CA1061250A - B, b-dichlorovinyl salicylamide and derivatives thereof as an agricultural and horticidal bactericide and fungicide - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention relates to use of the compound represented by following formula [I]

where X represents hydrogen atom, chlorine atom, bromine atom, methyl group or nitro group, Y represents hydrogen atom, methyl group, an alkylcarbonyl group where the alkyl group has from 1 to 12 carbon atoms, preferably, from 1 to 3 carbon atoms and may be substituted by one or more halogen atoms, a lower alkoxy carbonyl group, a lower alkylamino carbonyl group or a metal atom of which the valence is 1 or 2, Z represents hydrogen atom or chlorine atom and n represents 1 or 2, as an agricultural and horticultural bactericide and fungicide.

Description

: \

The present invention relates to the method for killing bacteria ; and fungi which cause plant diseases and an agricultural and horticultural bactericide and fungicide. The compounds used as an active compound in the present invention are represented by the following formula Cl \
CO~CHtC < ~ [I3 Z n where X represents hydrogen atom, chlorine atom, bromine atom, methyl group or nitro group~ Y represents hydrogen atom, methyl group, an alkylcarbonyl group where the alkyl group has from 1 to 12 carbon atoms, preferably, from 1 to 3 carbon atoms and may be substituted by one or more halogen atoms~ a lower alkoxy carbonyl group, a lower alkylamino carbonyl group or a metal atom of which the valence is 1 or 2, Z represents hydrogen atom or chlorine atom and n represents 1 or 2.
The compounds have remarkable exterminating activity against various kinds of bacteria or fungi ~hich harms agricultural and horticultural plants or crops and can be used for a folair treatment, seed treatment and soil treatment.
An excellent agricultural chemicals for the prevention of soil borne plant disease have not been discovered since the use of organic mercury compounds as agricultural chemicals was prohibited on account of toxic character of the compounds against men and beasts.
The compounds, particularly, exhibit an excellent effect on the prevention of soil borne plant diseases, for example, damping off of cucumber, fusarium wilt of cucumber and seedling blight of rice and don~t harm agricultural and horticultural plants and crops.
Representative compounds used in the present invention are shown in Table 1.

~- ~

Table 1 . . _ . . , Compound No. Compound M.P.25 Appearance or nD ;
~' ~ . _....... ~ _,, . _ ,,,,,,__ ~ CONHC~CC12 o . 1 ~ m.p. 160-4 C White crystals OH ::
._ . . _.. . __ .. : ,:

Cl CONHCH=CC12 o

2 ~ m.p. 208-10 C White crystals - OH
__ . . , . ': ~ ' Br CONHCH=CC12 o

3 ~ H m.p. 202-4 C White crystals , ., ::
CONHCH~C12 . .,

4 ~ m.p. 78-82C White crystals OH .~
CH3 .
, . . . .... ~

CONHCI~CC12 o ' :
~ m.p. 189-191 C White crystals .

- 20 CH3/ " " OH ~ .
.. . . . . , , . ....... ~
CONHCH=CC12 o ~ :
6 ~ m.p. 91-2 C White crystals - OC(O)CH3 :
. . ' . . __ __ . __ _A.__ Cl\ " ~ "CONHCH=CC12 .
7 l G ¦ m.p. 98-100 C White crystals OC(O)CH3 . :.
, , . . .. ... ~ ,~
Br coNHcH=ccl2 8 ~ m.p. 133-4C White crystals :
. ClO)CH3 :

Table 1 cont~d -,- ~ .. . ~
ompound No. Compound ~ c : or nD
, _ ... _ ,,,,, CONHCH=CC12 . ~ m.p. 37-8C ~hite crystals OC(O)C2H5 ' ~
. ., . ... _ ........... . .-CONHCH=CC12 ~ m.p. 124-5 C White crystals ~bc~o)c3H7(n) ' .
_ ,~ _ . .~
CONHCH=CCl 11 ~ / 2 m.p. 122-4 C White crystals "~" ~ C(O)C3H7(1) . ... ~ . . ., _ . . . ' ' .
CONHCH=CC12 . -.
12 ~ OC m-p- 53-4C White crystals ()CllH23(n) .. _ . . . ----- ....
coNHcH=
13 ~ OC(O)CH2Cl m.p. 93-5 C White crystals _ - . . .
~ CONHCH~C12 14 ~ OC(O)CHC12 m.p. 184-6 C White crystals . _,, . . .... ~ ~' CONHC~I=C~12 ~ OCH3 m.p. 111-2 C White crystals ..... _ . . .. __ '~ .
CONHCH=CCl2 16 ~ m.p. 72-3 C White crystals . OC(O)OCH3 . . . _ ~ _ . . _ _ . . ,.. __

5~,~
Table 1 cont~d Compound No. Compound ~~ or nD Appearance . _ _ .
CONHCH=CC1 17 ~ m.p. 70-2C White crystals \/ \OC(O)OC2H3 ~ . . . .
CONHCH=CC12 18 ~ CH nD5 1.5409 Transparent OC(O)OCH2CH / 3 liquid `

. . . _.. .. . . ~

, CONHCH=CC1 19 ~ m.p. 98-101 C White crystal OC(O)NHCH3 . . .. . .~ :, .
. coNHc~ccl2 . ' .
~ /
20 ~ O ~ m.p. 243 C Pale Yellow Na crystals (Decomposition) _ ,, _ __ _.. _ _ . ...... . !'.
Cl CONHCH=CC12 21 ~ _ + m.p. 280 C Pale Yellow Na over crystals . ~ ~ _ . ..... .
Br CONHCH=CC12 /`
22 ~ + m.p. 280C Pale yellow ~ O Na over crystals ... . _ . . . . ;.':
CONHCH~CC12 :~
23 ~ _ + m.p. 174 C Pale yellow O K (Decomposition) Crystals __ ~ .. ~ _ CONHCH=CC12 24 ~ \ ~ ~+ m.p. 158-160 C White crystals o (Zn )2 . . ~ ...... . ._. ....... _ .- - . .. __ __ . ..

~ 3 Table 1 conttd ~ompound No. Compound 25 Appearance r -- _ . . .
Br~"~,~ CONHCH=CC1 ~ ~o (Zn )2 m.p. 280 C White crystals . . _ .~ ~
CONHC~CC12 26 ~ m.p. 135 C Pale green --~ (CU )2 ~DeComposition) CryStals _ _ ',,, ., .' Br CONHCH=CC12 o 27 I ~ I m.p. 280 C Dark yellow ~ \0 (CU )2 over green crystals . . . .

CONHCH=CCl2 28 ~ ~ 1 m.p. 191 C Yellow grey _ J\ o (Mn )2 (DeCOmposltiOn~ CrYstal9 ,~
Br CONHCH=CC12 29 ~ \ _ ~+ 1 mOp. 280C Yellow grey o (Mn ) 2 over crystals ."

. . ._ . . .

Cl ~CONHC~CC12 ¦ O ¦ m.p. 280C Pale yellow O K over crystals ~ . . . _ . . . ,,~

31 CONHCH=CC12 m.p. 176-177C Pale yellow crystals . . . _ _ Cl ~,CONHCH=CC12 ; 32 ~ C(O)CH3 m.p. 130-132 C Whi~e crystals , . . ... ~ _ _ ,, . ,:

... . ..

Table 1 cont~d _ . .. , .. _ Compound No. Compound or nD Appearance .. . _._ ..
Cl CONHCH=CC1 33 ~ + m.p. 280C Pale yellow ~ \0 Na over crystals .,. ..,. _ ~ ~ ~ ' 34 Cl CONHCH=CC12 m.p. 280 C Pale yellow ~ O K o r crystals ~ _ _ , ~, CoNHc~ccl2 ., ~ m.p. 109-112 C Pale yellow ~ DC(0)CN3 crys~als . . .
''', ' "' '.
The compounds of the formula [I] are prepared as follows:
N-(0,~-dichlorovinyl) salicylamide is prepared by heating chloral with salicylamide, followed by treatment with a mixture of zinc and acetic .
acld.
A metallic salt of N-(~,B-dichlorovinyl) salicylamide is prepared by reacting a hydroxylmetal compound such as sodium hydroxide with N (~, diehlorovinyl) salicylamide.
The eompounds of the formula ~ H (II) wherein X and Z are defined as above are eondensed with chloral by a method similar to that shown in United States Patent 2,936,323. The products of - ~ 6 -the condensation are compounds of the formula ,_CONH~H-CC13 ~ OH (III) X '.. : ' These compounds are reduced with a reductant such as zinc in a suitable solvent such as acetic acid, methanol or ethanol at a temperature between room temperature and 120 C.
Compounds of the formula Cl - Z CO~C~C / ''~
~ / \ Cl X ~ OH

are obtained by the said reduction. The compound of the formula ~IV) is reacted with equivalent mole to 2 time moles of an alkyl halide~ an acyl chloride, an alkoxycarbonyl chloride or an alkyl isocyanate in the presence of a suitable base such as trimethylamine and triethylamine in an inactive solvent-at a temperature of 5 C to 120 C to obtain the compound -., Z Cl `
~ CONHCH=C < (V) ~O-Y~
X ',.
wherein Y~ represents methyl group, an alkylcarbonyl group where the alkyl group has from 1 to 12 carbon atoms and may be substituted by one or more halogen atoms3 a lower alkoxy carbonyl group, a lower alkyl amino carbonyl group, and X and Z are defined as above.
The alkyl halide is~ for example7 methyl iodide, ethyl iodide or propyl chlorine. The acyl chloride where alkyl group may be substituted halogen atoms is, for example, acetyl chloride, chloroacetylchloride, dichloroacetyl chloride, propionyl chloride, butyryl chloride, isobutyryl . . - . , ~ ~ ; :
- ; . ~

'.~V~
chloride or lauroyl chloride. The alkoxy carbonyl chloride is, for example, methyl chloroformate, ethyl chloroformate or propyl chloroformate. The ;
alkyl isocyanate iS9 for example, methyl isocyanate or propyl isocyanate.
The compound of the formula (IV) is reacted with equivalent of an alkali metal hydroxide in water at room temperature to obtain the formula z /Cl \ CONHCH=C
~ \Cl ~VI) X . '.
wherein Y" represents alkali metal such as sodium atom or potassium atom.
The alkali metal hydroxide is, for example, sodium hydroxide or potassium hydroxide.
The compound of the formula (IV) is reacted with equivalent of a metal halide except alkali metal halide, a metal acetate or a metal sulfate in the presence of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in water at room temperature to obtain the formuL~

CONHCH=C
~ (VII) wherein Y"~ represents metal atom except alkali metal atom and n represents 1 or 2.
The metal halide is, for example, zinc chloride or manganous chloride. The metal acetate is~ for example, zinc acetate or copper (II) acetate. The metal sulfate is~ for example~ copper sulfate.
Example 1.
Preparation of N~ -dichlorovinyl) salicylamide (Compound No. 1):
. , , The mixture of 27.4 g (0.2 mole) of salicylamide and 32.45 g (0.22 mole) of chloral was heated at 90 -100 C for 5 hours. The reaction ~. . . . ,, .. , . , ,., . , . ~.................... , j ..
., : , . , , ~ , , . , , " : .

. .. . . . ..

- ~ ~3~

product was washed with water and dried. Fifty-six point nine ~56.9) g of chloralsalicylamide (white crystals, m.p. 132-133C) were obtained.
Twenty eight point five (28.5) g (0.1 mole~ of chloralsalicylamide were mixed with 150 ml of acetic acid. Then 26 g (0.4 mole) of zinc powder were added to this solution under agitation below 50 C. After agitation was continued for 30 minutes at 70 -80 C, the reaction mixture was cooled at room temperature and filtrated. Water was added to the filtrate to precipitate *he crystals of the reaction product. The crystals were separated by filtrat-ion, washed with water and dried.
The yields of N-(~,~-dichlorovinyl) salicylamide (white crystals, m.p. 187 -189 C) were 15.1 g (70%).
Analysis of elements:
Calculated; C: 46.58%, H: 3.04%, N: 6.o4%
Found ; C: 46-57%, H: 2.87%, N: 6.22%
as C9 H7 N 2 C12 Example 2.
Preparation of N-(2~,2~-dichlorovinyl)-5-chlorosalicylamide (Compound No. 2) Thirty (30) g (0.09 mol) of N-(l~-h~droxy-2~,2',2'-trichloroethyl~
-5-chlorosalicylamide were dissolved in 150 ml of acetic acid. Nine point two (9.2) g (0.14 mol) of zinc powder were added into the solution under stirring at the temperature from 20 C to 40 C and the reaction was continued for 4 hours at the same temperature. The temperature was finally raised at 80 C and then excess zinc was removed by filtration. The filtrate was cooled to obtain 28g of crystals of N-(2l,2~-dichlorovinyl)-5-chloro- :
salicylamide was obtained. Melting point of it was 208 C-210 C. ~;
Elemental analysis for C9H6C13N02 Calculation: C: 40.56%, H: 2.27%, N: 5026%
Found : C: 40.37%, H: 2.23%, N: 5.65%

~ 9 -.:
: ~ :.,:.

xample 3.
Preparation of O-acetyl-N-(2,2-dichlorovinyl) salicylamide (Compound No. 6) -One hundred and fifty ~150) g (o.65 mol) of N-(2,2-dichlorovinyl) salicylamide was suspended into 450 ml of benzene. Two hundred (200) g (1.95 mol) of acetic anhydride was added into the suspension with stirring.
After 10 g (0.13 mol) of pyridine was added dropwise to the solution at 30 C - 40 C, the mixture was refluxed for 5 hours. After cooling, the reaction mixture was washed with water and an aqueous solution of 5%-sodium hydrogencarbonate, and again with water.
Then the reaction mixture was condensed under the reduced pr0s-sure to obtain a solid matter. The solid matter was recrystallized from -cyclohexane. One hundred and seventy (170) g of 0-acetyl-N-(2,2-dichloro- `
vinyl) salicylamide, m.p. 91-92 C, was obtained.
Elemental analysis for CllHgC12N03 Calculation: C: 48.20%, H: 3-31%3 N: 5.11%
Found : C: 48.30%, H: 3.06%, N: 5.o8%
Example 4.
, Preparation of O-methoxycarbonyl-N-(2~2-dichlorovinyl) salicylamide (Compound No. 16) Twenty (20) g (0.09 mol) of N-(2,2-dichlorovinyl) salicylamide `~
were dissolved into 100 ml of benzene.
Eight point one (8.1) g (0.09 mol~ of methyl chloroformate were added to the solution with stirring. After 9 g (0.09 mol) of triethyl-amine were added dropwise under 10 C the mixture was reacted for 3 hours at the room temperature and refluxed for 30 minutes to complete the reaction.
; After cooling, the reaction mixture was washed with water, an aqueous solution of 5%-sodium hydrogencarbonate, and finally with water to obtain the neutral reaction mixture. The neutral reaction mixture was concentrated - 10 - , under reduced pressure to obtain a solid matter. The solid matter was recrystallized from methanol. Twenty two point five (22.5) g of 0-(Nl-methoxy carbamoyl)-N-(2,2-dichlorovinyl)salicylamide, m.p. 72-73 C, was obtained.
Elemental analysis for CllH9C12N0 Calculation: C: 45.54%, H: 3.13%, N: 4.83%
Found : C: 45.30%, H: 3.10%, N: 4.61%
Example 5.
Preparation of 0-~N'-methylcarbamoyl)-N-(2,2-dichlorovinyl) salicylamide (Compound No. 19) Twelve (12) g (0.05 mol) of (N-(2,2-dichlorovinyl) salicylamide were dissolved in 100 ml of benzene and 4 g (0.07 mol) of methyl isocyanate were added with stirring at below 10C. S.LX point six ~6.6) g (0.07 mol) -of triethylamine were added dropwise to the solution. The mixture was reacted for 3 hours at room temperature and refluxed for 30 minutes. The reaction mixture was cooled and washed with water, then an aqueous solution of 5~-sodium hydrocarbonate and finally water to obtain the neutral reaction mixture. The neutral reaction mixture was concentrated to obtain a solid matter under the reduced pressure. The solid matter was recrystallized from methanol. Thirteen point five (13.5) g of 0-(N'-methylcarbamoyl)-N-(2,2-dichlorovinyl) salicylamide (m.p. 98-101 C) were obtalned.
Elemental analysis for CllHloC12N203 Calculated: C: 45.70%, H: 3.49%, N: 9.69% - i Found : C: 45.81%, H: 3.45%, N: 9.60%
Example 6.
Preparation of 0-acetyl-N-(2',2'-dichlorovinyl)-5-chlorosalicyl-amide (Compound No. 7) Five (5) g (0.018 mol) of N-(2',2'-dichlorovinyl)-5-chloro-salicylamide were dissolved in 30 ml of benzene, and 2.2g (0.022 mol) of - 11 - ;

acetic anhydride and a few drops of pyridine were added with stirring. The mixture was stirred for 4 hours at 50 C. The reaction mixture was washed with water, an aqueous solution of 5%-sodium hydrocarbonate and water~
successively. The reaction mixture was concentrated under the reduced pressure to obtain a solid matter. The so~lid matter was recrystalli~ed from benzene. Four (4) g of 0-acetyl-N-(2~,2'-dichlorovinyl3-5-chloro-salicylamide, m.p. 98-100 C, were obtained. -Elemental analysis for CllH7C13N0 Calculation: C: 42.82%, H: 2.61%, N: 4.54%
Found : C: 42-65~, H: 2.70%, N: 4.41%
Example 7.
The preparation of sodium salt of N-(~,~-dichlorovinyl) sali-cylamide (Compound No. 20): -Two hundred thirty two (232) g (1 mol) of N-(~,~-dichlorovinyl) salicylamide were added under agitation to the aqueous solution wherein 43g (1 mol ) of 93%-sodium hydroxide were dissolved in 300 ml of water and `;
then agitated at room temperature for 3 hours.
Water was evaporated under reduced pressure. The yields of sodium salt of N-(~,~-dichlorovinyl) salicylamide was 255g. The sodium salt was pale light brown crystals and decomposed at 243C.
Analysis of elements:
Calculated: C: 42.55%, H: 2.38%, N: 5-51%
Found : C: 42.32%, H: 2.40%, N: 5.40%
as C9H6C12N02Na The following metallic salts were prepared by the same method as the sodium salts.

' .. .. ... . , : . .. , : , . . .. ~ .

Table 2 ~ompo~nd No. Metallic Salt Uelt ng Point Appearance 23 Potassium salt 243 Pale llght brown (]Decomposition) crystals ..

24 Zinc salt 158-160 White crystals . __ _ "~ , ___ .. ,.. _ 26 Cupric salt 135 Pale green _ _ (Decomposition) crystals 28 Manganous salt 191 Yellow grey _ (Decomposition) ~r~

Example 8.
The preparation of sodium salt of N-(2~2~-dichlorovinyl)-5-chlorosalicylamide (Compound No. 21) Five (5) g (0.019 mol) of N-(2~,2~-dichlorovinyl)-5-chloro-salicylamide were added under agitation to the aqueous solution wherein 0.7 g (0.019 mol) of 93%-sodium hydroxide were dissolved in 30 ml of water and then agitated at room temperature for 1 hour.
Water was evaporated under reduced pressure. The yields of sodium salt of N-(2~,2'-dichlorovinyl)-5-chlorosalicylamide was 5.4. The sodium salt was pale light brown crystals and melting point of it was over 280C.
Elemental analysis as C9H5C13N02Na5 Calculated: C: 37.47%, H: 1.75%, N: 4.86%
Found : C: 37.33%, H: 1.73% N: 4.79%
Example 9.
The compounds shown in Table 3 were prepared.

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A preferred compound is a compound of the formula ~1] where X ;
represents hydrogen atom, chlorine atom, bromine atom, methyl group or nitro group, Y represents hydrogen atom, methyl atom, an alkylcarbonyl group where alkyl has from 1 to 3 carbon atoms or a metal atom of which the valence is 1 or 2, Z represents hydrogen atom or chlorine atom and n represents 1 or 2. The most preferred compound is a compound in the formula [1] where represents hydrogen atom~ chlorine atom, bromine atom~ methyl group or nitro group, Y represents an alkylcarbonyl group where alkyl has from 1 to 3 carbon atoms, Z represents hydrogen atom or chlorine atom and n is 1.
The methods of the present invention for killing bacteria and fungi which cause plant diseases comprise applying to said bacteria and fungi a bacteria and fungi a bactericidally and fungicidally effective amount of the compound.
The compounds~ themselves, may be directly applied to said bacteria and fungi. However, in general one or more compounds are mixed with suitable adjuvant and formed into bactericidal and fungicidal compositions ;~
such as an emulsifiable concentration, a wettable powder, a dust, granules and pellets.
The agricultural and horticultural bactericide and fungicide ~0 of the present invention comprise a bactericidally effective amount of the compound of formula [I] and adjuvants for an agricultural chemicals. The preferred bactericide and fungicide comprise 1-95% by weight of the compound and 99-5% by weight of said adjuvants.
The adjuvants used in the present invention include all the substances other than effective compounds, which substances are added so as to enhance, maintain and increase the effect of power of the active compound or to dilute the concentration of the active compound.
The adjuvants are, for example, various kinds of carriers and surface active agents. The carriers in the form of solid are, for example, .. - . . . . . , i . . ......................... . .

. . ~ . . .. . . . . ~ .

clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate or the like.
The carrier in the form of liquid are benzene, alcohols, acetone, xylene, methylnaphthalene, cyclohexanone, dimethylformamide, dimethylsulfoxide, animal and vegetable oils, fatty acids and their esters, various kinds of surfactants, etc.
It is also possible to enhance the effect by appropriately mixing the active compounds or the mixture of the compounds and carriers with auxiliary substances usually employed for agricultural preparations, such as an extending agent, an emulsifier, a wetting agent and a binding agent.
The present compounds may also be used in admixture with other agricultural fungicides, insecticides, herbicides, plant growth regulators, soil modifying agents or fertilizers.
When the composition in the form of a wettable powder, a water soluble concentration or an emulsifiable concentration is practically applied to bacteria or fungi which harms agricultural and horticultural plants or crops, it may preferably be diluted with water so that the present compounds is contained in an amount of about 30-8000 ppm, preferably 50-2000 ppm.
In the form of a dust, pellets or granules, the present compound is used in an amount of 0.03 kg - 1 kg / 10 ares. For the soil treatment, preferably, the present compound is used in the form of a dust, granules or pellets and the compound preferably is applied in an amount of 0.05 kg - 2 kg / 10 ares.
When the compound is used for seed treatment, the seeds are dipped into the diluted solution in which the compound is contained in an amount of about 0.05 - 1.0% or seeds are dressed with a dust in which the compound is contained. The amount of the compound dressed is 0.1 - 5% of seed weight.
The representative plant diseases which are prevented by the application of the present compound are as follows:

, (1) Foliar treatment Rice blast, the name of one of the most serious diseases of rice plant, caused by the fungus Piricularia oryzae, sheath blight of rice plant caused by Corticium sasakii, etc. downy mildew of cucumber caused by Pseudoperonospora cubensis, powdery mildew of cucumber caused by Sphaerotheca fuliginea, gray mold of tomato caused by Botrxtis cinerea, cucumber scab caused by Cladosporium cucumerinum, anthracnose of cucumber caused by Colletotrichum la~enarium, etc. -~ -Fruit crop diseases; black spot of Japanese pear caused by Alternaria kikuchiana~ ripe rot ofgrape caused by Glomerella cingulata, ; . - -- ., brown rot of peach caused by Sclerotinia laxa~ melanose of citrus tree ; j~
caused by Diaporthe citoi, common green mold of citrus tree caused by Penicillium digitatum, penicillium rot of citrus tree caused by Penicillium fructigenum, bacterial leaf blight of rice plant caused by Xanthomonas oryzae, canker of citrus tree caused by Xanthomonas citri, bacterial spot of cucumber caused by Pseudomonas lachr~mans, etc.
(2) Soil treatment Damping-off of cucumber, the name of a soil borne disease of cucumber, caused by the fungus Pellicularia filamentosa, fusarium wilt of cucumber caused by Fusarium oxysporum f, cucumerinum, southern blight of pepper caused by Corticium rolfsii, verticilium wilt of eggplant caused by Verticillium albo-atrum, club roo~ of cabbage caused by brassicae, etc.
(3) Seed treatment Seedling blight of rice plant caused by Pellicularia filamentosa and Fusarium moni iforme, cucumber scab caused by Cladosporium cucumerinum~
damping-off of cucumber caused by Pellicularia filamentosa, etc.
The present invention will be explained more in de~ail by ex~mples.
Parts used in composition Examples are parts by weight.

. :

.~3~
Composition Example 1~ Dust Three (3) parts of N-~2',2'-dichlorovinyl)-salicylamide (compound No. 1), 48 parts of talc and 49 parts of clay were uniformly mixed and crushed to give a dust. The dust was sprayed over crops and plants, applied to soil and mixed with seeds and/or tubers.
Composition Example 2. Wettable powder Eight ~80) parts of 0-acetyl-N-(2t,2~-dichlorovinyl)-salicyla-mide tcompound No. 6), 15 parts of kaolin, 3 parts of sodium alkylben~ene-sulfonate and 2 parts of sodium polyacrylic acid were uniformly mixed and crushed to give a wettable powder. The wettable powder was suspended into ! '' water and used as spraying liquid.
Composition Example 3. Granules Three (3) parts of sodium salt of N-(2~,2'-dichlorovinyl)-salicylamide (compound No. 20), 35 parts of diatomaceous earth, 23 parts of bentonite, 37 parts of talc and 2 parts of disintegrator were uniformly mixed and 18 parts of water added. The mixture was blended to become uniformly wet and formed into granules by means of a granulating machine having a sieve of o.6 mm to 1.0 mm and the wet granules were dried to obtain dry granules. The granules were sprayed to crops and plants and applied to soil.
Composition Example 4. Emulsifiable concentration Twenty ~20) parts of 0-isobutoxycarbonyl-N-(2',2~-dichlorovinyl) salicylamide (compound No. 18) were dissolved into 63 parts of xylene.
Seventeen (17) parts of the condensation products of alkylphenol and ethylene oxide were dissolved in the resultant solution to obtain an emulsifiable concentration. The concentration was diluted with water to form emulsion and the emulsion was used as spraying liquid. `
Then the effect of the present invention will now be explained by the following experimental examples.

,:

Experimental Example 1.
Exterminating test on seedling blight of rice plant.
Nursery boxes (60 x 30 x 3 cm) were filled with soil which were contaminated with pathogen (Fusarium sp. and Rhizoctonia sp.3 The dust in which the present compound was contained in a ratio of 5% by weight was added in the box in a ratio of 5 grams per box and mixed well with soil.
Thereafter, seeds of rice plant (variety: Nihonbare~ were sowed in drills at a rate of 0.3 liter per box and grown up in a lighting chamber at 17 C.
After 7 days from the sowing, the boxes were carried out in the field.
Furthermore, 10 days thereafter the observations were made. Four percent (4%) dust of 3-hydroxy-5-methyl isoxazol (hereinafter referred to as hydroxyisoxazol) on the market was used as a control and tested by the same ethod. The test results are shown in Table 2 with a "percentage of healthy ~;
seedlings". The flpercentage of healthy seedlings" was calculated as follows:

Percentage of Number of healthy seedlings healthy seedlings Number of observed seedlings X 100 . .
Table 2.
.
Amount of Percentage of 20Test compoundstreatment healthy seedlings Phytotoxicity (Number) (a.i.)~ (%) 0.25g/box 80.2 Nil 2 ~ 72-4 Nil 3 " 65-3 Nil 4 ~' 76.6 Nil " 62.o Nil

6 " 83.2 Nil ? 70.2 Nil 8 " 71-3 Nil 9 " 69.8 Nil " 72.1 Nil 11 " 68.7 Nil Table 2 cont~d Amount of Percentage of Test compounds treatment healthy seedlings Phytotoxicity (Number) (a.i.) 7~ (%) "

12 0.25g/box 65.o Nil 13 " 62.0 Nil 14 70.8 Nil 70.2 Nil 16 " 71-5 Nil 17 n 68.3 Nil 18 " 72.1 Nil 19 ~l 64-7 Nil " 74-9 Nil 21 " 70.7 Nil ~ -22 ~ 69.9 N;l 23 n 70.8 Nil 24 " 71-3 Nil ; -28 '~ 73.0 Nil 29 '~ 69.8 Nil n 71-4 Nil ',~
31 n 70.2 Nil 32 " 69.8 Nil 33 " 70.4 Nil 34 " 72.2 Nil ~ -n 71.2 Nil Control (Hydroxyisoxa~ol 0.20g/box 70.6 Nil 4% dust~
Untreated 34.2 ~Active Ingredient ~ . ,.
Experimental _xample 2 ~' -,,.
Exterminating test on cucumber scab.
The cucumber seeds (variety: Sagamihanjiro) were sown in pots (diamèter 18 cm). Eighty percent (80%) wettable powder (contents of active ~-compound: 80%) of the present invention was diluted with water to obtain a suspension. The suspension was sprayed over the cucumber seedlings of the .. ~ . . .

c~

stage of 3-4 leaves in an amount of 20 ml per pot. After 24 hours, these pots were inoculated by means of spray of spore suspension of Cladospo um cucumerinum. The thus-inoculated seedlings were placed in a moist chamber .
at 20 C for 24 hours. The pots were continuously kept in a greenhouse at 20 C. The following wettable powders on the market were used as controls.
Control (1) 70% wettable powder of 1,2-bis (3-methoxy carbonyl-2-thioureid) benzene (hereinafter referred to as "thiophanate methyl") on the market.
Control (2) 75% wettable powder of ethylene bis (dithiocarbamic acid) ;
manganese (hereinafter referred to as "maneb"3 on the market.
After 5 days of the inoculation, degrees attacked by the pathogen were observed and the results were shown in Table 3 with an "Infected Index".
The l'Infected Index" was calculated as follows:

Infected Index = (Ax3) + (Bx2) ~ (Cxl) (A+B~C+D) x 3 A : Number of leaves which were killed by hard attack B ~ Number of leaves severely attacked C ~ Number of leaves slightly attacked D : Number of healthy leaves Table 3.
Test compounds Concentration Infected Index Phytotoxicity (Number) (ppm) 1 500 9-4 Nil 2 " 11.0 Nil " 10.7 Nil .!
6 " 8.2 Nil 11 " 10.1 Nil 14 " 7-9 Nil " 8.9 Nil 13-7 Nil Table 3 cont'd Test compoundsConcentration Infected Index Phytotoxicity (Number) (ppm) 500 12.1 Nil Control (1) (Thiophanatemethyl 500 14.6 Nil 70% wettable powder) Control (2) (Maneb 75% wettable 1~500 12.5 Nil powder3 Untreated - 91.0 ~xperimental Example 3.
Exterminating test on damping-off of cucumber.
The pots (diameter, 12 cm) were filled with field soil and then soil infected by adding Rhizoctonia solani in an amount of 5 grams per pot uniformly into the pots. Thereafter, 10 seeds of cucumber (variety:
Azumamidori) were sown in each pot.
Eighty percent (80%) wettable powder of the present invention was diluted with water to obtain a suspension and each pot was drenched with the suspension in an amount of 50 milliliters. Then, the pots were transferred to the greenhouse. Fifty percent (50~) wettable powder of pentachloronitro benzene (hereinafter referred to as PCNB) on the market was used as a control and tested by the same method. After 10 days of the inoculation~ `
degrees attacked by the pathogen were observed and a "Percentage of healthy seedlings" was calculated. The "Percentage of healthy seedlings" was calculated as follows:
Number of healthy seedlings in treated pot Percentage of healthy seedlings - __ __ __ __ __ __ __ x 100 Number of germination in untreated and uninfected pot The results were shown in Table 4.
,:

,..... . . - .

.. . ..

Table 4.
:
~' compounds ConcentrationPercentage of Phytotoxicity (Number) (ppm)healthy seedlings (%) 1 1,000 100 Nil 2 " 95 Nil 3 " 70 Nil 4 " 90 Nil " 80 Nil 6 " 100 Nil 8 ~ 75 Nil 9 " 90 Nil ~ 100 Nil 11 " 100 Nil 12 " 70 Nil 13 ~' 100 Nil 14 tl 95 Nil ~ . -" 60 Nil 16 " 100 Nil ~:
17 ~' . 85 Nil , - :
18 ~' 100 Nil 19 ~' 65 Nil " 100 Nil 21 " 80 Nil 22 " 75 Nil 23 ~ 100 Nil 24 " 100 Nil ~' 80 Nil 26 ~' 100 Nil ~.
27 " 85 Nil 28 ~ 100 Nil .

29 " 55 Nil " 70 Nil 31 ~ 85 Nil 32 ~ 75 Nil 33 " 90 Nil 34 " 65 Nil " 95 Nil : 27 Table ~ co~t'd Percentage of compoundsConcentra~ion healthy seedlings Phytotoxicity (Number) ~ppm) (%) Control (PCNB 50~ 1~000 45 Nil wettable powder) Untreated - 0 (inoculated) Untreated - 100 (non-inoculated) Experimental Example 4 Exterminating test on Fusarium wilt of cucumber Twenty (20) grams of infected soil was added uniformly into each pot which was filled with steam sterilized field soil, then 18 seeds of cucumber (variety: Tokiwa~ibai) were sowed in each pot. Eighty percent (80%) wettable powder of the present invention was diluted with water to obtain a suspension, and each pot was drenched with the suspension in an amount of 100 ml. Fifty percent (50%) wettable powder of methyl-l-(butylcarbamoyl) 2-benzimidazol carbamate (hereinafter referred to as Benlate) on the market was used as a control and tested by the same method.
After two weeks of planting, degrees attacked by the pathogen was observed and a ~percentage of healthy seedlings~ was calculated as follows:

Number of healthy seedlings in treated pot Percentage of _ healthy seedlings - - -Number of emerged seedlings in untreated and uninfected pot The results are shown in Table 5.

' , ' ' ' ~ ' '' '-Table 5.
Percentage of Test CompoundsConcentration healthy seedlings Phytotoxicity (Number) (ppm) (%) 1 500 73.0 Nil 2 " 68.1 Nil 3 " 62.4 Nil " 68.7 Nil " 58.9 Nil 6 " 83.0 Nil

7 " 76-5 Nil

8 " 73-3 Nil

9 ~' 75.0 Nil ~' 70.0 Nil ~ 65.5 Nil 12 Nil 13 " 70-5 Nil 14 " 62.8 Nil " 51.2 Nil 16 " 38.2 Nil 17 " 47-5 Nil 18 " 42.0 Nil 19 " 38.o Nil " 45'5 Nil 21 'l 46.o Nil 22 " 48.o Nil 23 " 59-5 Nil 24 " 47-0 Nil " 49-5 Nil 26 ~ 58.o Nil 27 ~ 58.o Nil 28 " Nil 29 " 57-5 Nil ~ 58.o Nil 31 ~ 46.o Nil 32 n 73-0 Nil 33 " 48.o Nil 34 " 60.0 Nil " 79.0 Nil Table 5 cont'd Percentage of Test CompoundsConcentration healthy seedlings Phytotoxicity (Number) (ppm) ~%) Control (Benlate 50% 500 45-0 Nil wettable powder) Untreated - O -Experimental Example 5 Exterminating test on gray mold of tomato The seedlings of kidney beans (variety: Orient) of 5-6 leaves stage were employed in this test. Eighty percent (80%) wettable powder of the present invention was diluted with water and sprayed over the seedlings in an amount of 10 ml per pot. The leaves were cut from the plant at 24 hours after spraying, and placed in the petri dishes (12 cm in diameter).
Thereafter disks (5 mm in diameter) were cut with a cork borer from potato-dextrose agar on which the pathogen (botrytis cinerea) was cultured. The disks were placed on the leaves. The dishes were placed in such a moistural condition as to cause the pathogen to propagate. Thiophanate methyl 70%
wettable powder on the market was used as a control and tested by the same method.
After forty eight ~48) hours after inoculation, diameters of the lesions were observed, and an ~Effect Index" was calculated as follows:

Lesion diameter in treated leaves Effect (1- ----- ) x 100 Index Lesion diameter in untreated leaves The results are shown in Table 6.

Table 6 ` ~

; Test CompoundConcentration Effect Phytotoxicity (Number) (ppm) Index 1 1,000 84 Nil 2 " 79 Nil 6 " 75 Nil f ' .. . .
" 88 Nil 11 ~' 81 Nil " 85 Nil 21 " 80 Nil Control (Thiophanate-methyl 70~ 500 82 Nil wettable powder) Untreated - 0 ' .
Experimental Example 6 Exterminating test on citrus canker.
4-year-old summer orange seedlings, planted in unglazed pots having a diameter of 20 cm~ were employed in this test. Eighty percent ~-80%) wettable powder of the present invention was diluted with water, and sprayed over the seedlings in an amount of 50 ml per pot. The leaves of the seedlings -were inoculated anthomonas citri by means of a needle. After the inoculation, the seedlines were maintained in a moist chamber at 25C for 24 hours. Then the pots were transferred into the greenhouse. Streptomycin 20~ wettable powder was used as a control, and tested by the same method. A~ter 2 weeks after the inoculation, degrees of disease attack were observed3 and an ~Effect Index" was calculated as follows:
:
Effect Attack rate in treated pot Index (1 Attack rate in untreated pot ) x 100 where Number of leaves under slight attack x 1 Attack +Number of leaves under medium attack x 2 rate = +Number of leaves under severe attack x 3 Total number of leaves tested x 3 .
.. ..

Z~ 3 The results are shown in Table 7.
Table 7 Test compoundsConcentration Effect Index Phytotoxicity (Number) (ppm) 1 1,000 95.8 Nil 2 " 99.3 Nil 3 " 81.0 Nil ~ 5 " 98.2 Nil ; 6 " 96.1 Nil 13 67-3 Nil 14 " 73.2 Nil 17 n 68.3 Nil 21 " Nil 22 " 49.8 Nil 23 ~ 41-5 Nil " 80.6 Nil 26 " 47.5 Nil 28 It 73-6 Nil 29 ~- 56.2 ~il Control ' (Streptomycin 20% 200 28.7 Nil wettable powder) Untreated - O

Experimental Example 7 Exterminating test for seed treatment.
Cucumber seeds (variety: Oyashima) were dipped in the spores suspension of Cladospor _m cucumerinum and dried. After 1 day, the seeds were dressed with 80% wettable powder of the present invention. On the other hand3 other seeds were dipped in the solution of 80% wettable powder of the present invention. Five (5~ seeds treated by either dressing or dipping were placed on each potato dextrose agar plate. After 10 days after the treatm~e~t, degrees attacked by the pathogen were observed and the results were shown with an ~Effective Index~'. ;

:.

:~;
An ~Effective Index" was calc~llated as follows:
~` :
Number of diseased seeds in untreated plot Eff ti e -Number of diseased seeds in treated plot Index ~~ ~ ~ ~ X 100 Number of diseased seeds in untreated plot The results are shown in Table 8.
Table 8 ' Tested Gompounds Method ofConcentration (and Effective Phytoto-(Number) treatmentdipped time) Index xicity 1 dressed 1% 87 Nil ; 6 " ~ 95 Nil ~ " 9 Nil 1 dipped5,000 ppm (30 min.) 69 Nil 6 " " " 88 Nil ~ " " 81 Nil Untreated - - 0 Nil

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An agricultural and horticultural bactericide and fungicide com-prising a bactericidally and fungicidallly effective amount of the compound respresented by the formula [I]

where X represents hydrogen atom, chlorine atom, bromine atom, methyl group or nitro group, Y represents hydrogen atom, methyl group, an alkylcarbonyl group where the alkyl group has from 1 to 12 carbon atoms, and may be sub-stituted by one or more halogen atoms, a lower alkoxy carbonyl group, a lower alkylamino carbonyl group or a metal atom of which the valence is 1 or 2, Z
represents hydrogen atom or chlorine atom and n represents 1 or 2 and adju-vants for an agricultural chemical.

2. The bactericide and fungicide according to claim 1 wherein, in said formula, the alkyl group in said alkylcarbonyl group has from 1 to 3 carbon atoms, the lower alkoxy in said lower alkoxy carbonyl group has from 1 to 4 carbon atoms, and said metal atom is selected from the group consisting of sodium, potassium, zinc and manganese.

3. A method for killing the bacteria and fungi which harm plants comprising applying thereto a bactericidally and fungicidally effective amount of a compound of the formula [I]

where X represents hydrogen atom, chlorine atom, bromine atom, methyl group or nitro group, Y represents hydrogen atom, methyl group, an alkylcarbonyl group where the alkyl group has from 1 to 12 carbon atoms, and may be substi-tuted by one or more halogen atoms, a lower alkoxy carbonyl group, a lower alkylamino carbonyl group or a metal atom of which the valence is 1 or 2, Z
represents hydrogen atom or chlorine atom and n represents 1 or 2.

4. The method according to claim 3 wherein, in said formula, the alkyl group in said alkylcarbonyl group has from 1 to 3 carbon atoms, the lower alkoxy in said lower alkoxy carbonyl group has from 1 to 4 carbon atoms, and said metal atom is selected from the group consisting of sodium, potassium, zinc and manganese.

5. The bactericide and fungicide according to claim 1 wherein X, Y
and Z represent hydrogen atoms, and n represents 1.

6. The bactericide and fungicide according to claim 1 wherein X and Z
represent hydrogen atoms, Y represents methylcarbonyl, and n represents 1.

7. The bactericide and fungicide according to claim 1 wherein X and Z represents hydrogen atoms, Y represents ethylcarbonyl, and n represents 1.

8. The method according to claim 3 wherein X, Y and Z represent hydrogen atoms, and n represents 1.

9. The method according to claim 3 wherein X and Z represent hydrogen atoms, Y represents methylcarbonyl, and n represents 1.

10. The method according to claim 3 wherein X and Z represent hydrogen atoms, Y represents ethylcarbonyl and n represents 1.