Disclosed herein is a compound of the formula: ##STR1## wherein X is halogen, lower alkoxy or lower alkylthio, PA0 Y is hydrogen or chloro, PA0 R.sub.1 is hydrogen, lower alkyl, cyanomethyl, phenyl or benzyl, PA0 R.sub.2 is hydrogen, C.sub.1 .about.C.sub.7 - alkyl, C.sub.3 .about.C.sub.6 - cycloalkyl, lower alkoxy, phenyl, phenoxyphenyl, furyl, thienyl or benzyl and PA0 n=1 or 2 with a proviso that X and Y are not chloro at the same time, a fungicidal or bactericidal composition containing said compound as an effective component, a method for preventing diseases of agricultural or horticultural plant and a method for manufacturing said compound.

DETAILED DESCRIPTION OF THE INVENTION 
This invention relates to a compound of the formula: 
##STR2## 
wherein X is halogen, lower alkoxy or lower alkylthio, 
Y is hydrogen or chloro, 
R.sub.1 is hydrogen, lower alkyl, cyanomethyl, phenyl or benzyl, 
R.sub.2 is hydrogen, C.sub.1 .about.C.sub.7 -alkyl, C.sub.3 .about.C.sub.6 
-cycloalkyl, lower alkoxy, phenyl, phenoxyphenyl, furyl, thienyl or benzyl 
and 
n-1 or 2 
with a proviso that X and Y are not chloro at the same time, a fungicidal 
or bactericidal composition containing said compound as an effective 
component, a method for preventing diseases of agricultural or 
horticultural plant and a method for manufacturing said compound. 
The present invention relates to new N-cyanoalkylisonicotinamide 
derivatives usable as agricultural and horticultural fungicides or 
bactericides in paddy fields, upland or orchards. 
The prior fungicides include antibiotics, organophosphorus pesticides, 
synthetic organic fungicides, etc. It is disclosed in Japanese Pat. 
Laid-Open Nos. 167,978/1982 and 174754/1985 that heterocyclic compounds 
having a carbamoyl group are useful as fungicides. 
Furthermore, in Table on column 3 of U.S. Pat. No. 3,398,155 the compound 
of the formula: 
##STR3## 
are disclosed. Though the patent says the compound are highly effective as 
tranquilizer, it never says the compound (A) has any fungicidal or 
bactericidal activity. 
However, the isonicotinamide derivative having one halogen atom in pyridine 
ring of the present invention is new and there are no suggestions that the 
compound of the present invention show good fungicidal or bactericidal 
activity. 
The agricultural and horticultural fungicides used heretofore have defects 
that their effectiveness against rice blast and bacterial diseases such as 
bacterial leaf blight of rice and angular leaf spot of cucumber is 
insufficient, that bacteria and fungi resistant to agrochemicals causes 
trouble, that they are phytotoxic to crops, and that it is not 
economically advantageous. 
The present invention provides useful agricultural and horticultural 
fungicides free of these defects. 
The present inventors have found that when an N-cyanoalkylisonicotinamide 
derivative represented by the above formula (1) is used, a high 
controlling effect free of the defects of such prior fungicides is 
attained, and no adverse effect such as phytotoxicity is caused. The 
present invention has been completed on the basis of this finding. 
The compounds of the formula (1) of the present invention can be produced 
by a process which comprises reacting an isonicotinoyl chloride of the 
formula: 
##STR4## 
wherein X is halogen or lower alkoxy or lower alkylthio, and 
Y is hydrogen or chloro with the proviso that X and Y are not chloro at the 
same time, 
with a (cyanoalkyl)amine derivative of the formula: 
##STR5## 
wherein R.sub.1 is hydrogen, lower alkyl, cyanomethyl, phenyl or benzyl, 
R.sub.2 is hydrogen, C.sub.1 .about.C.sub.7 -alkyl, C.sub.3 .about.C.sub.6 
-cycloalkyl, lower alkoxy, phenyl, phenoxyphenyl, furyl, thienyl or benzyl 
and 
n is 1 or 2. 
in a solvent, occasionally in the presence of an acid-binding agent. 
Examples of the acid-binding agents used herein include alkali metal 
hydroxides such as NaOH and KOH, alkaline earth metal hydroxides such as 
Ca(OH).sub.2 and Mg(OH).sub.2, alkali metal alcoholates such as sodium 
alcoholate, alkali metal hydrides such as sodium hydride, alkali metal 
carbonates such as sodium carbonate and aliphatic and aromatic amines such 
as trialkylamines, for example, triethylamine, dialkylanilines, for 
example, dimethyl- and diethyl-anilines and pyridine. 
As the solvent, water or organic solvents can be used. Examples of the 
organic solvents include aromatic hydrocarbons such as benzene, toluene 
and xylene, aliphatic hydrocarbons such as hexane and heptane, halogenated 
hydrocarbons such as chloroform and dichloromethane, aprotic polar 
solvents such as dimethylformamide and dimethyl sulfoxide, ethers such as 
diethyl ether, tetrahydrofuran and dioxane, nitriles such as acetonitrile 
and propionitrile, ketones such as acetone and diisopropyl ketone, and 
esters such as ethyl acetate. The reaction temperature is -10.degree. C. 
to 100.degree. C., preferably 0.degree. C. to 50.degree. C., and the 
starting materials are used preferably in an equimolar proportion. On rare 
occasions, an excess of one of the reaction components may be used 
favorably. 
The crude product is obtained by a usual process, for example, by adding 
water to the reaction mixture and then by separating the phases. The crude 
product having a high purity obtained in a high yield can be used as it is 
or it can be purified by recrystallization or by column chromatography. 
The (cyanoalkyl)amines of the formula: 
##STR6## 
wherein R.sub.1, R.sub.2 and n are as defined above, 
can be produced by reacting a corresponding aldehyde with an amine of the 
formula: 
EQU R.sub.1 NH.sub.2 ( 4) 
wherein 
R.sub.1 is as defined above, 
in the presence of hydrocyanic acid under the Strecker reaction conditions 
(J. Chem. Soc., 1947, 1371). 
The isonicotinamide derivatives of the formula: 
##STR7## 
wherein X is halogen, lower alkyl or lower alkylthio, 
Y is hydrogen or chloro, and 
R.sub.2 ' is lower alkoxy, 
can be produced by reacting an N-cyanomethyl-isonicotinamide of the 
formula: 
##STR8## 
wherein X and Y are as defined above, 
with a halogenating agent in a solvent to obtain a halogenated intermediate 
of the formula: 
##STR9## 
wherein X and Y are as defined above, and 
Z is a halogen atom, and then reacting the intermediate with an alcohol of 
the formula: 
EQU R.sub.2 '--H (7) 
wherein 
R.sub.2 ' is lower alkoxy, in the presence of an acid-binding agent. 
As the solvents for halogenation, aliphatic halides such as 
dichloromethane, chloroform and carbon tetrachloride are preferred and 
further, esters such as methyl acetate and ethyl acetate can be used. The 
preferred halogenating agents are chlorine and bromine. The reaction 
temperature is 0.degree. to 100.degree. C., preferably 20.degree. to 
50.degree. C. Though the halogenated intermediate may be isolated, it is 
usually reacted directly with the alcohol. This reaction is conducted 
preferably in the presence of an acid-binding agent. The acid-binding 
agents include, for example, tertiary amines such as triethylamine, 
dimethylaniline and pyridine and inorganic bases such as sodium carbonate, 
potassium carbonate, sodium hydrogencarbonate, sodium hydroxide and 
potassium hydroxide. The reaction temperature is preferably in the range 
of -10.degree. to 50.degree. C. The crude product can be purified by 
recrystallization or silica gel chromatography. 
The halogens in the above formula (1) include chlorine, fluorine, bromine 
and iodine; the lower alkoxy groups include, for example, methoxy, ethoxy, 
propoxy, isopropoxy and butoxy groups; and the lower alkylthio groups 
include, for example, methylthio, ethylthio, propylthio and butylthio 
groups. The lower alkyl groups include, for example, methyl, ethyl, propyl 
and butyl groups and the alkyl groups having 1 to 7 carbon atoms include, 
for example, pentyl, hexyl and heptyl groups in addition to the 
above-mentioned lower alkyl groups. The cycloalkyl groups having 3 to 6 
carbon atoms include, for example, cyclopropyl, cyclobutyl and cyclohexyl 
groups. 
Preferred compounds of the present invention are those of the above formula 
(1) wherein: 
X is halogen, lower alkoxy or lower alkylthio, 
Y is hydrogen or chloro, 
R.sub.1 is hydrogen, methyl or benzyl, 
R.sub.2 is hydrogen, C.sub.1 .about.C.sub.7 -alkyl, C.sub.3 .about.C.sub.6 
-cycloalkyl, phenyl, phenoxyphenyl or benzyl, 
and n is 1 or 2, 
with the proviso that both X and Y are not chlorine atoms at the same time. 
Further preferred compounds are those of the above formula (1) wherein: 
X is halogen when Y is hydrogen and 
X is lower alkoxy or lower alkylthio when Y is chloro, 
R.sub.1 is hydrogen, methyl or benzyl, and 
R.sub.2 is hydrogen, C.sub.1 .about.C.sub.7 -alkyl, C.sub.3 .about.C.sub.6 
-cycloalkyl, phenyl, phenoxyphenyl or benzyl and 
n is 1 or 2. 
More preferred compounds are those of the above formula (1) wherein: 
X is halogen, 
Y is hydrogen, 
R.sub.1 is hydrogen, 
R.sub.2 is hydrogen, phenyl, benzyl or cyclohexyl, and 
n is 1 or 2. 
The most preferred compounds are those of the above formula (1) wherein: 
X is halogen, 
Y is hydrogen, 
R.sub.1 is hydrogen, 
R.sub.2 is hydrogen and 
n is 1 or 2. 
The fungi or bacteria which can be controlled by the compounds of the 
present invention used as a fungicide or bactericide are, for example, as 
follows: 
Pyricularia oryzae, Xanthomonas campestris p.v. oryzae, Pseudomonas glumae, 
Pseudomonas lachrymans, Xanthomonas cucurbitae, Xanthomonas campestris 
p.v. campestris, Pseudomonas maculicola, Xanthomonas vitans, Pseudomonas 
lachrymans, Xanthomonas vescatoria, Pseudomonas solanacearum, Pseudomonas 
cichorii and Xanthomonas vesicatoria. 
One or more of the compounds of the present invention may be used as the 
active ingredient(s) of an agricultural and horticultural fungicide or 
bactericide. 
According to the purposes of using the compound of the present invention as 
an agricultural and horticultural fungicide or bactericide, it may be used 
as it is or, alternatively, a formulation thereof such as dust, 
microgranule, granule, wettable powder, flowable agent or emulsion with an 
agricultural adjuvant prepared by a method usually employed in the 
preparation of pesticides can be used in order to improve or to stabilize 
their effects. 
In the practical use of these various formulations, they may be used either 
as such or after dilution with water to a desired concentration. 
The adjuvants used herein include carriers (diluents) and other adjuvants 
such as spreaders, emulsifiers, wetting agents, dispersants, fixing agents 
and disintegrators. 
The liquid carriers include aromatic hydrocarbons such as toluene and 
xylene, alcohols such as methanol, butanol and glycol, ketones such as 
acetone, amides such as dimethylformamide, sulfoxides such as dimethyl 
sulfoxide, methylnaphthalene, cyclohexane, animal and vegetable oils, 
fatty acids and their esters. 
The solid carriers include clay, kaolin, talc, diatomaceous earth, silica, 
calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina 
and saw dust. 
As the emulsifier or dispersant, surfactants are usually used. They include 
anionic, cationic, nonionic and amphoteric surfactants such as sodium 
salts of higher alcohol sulfates, stearyltrimethylammonium chloride, 
polyoxyethylene alkylphenyl ethers and laurylbetaine. 
The spreaders include polyoxyethylene nonylphenyl ether and polyoxyethylene 
lauryl ether; the wetting agents include polyoxyethylene nonylphenyl ether 
and dialkyl sulfosuccinates; the fixing agents include 
carboxymethylcellulose and polyvinyl alcohol; and the disintegrators 
include sodium ligninsulfate and sodium laurylsulfate. 
These preparations may be used either alone or in the form of a mixture 
with other agricultural and horticultural pesticides, insecticides, plant 
growth regulators and acaricides. 
The content of the compound used as the active ingredient of the 
agricultural and horticultural fungicide of the present invention is 
variable depending on the type of the preparation, the method of 
application and other conditions. The active ingredient may be used alone 
according to circumstances. It is used usually in an amount of 0.5 to 95 
wt. %, preferably 2 to 70 wt. %. 
Where the composition is applied to the plants, it is preferably sprayed on 
the leaves and stems in a concentration of the active ingredient of 10 to 
4,000 ppm, while in the case of soil application, the amount is preferably 
0.05 to 10 kg for 10 acres. 
The compounds of the present invention are used as agricultural and 
horticultural fungicides which exhibit an excellent effect of controlling 
paddy diseases such as rice blast, bacterial leaf blight of rice and 
bacterial grain rot of rice and the bacterial diseases such as angular 
leaf spot of cucumber in the application methods of treating the soil or 
the locus of the plants, spraying onto the stems and leaves and seed 
treatment. In addition, they are effective against fungi or bacterial 
resistant to agrochemicals and exhibit no adverse effect such as 
phytotoxicity to the plants.

The following examples will further illustrate the present invention. 
PREATION EXAMPLE 1 
Preparation of N-(2-cyanoethyl)-N-methyl-2-chloroisonicotinamide (No. 2) 
2 g (0.0136 mol) of 2-chloroisonicotinoyl chloride was added dropwise to a 
solution comprising 1.2 g (0.01136 mol) of N-methyl-N-(2-cyanoethyl)amine, 
1.9 ml (0.0136 mol) of triethylamine and 30 ml of acetonitrile under 
cooling at 5.degree. to 10.degree. C. The mixture was stirred at room 
temperature for 2 h and then poured into water. Ethyl acetate was added 
thereto to conduct extraction. 
The organic layer was washed with a saturated aqueous common salt solution 
and dried over anhydrous sodium sulfate. The solvent was distilled off and 
the resulting crude product was purified according to silica gel column 
chromatography to obtain 2.1 g (yield: 83.2%) of a light yellow oily 
product having n.sub.D.sup.25 of 1.5490. 
PREATION EXAMPLE 2 
Preparation of N-(2-thienylcyanomethyl)-2-chloroisonicotinamide (No. 10) 
3 g (0.017 mol) of 2-chloroisonicotinoyl chloride was added dropwise to a 
solution of 2.8 g (0.02 mol) of 2-amino-2-(2-thienyl)acetonitrile and 1.6 
g (0.02 mol) of pyridine in 30 ml of toluene while the temperature was 
kept at 10.degree. to 15.degree. C. The mixture was stirred at room 
temperature for 1 h. A saturated aqueous common salt solution was added 
thereto. The organic layer was separated and dried over anhydrous sodium 
sulfate. The solvent was concentrated under reduced pressure and the crude 
product was purified according to silica gel column chromatography to 
obtain 1.5 g (yield: 31.8%) of light brown crystals having a melting point 
of 123.degree. to 125.degree. C. 
PREATION EXAMPLE 3 
Preparation of N-(methoxycyanomethyl)-2-chloroisonicotinamide (No. 6) 
4.9 g (0.025 mol) of N-(cyanomethyl)-2-chloroisonicotinamide and 100 ml of 
dry ethyl acetate were stirred together under heating to dissolve the 
crystals. Then, dry ethyl acetate containing 4 g (0.025 mol) of bromine 
was added dropwise thereto while the temperature was kept at 45.degree. to 
50.degree. C. After stirring for about 10 min, nitrogen gas was introduced 
therein. Hydrogen bromide formed was removed and 30 ml of methanol was 
added to the residue. The resulting mixture was stirred at room 
temperature for 2 h. A saturated aqueous common salt solution was added 
thereto and the organic layer was dried over anhydrous sodium sulfate. The 
solvent was distilled off and the crude product was purified according to 
silica gel column chromatography to obtain 2.3 g (yield: 40.8%) of light 
brown crystals having a melting point of 75.degree. to 78.degree. C. 
Typical examples of the compounds of the present invention prepared in the 
same manner as in Preparation Examples 1 to 3 are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Compounds and physical properties 
##STR10## 
No. 
R.sub.1 R.sub.2 n m.p(.degree.C.) or (n.sub.D.sup.25) 
Appearance 
__________________________________________________________________________ 
1 CH.sub.3 H 1 (1.5547) colorless oil 
2 CH.sub.3 H 2 (1.5490) light yellow oil 
3 C.sub.4 H.sub.9 (n) 
H 1 (1.5156) light brown oil 
##STR11## 
H 2 (1.5826) light brown oil 
5 
##STR12## 
H 2 (1.5732) light yellow oil 
6 H OCH.sub.3 1 75-78 light brown crystals 
7 H 
##STR13## 1 62-65 light yellow crystals 
8 H 
##STR14## 1 140-142 light brown crystals 
9 H 
##STR15## 1 82.5-84.5 
light brown crystals 
10 H 
##STR16## 1 123-125 light brown crystals 
11 H 
##STR17## 1 126-127.5 
white crystals 
12 H 
##STR18## 1 (1.6300) brown oil 
13 CH.sub.2 CN 
H 1 (1.5391) light yellow oil 
__________________________________________________________________________ 
PREATION EXAMPLE 4 
Preparation of N-(cyanomethyl)-2-fluoroisonicotinamide (No. 14) 
2.4 g (0.056 mol) of sodium hydroxide was dissolved in 24 ml of water. 3.6 
g (0.017 mol) of aminoacetonitrile sulfate was added to the solution. 30 
ml of ether containing 3.0 g (0.017 mol) of 2-fluoroisonicotinoyl chloride 
was added dropwise to the solution while the temperature was kept below 
5.degree. C. The mixture was stirred at room temperature for 2 h to 
conduct a reaction. Water and ethyl acetate were added to the mixture to 
conduct extraction. The organic layer was washed with a saturated aqueous 
common salt solution and dried over anhydrous sodium sulfate. The solvent 
was distilled. The resulting crude crystalls were recrystallized from a 
solvent mixture of n-hexane and ethyl acetate to obtain 2.3 g (yield: 
75.3%) of white crystal having a melting point of 124.degree. to 
125.degree. C. 
PREATION EXAMPLE 5 
Preparation of N-(cyanomethyl)-2-n-propylthioisonicontinamide (No. 19) 
A solution of 2.0 g (0.01 mol) of 2-n-propylthioisonicotinic acid and 1.5 g 
(0.013 mol) of thionyl chloride in 50 ml of carbon tetrachloride was 
refluxed for 2 h to conduct a reaction. The solvent was distilled off 
under reduced pressure to obtain a crude product. 50 ml of ether was added 
thereto to obtain an acid chloride solution. Separately, 10 ml of an 
aqueous solution of 1.2 g (0.03 mol) of sodium hydroxide was added 
dropwise to a solution of 2.1 g (0.01 mol) of aminoacetonitrile sulfate in 
10 ml of water at a temperature of 10.degree. C. or below and the mixture 
was stirred for 30 min. The solution of the acid chloride in ether 
obtained as above was added dropwise to the latter solution while it was 
cooled to 0.degree. to 5.degree. C. The mixture was stirred at room 
temperature for 2 h and then poured into water. After extraction with 
ethyl acetate, the organic layer was washed with a saturated aqueous 
common salt solution and dried over anhydrous sodium sulfate. The solvent 
was distilled off. The resulting crude product was isolated and purified 
according to silica gel column chromatography to obtain 1.8 g (yield: 
74.6%) of a colorless oil having n.sub.D.sup.25 of 1.5718. 
PREATION EXAMPLE 6 
Preparation of N-(cyanomethyl)-2-chloro-6-n-butoxyisonicotinamide (No. 21) 
3.3 g (0.033 mol) of triethylamine was added to a solution of 1.9 g (0.02 
mol) of aminoacetonitrile hydrochloride in 30 ml of acetonitrile. The 
mixture was stirred at room temperature for 30 min. 2.5 g (0.01 mol) of 
2-chloro-6-n-butoxyisonicotinoyl chloride was added dropwise thereto under 
cooling at 5.degree. to 10.degree. C. The mixture was stirred at room 
temperature for 1 h, poured into water and extracted with ethyl acetate. 
The extract was washed with a saturated aqueous common salt solution and 
dried over anhydrous sodium sulfate. The solvent was distilled off under 
reduced pressure and the crude product was purified according to silica 
gel column chromatography to obtain 1.9 g (yield: 70.9%) of white crystals 
having a melting point of 72.degree. to 73.degree. C. 
Typical examples of the compounds of the present invention prepared in the 
same manner as in Preparation Examples 4 to 6 are shown in Table 2. 
TABLE 2 
______________________________________ 
Compounds and physical properties 
##STR19## 
No. X Y m.p.(.degree.C.) or (n.sub.D.sup.25) 
Appearance 
______________________________________ 
14 F H 124.about.125 
white crystals 
15 Br H 129.5.about.130.5 
light brown 
crystals 
16 I H 126.about.127 
white crystals 
17 SCH.sub.3 H 68.about.71 light brown 
crystals 
18 OCH.sub.3 H 99.about.100 
white crystals 
19 SC.sub.3 H.sub.7 (n) 
H (1.5718) colorless oil 
20 OCH.sub.3 Cl 160.about.161 
white crystals 
21 OC.sub.4 H.sub.9 (n) 
Cl 72.about.73 white crystals 
22 SCH.sub.3 Cl 159.about.160.5 
white crystals 
23 SC.sub.4 H.sub.9 (n) 
Cl 97.about.98 white crystals 
24 SC.sub.3 H.sub.7 (i) 
H (1.5640) light brown oil 
______________________________________ 
PREATION EXAMPLE 7 
Preparation of N-(cyanomethyl)-2-chloroisonicotinamide (No. 25) 
2.4 g (0.056 mol) of sodium hydroxide was dissolved in 24 ml of water. 3.6 
g (0.017 mol) of aminoacetonitrile sulfate was added to the solution and 
the mixture was stirred at room temperature for 1 h and then cooled to 
5.degree. C. or below. A liquid mixture of 3.0 g (0.017 mol) of 
2-chloroisonicotinoyl chloride and 30 ml of ether was added dropwise 
thereto at 5.degree. C. or below lest unfavorable heat generation should 
occur. The mixture was then stirred at room temperature for 2 h to conduct 
a reaction. Water and ethyl acetate were added thereto to conduct 
extraction. The extract was washed with a saturated aqueous common salt 
solution, dried over anhydrous sodium sulfate and concentrated. The 
resulting crystals were recrystallized from a liquid mixture of n-hexane 
and ethyl acetate to obtain 2.7 g (yield: 81.2%) of the intended product 
as white crystals having a melting point of 131.degree. to 132.degree. C. 
PREATION EXAMPLE 8 
Preparation of N-(1-cyano-2-methylpropyl)-2-chloroisonicotinamide (No. 29) 
2.0 g (0.02 mol) of 2-amino-3-methylbutyronitrile and 2.8 ml (0.02 mol) of 
triethylamine were dissolved in 30 ml of methylene chloride. The solution 
was cooled to 10.degree. C. or below and 3.0 g (0.017 mol) of 
2-chloroisonicotinoyl chloride was added dropwise thereto at 10.degree. C. 
or below lest unfavorable heat generation should occur. Then, the mixture 
was stirred at room temperature for 1.5 h to conduct a reaction. Water and 
ethyl acetate were added thereto to conduct extraction. The extract was 
washed with water, dried over anhydrous sodium sulfate and concentrated to 
obtain an oil, which was purified according to silica gel column 
chromatography to obtain 3.4 g (yield: 84.1%) of the intended product in 
the form of a colorless oil. 
The refractive index n.sub.D.sup.25 was 1.5276. 
Typical examples of the compounds of the present invention prepared in the 
same manner as in Preparation Examples 7 to 9 are shown in Table 3. 
TABLE 3 
______________________________________ 
Compound and Physical properties 
##STR20## 
m.p. .degree.C. or 
No. R.sub.2 n (n.sub.D.sup.25) 
Appearance 
______________________________________ 
25 H 1 131.about.132.degree. C. 
white crystals 
26 CH.sub.3 1 107.about.109.degree. C. 
light yellow 
crystals 
27 CH.sub.2 CH.sub.3 
1 70.about.72.degree. C. 
light yellow 
crystals 
28 CH.sub.2 CH.sub.2 CH.sub.3 
1 86.about.88.degree. C. 
light yellow 
crystals 
29 
##STR21## 1 (1.5276) colorless oil 
30 
##STR22## 1 125.about.126.degree. C. 
white crystals 
31 
##STR23## 1 (1.5275) light brown oil 
32 (CH.sub.2).sub.6 CH.sub.3 
1 (1.5180) light yellow oil 
33 H 2 113.about. 114.5.degree. C. 
white crystals 
______________________________________ 
The formulations are illustrated by the following Examples in which parts 
are given by weight, but the kinds and mixing proportions of agricultural 
adjuvants are not limited thereby and may be widely varied. 
FORMULATION EXAMPLE 1 
Dust 
2 parts of Compound No. 3 was mixed with 98 parts of clay and the mixture 
was pulverized to obtain a dust. 
FORMULATION EXAMPLE 2 
Wettable powder 
20 parts of Compound No. 24, 75 parts of kaolin, 3 parts of sodium salt of 
a higher alcohol sulfate and 2 parts of sodium ligninsulfonate were mixed 
together and pulverized to obtain a wettable powder. 
FORMULATION EXAMPLE 3 
Granules 
8 parts of finely pulverized Compound No. 8, 36 parts of diatomaceous 
earth, 24 parts of bentonite, 30 parts of talc and 2 parts of a 
disintegrator were mixed together. 18 parts of water were added to the 
mixture to wet it uniformly. The mixture was extruded by means of an 
injection molding machine to form granules. The granules were sized in a 
sizing machine and dried to obtain granules having a diameter of 0.6 to 1 
mm. 
FORMULATION EXAMPLE 4 
Microgranules 
5 parts of Compound No. 25 was dissolved in 5 parts of methanol. The 
solution was added dropwise to 95 parts of 80- to 250-mesh granular clay 
under stirring. The mixture was dried to obtain microgranules. 
FORMULATION EXAMPLE 5 
Emulsion 
30 parts of Compound No. 1 were dissolved in 52 parts of xylene. The 
solution was mixed with 18 parts of a mixture of an alkylphenol-ethylene 
oxide condensate and a calcium alkylbenzenesulfonate (8:2) to obtain an 
emulsion. 
This emulsion is to be diluted with water to obtain a dilute emulsion when 
it is used. 
The excellent effects of controlling various diseases of agricultural and 
horticultural crops exhibited by the compounds of the present invention 
are illustrated by the following Experimental Examples. 
EXPERIMENTAL EXAMPLE 1 
Tests of controlling rice blast by submerged application 
A rice plant (variety: Saitama-Mochi X) was raised in each plastic pot 
having a size of 11 cm.times.5 cm.times.10 cm for 2 weeks. A given amount 
of granules containing the compound of the present invention prepared in 
Formulation Example 3 as the active ingredient was applied to the soil in 
the pot. After 7 days, leaves of the rice plant were inoculated with 
Pyricularia oryzae by spraying its spore suspension. After keeping them in 
a humid chamber at 23.degree. C. for 2 days, the disease was further 
developed in a greenhouse. The symptoms of the disease were observed 10 
days after the inoculation, and the control index was calculated by the 
formula below. The results are shown in Table 4. IBP granul (active 
ingredient: S-benzyldiisopropyl phosphorothiolate) was used as the 
control. 
______________________________________ 
Degree of Disease 
Results observed 
______________________________________ 
0 no disease specks 
1 slight disease specks 
2 many disease specks 
3 extremely many disease specks, 
and only some blighted leaves 
4 many blighted leaves 
5 extremely many blighted leaves 
Control Index = 
##STR24## 
______________________________________ 
TABLE 4 
______________________________________ 
Tests of controlling rice blast 
(submerged application) 
Amount of 
active 
ingredient, 
Control 
Tested compound 
mg/pot index Phytotoxicity 
______________________________________ 
Compound 
1 20 89 none 
No. of the 
7 20 81 none 
present 8 20 88 none 
invention 
11 20 87 none 
14 20 90 none 
15 20 86 none 
17 20 81 none 
18 20 89 none 
19 20 80 none 
25 20 89 none 
26 20 78 none 
27 20 80 none 
28 20 77 none 
29 20 78 none 
30 20 79 none 
31 20 75 none 
33 20 89 none 
Control IBP granules 
20 65 none 
______________________________________ 
EXPERIMENTAL EXAMPLE 2 
Test of controlling rice blast by foliar spray 
A rice plant (variety: Saitama-Mochi X) was raised in each plastic pot 
having a size of 1 cm.times.5 cm.times.10 cm for 2 weeks. A liquid 
preparation of a given concentration obtained by diluting a wettable 
powder containing a compound of the present invention prepared in 
Formulation Example 2 as the active ingredient was sprayed on the stems 
and leaves of the rice plant. After air-dried, the plant was inoculated 
with a spore suspension of Pyricularia oryzae by spray. After keeping it 
in a humid chamber at 23.degree. C. for 2 days, the disease was developed 
in a greenhouse. The degree of the symptoms was observed 10 days after the 
inoculation, and the control index was calculated according to the formula 
given below. The results are shown in Table 5. An IBP emulsion (active 
ingredient: S-benzyldiisopropyl phosphorothiolate) was used as a control. 
______________________________________ 
Degree of disease 
Results observed 
______________________________________ 
0 no disease specks 
1 slight disease specks 
2 many disease specks 
3 extremely many disease 
specks, and only some 
blighted leaves 
4 many blighted leaves 
5 extremely many blighted leaves 
Control Index = 
##STR25## 
______________________________________ 
TABLE 5 
______________________________________ 
Tests of controlling rice blast of rice 
(foliar spray) 
Concentration 
of active 
ingredient, 
Control 
Tested compound 
ppm index Phytotoxicity 
______________________________________ 
Compound 
11 200 69 none 
No. of the 
14 200 70 none 
present 15 200 71 none 
invention 
18 200 69 none 
25 200 70 none 
26 200 67 none 
33 200 70 none 
Control IBP granules 
200 60 none 
______________________________________ 
EXPERIMENTAL EXAMPLE 3 
Tests of controlling bacterial leaf blight of rice by submerged application 
A rice plant (variety: Musashi-kogane) was raised in each plastic pot 
having a size of 15 cm.times.5 cm.times.10 cm for 1.5 months. Granules of 
the compound of the present invention prepared in Formulation Example 3 
were applied to the soil in the pot in a given amount. After two days, the 
leaves of the rice plant were inoculated with Xanthomonas campestris p.v. 
oryzae. After keeping them in a humid chamber at 30.degree. C. for 24 hr, 
the disease was further developed in a greenhouse. The length of the 
disease specks of the leaf was examined 21 days after the inoculation. 
The results are shown in Table 6. Probenazol granules (active ingredient: 
1,2-benzisothiazol-3-one 1,1-dioxide) were used as the control. 
TABLE 6 
______________________________________ 
Tests of controlling bacterial leaf blight 
of rice by submerged application 
Amount of Average 
active length of 
ingredient disease Phyto- 
Tested compound 
(mg/pot) specks toxicity 
______________________________________ 
Compound 
2 10 4.7 none 
No. of the 
3 10 4.2 none 
present 4 10 4.3 none 
invention 
5 10 4.6 none 
6 10 4.2 none 
9 10 4.3 none 
11 10 4.3 none 
14 10 4.1 none 
15 10 3.8 none 
17 10 4.0 none 
18 10 4.1 none 
19 10 4.4 none 
20 10 4.4 none 
23 10 4.7 none 
24 10 4.5 none 
30 10 4.8 none 
Control Probenazol 10 5.2 none 
granules 
Untreated -- 12.0 -- 
______________________________________ 
EXPERIMENTAL EXAMPLE 4 
Tests of controlling angular leaf spot of cucumber by foliar spray 
A solution having a given concentration prepared by diluting the wettable 
powder of the compound of the present invention prepared in Formulation 
Example 2 was sprayed on the stems and leaves of a cucumber plant 
(variety: Suyo) of a 4 leaves stage raised in each plastic pot having a 
diameter of 10 cm. After two days, suspension of angular leaf spot was 
sprayed on the cucumber leaves. The plant was kept in an inoculation box 
at 25.degree. C. for 2 days and the disease was developed in a greenhouse. 
The area of the disease specks was examined 10 days after the inoculation. 
The results were evaluated according to the following criteria: 
______________________________________ 
Criteria Results observed 
______________________________________ 
0 disease speck area: more than 70% 
1 disease speck area: 40 to 70% 
2 disease speck area: 10 to 40% 
3 disease speck area: less than 10% 
______________________________________ 
The results are shown in Table 7. A copper-based wettable powder (active 
ingredient: cupric hydroxide) was used as the control. 
TABLE 7 
______________________________________ 
Tests of controlling Pseudomonas 
lachrymans of cucumber by foliar spray 
Conc. of active 
Control Phyto- 
Tested compound 
ingredient, ppm 
index toxicity 
______________________________________ 
Compound 
15 500 3 none 
No. of the 
25 500 3 none 
present 33 500 3 none 
invention 
Control Copper-based 
800 1 none 
wettable 
powder 
______________________________________