Note: Descriptions are shown in the official language in which they were submitted.
~L~83922
BACKGR011ND OF THE INVENTION
. . _ ~
The present invention relates to a derivative of
azole represented by the formula (I):
~10 ~ A- =~
wherein R represents a phenyl group, a 4-chlorophenyl group,
a 4-fIuorophenyl group or a 2,4-dichlorophenyl group and A
represents a nitrogen atom or a methine group, a process for
producing the derivative of azole, and a method for controlling
fungi comprising applying to agricultural or horticultural .
plants a fungicidally effective amount of a derivative of
azole.~
Nowadays, the damage of the crops due to the various
plant diseases is enormous, and the problem of environmental
pollution due to a~ricultural chemicals has been taken up
frequently as a topic and has attracted the peoples'
concern.
Accordingly, the cry for the fungicide for use in
agriculture and horticulture, which is low in toxicity to
human, animals, birds and fish, is low in phytotoxicity to
useful plants, is high in safety in handling, gives little
~33~
effects to the environment and shows an excellent control
effect on the plant diseases of wide range, is very large.
The present inventors considered that in order to
develop such an epoch-making fungicide for use in agriculture
and horticulture, a simple modification of the conventional
chemicalcompounds had little possibility to succeed and it was
necessary to study novel chemical compounds, and as a result
of synthesizing a number of derivatives of azole and examining
the usefulness in practical use thereof, it has been found by
the present inventors that thederivatives of azole represented
by the formula (I):
HO CH2-N ~ ~
I ~ H2-R (I)
wherein R represents a phenyl group, a 4-chlorophenyl group,
a 4-fluorophenyl group or a 2,4-dichlorophenyl group and
A represents a nitrogen atom or a methine group, has the
above-mentioned specificities, and on the basis of their
finding, the present invention has been attained.
3L~83~2~
SUI ~ ~RY OF TEE INVENTION
The object of the present invention is to provide
novel derivatives of azole represented by the formula (I),
which is useful as an active ingredient of a fungicide for use
in agriculture and horticulture, and the process for producing
the derivatives of azole. Furthermore, the object of the
present invention is to provide a fungicide for use in agri-
culture and horticulture, which is low in toxicity to human,
animals, birds and fish and is low in phytotoxicity to useful
plants~
Still further, the object of the present invèntion
is to provide a fungicide for use in agriculture and horticul-
ture, which has an excellent fungicidal activity on the plant
diseases of vide range, at the same time, is excellent in the
safety of handling and in keeping an envir~nment clean and
contains the derivative of azole represented by the formula
(I) as an active ingredient.
BRIEF EXPLANATION. OF DRAWINGS:
The~attached drawings show the infrared absorption
spectra of the present compounds (the derivative of azole
accordlng to the present invention) and of the drawings as
follows:
Fig. 1: IR spectrum of Compound No. 1 in Table 1,
; Fig. 2: IR spectrum of Compound No. 2 in Table 1,
Flg. 3: IR spectrum of Compound No. 3 in Table 1,
Fig. 4: IR spectrum of Compound No. 4 in Table 1,
.
~ ~X~33~
Fig. 5 I~ sp,a r~ <,~ ~ S T~LI I,
Eig. 6: IR spectrum of Compound No. 6 in Table 1,
Fig. 7: IR spectrum of Compound No. 7 in Table 1 and
Fig. 8: IR spectrum of Compound No. 8 in Table 1.
DETAILED DESCRIPTION OF THE INVENT_ON:
The feature of the present invention lies in (1) the
derivative of azole represented by the formula (I):
2 R
wherein R represents a phenyl group, a 4-chlorophenyl group,
a 4-fluorophenyl group or a 2,4-dichlorophenyl group and A
represents a nitrogen atom or a methine group, (2) a process
for producing the above-mentioned derivative of azole, which
comprises the step of bringing a derivative of oxirane
~cpr_sente by the fo ~
1~839~
wherein R shows the same meanings as in the formula (I), into re-
action with 1,2,4-triazole or imidazole, and (3) a fungicide for
use in agriculture and horticulture containing the derivative
of azole represented by the formula (I) as an active ingredient.
The derivatives of azole represented by the formula
; (I) are novel chemical compounds not has been mentioned in
literatures, and the respective melting-points of some of the
derivatives of azole according to the present invention are
shown in Table 1.
: Table 1
~: _ __ _ _. .. _
~ Number of Indication in Formula (I) Melting point
: compound ._ ~-- (C)
. .. ~ . .~ .___ .
. 1 Phenyl N 140 - 141-
:: 2 Phenyl CH130 - 131
- 3 4-Chlorophenyl N 115 - 116
~; 4 4-Chlorophenyl CH115 - 116
- 5 4-Fluorophenyl N 135 - 136
6 4-Fluorophenyl CH139 - 140
7 2,4-Dichlorophenyl N 120 - 121
. 2~4-Dichlorophenyl CH 150 - 151
~ '
':
~ - 6 -
'..... .... :~ : ' '
. ' . ' ~ . ''
~:~83~
The respective infrared absorption spectra of the
compound in Table 1 are shown in the attached drawings.
The process for producing the derivatives of azole
represented by the formula (I) and the utilization of the
derivatives of azole according to the present invention as
a fungicide for use in agriculture and horticulture will be
explained hereinafter.
A derivative of azole according to the present
invention is produced by the following process.
Namely, by bringing a derivative of oxirane repre-
sented by the aforementioned formula (II) into reaction with
a triazole or an imidazole represented by the formula (III):
: :
U
wherein M is a hydrogen atom or an alkali metal and A
represents a nitrogen atom or a methine group, in the presence
of a diluting agent, the object derivative of azole represented
by the formula (I) is obtained.
The derivative of oxirane represented by the formula
(II) which is used as the starting substance is obtained by
bringing the ketone represented by the formula ~IV):
_ CH2-R (IV)
- 7 -
lX8:1~'3Z;~
wherein R shows the same meaning as in the formula tI), lnto
reaction with, for example, dimethyloxosulonium methylide or
dimethylsulfonium methylide in the presence of a diluting agent
(See Org. Syn. 49, 78 (1969), J. Amer. Chem. Soc. (1965), 1353).
In this connection, the compound represented by the
formula (IV~, for example, 2-substituted benzylcylopen~anone,
can be obtained from 2-alkoxycarbonylcyclopentanone and a
corresponding substituted benzyl halide by the method described
in Organic Synthesis, 45, 7 (1965) and Journal of Chemical
Society, (1950), 325.
, Further, the compound represented by the formula (IV)
can be obtained also from an enamine of cyclopentanone and
a corresponding substituted benzyl halide (refer ~o Journal of
Pharmaceutical Science, 68, 1501 (1979)).
As a diluting agent used in the production of the
chemisal compound represented by the formula (I) according
to the present invention, hydrocarbons such as benzene,
toluene, xylene, hexane, etc.; halogenated hydrocarbons such
as methylene chloride, chloroform, carbon-tetrachloride, etc.;
alcohols such as methanol, ethanol, etc.; ethers such as diethyl
ether, diisopropyl ether, tetrahydrofurane, etc.; acetonitrile,
acetone, dimethylformamide, dimethylsulfoxide, etc. may be
mentioned.
In addition, in the process according to the present
invention, the reaction may be carried out in the presence of
a base in addition to the above-mentioned diluting agent.
'~...~
~.
lZ835~2 - ~
As a base used in the above-mentioned reaction, carbonates of
an alkali metal such as sodium carbonate, potassium carbonate,
etc.; hydroxide of an alkali metal such as sodium hydroxide,
potassium hydroxide, etc.; alcoholates of an alkali metal such
as sodium methylate, sodium ethylate, potassium t-butylate,
etc.; alkali metal hydrides such as sodium hydride,
potassium hydride, etc.; triethylamine, pyridine, etc. may
be mentioned.
In the case where the process according to the
present invention is actually carried out, for example, into
a solution of an azole represented by the formula (III)
dissolved in an above-mentioned diluting agent, an oxirane
represented by the formula (II) is added in an amount of from
0.5 to 1.0 equivalent, if necessary, in the presence of an
above mentioned base, or in the reverse way with the above-
mentioned method, an alkali metal salt of the above-mentioned
azole is put into a solution of an above-mentioned oxirane in
a diluting agent.
~ As the reaction temperature of the above-mentioned
process, an optional temperature may be applied from the
soLidifying point to the boiling point of the diluting agent
used above, however, it is actually preferable to carry out
the reaction at a temperature in the range of from 0 to 100C
for from one to three hours. It is preferable to carry out
the reaction under stirring.
After the reaction is over, the obtained reaction
mixture is cooled and the organic layer is separated by
extracting with an organic solvent such as ethyl acetate,
chloroform, benzene, etc. in ice-cooled water, and after washing
the organic layer with water and drying thereof, the solvent
is distilled off under a reduced pressure. By subjecting the
thus obtained residue to purification treatment the object
compound can be obtained. In addition, the purification treat-
ment the object compound can be obtained. In addition, the
purification treatment can be carried out by subjecting the
reaction product to recrystallization, silica gel column
chromatography, etc.
The utilizability of the derivatives of azole
represented by the formula (I) as the active ingredient of the
fungicide for use in agriculture and horticulture will be
explained as follows:
The derivatives of azole according to the present
invention show a control effect on the following wide range
plant diseases:
Pyricularia oryzae, Cochliobolus miyabeanus,
Xanthomonas oryzae, Rhizoctonia solani, Helminthosporium
sigmoide-m and Gibberella fujikuroi on rice plant; Podosphaera
Ieucotricha, Venturia inaequalis, Sclerotinia mali, Alternaria
mali and Valsa mali on apple -tree; Alternaria kikuchiana,
Phyllactinia pyri, Gymnosporangium haraeonum and Venturia
. . _ . . _ __
nashicola on pear tree; Unccinula necator and Phakospora
ampelopsidis on grape-vine; Erysiphe graminis r. sp. hordei,
Rhynchosporium secalis, Puccinia graminis and Puccinia triformis
lZ839~Z
on barley; Puccinia recondita, ~ tritici, Puccinia
triformis and Erysi~e ~raminis f. sp. tritic~ on wheat;
Sphaerotheca uliginea on melon plant; Fusarlum oxys~_rum on
water-melon plant; Erysiphe cichoracearum and Alternaria solan
on tomato plant; Erysiphe cichoracearum on egg plant;
Sephaerotheca humuli on strawberry plant; Erysiphe cichoracearum
and Alternaria longipes on tobacco plant; Cercospora beticola
on sugar beet; Alternaria solani on potato plant; Septoria
glycines and Cercospora kikuchii on soy bean plant; Sclerotinia
cinerea on drupe fruit plant; and Botrytis cinerea and
Sclerotlnla sclerotiorum which violate various crop plants.
In addition, the derivatives of azole according to
the present invention exhibit not only the preventive effect
but also the curative effect on some of the above-mentioned
plant diseases.
In order to apply a derivative of azole represented
by the formula (I) as the fungicide for use in agriculture
and horticulture, the derivative itself or a composition
containlng the derivative admixed with a carrier (a diluent)
in the-form of powders, wettable powders,-granules, emulsions,
solutions, etc. is usable advantageously. Moreover, if
necessary, it is also possible to make the effect of the
derivative more reliable by adding an auxiliary agent other
than th~ above-mentioned carrier, such as a spreader, an
emulsifier, a wetting agent, a sticker, etc. to the compound
of the derivative of azole according to the present invention.
., ~ .~
.
. ' - ' ' ' '
~LZ839~2 `- ~ ~
In this connection, since the derivatives of azole
according to the present invention (hereinafter referred to as
the present compound) contains a 1,2,4-triazole ring or an imid-
azole ring in the molecule thereof, the present compound may
be used in the form of a salt o an organic or an inorganic
acid or a metal complex salt. In addition, since in the
present compound, an azolylmeth~l group and a substituted
benzyl group are contained respectively at l-position
and 2-position of the cyclopentane ring, stereochemical isomers
such as geometrical isomers of cis and trans and optical isomers,
etc. may exist. Ho~ever, the present invention includes all
of the single isomers and the mixtures thereof in any optional
ratio between them. Accordingly, it should be understood
that the fungicide for use in agriculture and horticulture
according to the present invention includes the fungicide con-
taining the above-mentioned sinyle isomer(s) or the mixture(s)
thereof as the active ingredient.
The following Examples 1 and 2 are those respectively
showing the preparation of the present compounds (the deriva-
tives of azole according to the present invention) and the
following Examples 3 and 4 are those showing the preparation
of the fungicide (the fungicidal composition) for use in
agriculture and horticulture.
~283~
EXAMPLE 1:
Preparation of 2-(2,4-dichloroben~yl)~ imidazole-
l-ylmethyl)cyclopentan-l-Ol (Compound No. 8 in Table 1):
Into 20 ml of anhydrous dimethylformamide, 336 mg of
sodium hydride (prepared by washing 60 ~ oily sodium hydride
with dried benzene) were added while stirring under helium
atmosphere, and after adding 950 mg of lH-imidazol into the
thus prepared mixture, the whole mixture was stirred at room
temperature until bubbling was over. A solution of 1.8 g of
4-(2,4-dichlorobenzyl)-1-oxaspiro[2.4]heptane in 10 ml of anhy-
drous dimethylformamide was dropped into the thus obtained
solution, and th~ whole mixture was stirred for 2 hours at
80C.
After leaving the thus obtained reaction mixture to
cool, it was poured into iced water, and the mixture was extracted
with ethyl acetate to obtain an organic layer. After washing
the organic layer with water and drying the layer on anhydrous
sodium sulfate, the solvent was distilled off from the layer
under a reduced pressure to obtain a residue. By recrystallizing
the residue with a mixture of hexane and ethyl acetate, 1.20 g
of the compound shown in the above title was obtained.
The results of determination of the physical properties
of the thus obtained compound are as follows and in addition,
NMR spectrum of the compound was determined by using TMS as
the internal standard and the results are shown by the
following marks (the same marks are used in other Examples):
~83~ l
s: singlet
d- doublet
m: multiplet
b: a broad line
Physical Properties
(1) Melting point: 150 - 151C.
(2) Infrared absorption spectrum (KBr method): vmax
3130, 2940, 1580, 1430 and 1100 cm 1,
~3) NMR spectrum (CDC13, ppm): ~
1.38 - 1.97 tbs, 7H), 2.50 - 3.18 (m, 2H), 3.53 (bs, lH),
3.83 (dl lH, J=14Hz), 4.22 (d, lH, J=14Hz), 7.03 (s, 2H),
7.27 - 7.55 (m, 3H) and 7.62 (s, lH).
EXAMPLE 2:
Preparation of 2-(4-chlorobenzyl)-1-(lH-1,2,4-triaæole-_
l~ylmethyl)cyclQpentan-l-ol (Compound No. 3 in l`able 1):
Into 15 ml of anhydrous dimethylformamide, 1.0 g of
4-(4-chlorobenzyl)-1-oxaspiro~2.4~heptane was added to be
dissolved while stirring under a helium atmosphere, and into
the thus prepared solution, 0.6 g of sodium salt o~ lH~1,2 f 4-
triazole of 90% in purity (commercial product, made by ALDRICH
Co.) was slowly added. The mixture was stirred for 2 hours
at 60~C.
After leaving the thus obtained reaction mixture to
be cooled, the cooled reaction mixture was poured into water
and the mixture was extracted with ethyl acetate to obtain an
~339~
organic layer. After washing the layer with water and drying
thereof on anhydrous sodium sulfate, the solvent was distilled
off from the layer under a reduced pressure to obtain a
residue.
By purifying the residue through silica gel column
chromatography, 0.6 g of the compound of the above title was
obtained, the physical properties thereof being shown as
follows:
Physical Properties
(1) Melting point: 115 - 116C.
(2) Infrared absorption spectrum (KBr method): v max
3260, 2940, 1280, 1140 and 670 cm 1
(3) NMR spectrum (CDC13, ppm): ~
1.35 - 2.13 (m, 7H), 2.48 - 2.77 (m, 2H), 3.02 (bs, lH),
- 4.18 (s, 2H), 7.18 (d, 2H, J=~Hz), 7.40 (d, 2H, J=9Hz),
; ~ 8.Q8 (s, lH) and 8.25 (s, lH).
The following two examples (Example 3 and 4) are
the examples of the preparation of a fungicide for use in
agriculture and horticulture containing a derivative of azole
according to the present invention as an active ingredient.
EXAMPLE 3:
_ ~ .. . . .
By pulverizing and mixing 3 parts by weight of one of
the present compounds (Compound No. 5 in Table 1), 40 parts
by weight of clay and 57 parts by weight of talk, a fungicide
dust was prepared.
The thus prepared fungicide dust is used by scattering
on the object.
~ --
EXAMPL~ 4
By pulverizing and mixing 50 parts by weight of one
of the present cornpounds (Compound No. 3 in Table 1), 5 parts
by weight of a salt of ligninsulfonic acid, 3 parts by weight
of a salt of an alkylsulfonic acid and 42 parts by weight
of diatomaceous earth, a fungicide wettable powder was prepared.
The thus prepared fungicide wettable powder is used
after diluting with water.
The following five examples (Examples S to 9) are
the examples showing the fungicidal effect of the fungicide
for use in agriculture and horticulture according to the
present invention.
EXAMPLE 5:
Pest control test against Erysiphe graminis f. sp.
trlticl on wheat:
Onto the leaves of seedling of wheat (variety: NORIN
No. 64, 16 seedlings per pot) at the second leaf stage cultured
in an unglazed pot, a fungicide wettable powder prepared
~according to the method in Example 4 diluted with water to a
predetermined concentration was sprayed at a rate of 5 ml/pot
(control pot was sprayed with water only). After natural
drying of the thus sprayed leaves, an aqueous suspension of
the spores of Erysiphe graminis f. sp. tritici collected from
the attacked leaves of wheat was sprayed onto the thus dried
leaves of the potted wheat and the thus treated seedlings
were kept for 24 hours at a temperature of 20 to 25C in a
highly humid atmosphere. Thereafter, the thus treated seedlings
were left in a green house made of glass. After 10 days of
the inoculation, the morbidity of the seedlings was
examined on the basis of the following standard and the
~ 16 -
1~ 9~:~
control value was calculated by the following formula from
the average morbidity per leaf:
Standard of the examination
Morbidity index Extent of disease infect
0 Not infected
0O5 A 1) is less than 10 ~,
1 A is from 10 to less than 20%,
2 A is from 20 to less than 40%,
3 A is from 40 to less than 60%,
4 A is from 60 to less than 80% and
A is larger than 80 %.
Note *l) : A is the area rate of disease infect on the
surface of the inoculated leaf.
: . .
; ; : Control value = (1 ~ morrbiditY Onn tcorn~rod pot) x 100 (%)
'
The results are shown in Table 2.
: :
:
:: ~
~ ~'
:
~83~
Table 2
. .~
Compound Concentration
number of the sprayed Control value
: (as in Table 1) liquid (ppm) (~)
. ... _ .. . _ . ...... ___
: 1 125 100
2 125 100
3 125 100
4~ 125 100
12,5 100
6~ 125 100
; : ~ ~ 7: ` ; 125 100
8 125 100
: _ . .. ~ ~. ~ .. __ . ...... .. _ __ ~
~Trladimefon 125 ____
Control~
; ~Note~ *l:~ Triadimefon is a commercial funyicide containing
the fol-10wlng compound as the active ingredient:
:: ~ : : O CH
C~ );CH-C ~--CH
: ~ :
~: :
: ~
: : - 18 -
~:~
~: . .
Example 6:
__ .__
Pest control test against Sphaerotheca fuliginea
on cucumber plant-
..._
Onto the leaves of seedling of cucumber (variety:
SAG~MI-HAMPAKU, one seedling per pot, 3 pots in a test of
one compound) at the second leaf stage cultured in an
: unglazed pot of 10 cm in diameter, a fungicide wettable
:~: powder prepared according to the method in Example 4 diluted
: : with water to a predetermined concentration was sprayed at
a: rate of 5 ml/~pot (control pot was sprayed with water only),
and then the spores of Sphaerotheca fuliginea of cucumber
were~scattered onto the thus sprayed leaves from the contracted
;leaf~of cucumber plant by using a brush to inoculate on the
~leaves, and the~thus treated pots were left in a glass green
: ~house.~ After 7~:days of the inoculation, the morbldity of the
: ~ l:eaf of seedlings (one leaf/pot, three pots/compound) was
examined~accordi~ng to the following standard, and the control
value was~calculated from the average morbidity per leaf while
~ut~llizing the~same formula~:as~ in Exsmple 5:
Standard of thè examination~
I ~ Morbidity index Extent:of disease infect
0 : : : Not infected
0.5 ~ A l) is less than 10 ~,
1 ~ A:is from 10 to less than 20 ~,
2 A is from 20 to less than 40 ~,
3 A is from 40 to less than 60 ~,
: : : 4 A is from 60 to less than 80 ~ and
A is larger than 80 %.
: ~
- 19 -
::
:~
i ,. ~ . ,
~: ~ . - .
.
l . . . _ . ' . _ : ' . _ ' ., ' . . . ~, _ _ . . _ ., . _, . ! . . _ ., _ .
~;~a39~2
Note *1): A is the area rate of disease infect on the
surface of the inoculated leaf.
The results are shown in Table 3.
,
Table 3
.. ,~
Compound ConcentrationControl value
n~m~er of the sprayed
(as in Table 1) liquid (ppm) (%)
: .. ., . ~
; ~ 1 62~5 100
` ~ 2 62~5 100
3 6~2~5 ~ 100
; 4 62~5 100
62~5 100
6 62~5 100
7 62~5 ; 100
~; ~ 8 ; ~2oS ~ ~ 95
: ~ ~ -
: commercia~ : I25;~ 100
::: :~: ~ fungicide 1) :
`~:: Control : -- 0
::
, ~ ~ , , .: ~
: Note~*l): A ungiclde of quinoxaline series represented
: ~ by the following formula:
X s,
- 20 -
~ ~'~ ,
. . . .
~ ' : , ~ '., , ' ,: . ` - `
lZ839~'~ .
EXAMPLE 7:
Pest control test against Puccinia recondita f. sp.
tritici on wheat:
Onto the leaves of seedling of wheat (variety:
NORIN No. 64, 16 seedlings per pot) at the second leaf
stage cultured in an unglazed pot of 10 cm in diameter, a
fungicide wettable powder prepared according to the method
in Example 4 diluted with water at a predetermined concen-
tration was sprayed at a rate of 5 ml/pot (control pot
was sprayed with water only). After natural drying of the
; thus sprayed leaves,an aqueous suspension of the uredospores
of Puccinia recondita f. sp. tritici collected from the
: ~ : :
attacked leaves of wheat was sprayed onto the thus dried
leaves~of the potted wheat, and the thus treated seedlings were
;kept for 24 hours at a temperature of from 20 to 25C in a
highly humid atmosphere. Thereafter, the thus treated
seed1ings were left in a glass green house, and after 7 days,
~the morbidity~was examined on the basis of the following
~standard. The control va1ue~of each of the fungicide was
calculated by the formula shown~in Example 5 from the average
morbidity p~er leaf of the 10 seedlings per pot:
Standards of the examination:~
The same as in Example 6.
The~results are shown in Table 4.
::: ~ :
: :
; ~ ~ - 21 -
:
,
~L~839;~
. Table 4
: :Compound Concentration Control value
number of the sprayed
(as in Table l) liquid (ppm) (%)
: ~ ._ _. . . .. . ... _ _ . _
; ~ l 200 lO0
; ~ 2 200: lO0
3 200 : lO0
~4 :2:00 lO0
200 lO0
:: ~ ~ 6~: ~ 200~ lO0
~,~ : '~; 7~ ~200 lO0
. ::
~ ~ 8 : ~200:~ lO0
~: ~ ~
~Triadimefon : : ~ 200 lO0
Control~ o
: :~ ~ :
~ = ~ '. ~
EXAMPLE~8~ :
Pest~control_test against:~Cochl1obolus miyabeanus
::on':rice~plant~
In the~ungla:zed~pots~of 10~cm in diameter,
the~seeds;~of~rice plant (variety:~SASANISHIKI) were sown
~;at a rate;~of 16 seeds/pot, and at~the~stage of 4 to 5
; ~leaves, the fungicide wettable powder prepared according
~to~the~method~in,Example 4;was diluted:with water to a
, ~:predeterm1ned~concentration, and~the thus prepared aqueous
; ; - 22 -
39'i~ 1
suspension of the fungicide was sprayed onto the seedlings of
rice plant at a rate of 5 ml/pot. After natural drying the
thus treated leaves of the rice seedlings, an aqueous suspension
of the spores of Cochliobolus miyabeanus (at a concentration
of lS spores in the visual field of a microscope of 150
magnification) preliminarily cultured was sprayed onto the leaves
of seedl~ings at a rate of 5 ml/pot for inoculation. After
inoculation, the pots were immediately taken into an inoculation
: ~ ~
room of 25C and of saturated humidity, and after keeping
thereof for 2 days, the pots were moved into a glass green
house to be~attacked. At the fi~fth day after the inoculation,
: the number of~the disease spots on 10 leaves per pot was
~enumerated, and the control value~of each of the fungicides
was càlculated according to the following formula:
Control value (%) = (1:- B ) x 100 ~
. ~ whereln A is~the number of di;sease spots in the treated pots
; l ~ and;~B:is~that in~the control pots (not being sprayed with the
funglcide)~
:~ The results;are shown~in Table 5.
: :: : ~
23 -
:: :
~ :
::
, . . .
~Z839'~'~
Table 5
; ~ .... _ . _ . . ... _
Compound Concentration
number of the sprayed Control value
(as in Table 1) liquid (ppm) (~)
~ ~ 1 300 100
; ~ 2 300 100
3 300 100
4 300 100
300 100
~:~ ~ ~ 6 ~ ~ 3ao lOO
: ~ 7 ~300 92
:~ ~ 8 300 100
~ ~ Ep * l J ~ 300 ~ ~ 88
: ~ ~ ,
:~ ~; ~Control ~ ~ O .
. ~ Note~*~ A~commercial~fungicide containing the following
compound as~cn active ingredient:
, ~ ~5:~5~
2 5
24
: - _
~;:: :
lZ839'~
EXAMRLE 9
In vitro test against several fungal species
Antifungal properties of the present compounds
against several fungal sp~cies were examined as follows:
After thoroughly mixing each of the present compounds
with the PSA culture medium at a prescribed concentration, the
thus prepared mixture was poured into dishes of 9 cm in
diameter in an amount of 10 ml. per dish to prepare plate
culture medium. On the other hand, each of the fungal species
cultured in a~plate culture medium was punched by a cork borer
of 6 mm in diameter and inoculated on the thus prepared plate
culture medium~in the dishes. After inoculating, each of the
~thus;inoculated fungi was cultured for from one to three days
~at~a;temperature suita~le;for each fungus, and the growth of
~the~fungus was~determined by the diameter of each fungal colony.
~The~results were compared to the result on the control (the ;
culture medlum not containing any fungicide), and on the basis
of the~following formula, the rate of control of the mycelial
~grGwth was obtained: ~
;~ ; R = (dc ~ dt) dc
~whereln R represents the rate of control of the mycelial
growth of a fungus, dt represents the diameter of the fungal
~colony on the culture medlum plate containing each of the
~present compound~and dc represent5 the diameter of the fungal
~ :
~ - 25 -
~ :::
. ~
colony on the culture medium plate not containing any fungicide
(control).
The thus obtained results were evaluated on the basis
of the following standard into 5 ranks and are shown in Tahle 6.
Standard for _valuation:
Index of growth control Rate _f control of mycelial_growth
from 100 to 90 %
~: ~ 4 from 89 to 70 %
: 3 from 69 to 40 %
::: :: ~
: ~ 2 from 39 to 20 %
~: : 1 less than 20 ~
::: :
~ ;:
: ~
~ : ~ - 25 -
:: :::
~ 33~
_ ,
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o
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a~ ~ ~
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al ~1 ~ u
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e u~ ~ In ~ o ~
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: ~1 aJ ~ a.~ rl ~ ~ 0 P~
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o u~ u~ In In u~ In Ln u~ ~ ~1 rl ~ ~1
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~o ~e
. ~ ~ E~ ~ ,~ ~ rl ~ a) o ~ ~
: ~ : ~ e o ~, ,~ S~ ~ ,~
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: h u~ _ o o o o o o o o `.,1 ~n ~ O ~: :~ X O
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o ~ ~ ~ ~ .~ o S~ ~ ~S ,1 o ~
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~: :
- 27 -
~`'"
