Note: Descriptions are shown in the official language in which they were submitted.
~'73~
This inven-tion rela-tes to an agricultural fungicideO
A wide varie-ty of agricultural fungicides have been
developed, bu-t some of them are not practiced because they
cause ecological pollu-tionO
We have conducted intensi~re stud.ies to find an
: agricultural fungicide ~hich possesses superior fungicidal
effect but has low toxicity and have fcund that a certain
urazole derivative has excellent fungicidal activityO
Accordingly, this invention provides a novel
agricul.tural fungicide which comprises as active ingredient
a l,2-substituted-4-~57dichlorophenyl) urazole represented
by the general formula:
X /.C~ "
R2
Y C~
wherein RI and R2 may be the same or different and represen-t
an alkyl, an alkenyl, an alki ~l, an aryl which ma~ have at
least one substituent, an acyl, alkylcarbamoyl, an alkoxycarbonyl,
~h/~carbo~
an alkylthiocarbamoyl and an (alkylthio) thiccarbamoyl and
they may be taken together to form an alkylene having 3 to 8
carbon atoms which may have branched methyl, and X and Y may
be the same or different and represent oxygen and sulfur~
It has already been found that some of l,2,4-substituted
urazole derivatives have fungicidal, herbicidal and insecticida]
activitiesO ~ompounds represented by the above general formula
are novel and possesses excellent fungicidal activity against
a wide variety of plant diseases but are nonpathogenic against
~. : :
- 2 -
'~ '
.. . .. .... . . ; ~ . . -
. . , . - . ..
3~
the host plant and have no or little toxicity agains-t humans
and fishesO
The fungicide according to this invention is especially
effective against rice sheath bl~ght disease, Botry-tis gray
mold d.isease, rice brown spot disease, Sclero-tinia rot and
Alternaria leaf spot and, in some cases, two or more diseases
are prevented simultaneouslyO
' ~he compound which is sui-table for this invention is
prepared through various routesO
Route A
A salt of ~-(3',5'-dichlorophenyl~ urazole is reacted
with an alkyl halide in a solvent, such as dimethylformamide,
alcohol and ace-tone at from room to an ele,~vated tempera-ture
for a few hours to produce -the desired productO -'
/CR
R - IN - - N
R ~
._. .
M - N - ~ // \\
I N -(/ \)
M ~ N - 11 ~ \RX ~CR
0CR \~ R - N
M - N ~
o 1 \CR CR
l I N - ~ ~\
' O \c,e .
wherein R and Rl ray be the same or different and represent
. ~ :
. .
,
~ '
~'7;~
an alkyl, an elkenyl, an alkinyl 9 an acyl, an alkoxycarbonyl
and an alkoxythiocarbonyl and M represents an alkali metal,
an al.kaline eRrth metal and NH4- and X represents a halogenO
By varying the molar propor-tion of the reactan-ts
and type of alk~l halide, monosubstituted and disubs-tituted
deriva-tives and disubstituted derivative containing different
substituents are preparedO
Route B
.....
In the presence of a solven-t, such as dimethylformamide,
acetone and tetrahydrofuran, 4-(3,5-dichlorophenyl) urazole
is reacted with an isocyanate or a thioisocyanate in the
presence of a basic catalys-t such as triethylamine and pyridine
at from room to an elevated temperature for a several hours to
prepare l-mono- or l,2-di-alkylcarbamoyl (or alkylthiocarbamoyl)
derivatives.
C~Xl ~ R~CXl ~ ` N ~ C~
\ 2RCNXl Oc,e
RCNXl
OC~
RHNCXl - IN ~ - N i~
RH~CXl --~
O\C~ ' -'-
wherein R represents an alkyl and Xlrepresents oxygen or
sulfur atomO
As in Route A, mono- or di-substituted derivative is
selectlvely prepared by varying the propor-tion of the reactantsO
~ 4 -
~ 7~
Route C
A sol.ution of 1,2-substituted-4-(3',5'-dichlorophenyl)
urazole in a solvent, such as xylene and cumene is -treated
with phosphorus pentasulfide under reflux for a few hours to
: 5 produce mono- or di-thio derivativeO
,C~ S C~
N ~ P2S~ Rl-l ~ N .~j ~ P2S5 ~ Rl N \N // 3
R -N ~ J R2-N~ R2-N - / \
2 " C~ " C~ S 'C~ . -
7\'
wherein Rl and R2 have the same meanings as above.
By varying the proportion of the reactants, monothio-
or di-thio-urazole is selectively preparedO
;, Route D
, 10 ~o a solution of 1,2-substituted-1-alkoxycarbonyl
~,
hydrazine in a solvent such as benzene, -toluene and xylene
is added in small increments 3,5-dichlorophenylisocyanate in
a stoichiome-tric amount to form 1,2-substituted-1-alkoxy-
carbonyl-2-(3',5'-dichlorophenyl) hydrazine which is precipitated
by distilling off -the solvent, filtered off and dried, and
which is dissolved in an aqueous solution o~ potassium :.
hydroxide or sodium alcoholate with agitation and heating, -- .
followed by coollng and adding an acid to precipitate
1,2-substi-tu-ted-4-(3',5'-dichlorophenyl) urazoleO
:-
.
' '~
~ ~ .
" ~
:
3~
c e ,c,e
Rl-NIH ~ OCN~ `\\ Rl-N--CNH- ~
R2-N-COOR --- \ R2-N-COOR" C~
c,e
c e
> I N_,~ ~
R2-N-_ ~J
o `c~
wherein Rl and R2 have the same meanings above and R" represents
a lower alkylO
Route E
A diene compound and 4-(3 I, 5'-dichlorophenyl) urazole
are reacted in the presence of an oxidising agent such as
lead nitrate, lead acetate and N204 to effect Diels-Alder
: reaction to prepare N-3,5-dichlorophenyl--l,2,3 ? 6-tetrahydro
pyridazine l,2-dicarboxylic imide which is then hydrogenated
in a solvent such as ethylacetate, tetrahydrofuran, acetic
acid and alcohol in the presence of a catalyst such as Pd-C
and Pt20 to give the desired compoundO
" c,e 2 R2 1 ,, c,e
~N ~ \ j ~ R ~ ~ ` N ~
~ 0~ c,e R ~ I R 14 0~ C~ :~
R4
R~
R2 1 ,, c,e
_, f I N-~/i 3
R3 -I O C~
R
wherein Rl to R4 may bc the same or different and represent
hydrogen and methylD
,
``; :
Rou-te ~
~ o a solution of 1,2-subs-tituted-1-alkoxycarbonyl
hydrazine in a solvent such as benzene, toluene, x~Jlene and
cumene is added dropwise 3,5-dichlorophenyl isothiocyanate
in a stoichiometric amount to produce 1,2-subs-tituted
l-alkoxycarbon~1-2-(3',5'-dichlorophenyl thiocarbamoyl)
hydrazine and the resulting reac-tion mixture is refluxed
for from a few to ten-odd hours to obtain a desired
monothiourazole productO
R~-NH ~~~~
SCN-(
R2-N-cooR
s ",,,,,,,,,C~ c,e s, c~
R1~N-CNH~" ~\ Rl Ni NJ~
R2~N-COOR ~ R2-N -- \ =_/ ,
O C~ ,
wherein R] and R2 have the same meanings as aboveO
Dithiourazole derivatives are prepared by similar
procedures using 1,2-substituted-1-alkox~carbonyl hydrazine~
Route G
A salt of 4-(3',5'-dichlorophenyl) urazole is reac-ted :
with an alkylene dihalide in a solvent such as water, an ~:
alcohol, dimethylformamide, te-trahydrofuran and benzene at
a -temperature of from room -temperature to 200C for a half
- to a few hours with agi-tationO
~ .
7 --
~ . . . ~ . - . '
~ 7 a~95~
N / ~ ~ Xl ~ Xl
O cl~
O C~
~ N ~ ( ~
wherein A represents an alkylene of 3 to 8 carbon atoms which may
have branched methyl, Xl represents a halogen, M represents a
metal or an amine of monovalent or bivalent and X' is 2 when M
is monovalent or 1 when M is bivalent.
The preparation o~ the compound which may be used as
active ingredient according to this invention will be explained
in detail by means of the following Reference Example.
~, To a suspension of 3.2g of dipotassium salt of
4-(3', 5'-dichlorophenyl~ urazole in 20 ml of dried N,N-
dimethylformamide was added 2.9g of methyl iodide, and the
reaction mixture was heated at a temperature of 60 to 70C for
one hour with agitation. After removing N r N-dimeth~l~oxmamide
by distillation in vacuo, the mass was poured into 200 ml of
water to precipitate solid material ~hich was recrystallized
~rom ethanol to obtain ~.6g of 1,2-dimethyl-4-(3', 5'-dichloro-
phenyl) urazole, the yleld being 95%.
The melting point and elementary analysis of the
product ara given in Table 1.
., . -
'` ' ~ ' "
--8--
,
;~.g~
Re~erence ~xample 2
~ o a solutiGn of 205g of L~_(3' 95~ d.ichlorophenyl)
urazo]e and lg of triethyl.amine in lO ml O:r N,~ dimethyl-
formamide was added dropwise lolg of ethylchloroformate with
agitationO Then the reaction was continued a-t room temperature
for one hour with agitation~ The reaction mass was mixed with
water to precipi-tate crystals which were filtered and recrys-
tallized from acetone-ethano1. to ob-tain 20 3g of l-ethoxycarbonyl-
4-(3',5'-dichlorophenyl) urazole in a yield o~ 72%o
Reference Example 3
To a solution of 206g of l-methyl-4-(3',5'-dichloro-
phenyl) urazole, which had been prepared by reac-ting 4-(3',5'-
dichlorophenyl) urazole and methyl bromide in an equimolar
proportion, and loOg of trie-thylamine in lO ml of ~
dimethylformamide was added 0~8g of acetyl chloride in small
increments at room tempera-ture wi-th agitationO After
completing the addition, the reaction was effected on a
wa-ter ba-th for 2 hours with agitationO The solvent was
~; removed by distillation in vacuo and the mass was poured in ~.
w~ter -to precipitate crys-tals which were recrystallized from
e-thanol -to obtain 203g of l-me-thyl-2-acetyl-4-(3',5'-
dichlorophenyl) urazole in a yield of 76%~
ReLerence Example 4
To a solution of 205g of ~r-(31,5'-dichlorophenyl)
urazole in lO ml of N,N-dimethylformamide were added a drop
of triethylamine and, in turn, 008g of methyl isocyanate
dropwise at room temperature with agita-tionO The reac-tion
was continued for further one hour under the same conditions
and the reac-tion mixture was poured in water to precipitate
crystals which were filtered and recrystallized from
: ~ : : ~ . ,- .
~3i~
acetone-ethano:L to obtain l-methy1carbamoyl-4-(3',5'-
dichlorophenyl) urs.zole in an amount of 201g (yield being
68%)o
Reference Example 5
A solution of 207g of 1,2-dimeth-yl-4-(3',5'-
dichlorophenyl) urazole in 25 ml of xylene and 404g of
phosphorus pentasulfide were mixed. and heated under reflux
for 8 hours with agitationO After cooling and filtration,
the filtrate was condensa-ted in vacuo. ~he residue was
recrystallized from ethanol to obtain 104g of 1,2-dimethyl-
4-(3',5'-dichlorophenyl) dithiourazole (the yield being 47%~0
Reference ~xample 6
~o a solution of 106g of 1~2-dimethyl-ethoxycarbonyl
hydrazine in 25 ml of benzene was added 109g of 3,5-
dichlorophenyl isocyanate in small increments at room
temperature wi-th agitationO By removing benzene in vacuo,
there was obtained crystals of 1,2-dime-thyl-1-ethoxycarbonyl-
2-(3',5'-dichlorophenyl carbamoyl) hydrazine having a melting
poin-t of 161 - 163Co ~he elementary assay as C12H15N203CR2 was:
C(%) H(%) N(%) C~(%)
Calculation 45001 4072 13012 22015
Found 45012 ~o78 13021 22.03
~hen, the resulting product was reacted with sodium
methoxide in equimolecular amoun-t in methanol under ref]ux
for 6 hours and, after cooling, water was added to the
reaction mixture -to precipitate crystals which were filtered
and recrystallized from ethanol to obtain 1,2-dimethyl-4-
(3',5'-dichlorophenyl) urazole in an amount of loOg (the
y1eld being 37%)0
~he mel-ting point was 209 - 211C and the elementary
_ 10 -
' ~
:
3'~
Y 10 9 3 ~
C (%) ~(,~) ~T(%) C,e(%)
Calcula-tion 43082 3031 15033 25087
Found 43049 3.30 15~42 25081
Reference Example 7
Procedures similar to those of Reference EXa~ple 6
were repeated using 3,5-dichlorophenyl isothiocyana-te to ~ .
; ob-tain 1,2-dimethyl-1-ethoxycarbonyl-2-(3',5'-dichlorophenyl
-thiocarbamoyl) hydrazineO
~he mel-ting point was 147 - 149C and the elementary
assay as C12H15C~2N2S2 was:
C(/0) H(%) N(%) C~(%) S(%)
~alculation 42086 4050 12050 21~09 9~54
~ound L~2091 L~o47 12042 21013 9059
The compound was subjected -to heat treatment in cumene
under reflux for 10 hours to obtain lo8g of 1,2-dimethyl-4-
(3',5'-dichlorophenyl) mono-thiourazole (the yield being 64%)o
Reference Example 8
~o a solution of 302g of 1-ethoxycarbonyl-4-(3',5'-
dichlorophenyl) urazole in 10 ml of N,N-dimethylformamide
were added, in sequence, a drop of triethylamine and 0085g
of isopropyl isocyanate dropwise at room temperature wi-th
agi-tationO After maintaining the same conditions for one
hour, -the reaction mixture was mixed with water to precipitate
crystals which were filtered and recrystallized from ethanol
to obtain l-ethoxycarbonyl-2-(isopropyl carbamoyl)-4-(3',5'-
dichlorophenyl) urazole in an amoun-t of 3~0g, a yield of 75%0
Reference Example 9
~o a solution of 1008g of phenyl hydrazine and lOolg
of triethylamine in 60 ml of benzene was added dropwise a
: : .
. ~ ,
solu-tion of 1.0O9g of ethyl. chloroforma-te in 40 r.~1 of 'benze-ne
over 20 minutes while the mix-ture was ma.intained <~t a
temperature of from 10 to 15C with agitationO
l`he reaction was continued at room tempera-ture for one
hour with agitationO After adding water under P~gi-ta-tion,
the reaction mixture was allowed to stand until there was
phase separationO The aqueous phase containing triethylamine
hydrochloric acid sal-t which was formed in the course of the
reaction was removedO ~he organic phase was dried wi-th
anhydrous sodium sulfateO At room tempera-ture, 1808g of
3,5-dichlorophenyl isocyanate was added dropwise to the
benzene solu-tion, then the mixture was heated on a water-bath
to effect -the reactionO
~he benzene was removed ~y distillation in vacuo to
obtain an oily product which was mixed with 200 ml of a 5%
aqueous potassium hydroxide and heated under reflux for about
2 hoursO After cooling and filtra-tion, the filtrate was
mixed with concen-trated hydrochloric acid to precipita-te
crystals which were filtered and recrystallized from e-thanol
to obtain 1-phenyl-4-(3',5'-dichlorophenyl) urazole in an
amount of 2302gg a yield of 72%o
~he melting point was above 250C and the elementary
Y 14 9 3 2 2
C(%) H(%) N(%) CR(%)
Calcula-tion 52019 2082 13004 22001
: Found 52042 2087 12095 21088
A mixture of 302g of the product thus produced, 20 ml
of N,N-dimethylformamide, and 006g of po-tassium hydroxide in
5 ml of water was agitated at room temperature for 30 minutes
to give a potassium salt, -then i_O4g of methyl iodide was added
- 12 -
.
. there-to and agi-tation wa~s continued .~i-t roorn temper~ture for
one hourO Af-ter completion of the reaction, water was added
to the mixture to precipi-tate crystals which ~ere separated
and recrys-tallized from ethanol to obtain l-phenyl-2-methyl-4-
(3',5'-dichlorophenyl) urazoleO
Reference Example lO
~ o a suspension of 29g of disodium 4 (3'~5'-dichloro-
phenyl) urazole in 200 ml of dried N,N-dimethylformamide was
added 26.4g of l,4-dibromopentane and the resulting mixture
was refluxed for one hour with agi-tationO After removing
N,N-dimethylformamide in vacuo, the residue was poured in
500 ml of water to give solid material which was filtered
. and recrystallized from ethanol to obtain 2302g of l,2-
pentamethylene-4-(3',5'-dichlorophenyl) urazole1 the yield
being 74%0
; Reference Example ll
Into a suspens1on of 2085g of 4-(3',5'-dichlorophenyl)
urazole was absorbed 007g of l,3-butadiene and a solution of
607g of lead tetraacetate in lOO ml of dichloromethane was
added dropwise o~er 30 minutes to the suspension which was
maintained at a temperature of from O to 5~ by coo~ing with
agitationO ~f-ter continuing agi.tation for a fur-ther 2 hours,
the dichloromethane was distilled off at a temperature below
30C in vacuoO
. 25 ~he residue was washed, in sequence, with each 75 ml ~.
of water, OolN nitric acid, OolN aqueous sodium hydroxide and :.
. water~and recrys-tallized from ethylacetate to ob-tain N-(3',5'-
: : dichlorophenyl) l,2,3,6-tetrahydropyridazine-l,2-dicarboxylic
imide (the yield being 208g and 82%)~
~he melting point was 167 - 168~ and -the ele~en-tary
- 13 -
.
. .
Y 12 9 3 2 2
C (%) H(C!/o) N(%) C~(%)
Calculation 48034 3~04 14009 23~79
~'ound 48031 3001 14025 23082
Into a solution of 105g of the produc-t thus produced in
50 ml of ethylaceta-te was passed through hydrogen under a
normal pressure i-n the presence of 0 lg of 5% Pd-C catalyst
until no absorption of hydrogen was detected~ After removing
the catalyst by filtra-tion, the ethylace-tate was distilled off
in vacuo to obtain 1,2-pentamethylene-4-(3',5'-dichlorophenyl)
urazole in an amount of 1.4g7 a yield of 95%0
Reference Example 12
A solution of 507g of 1~2-trimethylene-4-(3',5'- ~ -
dichlorophenyl) urazole (which was prepared according to
procedures in Reference Example 10) and 404g of phosphorus
pentasulfide in 50 ml of xylene was heated under reflux for
four hours with agitationO ~he reaction mixture was allowed
to cool to precipita-te solid ma-terial which was filtered outO
The solvent was removed in vacuo and the residuè was recrys-
.
20 tallized from ethanol to obtain 1,2-trimethylene-4-(3',5'-
dichlorophenyl3 monothiourazole in an amount of 205g, a yield
of 41%o
Reference hxample 13 :.
Two grams (OoOl mole) of 3,5-dichlorophenyl iso-thiocyanate
were added in small increments to a solution of lD7g of 1,2-
pentamethylene-l-e-thoxycarbonyl hydrazine with shaking, then ~ ~ -
1,2-pentamethylene-1-ethoxycarbonyl-2-(3',5'-aichlorophenyl
thiocarbamoyl) hydrazine was instan-taneously produced in a
quantltatlve amountO ~ part of the reaction mixture was -:
sampled and the solvent was removed therefrom to precipita-te
' ` .
- 14 -
.
` ~.
'7~
crystals; then -the melti~g point ~nd e~Lemen-trlry anal~sis
thereof were as followsO
Melting poin-t: 128 1~0C
~ry analysis ~s Cls~IlgC~2N302S
C% H% ~% C~% S%
Calcul~tion 47088 5009 11017 18084 8052
Found 47085 5006 11022 18075 8~48
The reaction mixture containing the product as above
was heated under reflux for 8 hours, allowed to cool and
diluted with petroleum ether to precipita-te crystals which
were collected by filtration, washed with petroleum e-ther and
recrystallized from ethanol/benzene to obtain 205g of 1,2-
pentamethylene-4-(3',5'-dichlorophenyl) monothiourazole
` corresponding to a 77% yieldO
Reference Example 14
~ ~ I ~s~f~oc~
A ~wo grams of 3,5-dichlorophenyl ioooyanato- were added
: to a solution of 1074g of 1,2-tetramethylene-1-(ethylthio)
~?/DCclr60~ z~
t~i-ocsarbc1ny~- in 1.0 ml of benzene with shaking, then there was
observecl precipitation of crystals of the following compound:
C~
S ,~
N - C - NH
N - ,C,SC2H5 \~
Mel-ting poin-t: 147 - 149C
Elem~ntary analysis as C14H17C~2N3S3:
C% H% N% CR% S%
C~lculation 42 63 4035 10065 17098 24~39
Found 42058 4031 10062 18004 24033
~he reac-tion mixture containing the crys-tals was
tr~sated as in Reference ~xample 13 -to obtain 204g (the yield
being 65%) of 1,2-tetramethylene-4-(3',5'-dichlorophenyl)
,
5 -
:;
.- . . ... . ; . . ~
~ . . ; - ; . ~ : . :
dithiourazol ~ O
Various compounds which are suitable as activ~
ingredient for the fungicide according to this invention
are given in ~able 1~
.
` :
,
- 16 -
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Note: (l) Known ~ompoundO
(2) ~`he compound. was p:roduced by -the Reference
~xample.
(~) The ~igures in upper line are calculation and
the figures in lower line are foundO
(4) Index of Refraction
Among the compounds listed in Table 1, following
compounds are found to be preferable as active ingredient
of the fungicide accord.ing -to this invention:
~0 1-methyl-2-acetyl-4-(3',5'-dichlorophenyl) urazole~
l-methyl-2-ethyl-4-(3',5'-dichlorophenyl) urazole,
l-methyl-2-n-propyl-4-(3',5'-dichlorophenyl) urazole,
1-methyl-2-isopropyl-4-(3'~5'-dichlorophenyl) urazole,
1,2-dimethyl-4-(3 ,5'-dichlorophenyl) urazole,
1-methyl-2-phenyl-4-(3',5'-dichlorophenyl) urazole,
; 1,2-(1"-methyl trimethylene)-4-(3',5'-dichlorophenyl) urazole,
1,2-(I"-methyl tetramethylene)-4-(3',5'-dichlorophenyl) urazole
and
1,2-pentamethylene-4-(3',5'-dichlorophenyl) urazoleO
20 ~hough 1,2-substituted-4-(3',5'-dichlorophenyl) urazolederiva-tives may be applied to plant as such for purpose of
agricultural fungicide, it is convenient to use the compound
diluted with a conventional adjuvan-t in -the form of an
emulslon, a we-ttable powder or a dustO
` 25 ~he adjuvant may be one which is conventionally used
for formulatlng an agricultural ~ungicide, including a
liquid or solid carrier, an emulsifier, a dispersing agent,
~a spreader, a penetrant and a surface active agentO
~xamples of -the liquid carrier which may be used
.~ 30 according to this invention include a wide variety of
.
- _ 28 - :
.
. . : : ~ .. - . . . . . ~ :: . .
3~
solvents, ~or exa~lple, wa-ter, an alcohol such as methyl
alcohol, ethyl alcohol and ethylene glycol, a ketone such
as acetone~ methyl e-thyl ke-tone and cyclohexar~one, an
ether such as methyl ether, dioxane and cellosolve, an
aliphatic hydrocarbon such as gasoline and kerosene, an
aromatic hydrocarbon such as benzene, toluene, xylene,
solvent naphtha and methyl naph-thalene, a halogenated
hydrocarbon such as dichloromethane, trichlorobenzene and
carbon tetrachloride, an acid amide such as dimethylformamide,
an ester such as ethylacetate, butylacetate, a glyceride of
an aliphatic acid, and a nitrile such as acetonitrileO
~ xamples of the solid carrier which may be used
according to this invention include, ~or example, clay,
kaoline, bentoni-te, talc, diatomaceous earth, gypsum,
vermiculite, alumina, sulfur, white carbon and carbo~ymethyl
; celluloseO Such solid carrier may be used alone or in a
mixture o~ two or more~
Suitable surface active agents may be, for example,
a nonionic type such as a polyoxyethylene alkylaryl ether
and a polyoxyethylene sorbitol monolaurate, a cationic type
such as an alkyl dimethylbenzyl ammonium chloride and an
alkyl pyridinium chloride, an anionic type, such as an
alkyl-benzene sulfonate, lignine sulfonate and a sulfate
of a higher alcohol and an amphoteric type, such as an
alkyl dimethyl be-taine and dodecylaminoethyl glycineO
:~ Such adjuvant may be used alone or in a mixture o~
~ two or moreO
:. ~he emulsion may be prepared by formulating 10 to 50
parts by weight of an active ingredient compound, lO to ~0
parts of a solvent and 5 to 20 parts o~ a sur~ace active
, ~ .
29
.
: agen-t to form a concen-tra-te which is diluted with ~ater to
a predetermined concen-tration and applied to plant or soil
by means of, ~or exam~le, sprayO
~he wettable powder may comprise l0 to 50 par-ts by
weight of an active ingredient compound, l0 to 40 par-ts of
a solid carrier and 5 to 20 parts of a surface active
ag~ntO ~he powder may be used after diluting with water~
~ he dust may be a uniform mixture of l to 5 parts by
weight of an active compound and 95 to 99 parts of a solid
carrier~
~ he agricultural fungicide according to this invention
may be used together with one or more o-ther active ingredients
which do not adversely a~fect fungicidal activity of the
useful compound such as insecticide, mitecide and other
fungicideO
~ he fungicide according to this invention may be
applicable to foliage and soil -treatments and the effective
dosage thereof is~ in general, from 500 to 1500 ppm in case
of foliage treatmen-t and from 50g to 300g per l00 m2 in case
of soil treatmentO
I-t has been found that the agricultural fungicide
according to this invention possesses a wide fungicidal
. spectrum for preven-ting various plant diseases which are
observed on fruits, such as apple and grape, vegetables
such as tomato and cucumber, beans and rice plant including
rice shea-th blight diesease, Botrysis gray mold disease,
rice brown spot disease, Al-ternaria leaf spot and Sclerotinia
spotO It has also been found that the fungicide is effective
against -two or more diseases simultaneously and shows
extremely low toxicity against human and fish and low phytoxityO :
- 30 -
~ :
- \
This inven-tion will be explained in de-teil by means
of the following Example and Tes-t Example, however it should
be unders-tood that this invention is in no way limi-ted by
these Examples in which "part" is by weigh-t unless otherwise
specifically limitedO
Example 1 (Dust)
The following ingredients were mixed and pulverized
to obtain dust:
Compound NoO 3 3 parts
A mixture of clay and talc 97 parts
Instead of compound 3, compound ~o~ 40 was employed
to formulate dust~
~xample 2 (Wettable powder)
The following ingredients were mixed and pulverized
to prepare wettable powder:
Compound ~o. 17 20 parts
' A mixture of clay and
diatomaceous earth 75 parts
Sodium alkylbenzene sulfonate 3 parts
. 20 Polyoxyethylene nonylphenyl
ether 2 parts
Instead of compound NoO 17, compound ~o~ 42 was
employed -to formulate wettable powderO
~xample 3 (Emulsion)
The following ingredients were mixed under agitation ~:
to prepare emulsionO
Compound ~oO 34 50 parts ~:
Xylene 40 parts
Polyoxyethylene nonylphenyl e-ther 6 parts
Sodium alkylbenzene sulfonate4 parts
, ~ .
~ - 3~ ~
~'
, ... ..
~, -, . .
~ 3~
Compound NoO 34 was replaced by cornpound NoO 41 to
formulate emulsionO
Test Example 1
Preventive effect ag~inst rice sheath blight disease~
Rice plan-ts (cultivar: Kinmaze)~ which were at 5 - 6
leaf s-tage and were grown in 9 cm pots in a green house and
cut at 20 - 30 cm height, were treated with suspensions of
wettable powder of the chemicals at various concentrations
in an amount of 20 ml per pot by spray applicationO After
air drying, the plants were inoculated with pathogenic
mycelia of Pellicularia sasakii which had been cultured on
a wheat bran medium for seven da~sO
These pots were covered with cases made of polyvinyl
chloride in order to preven-t escape of hu~idity and incubation
was effected in a chamber maintained at a temperature of
from 25 to 27Co After twnety days, the rating on the
disease severity index was determinedO
On the other hand, procedures similar to the above
were repeated but no chemical was applied to the rice plantsO
; 20 Then, the preventive value of the chemicals was
; calculated according to -the following equationO
Preventive value(%)
(A) - Disease severity index treated X 100 .::
Disease severity index untreated(being A)
~ 25 ~e r^,ul-ts are given in Table 2~
:` ~-~.
~.
_ ~2 - ~
.
. ' .
f~ '~f-'~
'l'able 2
. _ ,
Preventi ve value (%)
Compound ¦ _ _
~o .
1000 ppm 500 ppm 250 ppm
_
3 100 97.4 86.3
_ _ _
4 93.2 81 O4 70.8
____
79-6 74.3 68.5
_ _ _ _
6 92.0 80.~ 75 5
9 76.3 78.0 64.8
_ ....
91.4 89.6 85.3
_ . .
14 85.4 79 -6 73.1
_ _,
79.6 72.9 60.4
16 82.4 79~ 3 _ 70.4
_ ~.
17 97 5 89.7 83.4
..
19 73.2 64~8 60.3
_ . _ _
78.9 81.6 70.4 _
~_ _ _
21 98.4 92.2 8L~6
. .:
22 99 3 92.0 82.1
_ -I
26 98.4 95 7 84.2
: . _
27 86.3 85.2 71.4
_ .
28 83.5 72.4 63.5
_ ~_ _ _
29 92.6 81.8 73.2
_ I
3o 83.2 72.4 68.8
: ~
32 93.LI 81.6 73.2
.
33 85.6 69.7 72.4
. .
34 99.3 93.2 85.5
91.4 88.0 82.1 '
.
36 82.6 79.4 61.8
. .
cont .
-- 33 --
~. '
Preventive value (%)
Compoun d ~
No. 1000 ppm 500 ppm 250 ppm
_ ___. .___ ., . _ _ __
41 100 98.6 89.2
_.
42 100 97.3 88. L~
.~ .__ __
~4 92.1 85.3 76.4
____ ~ .
_ _ _
99 95 3 86.6
_
46 85.4 72-3 65.8
_ __
47 99~4 91.2 84.6
48 83.4 72.0 61.5
49 79 4 75.8 63.0
_
9~.6 92.4 89.6
_ -
51 90.8 8307 70.0
_ . ,
~ 52 91.4 86.3 72.5
. ~., ,
1 53 1 97.4 1 93.2 1 85.3
, ~ '
. 1 .
, - ~4 -
~` .
' :'
:', .
'
.
. ~
~es-t Ex~mple 2
Preventive effect a~ainst cucumber gray mold disease
Cotyledons which were cut from cucumber seedlings
(cultivar: ~agamihanziro) were dipped in aqueous suspensions
of wettable powder having various concentrations of the
chemicals and air driedD Pathogenic mycelia of Botrytis
cinerea was inoculated on to the cotyledons and incubated
in a himidic chamber maintalned at 25C. After 7 days,
the ra-ting on the disease severity index was determinedO
On the other hand, procedures similar -to the above
were repeated but no chemical was applied to cotyledonsO
Then, the preventive value was calculated according
-to the above equa-tionO
~he results are ~iven in ~able ~.
'
.
- 35 -
'l'able 3
Preventive value (%)
No. __ __
1000 ppm 5O ppm 250 ppm
___
2 96.5 93.2 91.8
_ - _.
~ 100 98.2 95-4
_ _.
7 96.2 95-4 90.6
8 98.4 91.5 82.3
11 100 98.6 92.0
: _
12 83.2 72.3 69.8
_ '~
13 97-3 90.4 83.4 ~
_ .
18 100 98.6 95 3 ~
., _
23 97-4 82.6 80.4 -
., . ____ l
24 83.2 76.~ 1 63.5
,:
100 96.3 91.5
. ~ I
31 ~ 85.4 ~ 73.2 65.4
37 100 92.4 1 86.3
.
,, ; contO
-~ 36 -
.
... ... ~
Preven-tive value (~/o)
Compound
No~ _ __
1000 ppm 500 ppm 250 ppm
_ _ _ . __ __
100 98.0 92.1
... , _ , _.~__ __,
41 96.4 92.3 88.5
_, _ _ ___ _,_ __ __. .
~ 42 100 95 - 7 90.4
. _ _ .
43 86.2 82.4 72.3
_ . _
_ 5 92.5 86.4 80.8
49 85.~ 79.0 68~4
_ _ . .'
98.6 89.3 82.1
~ .. ,
51 85.3 80.4 73.8
~, . _ .
53 91.6 a5.0 72.9
.. ~
:`` :
- 37 -
'` ~
. .. . . .. .
-, . .. . :. , .: ~ . : : - : . :
. . . .. :
~est Example 3
Preventive effect agains-t rice brown spot diseaseO
Rice plants (cul-tivar: Kinmaze), which were at 4 - 5
leaf stage and grown in 9 cm pots in a green house, were
5 treated with suspensions of various wettable powder of
chemicals at predetermined concen~trations by means of
spraying at a dosage rate of 20 ml per pot and air driedO
Then, a suspension containing pathogenic spores of
Cochliobolus miyabeanuswas was inoculated on the platns and
incubated in a 'numidic chamber at 25 ~ 27Co After 48
: hours, the number of lesions was counted
On the other hand, similar procedures were repeated
but no chemical was appliedO
The preven-tive value was calculated according to
the following equation: -
Preventive value (%)
(A) - number of lesions -trea-ted : :
- -- - X 100
; ~umber of lesions untreated (being A)
The results are given in Table 40
. . .
. - 38 -
.. . .
,.. ~:.. , ... :
rrable - Ll
__ Preventive value (%)
Co~pOOUnd __ _______ __ ___
; _ 500 ppm 250 ppm 125 ppm 62.5 ppm
3 ~ lO0 ~ 99~1 ~ 92.6 ~ ~6~7
8 97O L~ 92O6 81O9 72O4
13 lO0 9800 9502 8904
( 1 ) .
: Contro 1 98 0 6 .. _ _ _ __ 72O5 3~2 _ __
~ote : (1) Control chemical was ~-3,5-dichlorosuccinimide
. ~ .
.,
,
,'`' ~
; ,
~f.~ 3
Test Example ~l
Protec-tive e.~fect agains-t kidney bean gray rnold diesease.
Kidney bean plants of 2 leaf age were spray trea-ted with
suspensions of wettable powder of compounds to be tested in an
amoun-t of 25 ml and air dried.
~ hen, a 6 mm agar disc containing phathogenic mycelia
of Botrytis cinerea was inocula-ted on to the leave and incubated
in a humidic chamber at 2~C for 4 days.
~ hen, the protective value was calculated according
to the equation given in ~est Example 1.
~ he results are given in ~able 5.
`: :
. .
-- L~O --
: . . . .
3~5~
~abl e 5
Compound ~o. Protect ve
~'1
L~O 100
_
; L~l 96
.
42 89-7
. _ _ _. .'
4~ 78
~, _
100
_
~6 93-3
_ .
L~7 72
51 75 - : :
- `
41 -
