Note: Descriptions are shown in the official language in which they were submitted.
The present invention relates -to N-benzoylanthranilate
compounds of the formula,
C}~2 11~
wherein X is a hydrogen or 3-halogen atom or a 4--rnethoxy, 2,4-
dimethoxy, 3,4-dimethoxy, 3,4-methylenedioxy or 3,5-dimethoxy
group and R is a C2-C7 alkyl, C3-C6 cycloalkvl, C2-C4 alkellyl,
nalo-Cl-C3 alkyl or N,N-di-Cl-C2 alkylamino Cl-C4 alkyl group
useful as fungicides and their preparation.
The N-benzoylanthranilate compounds [1] have fungicidial
activity against ~;lytopathogenic fungi. This application is a di-
visional application of co-pending application No. 29~,028 filed
December 29, 1977.
Thus the N--benzoylanthranilate compounds [1] nave prominent
effects on such a wide scope of fungi as Piricularia oryzae,
Alternaria kikuchiana, Alternaria mali, Venturia inaequalis,
Diaporthe citri, Botrytis cinerea, Glomerella cingulata, Sclerotinia
cinerea and Phytophthora infestans. They are especially effective
in controlling the powdery mildew diseases of agricultural and
llorticultural crops such as cereals, fruit crops, vegeta~les and
ornamental plants which are caused by the phytopathogenic fungi such
as Podosphaera leucotricha, Phyllactinia pyri, Phyllantinia
kakicola F Uncinula necator, Sphaerotheca fuliginea, Erysiphe
cichoracearum, Sphaerotheca pannosa, Sphaerotlleca humuli, _ysiphe
graminis f. sp. _o~dei and Erysiphe graminis f. sp. tritici.
Recently, the emergence of plant pathogens resistant to fungicides
h.-ls bccn often not:iced in fields, becoming a serious practical
problem in crop protection with fungicide application. The N-
benzoylantilranilate compounds [1] were found to exhibit a strong
fungitoxic ty towards those fungicide-resistant pathogens. For
- 1 -
example, they have the same fungitoxic activity on the Benomyl-
resistant strain of Sphaerotheca fuliginea and Erysiphe clchoracearum
[Ann. Rev. Phytopathology, 14, 405 (1976)] as on the respective
: wild strains (susceptible strains). It can be therefore expected
tilat N~benzoylanthranilate compounds [1] exerts prominent control-
ling effect on plant diseases in the fields where fungicide-
resistant pathogens have already emerged. Advantageously, they
are extremely low in toxicity and have little detrimental action on
mammals and fishes.
The N-benzoylanthranilate compounds [1] of the present
invention structurally relate to some of the compounds disclosed
in the literature [J. Med. Chem., 11, 369 (1968)], but their
effectiveness in controlling the powdery mildew diseases are
superior to those of the latter compounds, and the N-benzoylanthrani-
late compounds [1] are still effective with the application at lower
dosages.
The present invention thus provides N-benzoylanthranilate
compounds ~1], which are useful as fungicides as well as for
fungicidal compounds containing them. The present invention also
provides a process for producing such N-benzoylathranilate com-
pounds [1].
The N-benzoylanthranilate compounds [1] can be prepared
by reacting an anthranilate of the formula,
O
Il
COCH2R [II]
NH2
wherein R is as deEined above, with a benzoyl chloride of the
formula,
~ ~COCQ
X ~ [III]
wherein X is as defined above.
The reaction is usually carried out by stirring a mix-
ture of the starting anthranilate compound [II] wi-th an equivalent
or excessive molar amount of the benzoyl chloride [III] at room
temperature (0 - 35C) in the presence or absence of an inert
solvent (e.g. benzene, toluene, xylene, tetrahydrofuran, dioxane,
cnlorobenzene, chloroform, carbon tetrachloride, nitrobenzene,
water, methanol, ethanol, methyl isobutyl ketone, acetone, methylene
dichloride, ordichloroethane).When desired, the reaction may be
performed while heating (up to reflux) and/or in the presence of
- a dehydrochlorinating agent (e.g. pyridine, triethylamine,
quinoline, N,N-dimethylaniline, N,N-diethylaniline, N-methyl-
morpholine, sodium methylate, sodium ethylate, sodium hydroxide, or
sodium amide) so as to accomplish the production of the objective
compound smoothly. The N-benzoylanthranilate compound ~I] thus
produced may be purified, if necessary by a per se conventional
procedure such as recrystallization, distillation and/or column
chromatography.
The preferable N-benzoylanthranilate compounds [1] as
an active ingredient of the fungicidal composition of the present
invention are those having the general formula [1] wherein X
is a hydrogen, 3-fluorine, 3-chlorine, 3-bromine or 3-iodine atom
or a 4-methoxy, 2,4-dimethoxy, 3,4-dimethoxy, 3,4-methylenedioxy
or 3,5-dimethoxy group and R is a C2-C7 alkyl, cyclopropyl, vinyl,
2-methylvinyl, chloromethyl, or N,N-dimethylaminomethyl group;
and the more preferable N-benzoylanthranilate compounds [1] are
those having the general formula [1] wherein X is a hydrogen atom
and R is a vin;rl group; those having the gen~ral formula [1]
wherein X is a 3-iocline atom and R is a ethyl, n-propyl, vinyl,
chloromethyl or N,N--dimethylaminomethyl group those having the
general formula [1] wherein X is a 4-methoxy group and R is an
ethyl, i-propyl or vinyl group; those having the general formula
.
.
[1] wherein X is a 3,4-dime-thoxy group and R is an ethyl, n-
propyl, i-propyl, vinyl, or N,N-dimethylamino-methyl group; and
tnose having the general formula [1] wherein X is a 3,4-methylene-
dioxy group and R is a methyl, ethyl or n-propyl group.
In actual application as fungicides, the N-benzoylanthrani-
late compounds [1] may be used alone without incorporation of any
other ingredients such as carriers and diluents or, for easier
application, in admixture with such solid carriers or diluents as
talc, clay and the like or with such liquid carriers or diluents
as organic solvents and the like. ~he fungicidal compositions
can be formulated into any of ordinarily adopted forms such as,
for example, dusts, wettable powders, oil sprays, aerosols, tablets,
emulsifiable concentrates and granules.
The foregoing preparations generally contain 1.0 to 95.0%
by weight, preferably 2.0 to 80.0% by weight of the active in-
gredient (including other ingredients mixed). A suitable amount of
the preparations applied is generally 10 g to lOOOg/10 are, and
the concentration of the preparations applied is preferably
within the range of 0.01 to 0.5% by weight. Since, however, the
amount and concentration depend upon the preparation forms,
application times, application methods, application sites, diseases
and crops, they may be properly increased or decreased irrespective
of the aforesaid ranges.
Further, the N-benzoylanthanilate compounds [I] may
be used in admixture with other fungicides such as, for example,
N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2dicarboximide,
S-n-butyl-S'-p-tert-butylbenzyl-N-3-pyridyldi-thiocarbonimidate,
0,0-dimethyl-0-2,6-dichloro-4-methylphenylphosphorothioate, methyl
l-(butylcarbamoyl)-2-benzimidazolecarbamate, N-trichloro-methylthio-
4-cyclohexene-1,2-dicharboximide, cis-N-(1,1,2,2-tetrachloroethyl-
thio)-4-cyclohexene-1,2-dicarboximide, Polyoxin, Streptomycin,
zinc ethylene-bis(dithiocarbamate), zinc dimethylthiocarbamate,
m~nganese ethylene-bis(dithiocarbamate), bis(dimethylthiocar-
bamoyl)disulfide, tetrachloroisophthalonitrile, 8-hydroxyquinoline,
dodecylguanidine acetate, 5,6-dihydro-2-methyl~ -oxathiine-3-
carboxanilide, N'-dichlorofluoromethylthio-N,N-dimethyl-N'-phenyl-
sulfamide, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-
butanone, 1,2-bis(3-methoxycarbonyl--2-thioureido)benzene and the
like; and the N-benzoylanthranilate compounds [I] also may be used
in admixture with insecticides such as, for example, 0,0-dimethyl-0
(4-nitro-m-tolyl)phosphorothioate, 0-p-cyanophenyl-0,0-dimethyl-
phosphorothioate, 0-p-cyanophenyl-0-ethylphenyl-phosphonothioate,
0,0-dimethyl-S-(N-methylcarbamoylmethyl)phosphorodithioate, 2-
- methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide, 0,0-dimethyl-
S;-(l-ethoxy-carbonyl-l-phenylmethyl)phosphorodithioate, ~-
cyano-3-phenoxybenzyl-2-(4-chlorophenyl)isovalerate, 3-phenoxy-
benzyl-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate,
3-phenoxybenzyl chrysanthemate and the like; and in every case,
no controlling effects of individual chemicals are decreased.
Accordingly, a simultaneous control of two or more injurious
fungi and insects is possible. In addition, they may be used in
admixture with such agricultural chemicals as nematocides and
miticides and with fertilizers.
Practical and presently preferred embodiments of the
present invention are illustratively shown in the following
examples, wherein parts and % are by weight.
Example 1
Preparation of the N-benzoylanthranilate compounds [I]:-
One tenth mole of an anthranilate of the formula [II]and 0.11 mole of triethylamine were dissolved in 200 ml of benzene,
and 0.1 mole of Denzoyl chloride of the formula [III] was added
thereto dropwise slowly at room temperature with stirring. After
the addition was finished, the mixture was heated under reflux
for 2 hours. The reaction mixture was filtered, and the filtrate
was concentrated under reduced pressure. The residue obtained was
- 5
recrystallized from an ethanol to obtain the objective N-benzoyl-
anthranilate compounds of the formula [I] in a high yield.
According to the above procedure, the N-benzoylanthrani-
late compounds [I] as shown in Table 1 were prepared.
~ 10
.
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l., ., X l
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: ~=o
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. _ _ g ~
3 ~1
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.: ~n o ~D ~ ~n ~ I_ . ~ ~ IJ "
:`: l 1- l l '
a~ l ~9~1 ul ) p
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o o o o ~C> o
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a~ ~ ~3
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o~ ~n ~ o o _~ . .
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ul ~ ~ ~ ~n ~ ~ ~ ul ~ ~ ~ ai~ ~ ~
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_ _ _ __ _ _
W, _~ C~, ~I ~ ~ ~n ~ ~ ~ ~ ~ ~n ci~ cS~
CO U~ ~ O ~D _l ~ ~I cn ~ .P .P a~ ~ ~
~ ~ CO ~ I_ ~ ~ co 1- ~ ~I ~D I_ ~D ~D
_ _ _ _ _ _
W W W W W W W W W W ~ W ~ W W
. . . . . . . . . . . . . .
w w ~ a~ ~ ~ ~ _l ~ ~ ~ ~ I_ ~ ~D
W ~D ~D W O _l ~ ~ O I~ 0~ ~ O ~ ~
- 9-
.~ W l l l N l l l N
H ~ H
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_ __ _ ___ __ _ _
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W ~. W ~ ~ CO U: O;~ O ~ ~ O C~ I_ O
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:~ W _J Cl~ 1 .P (~ ~ ~ ~ 6~ ~ ~ ~11 ~ ~
co ~ ~ o ~ ~ o c~ ul ~ ~P ~n _l ~ w
W ~ ~n _1 CO ~D O ~ O ~ ~ ~ ' 1- ~
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:
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~n ~ o o ~ ~ ~ ~n ~ w
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- ll
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a~ ~. ~ ~ a~ ~ _l
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IPW Ul O O W I_ cn ~c) ~1 ' .
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-
; Example 2
Formulation of compositions: -
- a) Dust
3 Parts of the compound (a) and 97 parts of talc were
thoroughly pulverized and mixed together to obtain a dust
containing 3% of the active ingredient. In application, the
; dust was dusted as such.
b) Granule
5 Parts of the compound (25), 93.5 parts of clay and
1.5 parts of a binder of the polyvinyl alcohol type were
thoroughly pulverized and mixed together, kneaded with water
and then granulated and dried to obtain a granule containing
5% of the active ingredient. I
The following examples show some typical test data
supporting the excellent activity of the N-benzoylanthranilate
compounds [1]. In these examples, the compound numbers
correspond to those in Table 1.
Example 3 Protective activity test on powdery mildew
of cucumber (Sphaerotheca fuliginea):
`` 20 When cucumber (var.: Sagami-hanjiro) was grown up
to a first true leaf stage in a flower pot of 9 cm in diameter,
the true leaves wère picked off and an aqueous solution of
each emulsifiable concentrate was sprayed on the cotyledon in
a rate of 10 ml per pot. After 1 day, the cucumber was in-
oculated by spraying the spore suspension of Sphaerotheca
fuliginea. After further 14 days, the infectious state was
observed. The disease severity was calculated by the following
method: The leaves examined were measured for a percentage of
infected area and classified into the corresponding disease
indiceswere summed up; and the disease severity was calculated
accordingto the following equation.
Disease lndex Infectious state
0 No colony on leaf surface
l Colony of less than 10% on leaf surface
2 " less than 30% "
- 3 " less than 60% "
4 " less than 95% "
" not less than 95% "
~isease = ~(Disease index x number of leaves)
severity 5 x (Total number of leaves examined) x 100
The test results are shown in Table 2. The compounds
of the present invention showed a more superior protective activity
than the control compounds, as is apparent from the test results.
''
... .
~ .
.:"
.
.~
Table 2
~ . ~
_. _ . , . , . , .. ...... . , ..... ~ ~ ~
Compound No. Concentration of Disease
active ingredientServerity
(ppm) - (%)
1 50 2.0
I ~ ' ~ 00
ll 0.0
. 10 6 ll 0.0
: 7 ll 1.0
8 ll 0.0
9 ~. 0.0
. 10 ' . 1.0
11 ll 1.0
12 ll 1.0
13 ~- 2.0
14 ll 0.0
ll 0.0
16 ll 2.5
` 17 ll 1.0
18 ll 0.0
.; 19 ll 0.0
20 . .- 3.0
21 ll 1.0
22 I~ 0.0
23 ll 0.0
24 ~ 1.0
ll 0.0
26 ,~ 0.0
27 ll 2.0
28 ll l.Q
. .
_ 15 -
:
29 50 ~ 0.0
~: 30 ll 0.0
31 ." - ~. 0.0
~ COOC4H 9 ( n ) * 1
_ 2 . . ... . . _ _
. ~ COOCH3 *2
.. ~ NHCOCH3 - _. 100.0 _
COOH *3
~ D NHCO- ~ ll 100.00
'' ..
,~ " COOCH3 *3
~- NHC ~ ~CH3 1 10~.0 .
---COOC2II5 *3 .
NHCO ~ Br .l 100.0
.. - . _
.~ ~ COOCH3 *3
HCO ~ i 98.0
. .
~ ~CONH ~ _._ 100.0 _
CONH~ ~ ~ 100.0
ONHC4H9 *6 50 7.5
NHCOOCH3 . .i
._. _._ .. . __._
No treatment _ 100 . O _
,
- .16 -
51
Note:
*l Compound disclosed in J. Med. Chem.,
Vol. 11, 369 (1968)
*2 Compound disclosed in Can. ~. Chem.,
Vol 46, 2589 (1968)
*3 Compounds disclosed in Bull. soc. chim.
; France, 337 (1960)
*4 Commercially available fungicide: supplied by the
trademark mebenil
*5 Commercially available fungicide: sa]icylanilide
*6 Commercially available fungicide: supplied by the
trademark benomyl
Example 4 Protective activity test on pesticides - resistant
pathogens:-
A protective activity test on powdery mildew of cucumber(Spllaerotheca fuliginea) was carried out in the same manner as in
Example 3, using Sphaerotheca fuliginea resistant to methyl
l-(butylcarbamoyl)-2-benzimidazolecarbamate. The investigation of
infection and the calculation of disease severity were carried out
in tlle same manner as in Example 3.
The test results are shown in Table 3. As is apparent
from a comparison between the test results of this example and
Example 3, the control compound, benomyl[methyl l-(butylcarbamoyl)-
2-benzimidazole-carbamate] displays a controlling effect on the
wild strains (susceptible strains), but it has little or no
controlling effect on the pesticides-resistant strains. While
the compounds of the present invention display a strong con-
trolling effect on the pestlcides-resistant strains as well as
on the susceptible strains.
Table 3
Compound No. ConcentratLon of Disease
ac-tive ingredient severity
_ (ppm) (~) _
'~ 10
' 10 8 ., 0.0
22 " 0.0
,~ 25 " 1.0 '.
- _
~0 ~C~Ug *l I "
No treatment ~ .
Note:
*l Commercially available fungicide: supplied by the trademark
benomyl
Example 5 Protective activity test on powdery mildew of barley
(Erysiphe graminis)
When barley (var: Akashinriki) was grown up to a first truè leaf
stage in a flower pot of 9 cm in diameter, an equeous solution of
each emulsifiable concentrate was sprayed on the leaves in a rate
of 10 ml of per pot. After the solution was air-dried,,the barley
was inoculated with Erysiphe graminis and cultivated for 10 days
under a fluorescent light at 18~C. Thereafter, -the infectious
state was observed. The investigation of infection and the
calculation of disease severity were carried out in the same manner
as in Example 3.
The test results are shown in Table 4. As is apparent
- 18 _
h~
from the rcsults, the compounds oE the presen-t invention showed
a more superior protective activity than the control compounds.
-
Table 4
... __ , ----
Concentration Disease
. of active in-severity
.. Compound ~o.gredient (%)
:~ (ppm)
: 2 50 0.0
0.5
..
~` 10 4 50 1 O
. 5 50 0.0
: 10 0.0
., __
. 6 50 0.0
' 10 0.0
.~ 1O 13 50
8 50 0.0
0.0
_
9 50 0.0
0.0
0.5
3.0
__ . _
- 20 11 15O 2 0
_
: 12 50 1.0
1.5
_
18 50 0.0
: 10 0.5 _
19 50 0.0
. . 10 0.0
,. _
22 50 0.0
0.0
_
24 50 1.0
3.0
0.0
0.0
26 50 0 0
27 50 2.5
. ¦ 10 6.5 L
lS
.
28 ~ 0.0
COOC~Hg(n) l ¦ ~o
NHCOCH3 50 100.0
COOH ~ *3 100.0
~ COOCH3 *3 1, 100.0
~ NHCO ~ CH3 .
N--'CO ~ ~r ,l 100.0
COOCH3 *3 9S.0 .
CH3 *4 . 100.0
~ CONH ~ .
.20 ~ OH ~5 : 100.0
CH3 *6 _ _
C H- N O 10 37 5
_
No treatment 100.0
: ~ 20 ~
Note:
*l Compound disclosed in J. Med. Cnem.,
Vol 11, 369 (1~368)
*2 Compound disclosed in Can. J. Chem.,
Vol. 46, 2589 (1~68)
*3 Compounds disclosed in sull, soc. chlm.
France, 337 (1960)
*4 Commercially available fungicide: supplied by the trade-
mark mebenil
*5 Commercially available fungicide: salicylanilide
'
*6 Commercially available fungicide: supplled by the trade-
mark tridemorph
; ~-ample 6 Protective activity test on powdery mildew of
apple (Phodospheara leucotricha) :-
Apple seedlings (var. Kougyoku) were sprayed with
an a~ueous solution of each emulsifia~le concentrate at a rate
of 40 ml per plant. After the solution ~las air-dried, the
test plants were inocula-ted with Podosphaera leucotricha and
cultivated for 14 days under a fluorescent light at 20C.
Thereafter, rates of infection were assessed and percentages of
disease severity were calculated in the same manner as in
E~ample 3.
The test results are shown in Table 5. As is apparent
from the results, the compounds of the present invention showed
a more superior protection activity than the control compounds.
21
." ' ' ~ . . ` ''
i5.~
Table 5
~__ . ~ ~
Concentra-tion Disease
Compound No. of active in- severity
~: ingredient (%)
_ (ppm)
~ I 100 5.0
6 ,. 0.0
. _
. 22 1 0.0
., I _
ll 5.0
_
CoOC4Hg(n) *1 ,l 72.5
~ NH2
..
COOCH3 *2 ll 85.0
NHCOCH3
_
COOH *3 - n 70.0
NHC ~
.
~ COOCH3 *3 100 80.0
.. NHCO ~ CH3
~ COOC2H5 *3 .l 75.0
~ NHCO- ~ Br
OOCH3 *3 ll 70.0
. ~ NHCO
Br
ONH- ~ ll 77.5
~OH ~ *5 ll 85.0
. ~ CONH~ ~
~' .
~ s:a
~u~n~ ~;o~ ~
No treatr,lent ¦ -
Note:
*l Compound disclosed in J. Med. Chem.,
Vol. 11, 369 (1968)
*2 Compound disclosed in Can. J. Chem.,
Vol. 46, 2589 (1968)
*3 Compound disclosed in Bull. soc. chim.
France, 337 (1960)
*4 Commercially available fungicide: supplied by the trademark
~lebenil
*5 Commercially available fungicide: salicylanilide
*6 Commercially available fungicide: supplied by the trademark
Dihocap
Example 7 Protective activity test on powdery mildew
of rose (Sphaerotheca pannosa)
Rose seedlings (var. Peace) in flower pots were sprayed
with an aqueous solution of each emulsifiable concentrate
at a rate of-30 ml per plant. After the solution was air-dried
the test plants were inoculated with Sphaerotheca pannose and
cultivated for 14 clays in a green house. Thereafter, rates
of infection were assessed and percentages of disease severity
were calculated in the same manner as in Example 3.
The test results are shown in Table 6. As is apparent
` from the results, the compounds of the present invention showed
a more superior protection activity than the control compounds.
~ Table 6
._ . ., ,, ,, ., _ . _
Concentration of Disease
.. Compound No. active ingredient severlty
. _ (ppm) _ (%)
: 13 100 0.0
:.~ . I
: _ 27 ll 0.0
.. 30 " 0.0
-COOC499(n) *1 1 " ~ 65.0
. 10 ~ COOCH3 *2 ll 62.5
~NHCOC1l3
. ~ COO~ ~ *3 ' ~
- ~ COOCH3 *3 ll 70.0
NHCO ~ CH3
~ ,COOC2H5 3 100 75.0
,- N~CO ~ Br . . .
.~ _
20~ CO~OCH3 *3 ll 67.5
... ~ NHCO
~: Br
CH3 *4 'l 72.5
.~ ~ CONH ~ . :
. ... -
~ ~OA~ ,~ ¦ 70. O
N02
2N ~ OCOCH=CHCH3
1 6 13
~13 _
- 24-
`s~
~; ~ ~ treat ent
Note:
*l Compound diselosed in J. Med. Chem.,
Vol. 11, 369 (1968)
*2 Compound diselosed in Can. J. Chem.,
Vol 46, 2589 (1~68)
` *3 Compound diselosed in Bull. soe. chim.
` Franee, 337 (1960)
: *4 Commercially available fungicide: supplied by the trade-
mark Mebenil
*5 Commercially available fungicide: salie lanilide
. ' ,
*6 Commereially available fungieide: supplied by the trade-
mark Dinoeap.
. , .
- 2
: `
