprayed 10 ml of a test solution of the compound diluted to a predetermined concentration. On the following day, the seedlings were inoculated by atomizing technique with a spore suspension of cucumber powdery mildew fungus (Erysiphe cicholrcearum). Ten days after the inoculation, percent lesion area (%) was investigated and the control value (%) was calculated according to the following equation. ##EQU6##
The results obtained are as shown in Table 8.
TABLE 8______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________165 200 100 0172 " 100 0224 " 100 0226 " 93 0232 " 80 0233 " 92 0234 " 100 0235 " 96 0236 " 90 0237 " 100 0238 " 100 0239 " 88 0240 " 92 0241 " 100 0242 " 100 0243 " 88 0244 " 93 0296 " 100 0297 " 100 0298 " 100 0Comparative 100 100 0chemical(Denmart)Non-treated -- 0 --______________________________________ (Note) ##STR111##
TEST EXAMPLE 8
Test for Control Effect on Pear Black Spot
The new shoots of pear (variety: Niju-seiki) was cut, leaving the developed leaves at the upper portion and then inserted into a 100 ml flask filled with 50 ml of water. Over the new shoots thus treated was sprayed 20 ml per two shoots a test liquid of the compound diluted to a predetermined concentration. On the following day, the shoots were inoculated by atomizing technique with a spore suspension of a pear alternaria leaf spot fungus (Alternaria kikuchiana), the spore concentration of which had been adjusted to become 50-60 spores per unit visible field under a microscope (Olympus) of 150 magnifications. After the inoculation, the shoots were kept in a humidified chamber at 25.degree. C., and three days thereafter percent lesion area of each treated leaf was investigated and the control value (%) was calculated according to the following equation. Furthermore, the phytotoxicity against the pear tree of the test compound was investigated according to the same procedure as in Test Example 1. The results obtained are as shown in Table 9. ##EQU7##
TABLE 9______________________________________ Concentration ControlCompound of spray liquid value Degree ofNo. (ppm) (%) phytotoxicity______________________________________207 500 92 0208 " 78 0210 " 100 0211 " 100 0212 " 100 0213 " 92 0Comparative " 90 0chemical(Captan)Non-treated -- 0 --______________________________________ (Note)- ##STR112##
TEST EXAMPLE 9
Test for Seed Treatment against "Bakanae" Disease of Rice
Artificially inoculated rice seeds were obtained by inoculating a concentrated spore suspension of Gibberella fujikuroi causing the "Bakanae" disease at the ear-sprouting stage of a rice plant, and the rice seeds thus obtained were subjected to seed selection with water and then air dried to prepare rice seeds to be used in the test. The test compounds used were prepared according to the general procedure of Example 25. The test rice seeds each weight 15 g, were put in a saran net bag. The seed disinfectation was conducted by immersing the unhulled rice-containing saran net bag at 15.degree. C. for 24 hours in a test liquid, the proportion by volume of the test liquid and the infected rice seeds being 1:1. After completion of the disinfectation, the rice seeds were subjected to preimmersion at 15.degree. C. for 4 days, followed by germination acceleration treatment at 30.degree. C. for 24 hours. The rice seeds thus treated were densely seeded in granular cultivation soil according to a standard seedling box method and then placed in a room kept at 30.degree. C. for 2 days, followed by cultivation in a plastic greenhouse, exercising necessary supervision. Thirty two (32) days after the seeding (the 5-leaf stage), the number of seedlings infected with rice "Bakanae" disease (elongated and dead seedlings) was visually investigated to obtain the infected seedling ratio, and the seed disinfection ratio was calculated according to the following equation. ##EQU8##
The results obtained are as shown in Table 10.
TABLE 10______________________________________ SeedCompound Concentration disinfection Degree ofNo. (ppm) ratio (%) phytotoxicity______________________________________1 1000 79 02 " 100 03 " 100 04 " 100 05 " 100 06 " 100 07 " 100 08 " 100 09 " 75 010 " 100 011 " 75 015 " 96 016 " 75 017 " 100 018 " 100 019 " 100 020 " 100 021 " 96 022 " 97 023 " 100 024 " 100 025 " 100 026 " 75 027 " 100 029 " 100 030 " 100 033 " 75 035 " 82 036 " 75 040 " 75 046 " 75 049 " 100 050 " 100 051 " 100 052 " 100 053 " 100 054 " 100 055 " 100 056 " 100 057 " 100 058 " 100 059 " 100 060 " 100 061 " 100 062 " 100 063 " 100 064 " 100 065 " 100 066 " 84 067 " 75 068 " 100 069 " 100 070 " 100 071 " 100 072 " 88 073 " 75 074 " 100 075 " 100 076 " 100 077 " 100 081 " 82 083 " 75 084 " 87 096 " 89 0104 " 75 0106 " 75 0109 " 76 0113 " 100 0114 " 100 0115 " 100 0116 " 100 0117 " 90 0118 " 100 0119 " 100 0120 " 100 0121 " 90 0122 " 100 0123 " 100 0124 " 100 0125 " 100 0126 " 100 0127 " 95 0128 " 100 0129 " 100 0130 " 100 0131 " 100 0132 " 100 0133 " 100 0134 " 85 0135 " 100 0136 " 90 0137 " 100 0138 " 100 0139 " 100 0140 " 100 0141 " 100 0142 " 100 0143 " 100 0144 " 80 0145 " 100 0146 " 100 0147 " 95 0148 " 100 0149 " 100 0150 " 100 0151 " 90 0152 " 100 0153 " 85 0154 " 100 0155 " 100 0156 " 75 0157 " 100 0158 " 100 0205 " 75 0207 " 100 0208 " 100 0209 " 100 0212 " 75 0213 " 100 0214 " 100 0216 " 93 0217 " 100 0218 " 100 0219 " 100 0220 " 95 0221 " 100 0222 " 100 0223 " 100 0224 " 100 0225 " 100 0226 " 100 0227 " 100 0228 " 100 0229 " 100 0230 " 90 0231 " 100 0232 " 96 0233 " 100 0234 " 100 0235 " 100 0236 " 92 0237 " 100 0238 " 93 0239 " 97 0240 " 100 0241 " 100 0242 " 100 0243 " 90 0244 " 100 0245 " 100 0246 " 100 0247 " 100 0248 " 100 0249 " 100 0252 " 100 0253 " 100 0254 " 90 0260 " 95 0262 " 100 0263 " 100 0264 " 100 0265 " 100 0266 " 100 0267 " 100 0268 " 100 0269 " 100 0270 " 100 0271 " 100 0272 " 100 0273 " 100 0274 " 100 0275 " 100 0276 " 100 0277 " 100 0278 " 100 0279 " 100 0280 " 100 0281 " 100 0282 " 100 0283 " 100 0284 " 100 0285 " 100 0286 " 100 0287 " 100 0288 " 100 0289 " 100 0290 " 100 0294 " 77 0299 " 100 0Comparative " 95 0chemical(Benomyl)Non-treated -- 0 --______________________________________ (Note)- ##STR113##
TEST EXAMPLE 10
Test for Seed Treatment against Brown Spot of Rice
The test was conducted in the same manner as in Test Example 9 and using the test compounds prepared according to Example 6, except that rice seeds (variety: Asominori) naturally infected with a rice brown spot fungus were used as the test seed rice. Twenty five (25) days after the seeding (the 3rd-leaf stage), the number of infected seedlings was visually investigated to obtain the infected seedling ratio and thereby to calculate the seed disinfectation ratio (%) according to the following equation. ##EQU9##
The results obtained are as shown in Table 11.
TABLE 11______________________________________ SeedCompound Concentration disinfection Degree ofNo. (ppm) ratio (%) phytotoxicity______________________________________2 1000 100 03 " 100 04 " 100 05 " 100 07 " 100 010 " 100 018 " 100 020 " 100 022 " 100 023 " 100 024 " 100 030 " 100 050 " 100 051 " 100 052 " 100 057 " 100 058 " 100 059 " 100 063 " 100 064 " 100 065 " 100 069 " 100 0143 " 100 0146 " 100 0147 " 100 0148 " 100 0149 " 100 0205 " 96 0207 " 96 0208 " 97 0213 " 94 0215 " 100 0216 " 100 0217 " 99 0218 " 98 0221 " 92 0222 " 100 0223 " 100 0224 " 100 0225 " 100 0226 " 100 0231 " 100 0232 " 100 0233 " 95 0234 " 100 0235 " 100 0236 " 95 0237 " 100 0238 " 100 0239 " 100 0240 " 96 0241 " 97 0242 " 100 0243 " 100 0244 " 100 0Comparative " 51 0chemical(TMTD)Non-treated -- 0 --______________________________________ (Note)- ##STR114##
TEST EXAMPLE 11
Test for Antifungal Activity against Various Pathogenic Fungi Causing Plant Diseases
The test compound is dissolved in acetone, and 1 ml of the solution and 20 ml of a medium (PSA medium pH 5.8) kept at about 60.degree. C. are mixed together in a 9 cm diameter petri dish to prepare a compound-containing agar plate having a predetermined concentration. After evaporating the acetone while removing the upper cover of the Shale overnight, the compound-containing agar plate medium is inoculated by means of platinum loop with a spore suspension of the test fungus previously cultured in a slant medium. After culturing at 24.degree. C. for 48 hours, the growth of the test fungus was investigated according to the following standard for determining the growth of fungus. The results obtained are as shown in Tables 12a and 12b.
Standard for determining the growth of fungus:
-: No growth of the fungus is recognized at all.
.perp.: Formation of only few colonies is observed at the portion where the spore suspension has been applied to, while the growth of the fungus is markedly prohibited.
+: Formation of many colonies is observed at the portion where the spore suspension has been applied to, but the whole surface of the applied portion is not covered yet by colonies, and the growth of the fungus is markedly prohibited.
++: The growth of the fungus is observed practically all over the surface of the applied portion, but the degree of the growth of the fungus is moderately poor.
+++: The growth of the fungus is observed all over the surface of the applied portion, and the fungus normally grows.
TABLE 12a__________________________________________________________________________ FusariumCompound Conc. oxysporum f. Cladosporium Glomerella Alternaria Pyricularia Cochliobolus ValsaNo. (ppm) cucumerinum fulvum cingulata kikuchiana oryzae miyabeanus mali__________________________________________________________________________ 1 50 .perp..about.+ - .perp. - - - -.about..perp. 2 " - - - - - - - 3 " - - - - - - - 4 " - - - - - - - 5 " + + - .perp. - - + 6 " + ++ .perp. - - - ++ 7 " - - - - - - - 8 " -.about..perp. - - - - - .perp..about.+10 " - .perp..about.+ - - - - .+-.15 " .+-. ++ .perp..about.+ .perp. - - .+-.17 " - .perp..about.- - - - - -18 " .+-. + - - - - .perp..about.+19 " -.about..perp. + - - - - .perp..about.+20 " .perp. + - - - - .perp..about.+21 " + .perp..about.+ - - - - .perp..about.+22 " - - - - - - -23 " .perp. -.about..perp. - - - - +24 " - - - - - - -25 " + +.about.++ + + - .perp. +26 " + ++ .+-. .perp..about.+ - - +27 " - - - - - - .+-.29 " + + - .perp..about.+ - - +30 " + + - - - - +31 " + ++ .perp. + - - +32 " + ++ + .perp..about.+35 " + + + .perp..about.+ + - - ++49 " .perp..about.+ - - -.about..perp. - - .perp.50 " - - - - - - .+-.51 " - - - - - - -52 " - - - - - - -53 " .perp. .perp. - - - - .perp..about.+54 " .perp. - - - - - +55 " - - - - - - -56 " + .perp. - .perp. - - +.about.++57 " - .perp. - - - - -58 " - - - - - - .perp.59 " - - - - - - -60 " -.about.+ -.about.+ -.about..perp. -.about..perp. - - -.about.+61 " .perp..about.+ - - - - - +62 " + + - -.about..perp. - - +.about.++63 " - .perp. - - - - -64 " - - - - - - .perp..about.+65 " - - - - - - -66 " +.about.++ .perp..about.+ - - - - +67 " + .+-. - - - - +68 " + + - .perp..about.+ - - +.about.++69 " - .perp. - - - - -70 " .perp..about.+ -.about.+ - - - - .perp..about.+71 " - - - - - - -72 " + + -.about..perp. - - - +73 " .perp..about.+ - - - - - +74 " +.about.++ .perp..about.+ - - - - +.about.++75 " .perp..about.++ .perp..about.+ -.about..perp. - - - .perp..about.+76 " - - - - - - .perp..about.+77 " - - - - - - -78 " .perp..about.++ .perp..about.+ -.about..perp. -.about..perp. - .perp..about.+ +.about.++79 " + + .perp. -.about.+ - - +84 " ++ ++ + + - - +85 " + ++ -.about..perp. +.about.++ - - ++86 " + ++ .perp..about.+ .perp. - - +96 " - - - - - - -__________________________________________________________________________
TABLE 12b__________________________________________________________________________Compound Conc. Gibberella Cladosporium Glomerella Alternaria Pyricularia Cochliobolus ValsaNo. (ppm) Fujikuroi fulvum cingulata kikuchiana oryzae miyabeanus mali__________________________________________________________________________113 20 - .perp. .perp. - - - +114 " - + .perp. - - - ++115 " - -.about..perp. .perp. - - - .perp.116 " - .perp. .perp. - - - +117 " + ++ ++ ++ - +.about.++ ++118 " - - - - - - -.about.+119 " - .perp. .perp. - - - .perp.120 " - .perp. .perp. - - - .perp.122 " .perp. ++ .perp. .perp. - - ++123 " .perp..about.+ ++ .perp. + - .perp. +124 " - + .perp. - - - +125 " - + - .perp. - - +126 " .perp. + .perp. .perp..about.+ - - +127 " + ++ + ++ - - +128 " - + + - - - +129 " - + .perp..about.+ - - - +130 " ++ ++ ++ ++ - + ++131 " - .perp. .perp. - - - +132 " - + .perp..about.++ - - - +133 " - ++ .perp. - - - +134 " + + + +.about.++ - - ++135 " ++ + + ++ - - +136 " ++ + ++ ++ - .perp. ++137 " - + .perp. .perp. - - +138 " ++ ++ + ++ +.about.++ ++ ++139 " - .perp. .perp. - - - .perp.140 " - .perp. .perp. - - - .perp.141 " - .perp. .perp. - - - +142 " - .perp. .perp. - - - .perp.144 " .perp. .perp..about.+ .perp. .perp. - - ++145 " - - - - - - ++146 " ++ .perp..about.+ .perp. .perp..about.+ - - ++147 " ++ + .perp. ++ - - ++148 " ++ + - ++ - - ++149 " ++ .perp..about.+ - ++ - - ++151 " ++ +.about.++ - ++ - - ++155 " .perp. .perp. .perp. .perp. - - ++156 " ++ ++ ++ ++ - - ++157 " ++ ++ ++ ++ - - ++158 " + ++ .perp. ++ - - ++246 " - - - - - - -247 " - .perp. .perp. - - - -248 " + + + - - - +249 " - + .perp. - - - +252 " - .perp. - - - - .perp.253 " + ++ + + - - ++256 " .perp. + .perp. - - - +257 " .perp. + + .perp. - - +258 " .perp. + + .perp. - - +259 " + + + + - - +260 " - + - - - - +262 " - .perp. .perp. .perp. - .perp. +263 " - .perp. .perp. .perp. .perp. .perp. +264 " - - .perp. - - - .perp.265 " + + + + - .perp. +267 " + + + .perp. - - +269 " ++ + + + - - +270 " .perp. .perp. .perp. .perp. - - +271 " + + + + - - +273 " + ++ + + - - +274 " - .perp. .perp. - - - +275 " .perp. + + - - - +276 " - + + + - - +280 " + .perp. + ++ .perp. + +281 " + .perp. - + - - ++282 " .perp. .perp. .perp. + .perp. .perp. +283 " - - .perp. - - - .perp.284 " .perp. .perp. + + .perp. - +285 " + + + + .perp. - +286 " .perp. .perp. - - .perp. .perp. .perp.288 " .perp. .perp. + .perp. - - +289 " + + + + .perp. - +291 " .perp. + .perp. - - - +294 " - + - - - - +295 " - + .perp. - - - +297 " + + + - - - +298 " - ++ .perp. - - - +300 " - + .perp. - - - +301 " - - .perp. - - - .perp.303 " + + + ++ - - +304 " + .perp. - + - - .perp.305 " - .perp. - - - - .perp.306 " - - - - - - +307 " - .perp. - - - - +308 " - - - - - - .perp.309 " - + + - + - -310 " - + + .perp. - - +311 " + + .perp. .perp. - .perp. +312 " - .perp. - - - - +313 " .perp. .perp. .perp. .perp. - - +314 " - .perp. - - - - +315 " .perp. + .perp. .perp. - - +316 " - .perp. - - - - +317 " - + - - - - +318 " .perp. + - - - - +319 " - .perp. - - - - +320 " - .perp. - - - - +322 " + + .perp. - - - +323 " - .perp. - - - - +324 " .perp. + .perp. - - - +325 " + + - + - - +326 " .perp. .perp. .perp. .perp. - - +327 " - .perp. - - - - +328 " .perp. .perp. - - - - +329 " + + .perp. .perp. - - +330 " .perp. + - - .perp. - +332 " .perp. + - .perp. - - +333 " .perp. + - - - - .perp.334 " + + .perp. .perp. - - +335 " .perp. + - + - - +336 " + + + + + + +339 " .perp. + .perp. - - - +__________________________________________________________________________

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