CA1111051A - N-benzoylanthranilate derivatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

N-benzoylanthranilate compounds of the formula,

Description

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 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]

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 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.

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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.

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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 -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 __ . _ _ : 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 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 _ _ _ 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.

." ' ' ~ . . ` '' 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 _ 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

2N ~ OCOCH=CHCH3 ~13 _ `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.

. , .

: `

Claims (20)

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

1. A compound of the formula, wherein X is a hydrogen or 3-halogen 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, C3-C6 cycloalkyl, C2-C4 alkenyl, halo-C1-C3 alkyl or N,N-di-C1-C2 alkylamino C1-C4 alkyl group.

2. The compound according to claim 1, wherein X
is a hydrogen atom and R is a vinyl group.

3. The compound according to claim 1, wherein X is a 3-iodine atom and R is an ethyl, n-propyl, vinyl, chloromethyl or N,N-dimethylaminomethyl group.

4. The compound according to claim 1, wherein X is a 4-methoxy group and R is a i-propyl or vinyl group.

5. The compound according to claim 1, wherein X is a 2,4-dimethoxy group and R is a n-propyl group.

6. The compound according to claim 1, wherein X is a 3,4-dimethoxy group and R is an ethyl, n-propyl, i-propyl, vinyl or N,N-dimethylaminomethyl group.

7. The compound according to claim 1, wherein X is a 3,4-methylenedioxy group and R is an ethyl or n-propyl group.

8. The compound according to claim 1, wherein X is a 3-iodine atom and R is a n-propyl group.

9. The compound according to claim 1, wherein X is a 4-methoxy group and R is a vinyl group.

10. The compound according to claim 1, wherein X is a 3,4-dimethoxy group and R is a n-propyl group.

11. The compound according to claim 1, wherein X is a 3,4-dimethoxy group and R is a vinyl group.

12. The compound according to claim 1, wherein X is a 3,4-methylenedioxy group and R is an ethyl group.

13. The compound according to claim 1, wherein X is a 3,4-methylenedioxy group and R is a n-propyl group.

14. A process for preparing an N-benzoylanthranilate of the formula, wherein X is a hydrogen or 3-halogen 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, C3-C6 cycloalkyl, C2-C4 alkenyl, halo-C1-C3 alkyl or N,N-di-C1-C2 alkylamino C1-C4 alkyl group which comprises reacting an anthranilate of the formula, wherein R is as defined above with a benzoyl chloride of the formula, wherein X is as defined above.

15. A method of controlling fungi which comprises contacting the fungi with a fungicidally effective amount of a compound as claimed in claim 1,2 or 3.

16. A method of controlling fungi which comprises contacting the fungi with a fungicidally effective amount of a compound as claimed in claim 4, 5 or 6.

17. A method of controlling fungi which comprises contacting the fungi with a fungicidally effective amount of a compound as claimed in claim 7, 8 or 9.

18. A method of controlling fungi which comprises contacting the fungi with a fungicidally effective amount of a compound as claimed in claim 10, 11 or 12.

19. A method of controlling fungi which comprises contacting the fungi with a fungicidally effective amount of a compound as claimed in claim 13.

20. A method of controlling fungi which comprises contacting the fungi with a fungicidally effective amount of a compound as claimed in claim 1, 2 or 3 , the fungi being those causing powdery mildew of cereals, fruit, crops, vegetables and ornamental plants.