CA1159458A - Benzoxazolone derivative, processes for preparation thereof and compositions containing them - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
A benzoxazolone compound of the general formula:

Description

~ 3 FIELD OF THE INVENTION:
This invention relates to new benzoxazolone deriva-tives, to process for the preparation thereof, to fungicidal and bactericidal compositions containing the derivatives and to methods of combating various fungi and bacteria using the derivatives and the compositions.
BACKGROUND OF THE INVENTION:
It is known in the art that certain benzoxazolone derivatives are useful as fungicides and bactericides for agricultural and horticultural purposes. For exa~ple, German Patent Specification No. 1,023,627 describes the anti-fungal and anti-bacterial properties of some benzo-xazolone derivatives whose benzene ring bears a substituent such as 5-chloro, 5,6- or 5,7-dichloro or 4,5,7-trichloro group but no alkyl substituent. German Patent Specifica-tion No. 1,147,007 discloseR the antimicrobial properties of 4,5,6,7-tetrachlorobenzoxazolone, while U.S.S.R. Patent Specification No. 355,008 teaches such properties of 4,5,6-trichlorobenzoxazolone.
Further, Japanese Patent Publication No. 23,519/65 describes the fungicidal and bactericidal properties of benzoxazolone derivatives of the formula:

2 ~ N

1 2 R3=H ; Rl=Cl, R2=R3=H ; R2=Cl, Rl=R =H ;

4~

Rl=R2=Cl, R3=~l ; or Rl=R2=R3=Cl ; and R4 is phenyl optionally substituted by halogen, nitro, lower alkyl or lower alkoxy.
We have synthesized and carefully studied a variety of other benzoxazolone derivatives in an attempt to develop new benzoxazolone microbicides whichpossesg a low toxicity and good safety and exhibit a high activity against a wide range of fungi and bacteria. As a result, we have now diqcovered new benzoxazolone derivatives which have not been described in literatures and which are very useful as fungicides and bactericides. The new derivatives of thi~ invention carry in the benzene ring either at least one lower alkyl and at least one halogen substituents or 5,6,7-trichloro substituent. These new derivatives of the invention have been found to posses~ considerably improved fungicidal and bactericidal properties over those of known 4,5,7-trichlorobenzoxazolone and 4,5,6-trichlorobenzoxazolone as will be clearly seen from Examples hereinafter.
An object of this invention is to provide new benzoxazolone derivatives useful as anti-fungal and anti-bacterial agents of non-medical utility. Another object of the invention is to provide proce~ses for the preparation of these benzoxazolone derivatives.
Further object of this invention is to provide fungicidal or bacteridical compositions for non-medical uses containing the derivatives as active ingredient.
Still further object of the invention is to provide a ~lS~4~8 method of combating fungi and bacteria using the derivatives or the compositions containing th0m.
Other objectq and advantage~ of this invention will become Ppparent from the following description.
DETAILED DESCRIPTION OF THE INVENTION:
According to this invention, there is provided a benzoxazolone compound of the general formula:

m' ~ N> (I) n R
wherein X represents a lower alkyl group; Y rspresents a halogen atom; m is O or an integer of 1 to 3; n is an integsr of 1 to 3 and the sum of m + n is an integer of 2 to 4; and R represent~ hydrogen atom or an alkyl, alkylcarbonyl, haloalkylcarbonyl~ alkyoxycarbonyl, alkenylcarbonyl~ alkenyloxycarbonyl, mono- or di-alkylaminocarbonyl, alkylsulfonyl~ phenylsulfonyl or optionally -~ubstituted benzoyl or phenylaminocarbonyl group~ provided that when m is zero, Yn stands for 5~6~7-trichloro groups and R stand~ for an aklenylcarbonyl or alkenyloxycarbonyl group.
In general formula (I), X is a lower alkyl group containing 1 - 4 carbon atoms such a~ methyl, ethyl, n-propyl~ isopropyl or butyl group, among of which is preferably methyl group~ and Y is a halogen atom such as bromine or preferably chlorine.
R may be an alkyl group, particularly an alkyl group of 1-4 carbon atoms; an alkylcarbonyl group, particularly a (Cl 4)alkylcarbonyl group; a ha:Loalkylcarbonyl group, particularly a chloro(Cl 4)alkylcarbonyl group; an alkyloxycarbonyl group, particularly a (Cl 4)alkyloxy-carbonyl group; an alk~nylcarbonyl group, particularlya (C2 4)alkenylcarbonyl group, an alkenyloxycarbonyl group, particularly a (C2 4)alkenyloxycarbonyl group; a mono- or di-alkylaminocarbonyl group, particularly a mono- or di-(Cl 4)alkylaminocarbonyl group; an alkyl-sulfonyl group, particularly a (Cl 4)alkyl 8Ul fonyl group;or phenyl~ulfonyl group. R may also be an optionally ~ubstituted benzoyl group, including unsubstituted benzoyl group and substituted benzoyl group such as methylbenzoyl and chlorobenzoyl; as well as an optionally substituted phenylaminocarbonyl group, including unsubstituted phenylaminocar~onyl group and a substituted phenylamino-earbonyl group such as mono- or di-chlorophenylamino-carbonyl group.
A preferred class of the new compound of this ZO invention includes those of formula (I) in which m is zero~ Yn is 5,6,7-trichloro group and R is an alkenyl-carbonyl or alkenyloxyearbonyl group; and those of formula (I) in whieh m is 1, X is methyl or ethyl, n i8 2 and each Y is ehloro, and speeially in whieh Xm i~ 7-methyl and Yn is 5~6-diehloro group.
Specific examples of the compounds of this inven-tion are listed in Table 1 below.

~s~

Table 1 y~ ~r > C=o Com~ound No.Structur 1 ~ormula l'~Ieltin~ Point (C) C~ O
1 ~ /C=0 . 182 - 184 2 ~ /C=0 150 - 159 C~ I

3 COCE3 C~ ~ /c=o 140 - 141 CQ ~ oCk3 CH ~ ~r/C= 115 - 117 3 COOC2~5 C~ CH3 ~ \C=0 254 - 257 -- 6 _ 6c,e~'-- / 232 - 234 C~ ~ C=O 93 ~ 94 C2N5'~XO/ C=O 126 - 130 C2H5 \[~ ~ C=O 101 ~ 103 COC~3 lO ce~ ~ 106 - 110 C0CH2C~

,8 c~
=o 115 ~ 116 C ~ J~V
2~ 5 CH
12 c,e~O~c=O 251~ 252 c,e N/
H
CX
c.e 1 3 13 ~N/ C=O 122 ~ 123 C~ CH
C~ I
14 '~~C=O 168~ 169 C~ Nl/

CH
c,e 1 3 \~ C=O 54 ~ 56 C OC4Hg-n ~L~S945l~

c,e 1 3 16 \~/c=o 165 ~ 166 ce/ N
C~) c,e 1 3 17 ~1/0~1-- \ 213 - 215 C,e \~~ N/
CO~C~

c,e CH3 18 ~~ C=O 135 ~ 138 c,e COOC~3 c,e CH3 19 C~O/ C=O 170 - 172 c,e CH3 C e J~ N / CH 179 ~ 180 CON~ 3

4~3 . CEi3 C~ 1 21 X ~ ~ J ~ 152 c~ CONH~
CH
C~ 1 3 22 ~~C O 221~ 222 N/ C~
COI`~

23 C~o\c=o l9g~ 200 C~ N/

CQ
24 ~0~1--~ 191 - 193 c,e~--N/
- S02~>
CQ
c,e~ \C=O 248 - 250 4~j~

C~
C~ I
26 3 ~ C=O 133 - 135 CO~H3 C~

27 3 ~ C=O :l49 - 151 C~

28 ~ ~ 218 - 219 R~
29 ~ O ~ \ 136 ~ 138 C~

C~

C=O 103 ~ 105 c~

31 ~ ~C=0 127 ~ 1~0 C~ N /
C~3 COOC~3 C~

32 i-C H ~ \ / ~ 216 - 217 C~
C~ I
33 ~ \C=0 133 ~ 135 C~ .

34 ~ ~ ~ ~ C=0 150 ~ 152 CH

~ - \C=0 262 - 264 C~ N/

:~15 ~-3 36 ~`1~- \C=O 173~ 175 CQ I /
COC~3 CF.3 ~ \ C o 224 ~ 225 C~ CH3 38 ~/c=o 158- 159 CH3 cNocx3 CH

39c~ \C O 236 ~ 239 ce H
CH
C~ 13 40\~0~--\ C o 134 - 135 CQ \r~ N~
ce COCH3 ~s~s~

c~
c~ L
~ o 41 1 0 1 \C=O 25~ ~ 256 C~

42 ~ `-- \ 155 ~ 1~7 CH3 ~ N/

C~ COCH3 C~
C~ I
\~ O
43 1 0 \C=O 174 ~ 176 CH3 ~/--IN/
C~ COOCH3 C~

44 ~ \C=O 275 ~ 277 C~ ~ N/

C~

C~ ~ ~ C=~ 125 ~ 127 "i8 C~
46 ~3r~ \C=O 288 - 289 C~ N/
CF H

c,e ~3r 47 ~ \C O 142 - 144 c,e ~'--N/

3 _ C~

48 3~J`-- \C=O 271 - 272 c,e~~ H

C~
CH3 1 .
49 ~O~~ C=O 117- 118 C~

CE

5 \~~\ C 161 - 163 COCH=CH2 c~

51 C~ ~ \C=O ~6 ~ 98 C~OOCX2Cr~2 The compounds of this invention can be prepared by the reaction routes outlined in Schemes A, B and C
as ~hown below, and some of the compounds may be made by the method as shown in Scheme D hereinbelow:
Scheme A

R ~o=C ~ ~ ~ R~ =O
~II) (III) ~I) In general formulae (I) and (II), the symbols R, X, Y, m and n have the same meanings as giv-en hereinbefore.
The compounds of formula (II) in which R is, for example, acetyl group may be prepared in a high yield by acetylating the aminophenol or the appropriate lower alkyl-substituted orthoaminophenol in a conventional manner and then halogenating the acetylation product with a required equivalent of a halogen. The compound thus obtained may be hydrolized, for example, with dilute hydrochloric acid to give the corresponding compound of formula (II) in which R i~ hydrogen atom. The latter compound can be alkylated or acylated by any conventional method to afford a variety of . - 16 -~ 5'~i8 compounds (II).
In general formula (III), the symbols A and B
which may be the same or different each represents halogen, alkoxy, haloalkoxy, alkylthio or amino group.
The compounds of formula (III) include phosgenic compounds such as phosgen and diphosgen (i.e. trlchloromethyl chloroformate), haloformates, halothiolformates, carbonic die 9 ters and urea.
According to Scheme A, it is generally believed that the compound (I) may be produced in two stages wherein compounds HA or HB is eliminated upon the reaction between the compound (II) and the compound (III) to form an intermediate, which is further reacted with the compound (III) to allow further elimination of compound HB or HA, respectively. Thus~ if a stable intermediate is formed depending upon the nature of the compounds (III) used, it may be isolated on the way and then cyclized to produce the final compound (I). Such stable intermediate may be formed in an alternative route without resort to the reaction between the compound (II) and the compound (III) and then cyclized to give the compound (I).
The reaction between the compounds (II) and (III) may be carried out in the absence of any solvent but preferably in the presence of an organic solvent which may possibly be an excess of the compound (III) itself.
Examples of the solvent to be used include hydrocarbons, halogenated hydrocarbons, ethers, esters, acid amides, alcohol~ and dimethylsulfoxide, among which a ~uitable solvent will be selected for use depending upon the nature of the compounds (III). An acid-binding agent may be used to smoothly advance the reaction, as some of the compounds (III) may lead to the formation of an acid during the course of the reaction. The acid-binding agent to be used for this purpose includes organic amines such as triethylamine and pyridine and inorganic bases such as potas3ium carbonate. The reaction may be effected at ambient temperature, although it can be completed in a reduced period of time when carried out at an elevated temperature.
After the completion of the reaction, the object compound of formula (I) may be isolated and purified by any conventional method. For instance, a salt or salts of the acid-binding agent precipitated in the reaction mixture may be filtered off where the binder is used, and then the solvent be evaporated off from the filtrate to leave the compound (I). Alternatively, water and/or a suitable organic solvent such as benzene, chloroform, ether and tetrahydrofuran may be added to the reaction mixture to fractionally precipitate the object compound therefrom.
Particulars of the method according to Scheme A
are given hereinafter in Examples 1 - 4 and 12.
Scheme B

5~

> O + Halogen ting----7 > C-0 R R
(IV) (V) (I) In general formula (IV), R, X and m are as defined hereinabove, Z is halogen atom and p is 0, 1 or 2. The compounds of formula (IV) may be made according to the method as mentioned above for Scheme A. Example~ of the halogenating agent (V) to be used include halogens such as chlorine or bromine and sulfuryl chloride alone and combinations of a hydrohalogenic acid and an oxidizing agent such as bleaching powder, potassium chlorate or manganese dioxide.
In Scheme B, the halogenation reaction is usually carried out in a solvent and at an elevated temperature to accelerate the reaction in the caqe where the halo-genation is effected with a halogen such as chlorine or bromine or with sulfuryl chloride. The solvent which may be used in that caqe includes water, acetic acid and halogenated hydrocarbons. If the halogenation is conducted uqing a combination of an acid such as hydrochloric or hydrobromic acid and an oxidizing agent such as bleaching powder, potassium chlorate or manganese dioxide, then the compound (IV) may be dissolved in the acid with subsequent addition of the powder of the oxidizing agent or a concentrated aqueous solution thereof. A solvent such as acetic acid may, if necessary, be ll~ed.
The pre~ence of a catalyst, for example, iron chloride, phosphorus compound, aluminium chloride or antimony chloride or the radiation of ultraviolet rays ~erves to smoothly ad~ance the reaction of Scheme B.
After the completion of the reaction, the object compound (I) may be recovered from the reaction solution directly by evaporation of the solvent or possibly by addition to the reaction solution of water and/or an appropriate organic ~olvent such as benzene, chloroform, ether or tetrahydrofuran for the purpose of fractional extraction.
Particulars of the method according to Scheme B
are indicated hereinafter in Examples 5-7.
Scheme C

Xm ~ N> (Acid binder) ~" / N

n n (VI) (VII) (I) In formula (VI), X, Y, m and n have the same meanings as given hereinbefore. In formula (VII), R is one of the groups as defined hereinabove other than hydrogen atom and D stands for halogen atom such as chlorine and bromine.
When the group R to be introduced into the starting compound of the formula (VI) is an alkyl group, the reagent of th~ formula (VII) may be a di-alkyl sulfate of the formula R0 ~ S02 where R i9 an alkyl group. Thus, the compounds of formula (VII) may include alkyl halides, acyl halides, dialkyl sulfates, alkenoyl halides and alkenyl haloformates.
These compounds can easily be made by conventional methods known per se.
The reaction between the compound (VI) and the compound (VII) according to Scheme C may be carried out in the absence of any solvent but preferably in the presence of an organic solvent which may possibly be an excess of the compound (VII) itself. Examples of the solvent to be used include hydrocarbons, halogenated hydrocarbons, ethers, esters~ ketones, acid amides, alcohols and dimethylaulfoxide.
The acid binder for use in the reaction includes organic amines such as triethylamine and pyridine and inorganic bases such as potassium carbonate. The reaction may be effected at ambient temperature or conveniently at an elevated temperature. The reaction time to be required will, of course, depend on the nature of the compound (VII) used, the nature of the solvent if used and the reaction temperature employed, although it may be rehuced when the reaction is performed in a polar organic solvent.
For recovery of the object compound after the completion of the reaction, the resulting reaction solution 4~

may b0 filtered to remove a salt of the acid binder precipitated therein and the filtrate be evaporated to leave the desired compound.
In certain cases, water and/or a suitable organic solvent ~uch as benzene, chloroform, ether and tetra-hydrofuran may be added to the reaction mixture to fractionally extract the object compound.
Particulars of the method according to Sche~e C
are given hereinafter in Examples 8-10 and 13.
Scheme D

X ~0> Xm ~ O

n n CONHR' (VI) (VII) (IX) In formulae (VII) and (IX), R' stands for alkyl group or optionally substituted phenyl group. Thus, the method as shown in Scheme D is of formula (I) in which R
represents alkylaminocarbonyl or optionally substituted phenylaminocarbonyl group.
The reaction between the compounds (VI) and (VII) may be carried out in the absence of any solvent but preferably in the presence of an organic solvent which may possibly be an excess of the compound (VII) itself.
The solvent to be used must be inert to the compounds (VII) under the reaction conditions and includes, for example, hydrocarbons, halogenated hydrocarbons,ethers, 4~t3 esters and ketones. If a small amount of an organic amine such as triethylamine or pyridine is present as cata~yst, the reaction will proceed very smoothly. The reaction may be satisfactorily conducted at ambient temperature or possible at an elevated temperature, The duration to be required for the reaction will depend upon the nature of the compound (VII) used and other reaction conditions, although the reaction may be usually completed in a relatively short time.
After the completion of the reaction, the object compound can be isolated from the reaction mixture by filtering off the crystals of the compound precipitated or by evaporation of the solvent as the case may be.
The method according to Scheme D is illustrated in more detail with reference to Example 11.
According to a further aspect of this invention, therefore, there is provided a process for preparing a compound of general formula (I) according to Claim 1, which comprises:
(a) reacting a compound of the formulas Xm ~ OH (II) NHR

wherein X, Y, m, n and R are as defined in Claim 1~ with a carbonyl compound of the formula:

A

0 = C ~ (III) 4~:~B

wherein A and B, which may be ~ame or different, each repre~ent~ halogen atom or alkoxy~ haloalkoxy, alkylthio or amino group;
(b) halogenating a compound of the formula:

m ~ >C=0 (IV) ~ N

P R
wherein X~ m and R are as defined in Claim 1~ Z repre~ents halogen atom and p i~ 0, 1 or 2 to produce a compound of formula (I) bearing in the benzene ring a halogen or halogens whose number is one more than that of the halogen(~) initially present in the qtarting compound of formula (IV);
,, (c) reacting in the pre~ence of an acid binder a compound of the formula:

Xm ~ > C=0 (VI) Yn wherein X~ Y~ m and n are as defined in Claim 1, with a compound of the formula:
RD (VII) wherein R i8 a~ defined in Claim 1 except for hydrogen atom and D repreqents halogen atom, or with a di-alkyl sulfate of the formula:

where R is an alkyl group~ to produce a compound of ~5~

fo~mula (I) in which R is other than hydrogen atom; or (d) reacting a compound of formula (VI) above with an isocyanate compound of the formula:
R'NC0 (VIIX) wherein R' represents alkyl or optionally substituted phenyl group to produce a compound of formula (I) in which R is a group of -CONHR'.
The compounds of this invention are highly active against a wide range of fungal and bacterial diseases, particularly including the following:
Piricularia orvzae (blase) on rice, Pellicularia sasaki (sheath blight) on rice~
Cochliobolu~ mi~abeanus (brown spot) on rice, Xanthomonas oryzae (bacterial leaf blight) on rice, Alternaria kikuchiana (black spot) on pear, Glomerella cin~ulata (ripe rot) on vine, -Cladosporium fulvum (leaf mold) on tomato, Phvtophthora infestans (late blight) on tomato, Sclerotinia sclerotiorum (stem rot) on French bean, Sphaerotheca fuli~inea (powdery mildew) on cucumber, Fusarium oxvsporum (fusarium wilt) on cucumber, Psendoperonospora cubensis (downy mildew) on cucumber, Colletotrichum la~enarium (anthracnose) on cucumber, Erwinia aroidea (soft rot) on Chinese cabbage.
Some of the compounds are significantly active as seed dressings, for example, against Gibberella fuiikuroi (Bakanae disease) and Cochliobolus mivabeanus on rice.

The compounds of the invention are active not only to combat the fungal and bacterial diseases as mentioned above in the agricultural and horticultural applications but also to control the growth of various fungi and bacteria being capable of deteriorating industrial materials. Thus, where the compounds are applied to general industrial products quch as paints, wood, paper, pulp, textiles, cosmetics, leathers, ropes, plastics, rubbers and adhesives, it i9 possible to prevent the product.~ from deterioration or decay which may otherwise be caused by the fungi and bacteria.
The compounds may be used aY such for fungicidal and bactericidal purposes but are more conveniently formulated into compositions for such usage. This inven-tion, therefore, also provides a fungicidal or bactericidal composition for non-medical uses comprising a compound of general formula (I) above as active ingredient, in association with a carrier or diluent for the active ingredient.
This invention further provides a method of controlling the growth of fungi and bacteria in a plant or an industrial material, which method comprise~ applying a compound of general formula (I) to the plant or the industrial material or to the locus of the plant which is infested or likely to beco~e infested with the fungi and bacteria.
For the purposes as described above, the compounds L~

of this invention are preferably used in the from of a composition. The type of the compositions used in any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dusting 5 powders or granules comprisine the active ingredient and a solid diluent or carrier, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, clay, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth and diatomaceous earth. Compositions for dressing seed~ for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed.
The compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersions or emulsions may be prepared by di~solving the active ingredient(s) in an organic 2~ solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable solvents are dimethylsulfoxide, dimethylformamide, formamide and aliphatic alcohols.
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a 4~8 propellant, e.g. fluorotrichloromethane or dichlorodifluoro-methane.
By including suitable additive~, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different composition~ can be better adapted for various utilities.
The active ingredient can be used as mixtures with fertilizers (e.g. nitrogen- or phosphorus-containing fertilizers).
The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally - aqueous disper~ions or emulsions containing the active ingredient in the presence of one or more wetting agent(s~, dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic or non ionic agents.
Suitable cationic agents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl ~ulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates). Suitable non-ionic agents are the condensation products of éthylene oxide with fatty alcohols such as oleyl alcohol or - 28 _ ~s'~

cetyl alcohol, or with alkyl phenoLs such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived frorn long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrolidone and sodiwD carboxymethyl-cellulose), and the vegetable gums (for example gum acacia and gum tragacanth)O
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conven-tional spray equipment. The concentrates may conveniently contain 10-95~, generally 25-60~, by weight of the active ingredient. When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 1 x 10 5~ to 10~ by weight of the active ingredient may be used.
When the composition of this invention is in the form of dusting powders or granules, the composition will generally be applied as such to the plant~ to be treated at a rate of 2 to 4 Kg per 10 ares (or at a rate of 10 to 1,000 g of active ingredient per 10 ares). Where the cornposition is in the form of wettable powder, -emulsifiable concentrate or flowable preparation, it will usually be diluted with water before u~e to give an active ingredient concentration of 10 to 5,000 ppm, the dilute formulation being generally applied to the plants at a rate of 50 to 300 ~ per 10 ares. For treatment of industrial materials such dilute formulation comprising 10 to 5,000 ppm of active ingredient will be applied at an appropriate rate which may vary over a wide range.
The compositions of this invention can comprise also one or more other compounds having biological activity, for example, other known fungicides, bactericides, plant growth regulators, herbicides and insecticides. In particular, some of the compounds have been found to achieve a noticeable synergistic effect when used in admixture with certain known fungicides.
Examples of fungicides and bactericides which may be used in admixture with the compounds of this invention include the following:-carbamate fungicides such as 3,3'-ethylenebis (tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazine-2-thione), zinc or manganese ethylenebis(dithiocarbamate), bis (dimethyldithiocarbamoyl)disulfide, zinc propylenebis 5 5~ 4 ~ 8 (dithiocarbamate), bis(dimethyldithiocarbamoyl)ethylenediamine, nickel dimethyldithiocarbamate, methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, l-isopropylcarbamoyl-3-(3,5-dichlorophenyl)hydantoin, potas~ium N-hydroxymethyl-N-methyldithiocarbamate and 5-methyl-10-butoxycarbonylamino-10,11-dehydrodibenzo (b, f)azepine; pyridine fungicides ~uch as zinc bis(l-hydroxy-2(lH)pyridinethionate) and 2-pyridinethiol-1-oxide sodium salt; phosphorus fungicides 3uch as 0,0-diisopropyl S-benzylphosphorothioate and 0-ethyl S,S-diphenyldithiophosphate; phthalimide fungicides such as N-(2,6-diethylphenyl)phthalimide and N-(2,6-diethylphenyl)-4-methylphthalimide; dicarboxyimide fungicides such as N-trichloromethylthio-4-cyclohexene-1,2-dicarboxy-imide and N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboxyimide; oxathine fungicides such as 5,6-dihydro-2-methyl-1,4-oxathine-3-carboxanilido-4,4-dioxide and 5,6-dihydro-2-methyl-1~4-oxathine-3-carboxanilide~
naphthoquinone fungicide such as 2,3-dichloro-1,4-naphthoquinone, 2-oxy-3-chloro-1,4-naphthoquinone copper sulfate; pentachloronitrobenzene; 1,4-dichloro-2,5-dimethoxybenzene; 5-methyl-S-triazol~3,4-b)benzothiazole;
2-(thiocyanomethylthio)benzothiazole; 3-hydroxy-5-methylisooxazole; N-2,3-dichlorophenyltetrachlorophthalamic acid; 5-ethoxy-3-trichloromethyl-1-2,4-thiadiazole; 2,4-dichloro-6-(0-chloroanilino)-1~3~5-triazine; 2,3-dicyano-1,4-dithioanthraquinone; copper 8-quinolinate; polyoxine;

~3L~

varidamycin; cycloheximide, iron methanearsonate;
diisopropyl-1,3-dithiolane-2-iridene malonate;
3-allyloxy-1,2-benzoi~othiazol-1,1-dioxide; kasugamycin;
~lasticidin S; 4,5,6,7-tetrachlorophthalide; 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyloxazolizine-2,4-dione;
N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxyimide; S-n-butyl-5'-para-t-butylbenzyl-N-3-pyridyldithiocarbonylimidate; 4-chlorophenoxy-3,3-dimethyl-l-(lH,1,3,4-triazol-1-yl)-2-butanone; methyl-D,L-N-(2,6-dimethylphenyl)-N~(2'-methoxyacetyl)alaninate;
N-propyl-N-(2-(2,4,6-trichlorophenoxy)ethyl)imidazol-1-carboxamide; N-(3,5-dichlorophenyl)succinimide; tetra-chloroisophthalonitrile; 2-dimethylamino-4-methyl-5-n-butyl-6-hydroxypyrimidine; 2,6-dichloro-4-nitroaniline;
3-methyl-4-chlorobenzthiazol-2-one; 1,2,5,6-tetrahydro-4H-pyrrolo-(3,2,1-i,~)quinoline-2-one; 3'-isoproroxy-2-methylbenzanilide; 1-(2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxorane-2-ylmethyl)-lH,1,2,4-triazol; 1,2-benzisothiazoline-3-one; basic copper chloride; basic copper sulfate; N'-dichlorofluoromethylthio-N,N-dimethyl-N-phenylsulfamide;
ethyl-N-(3-dimethylamino-propyl)thiocarbamate hydrochloride;
piomycin; S,S-6-methylquinoxallne-2,3-diyldithiocarbonate;
complex of zinc and maneb;dizinc bis(dimethyldithiocarbamate~
ethylenebis(dithiocarbamate).
Examples of plant growth regulations and herbicides which may be used in combination with the compound of this invention includes the following:-4.~

isourea patent growth regulators such as N-methoxycarbonyl-N'-4-methylphenylcarbamoylethyliqourea and l-(4-chlorophenylcarbamoyl)-3-ethoxycarbonyl-2-methylisourea; another type of patent growth regulators such as sodium naphthaleneacetate, 1,2-dihydropyridazine-3,6-dione and gibberellins; triazine herbicides such as 2-methylthio-4,6-bisethylamino-1,3,5-triazine, 2-chloro-4,6-bisethylamino-1~3~5-triazine~ 2-methoxy-4-ethylamino-

6-isopropylamino-1,3,5-triazine, 2-chloro-4-methylamino-6-isopropylamino-s-triazine~ Z-methylthio-4~o-bis (iqopropylamino)-s-triazine and 2-methylthio-4-ethylamino-6-i~opropylamino-s-triazine; phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid and-methyl, ethyl and butyl esters thereof, 2-chIoro-4-methylphenoxyacetic acid, 4-chloro-2-methylphenoxyaceticacid and ethyl 2-methyl-4-chlorophenoxybutylate; diphenylether herbicides such as 2,4,6-trichlorophenyl-4'-nitrophenylether, 2,4-dichlorophenyl-4'-nitrophenylether and 3,5-dimethylphenyl-4~-nitrophenylether;urea herbicides ~uch as 3-(3~4-dichlorophenyl)-l-methoxy-l-methylurea, 3-(3,4-dichloro-phenyl)-l,l-dimethylurea and 3-(4-chlorophenyl)-1,1-dimethyl urea; carbamate herbicides such as 3-methoxycarbonylaminophenyl-N-(3-methylphenyl)carbamate, isopropyl-N-(3-chlorophenyl)carbamate and methyl-N-(3,4'-dichlorophenyl)carbamate; uracil herbicides such as 5-bromo-3-sec-butyl-6-methyluracil and 1-cyclohexyl-3,5-propyleneuracil; thiocarbamate herbicides such as B

S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate, S-ethyl-N-cyclohexyl-N-ethylthiolcarbamate and S-ethyl-hexahydro-lH-azepine-l-carbothioate and S-ethyl-N,N-di-n-propylthiocarbamate; pyridinium herbicide~ ~uch as l,l'-dimethyl-4,4'-bispyridinium dichloride; pho~phoric herbicides ~uch as N-(phosphonomethyl)glycine; aniline herbicides ~uch as L,L,L-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline and N3,N3-diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; acid anilide herbicides such as 2-chloro-2',6'-diethyl-N-(butoxymethyl) acetoanilide, 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetoanilide, and 3,4-dichloropropioneanilide; pyrazole herbicide~ such as 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(p-toluenesulfonyloxy)pyrazole; 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazoline-2-one;
2-(N-isopropyl, N-(4-chlorophenyl)carbamoyl)-4-chloro-5-methyl-4-isooxazoline-3-one; 3-isopropyl-benzo-2-thia-1,3-diazinone-(4)-2,4-dioxide and 3-(2-methylphenoxy) pyridazine.
Examples of insecticides which may be mixed with the compounds of this in~ention include the following;-phosphoric insecticides such a~ 0,0-diethyl 0-(2-isopropyl-4-methyl-6-pyrimidinyl)phosphorothioate, 0~0-diethyl S-2-~(ethylthio)ethyl)phosphoroditioate, 0~0-dimethyl 0-(3-methyl-4-nitrophenyl)thiophosphate, 0,0-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate~
0,0-dimethyl S-(N-methyl-N-formylcarbamoylmethyl) phosphorodithioate, 0,0-dimethyl S-2-((ethylthio)ethyl~
phosphorodithioate, 0,0-diethyl S-2-~(ethylthio)ethyl) phoqphorodithioate, 0,0-dimethyl 1-hydroxy-2,2,2-trichloroethylpho~phonate, 0,0-diethyl-0-(5-phenyl-3-isooxazolyl)phosphorothioate, 0,0-dimethyl 0-(2,5-dichloro-4-bromophenyl)phosphonothioate, 0,0-dimethyl 0-(3-methyl-4-methylmercaptophenyl)thiophosphate, 0-ethyl 0-p-cyanophenyl phenylphosphonothioate, 0,0-dimethyl S-(1,2-dicarboethoxyethyl)phosphorodithioate, 2-chloro-(2,4,5-trichlorophenyl)vinyldimethyl phosphate, 2-chloro-1-(2,4-dichlorophenyl)vinyldimethyl phosphate, 0~0-dimethyl 0-p-cyanophenyl phosphorothioate~ 2,2-dichlorovinyl dimethyl phosphate, 0,0-diethyl 0-2,4-dichlorophenyl phosphorothioate, ethyl mercaptophenylacetate 0,0-dimethyl phoqphorodithioate, S-((6-chloro-2-oxo-3-benzooxazolinyl)methyl)0~0-diethyl phosphorodithioate, 2-chloro-1-(2,4-dichlorophenyl)vinyl diethylphosphate, 0,0-diethyl 0-(3-oxo-2-phenyl-2H-pyridazine-6-yl) pho~phorothioate, 0,0-dimethyl S-(l-methyl-2-ethylqulfinyl) ethyl phosphorothiolate~ 0~0-dimethyl S-phthalimidemethyl phosphorodithioate~ 0~0-diethyl S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl)phosphorodithioate, 0,0-dimethyl S-(2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-(4)-methyl) dithiophosphate, 2-methoxy-4H-1,3,2-benzooxaphosphorine 2-sulfide~ 0~0-diethyl 0-(3,5,6-trichloro-2-pyridyl) - 35 ~

h~

phosphorothioate, 0-ethyl 0-2,4-dichlorophenyl thionobenzene phosphonate~ S-(4,6-diamino-s-triazine-2-yl-methyl)0,0-dimethyl phosphorodithioate, 0-ethyl 0-p-nitrophenyl phenylphosphonothioate, 0,S-dimethyl N-acetyl pho~phoroamidothioate, 2-diethylamino-6-methylpyrimidine-4-yl-diethylphosphorothionate, 2-diethylamino-6-methylpyrimidine-4-yl-dimethylphosphoro-thionate, 0,0-diethyl 0-p-(methylsulfinyl)phenyl phosphorothioate, 0-ethyl S-propyl 0-2,4-dichlorophenyl phosphorodithioate and cis-3-(dimethoxyphosphinoxy)N-methyl-cis-crotoneamide; carbamate insecticides ~uch as l-naphthyl N-methylcarbamate, S-methyl N-((methylcarbamoyl) oxy)thioacetoimidate, m-tolyl methylcarbamate, 3,4-xylyl methylcarbamate, 3,5-xylyl methylcarbamate, 2-sec-butylphenyl N-methylcarbamate, 2,3-dihydro-2,2-dimethyl-

7-benzofuranylmethylcarbamate, 2-isopropoxyphenyl N-methylcarbamate, 1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride and 2-diethylamino-6-methylpyrimidine-4-yl-dimethylcarbamate; and another insecticides such as N,N-dimethyl N'-(2-methyl-4-chlorophenyl)formamidine hydrochloride, nicotine sulfate, milbemycin, 6-methyl-2,3-quinoxalinedithiocyclic S,S-dithiocarbonate, 2,4-dinitro-6-sec-butylphenyl dimethylacrylate, l,l-bis(p-chlorophenyl)2,2,2-trichloroethanol, 2-(p-tert-butylphenoxy)isopropyl-2'-chloroethylsulfite, azoxybenzene, di-(p-chlorophenyl)-cyclopropyl carbinol, di(tri(2,2-dimethyl-2-phenylethyl) tin)oxide, 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl) 4~

urea and S-tricyclohexyltin O,O-d.Li~opropylpho~phoro-dithioate.

~ 37 -Th~s lnvention is furtner illustrated but not limited by the following Examples, in which ~ and parts are all by weight.
Example 1 Preparation of compound No. 6 in Table 1 (Scheme A) 15.8 g of 2-amino-4-chloro-6-methylphenol, 27.6 g of anhydrous potassium carbonate and 150 ml of toluene were placed in a 300 mæ round-bottom flask and 9.9 g of phosgen was slowly added to the mixture with stirring under cooling on ice-water bath. The resulting mixture was heated at reflux temperature for one hour and the reaction solution was then cooled and transferred to a 500 m~ separating funnel.
150 m~ of tetrahydrofuran and 150 m~ of water were added into the funnel and the organic layer was separated, dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated to remove the solvent, leaving brown colored crystals. The crystal~ were recrystallized from a mixed solvent of hexane and acetane to give 15.6 g of 5-chloro-7-methylbenzoxazolon as yellowish brown crystals having a melt-ing point of 232 - 234C.
Example 2 Preparation of comPound No. 48 (Scheme A) 21.2 g of 2-amino-3,5-dimethyl-4,6-dichlorophenol, 27.6 g of anhydrous potassium carbonate and 150 m~ of ethyl acetate were placed in a 300 m~ round-bottom flask and a solution of 9.9 g of diphosgen (trichloromethyl chloroformate) dissolved in 50 m~ of ethyl acetate was added dropwise to the mixture with stirring under cooling on ice-water bath.
The resulting mixture was heated at reflux temperature for one hour and the reaction solution was then cooled and subjected to suction filtration to remove insoluble salts.
The filtrate was concentrated to dryness under reduced pres-sure to afford yellow crystals, which were recrystallized from methanol/acetone to give 20.9 g of 4,6-dimethyl-5,7-dichlorobenzoxazolone as pale yellow crystals with a melting point of 271 - 272C.
Example 3 Preparation of__omPound No. 1 tScheme A) 23.0 g of 2-ethoxycarbonylamino-4-methyl-5-chloro-phenol (made from 2-amino-4-methyl-5-chlorophenol and ethyl chloroformate), together with 50 m~ of dimethylformamide and 0.5 g of anhydrous potassium carbonate, was placed into a 100 m~ round-bottom flask, and the mixture was heated with stirring at 140C for 4 hours. After cooling the resultant solution, 100 mQ of water was added to the latter to pre-cipitate crystals, which were then separated by suction filtration and dried in air at 80C for 2 hours to afford yellow crystals. Recrystallization from methanol gave 15.6 g of sale yellow crystals of 5-methyl-6-chlorobenzoxazolone with a melting point of 182 - 184C.
Example 4 Preparation of comPound No. 33 in Table 1 (Scheme A) 15.1 g of 2-amino-4-isopropylphenol and 100 m~ of acetic acid were placed in a 300 m~ round-bottom flask, followed by addition of 10.2 g of acetic anhydride under ice-water cooling. The mixture was heated at 60C for one hour to complete the reaction, resulting in formation of 2-acetamino-4-isopropylphenol. 15.6 g of gaseous chlorine was then passed into the reaction mixture at a temperature of 80 - 90C and the resulting reaction solution was cooled and evaporated under reduced pressure to leave 25.6 g of 2-acetamino-4-isopropyl-5,6-dichlorophenol as a brown oil.
The oil was placed in a 300 m~ round-bottom flask, to which was added 150 m~ of tetrahydrofuran followed by 9.6 g of sodium hydride (50% suspension in oil). 9.9 g of phosgen was then introduced into the mixture under ice-water cooling and the resultant mixture was agitated at room temperature for one hour. The reaction solution was transferred to a 500 m~
separating funnel, into which were added 150 m~ of benzene and 150 m~ of water and the organic layer was separated, dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated to remove the solvent, leaving brown crystals.
The crystals were recrystallized from a mixed solvent of hexane and acetone to give 24.5 g of N-acetyl-5-isopropyl-6,7-dichlorobenzoxa2010ne as yellowish brown crystals having a melting point of 133 - 135C
Example 5 Preparation of compound No. 12 (Scheme B) 18.4 g of 5-chloro-7-methylbenzoxazolone and 150 m~ of acetic acid were placed in a 300 m~ round-bottom flask and the mixture was heated to 80 - 90C, followed by passage of 7.8 g of gaseous chlorine. The reaction solution was concentrated by evaporation of the acetic acid to yield 20.7 g of yellowish brown crystals. Recrystallization from methanol/acetone gave pink crystals of 5,6-dichloro-7-methyloxazolone with a melting point of 251 -252C.
Example 6 Preparation of comPound No. 35 (Scheme B) la.4 g of 5-chloro-7-methylbenzoxazolone and 150 m~
of acetic acid were placed in a 300 m~ round-bottom fla~k, and to the mixture so obtained was added dropwise a solu-tion of 17.6 g of bromine in 30 m~ of acetic acid. The resultant admixture was heated at 95C for 4 hours, and then the reaction solution was concentrated under reduced pressure by evaporation of the acetic acid to leave reddish brown crystals. Recrystallization from methanol/acetone gave 22.3 g of brown crystal of 5-chloro-6-bromo-7 methylbenzoxazolone with a melting point of 262 - 264C.
Example 7 Preparation of compound No. 45 (Scheme B) 26.0 g of N-acetyl-4-methyl-5,7-dichlorobenzoxazolone and lS0 m~ of chloroform were placed in a 300 m~ round-bottom flask, to which was then added 16.5 g of sulfury chloride at ambient temperature. The mixture was heated at reflux temperature for two hours and the reaction solution so obtained was evaporated under reduced pressure to leave yellowish white crystals. Recrystallization from hexane/
acetone gave 23.6 g of white crystals of N-acetyl-5,6,7-trichlorobenzoxazolone with a mel-ting point of 125 - 127C.
Exam~le 8 Preparation of comPound No. 13 in Table 1 (Scheme C) 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 2.8 g of anhydrous potassium carbonate, 2.5 g of dimethyl sulfate and 50 m~ of acetone were charged in a 100 m~ round-bottom flask and the contents of the flask were heated under reflux for 2 hours. Subsequently, the reaction solution was evaporated under reduced pressure and the residue was poured into 50 m~ of water. The yellowish brown crystals deposited were collected by filtration and recrystallized from hexane/acetone to give 3.9 g of pink crystals of N-methyl-5,6-dichloro-7-methylbenzoxazolone with a melting point of 122 - 123C.
Example 9 PreParation of com~ound No. 16 in Table 1 (Scheme C) 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 2.8 g of benzoyl chloride and 50 m~ of acetone were placed in a 100 m~ round-bottom flask, into which was then added dropwise 2.0 g of triethylamine under ice-water cooling and stirring. After completion of the addition, the resultant mixture was heated under reflux for one hour to accomplish the reaction, whereupon the reaction solution was allowed to cool and filtered to remove the precipitated salts. The filtrate was evaporated to leave yellowish white crystals, which were recrystallized from acetone to give 5.5 g of white crystals of N-benzoyl-5,6-dichloro-7-methyl-benzoxazolone with a melting point of 165 - 166C.
Example 10 Preparation of com~ound No 18 in Table 1 (Scheme C) Following the same procedure as described in Example 9 except that the benzoyl chloride was replaced by 1.9 g of methyl chloroformate, 4~6 g of N-methyoxycarbonyl-5,6-dichloro-7-methylbenzoxazolone was obtained as pink crystals of m.p. 135 - 138C.
Example 11 Preparation o __s~E~ound No. 22 in Table 1 (Scheme D) 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 3.8 g of 3,5-dichlorophenylisocyanate, 50 m~ of acetone and three drops of triethylamine were placed in a 100 m~ round-bottom flask, and the mixture was agitated at ambient temperature for one hour. The precipitate was separated by filtration to give 7.4 g of pi~k crystals which were identified as N-3,5-dichlorophenylcarbamoyl-5,6-dichloro-7-methyl-benzoxazolone of m.p. 221 - 222C.
Example 12 PreParation of comPound No. 50 in Table 1 (Scheme A) The procedure of Example 1 was repeated starting from 22.6 g of 3-chloro-6-acryloylamino-2,4-xylenol (pre-pared by reacting 3-chloro-6-amino-2,4-xylenol with acryloyl chloride) in place of the 2-amino-4-chloro-6-methylphenol.
Recrystallization the resultant crude, yellow crystals from acetone gave 20.4 g of N-acryloyl-5,7-dimethyl-6-chloro-benzoxazolone as yellowish white crystals of m.p. 161 - 163C.

Exam~le 13 Preparation of compound No. 51 in Table 1 (S~heme C) (a) 21.3 g of 6-amino-2,3,4-trichlorophenol, 27.6 g of anhydrous potassium carbonate and 150 m~ of toluene were placed in a 300 m~ round-bottom flash and 9.9 g of phosgen was slowly introduced into the mixture with stirring under cooling on ice-water bath. The resulting mixture was heated at reflux temperature for one hour and the reaction solution was then cooled and transferred to a 500 m~ separating funnel. 150 m~ of tetrahydrofuran and 150 m~ of water were added into the funnel and the organic layer was eparated, dried over anhydrons sodium solfate and filtered. The filtrate was evaporated to remove the solvent, leaving 23.5 g of yellowish white crystals. me crystals were recrystallized from a mixed solvent of methanol and acetone to give 5,6,7-trichlorobenzoxazolone as white crystals having a melting point of 253 - 254C.
(b) The crystalline 5,6,7-trichlorobenzoxazolone obtained as above was placed in a 300 m~ round-bottom flask to which were then added 150 m~ of acetone and 12.0 g of allylchloroformate. m e content of the flask was cooled by ice, followed by dropwise addition of 10.1 g of triethylamine.
The content of the flask was subsequently heated under reflux to accomplish the reaction, and the reaction solution was cooled. The salt deposited was removed by filtration and the filtrate was concentrated to deposit yellow crystals.
Recrystallisation ~rom acetone gave 27.4 g of ~ &

N-allyloxycarbonyl-5,6,7-trichlorobenzoxazolone as yellowish white crystals of a melting point of 96 - 98C.
Example 14 Emulsifiable Concentrate formulation . _ An emulsifiable concentrate comprising 20% of the active ingredient was rnade up by uniformly mixing the in-gredients set out below and stirring the mixture until all the ingredients were dissolved.
Parts Compound No. 17 or Compound No. 5020 Dimethylformamide 30 Xylene 35 Polyoxyethylene alkyl aryl ether 15 Example 15 Flowable formulation A flowable formulation comprising 40% of the active ingredient was prepared by uniformly mixing together the following ingredients:
Parts Compound No. 13 or No. 51 (ground to particle sizes below 10~)40 Lauryl sulfate 2 Sodiurn alkylnaphthalene sulfonate 2 Hydroxypropyl cellulose Water 55 Example 16 Wettable powder formulation A wettable powder containing 20~ of the active in-gredient was made by uniformly mixing the ingredients listed below and then grinding the mixture.
Parts Compound No. 29 or Compound No. 50 20 Polyoxyethylene alkyl aryl ether 5 Calcium lignosulfonate 3 Kieselguhr 72 Example 17 ustin~ powder formulation A dusting powder containing 3% of the active in-gredient was made up by uniformly mixing the ingredients set out below and grinding the resultant mixture.
Parts Compound No. 34 or Compound No. 51 3 Fine powder of silicic an~ydride (silica) 0.5 Calcium stearate 0.5 Clay 50 Talc 46 ExamPle 18 Cranular formulation A composition in the form of granules was prepared by uniformly mixing the ingredients set out below and then granulating the mixture in the presence of added water. me resultant mixture was dried and passed through a sie~e to obtain the desired size of grains.

Parts Compound No. 2 or Compound No. 51 5 Calcium lignosulfonate Bentonite 30 Clay 64 This Example illustrates the fungicidal activity of the benzoxazolone derivatives against Piricularia oryzae (blast on rice)-A wettable powder formulation prepared as described in Example 16 was diluted with water to make up test for-mulations containing the re~uired concentrations of the active ingredient. The test formulation was applied onto aquatic rice seedlings ("Asahi" variety, three-foliage stage) which had been scil-cultured in biscuit pots-of 9 cm diameter in a green house. One day after application, the treated seedings were inoculated by spraying with a spore suspension of Piricularia oryzae and incubating in a moist chamber of a relative humidity of 95 - 100% and a temperature of 24 - 25C. 5 Days after inoculation, the number of blast lesions per leaf at the three-foliage stage was evaluated and disease control was calculated by the following equation:
Desease =/1 _ Number of lesions in treated plots control (%) ~ ) Number of lesions in untreated plots x 100 The desease control is an average value of the results of the tests which were conducted in two replicates at each concentration of the active ingredient. The phytotoxicity towards rice plants was also assessed visually by follow-ing grading:
5 Gradin~ Extent of phvtotoxicitv Severe damage 4 Great damage 3 Moderate damage 2 Light damage 1 Slight damage O No damage The test results are shown in Table 2 below. InTables given hereinafter, controls A; B, C and D indicate the use as the active ingredient of the following compounds disclosed in the literatures noted:

c~
A~ \ (German Patent No. 1,023,627) C~

C~ CQ
B: ~ C=0 (German Patent No. 1,147,007) C~'A" " ~~N/
C~

C~
C: ~ ~ \C=0 (Japanese Patent Publication C~ ~ N/ No. 23519/65) CO~

CQ
D: ~ C-0 (Ja~2nese Patent Publication ~ N No. 23519/65) C~ CO~

Table 2 ~ ~ ~

Concentrations Disease Phyto-Com~ound (~m) control(~o~ toxicit~

3 " 92 0 4 " 96 0

8 " 82 0 11 " 98 0 12 " 88 0 14 " 98 0 17 " 98 0 18 " 100 0 19 " 100 22 " 98 27 " 92 0 28 " 98 0 31 " 98 0 34 " 100 0 42 " 100 0 43 " 100 0 " 98 0 47 " 96 0 49 " 94 0 5 " 100 0 51 " 100 0 Control A " 52 Control B " 63 2 Control C " 30 Control D " 30 IBP(Control)* 480 75 0 Untreated - o O
( 3H70)2P SCH

Example 20 This Example illustrates the activity of the benzoxazolone derivatives against Cochliobolus miyabeanus (brown spot on rice).
The tests were carried out by the same procedure as in Example 19 except that rice seedllngs at the four-foliage stage were inoculated with a spore suspension of Cochliobolus miYabeanus.
The results are set out in Table 3 below.

Table 3 Compound Con- Disease Phytotoxicity No. centrationscontrol (ppm) (~) . . _ . . .

2 " 98 0 3 " 82 0 4 " 96 0 " 76 0 6 " 76 0 7 " 72 0 8 " 88 0

9 " 80 0 " 92 0 11 " 88 0 12 " 100 0 13 " 96 0 14 " 100 0 " 94 0 16 " 96 0 17 " 100 0 18 " 100 19 " 98 0 " 100 0 21 " 96 0 22 " 100 . 0 ~ ~ s~ L~

Table 3 (continued~

24 " 98 0 " 96 0 2~ " ~8 0 27 " 98 0 28 " 98 0 " 76 0 " 72 0 " 98 0 33 " 76 0 " 88 0 " 94 0 36 " 98 0 37 " 73 0 38 " 88 0 39 " 98 0 " 100 o 41 " 98 0 42 " 96 0 43 " 100 0 44 " 76 0 " 82 0 46 " 80 0 47 " 100 o 48 " 72 0 ~s~

Table 3 (continued) 49 " lC)O O
" lOO O
51 " lOO o .
Control A " 32 3 Control B " 54 4 Control C " 25 Control D " 30 2 Triazine* " 93 o (Control) -Untreated - O
_ _ _ . . ... . _ . . _ _ _ .

* Triazine: C~
N l N C~
101 >~
C~ N '~NH

Exam~le 21 In this Example, the benzoxazolone derivatives were tested against Phytophthora infest.ans (late blight on tomato).
Dilute formulations of a wettable powder containing the required concentrations of the active ingredient were prepared as described in Example 16. The test formula-tion was applied at a rate of 10 m~ per pot onto young seedlings of tomato ("Sekaiichi" variety) at the three-true leaf stage which had been soil-cultured in biscuit pots of 9 cm diameter in a greenhouse. 5pores of Ph Phytophthora infestans which had been produced on potato tubers were suspended in sterilized water to give a spore concentration at which 20 - 30 spores were detectable within one sight under a microscope.of 150 magnification.
One day after application, the leaves of the tomato seedlings were inoculated with drops of the spore suspension and the seedlings were then kept at 20C in a humid room to allow development of the disease. 3 Days later, the seed-ings were removed from the room and the number of attacked leaves was counted. The percentage of attacked leaves and disease control were calculated by the following equations:

Percentage of Number of attacked leaves = ~ , '^O
attacked leaves ~Number of inoculated leaves x Percentage of attacked leaves Disease ~ in treated plots = 1 - Ix 100 control (%) Percentage of attacked leaves in untreated plots The phytotoxicity towards tomato plants was also evaluated by the same grading as defined in Examp~ 19. The results are set out ln Table 4 below.

Table 4 Compound Concentra- Disease Phytotoxicity No. tions (ppm~ Control (~) 1 500 .98 0 2 " 96 0 " 97 0 11 " 94 o 12 " 98 0 14 " 94 0 17 " 99 0 18 " 100 0 19 " 100 0 22 " 98 0 23 " 96 0 31 " 100 0 32 " 98 0 37 " 98 0 " 98 0 Table 4 (Continued)) 41 " 98 0 42 " 90 0 43 " 100 0 48 " 92 0 49 " 98 0 " 100 o 51 " 100 0 Control A ~ o 0 Control B " 0 0 Control C " o o Control D " 0 M&neb " 87 0 (Control) .
Untreated - 0 ~Maneb: S
CH2HNCS~
I >Mn S

Exam~le 22 This Example illustrates the activity of the deriva-tives against Sphaerotheca fuliginea (powdery mildew on cucumber).
The dilute formulation prepared as in Example 16 was applied at a rate of 10 m~ per pot onto cucumber seedlings ("Sagamihan~iro" variety) at the one-leaf stage which had been soil-cultured in biscuit pots of 9 cm diameter in a greenhouse. On the following day, the seedlings were ino-culated by spraying with a spore suspension of Sphaerothecafuliginea. Ten days after inoculation, assessment was made of the percentage of lesion area on the seedlings and disease control was calculated by the following equation:

Percentage of lesion area Disease ~1 in treated area )x 100 control (%) \ Percentage of lesion area in untreated p~ots The results are tabulated in Table 5 below.

Table 5 Compound Concdntra- Disease Phytotoxicity No. -tions (ppm) Control (%) _ " 85 0 14 " 92 0 17 " 96 0 22 ll 94 0 26 " lOO O
28 " 98 0 33 " lOO o 36 " lOO O

Table 5 (Continued) 39 " 100 0 " 100 o 41 " 100 0 42 " 100 0 44 " 97 " 100 0 46 " 99 0 47 " 100 0 " 100 0 51 " 100 0 . .
Control A " 20 Control B " 10 Control C " 10 Control D " 13 Dimethirimol " 95 0 (Control) Untreated - O

* Dimethirimol:
n-C4Hg CH3 ~ OH
I OJ
N ~ N
N(CH3)2 E~am~le 2~
The benzox~zolone derivatives ~ere tested against Pseudo~eronos~ora c~bensis (do~ny mildew on cucumber).
The dilute formulation prepared as in Example 16 was applied at a rate of 10 m~ per pot to the back faces of leaves of cucumber young seedlings ("Sagamihanjiro"
variety) at the one-true leaf stage which had been soil-cultured in biscuit pots of 9 cm diameter in a greenhouse.
Spores of Pseudo~eronospora cubensis which had been produced on cucumber leaves in a disease-development environment were brushed away into deionized water containing 50 ppm of Tween 20 (trade name of polyoxyethylene sorbitan mono-laurate, product of Kao Atlas Co ) so as to give an inoculum having a spore concentration at which 20 - 30 spores were detectable within one sight under a microscope of 150 magnification.
One day after application of the formulation, the leaves of the cucumber seedlings were inoculated on their treated back faces by spraying with the inoculum. After completion of the inoculation, the seedlings were first placed in a humid room at 20C and then kept in a green-house at 24C to allow development of the disease. Six days later, the seedlings were remo~ed from the greenhouse and assessment was made of the percentage of lesion area on the seedlings. Disease control (~o) was calculated by the equation as indicated in Example 21 and phytotoxicity to cucumber plants was evaluated by the same grading as in E~ample 19.
The test results are set ou~ in Table 6 below.

Table 6 No. Concentrations Disease Phyto-2 " 88 0 4 " 99 0 12 " 98 0 14 " 100 0 18 ll 100 0 " 92 0 26 " 98 0 27 " 100 0 28 ll 94 o 31 " 100 0 32 " 100 0 33 " 98 0 34 " 100 - 0 36 " 96 0 41 " 96 0 42 " 100 0 43 " 100 0 44 " 100 0 49 " 99 0 " 100 0 51 " 100 0 - 61 - Cont'd Table 6 (Continued) Control A 500 20 Control B " 25 Control C " 30 Control D " 36 Maneb (control) " 90 0 Untreated - O

Exam~le 24 The benzoxazolone derivatives were tested against Collectotrichum lagenarium (anthracnose on cucumber), The dilute formulation prepared as in Example 16 was applied at a rate of 10 m~ per pot to the leaves of cucumber young seedlings ("Sagamihanpaku" variety) at the one-true leaf stage which had been soil-cultured in biscuit pots of 9 cm diameter in a greenhouse. Spores of Collectotrichum la~enarium produced by incubation on an oatmeal-agar medium at 24C for 10 days were suspended in sterilized water containing 50 ppm of Tween 20 so as to give a suspension of a spore concentration at which about 100 spores were detectable within one sight under a micro-scope of 150 magnification.
One day afte~ application of the formulation, the treated leaves of the cucumber seedlings were inoculated by spraying with the aforesaid spore suspension. The seedlir.gs thus inoculated were subsequently treated in the sa~e way as noted in Example 23 and disease control was calculated by the following equation:
Number of lesions in treated ~lots ~ x 100 Disease control(~o) = (1 ~ Number of lesions in untreated plots The results are shown in Table 7 below.

Table 7 CompoundConcentretions Disease Phyto-4 " 97 0 9 " 94 12 " 98 0 14 " 100 0 17 " 100 0 18 " 100 0 22 " 98 0 " 96 0 27 " 100 0 " 99 31 " 100 0 " 98 0 36 " 100 0 39 ~I 100 0 41 " 94 0 43 " 100 0 - 63 - Cont'd t~

Table 7 (Continued) 51 t~ 100 0 . . .
Control A " 45 5" B " 37 " C " 35 " D " 43 (control) 98 0 _ . . _ . . . .
Untreated - o * TPN: C~
C~ ~ CN

10 1 C~ C~

C~

Exam~le 25 Some of the benzo~æzolone derivatives were tested against Pellicularia sasaki (Sheath blight on rice).

The dilute formu]ation prepared as in E~ample 16 was applied at a rate o~ 40 m~ per three pots to rice seedlings at the six-foliage stage which had been soil-cultured in biscuit pots of 9 cm diameter in a glasshouse.

On the following day, the infection of the seedlings with the fungal disease was effected by putting on the second leaf sheath an agar disc obtained by boring with a cork borer of 5 mm diameter the edge of the colony of Pellicularia sasaki fungus which had been incubated on . .
potato-sucrose agar medium at 27C for 48 hours. The infected seedlir~gs were then kept overnight in a moist room. 4 Days after infection, assessment was made of the length of lesions per stem and disease control was calculated by the following equation:

~ ength of lesions in Disease control(~o) = (l - tLrergthdofllesions in ) ~ 100 untreated plots The test results are shown in Table 8 below.

Table 8 Com~ound No. Concentrations (~m) Disease control(%~
lO 50 500 lOO

. .
Control A " 15 B " O
" C " 10 15" D l~ O

(Control) 125 90 Untreated - O

- 6~ -

Claims (20)

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

1. A benzoxazolone compound of the general formula:

(I) wherein X represents a C1 to C4-alkyl group; Y represents a halogen atom selected from chlorine and bromine; m is an integer of 1 to 3; n is an integer of 1 to 3; wherein the sum of m + n is an integer of 2 to 4; and R represents a group selected from C1 to C4-alkyl, C1 to C4-alkylcarbonyl, chloro-C1 to C4-alkylcarbonyl, C1 to C4-alkyloxycarbonyl, C2 to C4-alkenylcarbonyl, C2 to C4-alkenyloxycarbonyl, C1 to C4-alkylsulfonyl and phenylsulfonyl.

2. A benzoxazolone compound according to claim 1, which is of the general formula:

(Ia) wherein X represents a C1 to C4-alkyl group; Y represents chlorine atom; n is an integer of 1 to 3; and R represents a group selected from C1 to C4-alkyloxycarbonyl, chloro-C1 to C4-alkylcarbonyl, C1 to C4-alkylsulfonyl and phenylsulfonyl.

3. A benzoxazolone compound according to claim 1 or 2, wherein R represents a C1 to C4-alkyloxycarbonyl group.

4. A benzoxazolone compound according to claim 1 or 2, wherein R represents a C1 to C4-alkyloxycarbonyl group; and X represents a group selected from methyl and ethyl.

5. A benzoxazolone compound according to claim 1 or 2, wherein R represents a C1 to C4-alkyloxycarbonyl group; X
represents 7-methyl; and Yn represents 5,6-dichloro.

6. A benzoxazolone compound according to claim 1 or 2, which is N-chloroacetyl 6-chloro-5-ethylbenzoxazolone.

7. A benzoxazolone compound according to claim 1 or 2, which is selected from the group consisting of N-methoxycarbonyl 6-chloro-5-ethylbenzoxazolone, N-methoxycarbonyl 7-methyl-5,6-dichlorobenzoxazolone, N-methoxycarbonyl 6,7-dichloro-5-methyl-benzoxazolone, N-methoxycarbonyl 5,7-dichloro-4-methylbenzoxazolone and N-methoxycarbonyl 4,6,7-trichloro-5-methylbenzoxazolone.

8. A benzoxazolone compound according to claim 1 or 2, which is selected from the group consisting of N-methylsulfonyl 7-methyl-5,6-dichlorobenzoxazolone and N-phenylsulfonyl 7-methyl-5,6-dichlorobenzoxazolone.

9. A benzoxazolone compound according to claim 1, which is of the general formula:

(Ib) wherein X represents a C1 to C4-alkyl group; Y represents a halogen atom selected from chlorine and bromine; n is an integer of 1 to 3; and R represents a C1 to C4-alkylcarbonyl group.

10. A benzoxazolone compound according to claim 9, wherein X represents a group selected from methyl and ethyl.

11. A benzoxazolone compound according to claim 10, wherein X represents methyl.

12. A benzoxazolone compound according to claim 9, which is selected from the group consisting of N-acetyl 6-chloro-5-methylbenzoxazolone, N-acetyl 7-methyl-5-chloro-benzoxazolone, N-acetyl 6-chloro-5-ethylbenzoxazolone, N-acetyl 5,6-dichloro-7-methylbenzoxazolone, N-valeryl-5,6-dichloro-7-methylbenzoxazolone, N-acetyl 5-methyl-6,7-dichlorobenzoxazolone, N-acetyl-4-methyl-5,7-dichlorobenzoxa-zolone, N-acetyl 6,7-dichloro-5-isopropylbenzoxazolone, N-acetyl 7-methyl-6-bromo-5-chlorobenzoxazolone, N-acetyl 7-methyl-4,5,6-trichlorobenzoxazolone, N-acetyl 5-methyl-4,6,7-trichlorobenzoxazolone, N-acetyl 4-methyl-5,6,7-tri-chlorobenzoxazolone and N-acetyl 4-methyl 6-bromo-5,7-dichlorobenzoxazolone.

13. A 5,6,7-trichlorobenzoxazolone compound according to claim 1, which is of the general formula:

(Ic) wherein R represents a C2 to C4-alkenyloxycarbonyl group.

14. A benzoxazolone compound according to claim 13, which is N-alkyloxycarbonyl 5,6,7-trichlorobenzoxazolone.

15. A benzoxazolone compound according to claim 1, which is of the general formula:

(Id) wherein X represents a C1 to C4-alkyl group; Y represents chlorine atom; m is an integer of 1 or 2; and R represents a C2 to C4-alkenylcarbonyl group.

16. A benzoxazolone compound according to claim 15, which is N-vinylcarbonyl 6-chloro-5,7-dimethylbenzoxazolone.

17. A benzoxazolone compound according to claim 1, which is of the general formula:

(Ie) wherein X represents a C1 to C4-alkyl group; Y represents chlorine atom; m is an integer of 1 or 2; n is an integer of 1 or 2; and R represents a C1 to C4-alkyl group.

18. A benzoxazolone compound according to claim 17, which is selected from the group consisting of N-methyl 5,6-dichloro-7-methylbenzoxazolone and N-methyl 4-methyl-5,7-dichlorobenzoxazolone.

19. A process for preparing a compound of the general formula (I) according to claim 1, which comprises:
(a) reacting a compound of the general formula:

(II) wherein X, Y, m, n and R are as defined in claim 1, with a carbonyl compound of the general formula:

(III) wherein A and B independently represent a group selected from halogen atom, alkoxy, haloalkoxy, alkylthio and amino;
(b) chloronating or bromonating a compound of the general formula:

(IV) wherein X, Y, m, n and R are as defined in claim 1;
(c) reacting in the presence of an acid binder a compound of the general formula:

(VI) wherein X, Y, m and n are as defined in claim 1;
(i) with a compound of the general formula:

RD (VII) wherein R is as defined in claim 1, and D represents a halogen atom; or (ii) with a di-alkyl sulfate of the general formula:

wherein R represents a C1 to C4-alkyl group, to produce a compound of general formula (I) wherein R represents a C1 to C4-alkyl group; or (d) reacting a compound of the general formula (VI) with an isocyanate compound of the general formula:

R'NCO (VIII) wherein R' represents a C1 to C4-alkyl group, to produce a compound of general formula (I) wherein R represents the group -CONHR', wherein R' is as defined above.

20. A method of controlling the growth of fungi and bacteria in a plant, which method comprises applying an effective amount of a compound of general formula (I) as defined in claim 1 to the plant or the locus of the plant which is infested or is susceptible to being infested with fungi and bacteria.