NL8100395A - BENZOXAZOLONE DERIVATIVES, METHODS FOR THE PREPARATION THEREOF, AND PREPARATIONS CONTAINING THESE COMPOUNDS. - Google Patents

Description

-1 -, i

Benzoxazolone derivatives, methods for their preparation, and preparations containing these compounds.

The invention relates to new benzoxazolone derivatives, methods for their preparation, fungicidal and bactericidal compositions containing these compounds, as well as methods for controlling various fungi and bacteria using these derivatives and preparations.

Certain benzoxazolone derivatives are known to be useful as fungicides and bactericides for agricultural and horticultural purposes. For example, German Pat. such as a 5-chloro, 5,5- or 5,7-dichloro or 4,5,7-trichloro group, but no alkyl substituent. German patent 1,147,007 describes the anti-microbial properties of 4,5,6,7 -tetrachlorobenzoxazolone, while Russian patent 355008 discloses such properties for 4,5,6-trichlorobenzoxazolone.

Furthermore, Japanese patent application 23519/65 describes the fungicidal and bactericidal properties of benzoxazolone derivatives of formula 1, wherein R 2 = R 2 = R 2 = H; R ^ = Cl, R2 = R3 = H; 20 R2 = Cl, R = R3 = H? R = R2 = Cl, R3 = H; or Rj = R2 = R3 = Cl; and R 1 is a phenyl group, optionally substituted by halogen,. nitro, a short chain alkyl, or short chain alkoxy group.

We have synthesized and carefully studied a variety of other new benzoxazolone derivatives in an effort to develop new * 25 benzoxazolone microbicides, which have low toxicity, good safety and high activity against a wide range of fungi and bacteria. We have now found novel benzoxazolone derivatives, which have hitherto not been described in the literature, and which are very useful as fungicides and bactericides. The derivatives of the invention contain in the benzene ring or at least one short chain alkyl group and at least one halogen substituent or instead a 5,6,7-trichloro substituent. These new derivatives according to the invention have been found to be considerable.

It appears to have improved fungicidal and bactericidal properties compared to the known compounds 4,5,7-tri-chlorobenzoxazolone and 4,5,6-trichlorobenzoxazolone, as clearly shown in the Examples below .

The object of the invention is to provide new benzoxazolone derivatives which are useful as anti-fungus and anti-bacterial agents for non-medical applications. It is also an object of the invention to provide methods for preparing these benzoxazolone derivatives.

Another object of the invention is to provide fungicidal and / or bactericidal preparations for non-medical use, containing the said derivatives as active ingredients.

It is also an object of the invention to provide a method for controlling fungi and bacteria by means of the derivatives or preparations containing these derivatives.

According to the invention, new benzoxazolone compound-15 is provided and of formula 2, wherein X is a short chain alkyl group; Y is a halogen atom; m = * 0 - 3, n = 1 - 3 and the sum of m + n equals 2-4, where m and n are integers, provided that if m = 0, then n = 3 and Yn is a 5,6,7-trichloro group; and R is hydrogen or an alkyl 20, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, mono- or di-alkylaminocarbonyl, alkylsulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group.

In formula 2, X is a short chain alkyl group with 1-4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl or butyl group, with the methyl group being preferred, and Y is a halogen atom, such as bromine or , preferably, chlorine.

R may be an alkyl group, especially with 1-4 C atoms; an alkyl carbonyl group, especially having 1-4 carbon atoms in the alkyl group; a haloalkylcarbonyl group, especially with 1-4 C atoms in the alkyl group; an alkoxycarbonyl group, in particular with 1-4 C atoms in the alkoxy group; an alkenylcarbonyl group, especially having 2-4 C atoms in the alkenyl group; an alkenyloxycarbonyl group, especially 35 having 2-4 C atoms in the alkenyl group; a mono- or di-alkylamino-carbonyl group with 1-4 C atoms in the alkyl group (s); an alkyl sulfonyl group, especially having 1-4 C atoms in the alkyl group; or a phenylsulfonyl group. R may also be an optionally substituted benzoyl group, including an unsubstituted benzoyl group and a substituted benzoyl group, such as methylbenzoyl or chlorobenzoyl; as well as an optionally substituted phenylaminocarbonyl group, including an unsubstituted phenylaminocarbonyl group and a substituted. a phenylaminocarbonyl group, such as mono- or dichlorophenyl-5-aminocarbonyl group.

A preferred group of compounds of formula 2 are the. compounds of formula 2, wherein m = 0 and Yn is a 5,6,7-trichloro group. Another preferred group of compounds' are the compounds of formula 2, wherein Xm is a methyl, especially 7-methyl group and Yn dichlor, especially 5,6-dichloro group.

Specific examples of compounds of the invention are summarized in Table A below.

Table A, 15 Formula 2

Connection Structural Formula_Smpt.

cz

CZ I

VOy ° •. 1 | / C-C 253 - 254 C £ cz l 2 I Ü i c = 0 135 - 1.39 CH ^ 4,

CZ

CZs' 3 YY V ° 171 ~ 172 ci r ccch 5

Cl c ^ A. ° x 4 I U! C = 0 161 - 162 COC2H5 8 1 0 0 39 5. I ir - 3a - • Ci 5 0 £ 'jpT °) - 0 ΐώ U2 GOC ^ Hgii

Ci 6 ΙΟΙ C = 0. 187-188 f COCH2Ci Ci

Gi I

7 TO "0 ^ = 0 188-190 r /

Ci

Ci ToT ° 0 = 0 198 - 200 »<2> 9 £ ctfi

Qg Jv.

5 9 'Tq'i ° ^ c = ° 157 ~ l59

Ci '^ Vs ^ X ^' N .-- CO ^ O) - CH3 CH3 i * 8100395 - 3b - *

Ci 'ΎοΓ °> ° 1> 63'164 GOOCH ^

Ci 11 CiToT ° Vo 173 - 175 f CQKHCH ^

Ci 12 ΤθΓ °> = ° 12 7-129 k-- yy / C 1 CON (CH5) 2

Ci

Ci 'k / ·' nY "" - "^ ^ loil ~ 1 ^ 5 13! (J I c = o 5

Ci

Cl JL

5 11 Toll> = 0 235 - 237 ci: i

Go: ïh-70) '^ ci 8100395 _ 9 i - 3c -

Cl

, C1Q

15 [o [r ° 2i®219 ci'X / 'r SO2CH5

Cl 16 ToT ° 0 = 0.197 - 198 C ©

Cl 17 ΤθΤ ° \ = ο 99 - 100

Cl 'f COOC2H5

Cl

Cl 1 ^ 18 Tof xo = o 109 -109 C00C, H7-n Cl.

Cl I

vA, ^ 0 5 19 | Ol C = 0 129 - 130 f C00C, H ^ -iso J i 8 1 0 0 39 5 - 4 -.

20 ^ = 0 ΐί2 '184 Η C £ 21 Υθ] [^ / C = 0 150' 159

pu I

^ 3 COCH ^ cV ~ v, o 22 jOj) .0 140 - 141 OH, f, -> 3 OT - @>

Ch-z

Ci ^ 5 J5 ί Ο I ° 'c = 0 115 - r7 * v /

Cil3 io'OC K

Ch%

Ci I '5 2t YqI / = ° 2¾ - 257

H

8 1 0 0 3 9 5 - 4a -

CH

25 ΙΟΙ Nc = ° 252 '234, ΛΛν / C £ ^ l

H

ch5 26 foT0 ^ = 0. 95 - 94

Ci ^ f COCH ^ C £ ..

27 TOT °) c = ° 126 "130 u2n5 1

H

C £ 26 T5r \ = o 101 -103 02Ef ^^ / COCH ^

Ci \ / X o 5 29 ΙΟΓ / 0 = 0 106 - 110 "2H5 COCHpCi 8100395 - 4b - *

Ci ^ n ^ p, 115 “H6 30 i (J ^ 0 = 0 ΐ 2 3 COOCH ^ CH ^») §>. ~ - ** 0 £ h CH, <u 1 V> y0 \ 122 ~ 123 * J51./ “c £ CH, CH, 3 Ci 1 Y ^ Y" ° \ 163 - 169 33 UI C = 0 _ / \ A w

Ci i COCH ^ CH,

Ci) ° D “n ƒ i w C0C4Hg-n 8100395 ': - 5 - 4 Ü * · • *

V

/ CII5 "" jor>. * "" I- © C ïï5 * ") §>

C 1 -C 10 O -Ci CH,

Ci, 3 37 I§r ° / c = o 135-128

Ί Λ I

COOCH ^ CH,

Ci, A | O I VC = 0 170 - 177 ioNHCH ^ CH,

Ci | 3 • ^ ü \ 5 '3Q U / C = 0 179 ~ U' °

Nν7 nH

Ci ^ i / CH3 C0N \ D CH ^ 8 1 0 0 39 5 - 5a - i, CH3 ci 1 40 7θΓ ° ^ 0 150 · 152 Cïï

Ci. ^ Y ^ Sr-0 \ 221 ~ 222 4! (j I C = 0

N / y_JM

C 1 -C OH- <2 O ^

Si CH ^ cii.

42 ΤθΤ °) θ = 0 199 - 200 C / V ^ Ir

"I

so2ch3 CH, cixl 0 43. 1910ν 191-193 "Sg>

Ci cVVo 5 44 [O! , T) C = 0 243, 250

chP ^ '""' ^ I

810035 ~ - 5b -

... X X

V

Ci

Ci 45 | 0 | °) ° = 0 133 '135 CH f * COCH ^

Ci 46 Q [XC = 0 149 - 151 2 COOCH ^

Ci 47 fO | ° XC = 0 218 - 219 «'Yë CH, 48.f (V ^ = 0 136-138 6h3. Ch3

Ci r ^ N \ __ Ό 5 49 Q X c = 0 103 ~ 105

Ci ^ V ^ Y

CH3 coch5 8 1 0 0 39 5 - 6 - -, •% C £ 50 Vo ° Vo 127 - 130 cfV ^ Ï7 CH ^ COOCH ^ C £ 51 “ΥΟΓ0 0 = 0 216 - 217 C £

C £ I.

52 xfor °> ° 133 135

1-C hr, I

5 f COCH ^ C £

VV

53 · I O I CiO 150 - 152

, _P U I

QT1 COOCH ^ CH-z ΒΓγ \ / °.

5 54 TqI y ° = 0 262 ~ 264 Z £ h 8 1 0 0 39 5 - 6a - "-% V-1 CR,

BrY ^ L0 55 TOf) c = 0 W - 175 C0CH5 CH3 «y ^ yo 56 Or XC = 0 224 ~ 225 C CYY '^ Ϋ

2 H

CH,

Ci I2 57 YofVo 158-159 nil ^ N7 2 COCH ^ CH, ci 0 58 · L ^ Y ^ = 0 256 ~ 239 ΟΓ /

Ci H

CH,

Ci 1 3 5 59 IQ C = ° 154 - 155 c / v ^ 1? 7 01 COOH, 8 1 0 0 39 5 - 6b i • *

Ci

ci X, Q

βο YoT> = o 254 ~ 2,) ft CH, I H 3 Ci C i ωΤοΤ \ *

ChUNU ^ 7 7 COCH ^

Ci

Ci .1 '* 62 ίο f °> = 0 174 - 176 ch5a> kr ^ Ci COOCH-j Ci 0 67, | U | W? 7S "777 'i' * '" 3

Ci

Ci 5. 64 CofV-0 125 -! - / 3s. .3—. «T /

"" H

nl T 1 CH, -Uvh'5 .. 8 1 0 0 3 9 5 .-- 1 1 - 6c -> ci

Br 65 ΤθΤ °> -0 2BB-m C £ T H CH5

Ci

Br! ν'VO, 66 I Q j Xc = 0 142-144 CH ^ CÜCli3 Ci 67 Ol λ ° = ° 271 - 277

Ci j h, 'C, 13 C 1 CH 3 ^ 6s. ·] O J XC. = 0 117 "118"

Ci ^ N7. ch5 cooh3 CH- * CVS "<\ 5 · 69 IQ I ^ 0 = 0 161 - 16 3 CCCH-CHp 81 0 0 39 5." - 7 -

Ci

Ci Λ. η O.

70 96-98

O Xr I

cöüch2ch = ch2

The compounds of the invention can be prepared according to the reactions shown in schemes Ά, B and C of the formula sheet and some compounds can be prepared according to scheme D.

In formulas 2 and 3, the symbols R, X, Y, m and n have the same meaning as mentioned above. The compounds of formula 3, wherein R e.g. is an acetyl group, may be prepared in high yield by acetylating the appropriate optionally short chain alkyl group-substituted ortho-aminophenol in the usual manner and then halogenating the acetylation product with a required equivalent of a halogen. obtained compound can be hydrolyzed, e.g. with dilute hydrochloric acid to give the corresponding compound of formula 3 wherein R is hydrogen. The latter compound may be alkylated or acetylated by any conventional method to yield 20 different compounds of formula 3.

In formula 3, symbols A and B, which may be the same or different, each represent halogen, alkoxy, haloalkoxy, alkylthio or amino group. The compounds of formula IV include phosgene-based compounds such as phosgene and di-phosgene (i.e. trichloromethyl chloroformate), haloformates, halothiol formates, carbonic diesters and urea.

* According to scheme A, it is believed that a compound of the formula II can be formed in two stages, * in which a compound HA or HB is removed in the reaction between the compound of the formula 3 and the compound of the formula 4 to form an intermediate, which is further reacted with the compound of formula 4 to also remove compound of formula HB or HA, respectively.

Thus, when a stable intermediate is formed depending on the nature of the compound of formula 4 used, this intermediate can be isolated in the meantime and then cyclized to provide the final product of formula 2. Such a stable intermediate can be also be formed by other means without using the reaction between the compound of formula 3 and the compound of formula 4, and then ring-closed to provide the compound of formula 2 .

The reaction between the compounds of formula 3 and formula 5 4 may be carried out in the absence of any solvent, but is preferably carried out in the presence of an organic solvent, which may optionally consist of an excess of the compound of formula 4 itself. the solvent to be used are hydrocarbons, halogenated hydrocarbons, ethers, esters, acid amides, alcohols and dimethyl sulfoxide. From this one can choose a suitable solvent for use, depending on the nature of the compound of formula (4) in question. can be used to allow the reaction to proceed gradually, since some compounds of formula IV may give rise to the formation of an acid during the course of the reaction. The acid binding agent used for this purpose may e.g. consist of an organic amine, such as triethylamine and pyridine, or an inorganic base, such as potassium carbonate. The reaction can be run at room temperature, although it can be completed in a shorter time when it is run at elevated temperature.

After completion of the reaction, the intended compound of formula 2 can be isolated and purified by any conventional method. a salt or salts of the acid-binding agent which are precipitated in the reaction mixture are filtered off when such a binder is used, and then the solvent of the filtrate is evaporated, leaving the compound of formula II a. thereof, water and / or a suitable organic solvent, such as benzene, chloroform, ether and tetrahydrofuran, can be added to the reaction mixture to fractionally precipitate the intended compound therefrom.

Details of the method of scheme A are set forth below in Examples I-IV, XI-XIV and XXIII.

In scheme B in formula 5 R, X and m have the above meaning, Z is a halogen atom and p is equal to 0, 1 or 2. The compounds of formula 5 can be prepared according to the method mentioned above for scheme A. Examples of The halogenating agent of the formula 5 used is halogens, such as chlorine or bromine, and sulfutyl chloride as such, and combinations of a hydrogen bisophic 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 elevated temperature to accelerate the reaction in case the halogenation is carried out with a halogen such as chlorine or bromine, or with sulfuryl chloride. The solvent used in such case can be, e.g. water, acetic acid or a halogenated hydrocarbon. When the halogenation is carried out using a combination of an acid, such as hydrochloric or hydrobromic acid, and an oxidizing agent, such as bleaching powder, potassium chlorate or manganese dioxide, the compound of formula 5 can be the acid can be dissolved with subsequent addition of the powder of the oxidizing agent or a concentrated aqueous solution thereof. If necessary, a solvent such as e.g. acetic acid, 20 are used.

The presence of a catalyst, e.g. iron, ferric chloride, a phosphorus compound, aluminum chloride or anti-moon chloride or ultraviolet irradiation is used to allow the reaction of scheme B to proceed gradually.

After completion of the reaction, the intended compound of formula 2 can be recovered directly from the reaction solution by evaporation of the solvent or optionally by adding water and / or a suitable organic solvent such as benzene, chloroform, ether to the reaction solution. or tetrahydrofuran to effect fractional extraction.

Details of the scheme B scheme are set forth in Examples V, VI and XV-XVII below.

In scheme C, in the compound of formula 7, X, Y, m are 35 and n have the same meanings as mentioned above. In the compound of formula 8, R is one of the groups defined above with the exception of a hydrogen atom and D represents a halogen atom When the group R to be introduced into the starting compound of formula 7 is an alkyl group 40, the reagent of formula 8 may be a di-alkyl sulfate, 81 0 0 39 5 * t- - 10 - wherein the alkyl groups are both R. For example, the compounds of formula 8 may consist of an alkyl halide, acyl halide, dialkyl sulfate, alkenoyl halide or alkenyl halo formate. These compounds are readily prepared by conventional methods known per se.

The reaction between the compound of formula 7 and the compound of formula 8 according to scheme C can be carried out in the absence of any solvent, but preferably it is carried out in the presence of an organic solvent 10, which may optionally consist of an excess of the compound with Formula 8 itself. Examples of the solvent to be used are hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, acid amides, alcohols and dimethyl sulfoxide. As an acid binding agent for use in the reaction, an organic amine such as triethylamine or pyridine can be used , or an inorganic base, such as potassium carbonate.

The reaction may be carried out at room temperature, or suitably at an elevated temperature. The reaction time required will of course depend on the nature of the compound of Formula 8 used, the nature of the solvent used and the reaction temperature employed, although it may be reduced when the reaction is carried out in a polar organic solvent.

To recover the target compound after completion of the reaction, the resulting reaction solution can be filtered to remove a salt of the acid-binding agent deposited therein and the filtrate evaporated to leave the desired compound. In some cases, water and / or suitable organic solvents, such as benzene, chloroform, ether and tetrahydrofuren, are added to the reaction mixture to extract the target compound.

Details of the scheme according to scheme C are given below in Examples VII-IX, XVIII-XX and XXIII. In Scheme D, in the compounds of formulas 9 and 10, R 'represents an alkyl group or an optionally substituted phenyl group. Thus, the method shown in Scheme D is useful for the preparation of compounds of formula 2, wherein R is an alkylaminocarbonyl or optionally substituted phenylamino -40 is carbonyl group.

8 1 0 0 39 5 - 11 -,

The reaction between the compounds of formula 7 and formula 9 can be carried out in the absence of any solvent, but is preferably carried out in the presence of an organic solvent, which may optionally consist of an excess of the compound of formula 9 itself. The solvent to be used must be inert to the compounds of formula 9 under the reaction conditions, and may e.g. consist of a hydrocarbon, a halogenated hydrocarbon, an ether, an ester or a ketone. When a small amount of organic amine, such as triethylamine or pyridine, is present as a catalyst, the reaction proceeds very gradually. The reaction can be satisfactory be conducted at room temperature or optionally at elevated temperature. The time required for the reaction will depend on the nature of the compound of formula 9 used and other reaction conditions, although the reaction is usually completed in a relatively short time.

After completion of the reaction, the target compound can be isolated from the reaction mixture by filtering out the crystals of the precipitated compound, or by evaporating the solvent, as appropriate.

The method according to scheme D is further explained in Examples X and XXI.

According to another embodiment of the invention, there is therefore provided a method of preparing a compound of formula 2 according to claim 1, wherein a) a compound of formula 3, wherein X, Y, m, n and R are those mentioned in claim 1 meaning, is reacted with a compound of formula 4 wherein A and B, which are the same or different, are each a halogen atom or an alkoxy, haloalkoxy, alkylthio or amino group; b) a compound of formula 5, wherein X, m and R have the meaning as defined in claim 1, Z is a halogen atom and p is equal to 0, 1 or 2m halogenated, whereby a compound of formula 2 is obtained which is the benzene ring contains one or more halogen atoms, the number of which is one more than in the starting compound of formula 5; c) a compound of formula 7, wherein X, Y, m and n have the meaning defined in claim 1, is reacted in the presence of an acid-binding agent with an 8 1 0 0 39 5 - 12 - * compound with formula 8, wherein R has the meaning defined in claim 1, with the exception of the hydrogen atom, and D is a halogen atom, or with a dialkyl sulfate, to give a compound of formula 2, wherein R is not a hydrogen atom; or d) a compound of formula 7 as mentioned above is reacted with an isocyanate compound of formula 9, wherein R 'is an alkyl group or an optionally substituted phenyl group to give a compound of formula 2.10, wherein R is a group -CONHR '.

The compounds according to the invention are extremely effective against a wide range of diseases caused by fungi and bacteria, including in particular the following: Piricularia oryzae on rice,

Pellicularia sasaki on rice,

Cochiliobolus miyabeanus on rice Xanthomonas oryzae on rice Alternaria kikuchiana on pears, 20 Glomerella cingulata on vine or vine,

Cladosporium fulvum on tomatoes Phytophthora infestans on tomatoes,

Sclerotinia sclerotiorum on string beans and green beans, Sphaerotheca fuliginea on cucumber, 25 Fusarium oxysporum on cucumber,

Pseudoperonospora cubensis on cucumber,

Colletotrichumlagenarium on cucumber,

Erwinia aroidea on Chinese cabbage

Some of the compounds are remarkably active as seed coatings against e.g. Gibbere11a fuiikuroi and Cochiliobolus miyabeanus on rice.

The compounds of the invention are not only effective in controlling fungi and bacteria-induced diseases, as mentioned above, in agricultural and horticultural applications, but are also suitable for controlling the growth of various fungi and bacteria which are able to attack industrial materials, such as when the compounds are applied to general industrial products, such as paint, wood, paper, pulp, tex-40 textile, cosmetics, leather goods, ropes, plastics, rubbers and 81 0 0 39 5 - 13 - Adhesives, possible to prevent deterioration or degradation of the products, as otherwise may be due to fungi and bacteria.

The compounds can be used as such for fungicidal and bactericidal purposes, but it is easier if they are formulated in compositions for such use. The invention therefore also provides a fungicidal or bactericidal composition for non-medical applications which consists of from a compound of formula 2 described above as active ingredient, together with a carrier or diluent for the active ingredient.

The invention further provides a method for controlling the growth of fungi and bacteria in a factory or industrial material, wherein a compound of formula II is applied to the factory or industrial material, or to the site of the factory , which is affected or likely to be affected by the fungi or bacteria.

For the purposes described above, the compounds of the invention are preferably used in the form of a composition. The nature of the composition used in a particular case will depend on the particular purpose intended.

The formulations may be in the form of dusting powders or granules containing the active ingredient and a solid diluent or solid carrier, such as e.g. kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, clay, magnesium powder, Fuller's earth, gypsum, Hewitt's earth and diatomaceous earth. Preparations for coating seeds can e.g. an agent (such as, for example, mineral oil) for promoting adhesion of the composition to the seed.

The compositions may also be in the form of dispersible powders or granules containing a wetting agent to facilitate dispersion in liquids for the powder or granules, which also contain fillers and suspending agents.

The aqueous dispersions or emulsions can be prepared by dissolving the active ingredient (s) in an organic solvent, optionally containing wetting, dispersing agents or emulsifying agent (s). Suitable solvents 40 are dimethyl sulfoxide, dimethylformamide, formamide and aliphatic alcohols.

The preparations to be used as sprays .....

may also be in the form of aerosols, the formulation being pressurized in a container in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

By incorporating suitable additives, e.g. additives to improve distribution, adhesion and resistance to rain on treated surfaces, 10 the different preparations can be better adapted to different applications. The active ingredient can be used in mixtures with fertilizers (* eg nitrogen or phosphorus-containing fertilizer).

The formulations may also be in the form of liquid formulations for use as dip liquids or sprays, which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more humectants, dispersants, emulsifiers or suspending agents. These agents can be cationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, e.g. Cetyl trimethyl ammonium bromide. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (eg sodium lauryl sulfate), and salts of sulfonated aromatic compounds (eg sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butylnaphthalene, butylnaphthalene, butylnaphthalene) and triisopropyl naphthalene sulfonates) Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other nonionic agents are the partial , which are derived from long chain fatty acids and hexitol anhydrides, the condensation products of these partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (eg polyvinylpyrrolidone and sodium carboxymethyl cellulose), and the vegetable gums (eg acacia gum and tragacanth) .

The formulations used as aqueous dispersions or emulsions are generally supplied in the form of 8100395-15 - a concentrate containing a high concentration of the active ingredient, the concentrate being used prior to use. Diluted with water.These concentrates often need to be capable of long-term storage and after such a storage period be able to be diluted with water to form aqueous preparations, which remain homogeneous long enough to be used with conventional spray equipment. The concentrates may suitably contain 10-95 wt%, generally 25-60 wt% active ingredient. When diluting to form aqueous preparations, such compositions may contain varying amounts of active ingredient, depending on the intended purpose, (but an aqueous -5 preparation containing 1x10 wt% to 10 wt% active ingredient can be used.

* 15 When the preparation according to the invention is in the form of dusting powders or granules, the preparation is generally applied as such to the plants to be treated in an amount of 2-4 kg per 10 ares (or in an amount of 10- 1000 g active ingredient per 10 are) When the composition is in the form of wettable powder, emulsifiable concentrate or liquid preparation, it is usually diluted with water before use to provide a concentration of active ingredient of 10-1000 ppm , and the dilute formulation generally applied to the plants in an amount of 50-300 L per 10 acres. For treatment of industrial materials, such dilute formulations are applied at 10-5000 ppm active ingredient in an appropriate amount, which can vary within wide limits.

The compositions of the invention may also contain one or more other biologically active compounds, e.g. other known fungicides, bactericides, plant growth regulators, herbicides and insecticides. More particularly, it has been found that some of the compounds of the invention exhibit a marked synergistic action when used in combination with certain known fungicides, as can be seen from the results. are listed in Example XLVII below.

Examples of fungicides and bactericides which can be used in mixtures with the compounds of the invention are: 81 0 0 39 5-16 * 1 carbamate fungicides, such as 3,3'-ethylenebis (tetrahydro-4, 6-dimethyl-2H-1,3,5-thiadiazine-2-thion), zinc or manganese ethylene bis (dithiocarbamate), bis (dimethyldithiocarbamoyl) disulfide, zinc propylene bis (dithiocarbamate), bis (dimethyldithio-5 carbamoyl) ethylenediamine; nickel dimethyldithiocarbamate, methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, l-isopropylcarbamovl-3- (3,5-dichlorophenyl) hydantoin, potassium N-hydroxymethyl -N-methyl dithiocarbamate and 5-methyl-10-butoxycarbonylamino-10,11-dehydrodibenzo (b, f) azepine; pyridine fungicides, such as zinc bis (1-hydroxy-2 (1H) pyridinethionate) and 2-pyridinethiol-1-oxide sodium salt; phosphorus-containing fungicides, such as Ο, Ο-di-isopropyl S-benzylphosphorothioate and 0-ethyl S, S-diphenyldithio-phosphate; phthalimide fungicides, such as N- (2,6-diethylphenyl) -15 phthalimide and N- (2,6-diethylphenyl) -4: -methylphthalimide; di-carboxyimide fungicides, such as N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyimide and N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboxyimide; oxathine fungicides, such as 5,6-di-hydro-2-methyl-1,4-oxathine-3-carbonanilido-4,4-dioxide and 5,6-dihydro-2-methyl-1,4-oxathine-3 carbonanilide; naphthoquinone fungicides, 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-triazole (3,4-b) -benzthiazole; 2-thiocyanomethylthio) benzthiazole; 3-hydroxy-5-25 methylisoxazole; N-2,3-dichlorophenyltetrachlorophthalamic acid; 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole; 2,4-dichloro-6- (o-chloroanilino) -1,3,5-triazine; 2,3-dicyano-1,4-dithioanthraquinone; copper 8-quinolinate; polyoxin; varidamycin; cyclohex-. imide; iron methane arsonate; diisopropyl-1,3-dithiolan-2-in-30 dene malonate; 3-allyloxy-1,2-benzoisothiazol-1,1-dioxide, ka-sugamycin; Blasticidin 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-tert-butylbenzyl-N-3-pyridyldithiocar-35-bonylimidate; 4-chlorophenoxy-3,3-dimethyl-1- (1H, 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) imidazole-1-carboxamide; N- (3,5-dichlorosuccinimide; tetrachloroisophthalonitrile; 2-dimethylamino-4-methyl-5-n-butyl-40 6-hydroxypyrimidine; 2,6-dichloro-4-nitroaniline; 3-methyl-8100395 - 17 - 4-chlorobenzothiazol-2-one; 1,2,5,6-tetrahydro-4H-pyrrolo (3,2,1-i, j) quinolin-2-one; 31-isopropoxy-2-methylbanzanilide; 1- (2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxoran-2-ylmethyl) -1H, 1,2,4-triazole; 1,2-benzisothiazolin-3-one; basic copper chloride; 5 basic copper sulfate; N1-dichlorofluoromethylthio-N, N-dimethyl-N-phenylsulfamide; ethyl-N- (3-dimethylaminopropyl) thiocarbamate hydrochloride; piomycin; S, S-6-methylquinoxaline-2,3-diyldi-thiocarbonate; zinc complex and maneli, dizink bis (dimethyldithiocarbamate) ethylene bis (dithiocarbamate).

Examples of plant growth regulators and herbicides which can be used in combination with the compounds of the invention are: isourea plant growth regulators, such as N-methoxycarbonyl-N'-4-methylphenylcarbamoylethyl isourea and 1- (4-chlorophenylcarbamo-15 yl) -3-ethoxycarbonyl -2-methylisourinim; another type of plant growth regulators, such as sodium naphthalene acetate, 1,2-dihydro-pyridazine-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-ethylamino-6-isopropylamino-s-triazine; 2-methylthio-4,6-bis (isopropylamino) -s-triazine and 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine; phenoxy herbicides, such as 2,4-dichlorophenoxyacetic acid and methyl, ethyl and butyl esters thereof, 2-chloro-4-methyl-phenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid and ethyl 2-methyl-4-chlorophenoxybutylate; diphenyl ether herbicides, such as 2,4,6-trichlorophenyl-41-nitrophenyl ether, 2,4-dichlorophenyl-41-nitrophenyl ether and 3,5-dimethylphenyl-41-nitrophenyl ether; urea herbicides, such as 3- (3,4-dichlorophenyl) -1-methoxy 30 -1-methyl urea, 3- (3,4-dichlorophenyl) -1,1-dimethyl urea 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-3-35 sec-butyl-6-methyluracil and 1-cyclohexyl-3,5-propylene uracil; thiol carbamate herbicides, such as S- (4-chlorobenzyl) -N, N-diethylthiol carbamate, S-ethyl-N-cyclohexyl-N-ethylthiol carbamate and S-ethyl-hexahydro-1H-azepine-1-carbothioate and S-ethyl- N, N-di-n-propylthiol carbamate; pyridinium herbicides, such as 1,1'-dimethyl-4,4'-bispyridinium dichloride; phosphorus 8 1 0 0 39 5 - 18 -

t A

herbicides, such as N- (phosphonomethyl) glycine; aniline herbicides such as alpha, alpha, alpha-trifluoro-2,6-dinitro-N, N-dip'ropyl-p-toluldine, 4- (methylsulfonyl) -2,6-dinitro-N, N-dipropylaniline, 3 and N, N-diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylene-di-5 amine; acid anilide herbicides, such as 2-chloro-21,6'-diethyl-N- (butoxymethyl) accetanilide, 2-chloro-21,6'-diethyl-N- (methoxymethyl) acetanilide and 3,4-dichloropropionanilide; pyrazole herbicides, such as 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole and 1,3-dimetyyl-4- (2,4-dichlorobenzoyl) -5-10 (p-toluenesulfonyloxy) pyrazole; 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one; 2- (N-isopropyl, N- (4-chlorophenyl) carbamoyl) -4-chloro-5-methyl-4-isoxazolin-3-one; 3-Isopropylbenzo-2-thia-1,3-diazinone- (4) -2,4-dioxide and 3- (2-methylphenoxy) pyridazine.

Examples of insecticides which can be mixed with the compounds according to the invention are the following: phosphorus insecticides, such as 0,0-diethyl O- (2-isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate, Ο, Ο-diethyl S-2 - ((ethyl- 'thio) ethyl) phosphorodithioate, 0,0-dimethyl 0- (3-methyl-4-20 nitrophenyl) thiophosphate, 0,0-dimethyl S- (N-methylcarbamoylme-) thyl) 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) phosphorodithioate, 0,0-dimethyl-1-hydroxy-2,2,2-trichloro-ethyl-phosphonate, 0,0-diethyl-0- (5-phenyl-3-isoxazolyl) phosphorothioate, 0,0-dimethyl 0- (2,5-dichloro-4-bromophenyl) phosphonothioate, 0,0-dimethyl 0- (3-methyl-4-methyl mercaptophenyl) thiophosphate, 0-ethyl 0-p-cyanophenyl phenylphosphonothioate, 0,0-dimethyl-S- (1,2-dicarboethoxyethyl) phosphorodithioate, 2-chloro-30 (2,4,5-trichlorophenyl) vinyl dimethyl phosphate, 2-chloro-1- (2,4- .. .- j dichlorophenyl) vinyl dimethylphosph ate, 0,0-dimethyl Q-alpha-cyanophenylphosphorothioate, 2,2-dichlorovinyl-dimethylphosphate, 0,0-diethyl 0-2,4-dichlorophenylphosphorothioate, ethyl mercaptophenyl acetate 0,0-dimethylphosphorodithioate, S - ((6 -chloro-2-35 oxo-3-benzoxazolinyl) methyl) 0,0-diethyl phosphorodithioate, 2-chloro-1- (2,4-dichlorophenyl) vinyl diethyl phosphate, 0,0-diethyl 0- (3-oxo-2 -phenyl-2H-pyridazin-6-yl) phosphorothioate, 0,0-dimethyl S- (1-methyl-2-ethylsulfinyl) -ethyl phosphorothioate, 0,0-dimethyl S-phthalimidomethylphosphorodithioate, 0,0-diethyl 40 S- (N-ethoxycarbonyl-N-methylcarbamoylmethyl) phosphorodithioate, 8100395 - 19 - Λ Λ

OfO-dimethyl S- (2-methoxy-1,3,4-thiadiazole-5- (4H) -oxyl- (4) -methyl) dithiophosphate, 2-methoxy-4H-1,2,2-benzooxaphosphorine 2-sulfide 0,0-diethyl 0- (3,5,6-trichloro-2-pyridyl) phosphorothioate, 0-ethyl 0-2,4-dichlorophenyl thionobenzene phosphonate, S-5 4,6-diamino-s-triazine -2-yl-methyl) 0,0-dimethylphosphorodithioate, 0-ethyl 0-p-nitrophenyl phenyl phosphonothioate, 0,1-Dimethyl N-acetyl phosphoroamidothioate, 2-diethylamino-6-methylpyrimidin-4-diethylphosphorothionate, 2-diethylamino-6-methylpyrimidin-4-yl-dimethylphosphorothionate, 0,0-diethyl 0-p- (methylsulfinyl) 10 phenyl phosphorothioate, 0-ethyl S-propyl 0-2,4-dichlorophenyl phosphorodithioate and cis-3- ( dimethoxyphosphinoxy) N-methyl-cis-crotonamide; carbamate insecticides, such as 1-naphthyl N-methyl-carbamate, S-methyl N- (methylcarbamoyl) oxy) thioacetoimidate, m-tolyl methylcarbamate, 3,4-xylyl methylcarbamate, 3,5-xylyl methylcarbamate, 2-sec-butylphenyl N-methyl carbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranylmethyl carbamate, 2-isopropoxyphenyl N-methyl carbamate, 1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride and 2-diethylamino-6-methylpyrimidin-4-yl-dimethyl carbamate? and other insecticides such as Ν, Ν-dimethyl N '- (2-methyl-4-chlorophenyl) formamidine hydrochloride, nicotine sulfate, milbemycin, 6-methyl-2,3-quinoxaline dithiocyclic S, S-dithiocarbonate, 2,4-dinitro- 6-sec.-butylphenyl dimethyl acrylate, 1,1-bis (p-chlorophenyl) -2,2,2-trichloroethanol, 2- (p-tert-butylphenoxy) isopropyl-2'-25-chloroethylsulfite, azoxybenzene, di- (p- chlorophenyl) cyclopropylcarbinol, di- (tri (2,2-dimethyl-2-phenylethyl) tin) oxide, 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea and S-tricyclohexyltin 0 .0-diisopropylphosphorodithioate.

The invention is further illustrated by the Examples below, in which all parts are by weight.

Example I

Preparation of Compound No. 1 from Table A (Scheme A) 21.3 g of 2-amino-4,5,6-trichlorophenol, 27.6 g of anhydrous potassium 35 carbonate and 150 ml of toluene were placed in a 300 ml round bottom and 9 0.9 g of phosgene were slowly introduced into the mixture with stirring while cooling on an 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 ml separating funnel. the separating funnel 8100395. 150 ml of tetrahydrofuran and 150 ml of water were added and the organic layer was separated, dried, anhydrous sodium sulfate, and filtered. The filtrate was evaporated to remove the solvent, leaving yellowish-white crystals. The crystals were recrystallized. from a mixed solvent of methanol and acetone to yield 22.7 g of 5,6,7-trichlorobenzoxazolone as white crystals with a melting point. of 253-254 ° C.

Example II 10 Preparation of Compound No. 1 (Scheme A) 21.3 g of 2-amino-4,5,6-trichlorophenol, 27.6 g of anhydrous potassium carbonate and 150 ml of ethyl acetate were placed in a 300 ml round bottom and a solution of 9.9 g of phosgene (trichloromethyl chloroformate), dissolved in 50 ml of ethyl acetate, were added to the mixture dropwise with stirring and cooling on an ice-water bath. The resulting mixture was heated at reflux temperature for one hour and the reaction solution was then cooled and filtered with suction to remove insoluble salts. The filtrate was concentrated to dryness under reduced pressure for 20 to yield yellowish white crystals which were recrystallized from methanol / acetone to give 19.6 g of 5.6.7 trichlorobenzoxazolone were obtained as white crystals with a melting point. of 253-254 ° C.

Example III

Preparation of Compound No. 1 (Scheme A) 18.1 g of 2-ethoxycarbonylaminophenol (prepared from 2-aminophenol and ethyl chloroformate) were dissolved in 200 ml of acetic acid and 23.4 g of chlorine gas were passed into the solution at a temperature of 80 -90 ° C. The reaction solution thus obtained was cooled and evaporated to remove the acetic acid, leaving 27.9 g of yellow crystals of 2-ethoxycarbonylamino-4,5,6-trichlorophenol, mp 190-193 ° C.

The crystals, along with 45 ml of dimethylformamide and 35.5 g of anhydrous potassium carbonate, were placed in a 200 ml round bottom and the mixture was heated at 140 ° C with stirring for 4 hours. After cooling of the resulting solution, 100 ml of water were added thereto. was added to precipitate crystals, which were then separated by filtration with suction 8 1 0 0 39 5 - 21 - - - Λ 1 and air dried for 2 hours to yield pale yellow crystals. acetone gave 19.1 g of white crystals of 5,6,7-trichlorobenzoxazolone with m.p. of 253-254 ° C.

Example IV

Preparation of Compound No. 3 from Table A (Scheme A) 10.9 g of O-aminophenol and 100 ml of acetic acid were placed in a 300 ml round bottom, after which 10.2 g of acetic anhydride were added under ice-water cooling. heated at 60 ° C for one hour to complete the reaction to form 2-acetamnophenol. Then, 23.4 g of chlorine gas at a temperature of 80-90 ° C were introduced into the reaction mixture and the resulting reaction solution was cooled and evaporated under reduced pressure to yield 24.9 g of yellow crystals of 2-acetamino-4,5,6-trichlorophenol, m.p. 200 ° C (dec.).

The crystals were placed in a 300 ml round bottom, to which 150 ml of tetrahydrofuran was added, followed by 9.6 g of sodium hydride (50% suspension in oil), then 9.9 g of phosgene were introduced into the mixture under ice-water cooling and the resulting mixture was stirred at room temperature for one hour. The reaction solution was transferred to a 500 ml separating funnel, to which 150 ml of benzene and 150 ml of water were added, and the organic layer was separated, dried over anhydrous sodium sulfate and filtered. evaporated to dryness to remove the solvent, leaving yellow crystals. The crystals were recrystallized from a mixed solvent of hexane and acetone to give 25.2 g of N-acetyl-5,6,7-trichloro-benzoxazolone as white crystals with m.p. mp 171-172 ° C.

Example V Preparation of Compound No. 1 (Scheme B) 20.4 g of 5,7-dichlorobenzoxazolone and 150 ml of acetic acid were placed in a 300 ml round bottom and the mixture was heated at 80-90 ° C, then 7.8 g Chlorine gas was passed through. The reaction solution was concentrated by evaporating the acetic acid to give yellow crystals. Recrystallization from methanol / acetone gave 23.4 g of white crystals of 5,6,7-trichlorobenzoxazolone, mp. 253-254 ° C.

8 1 0 0 39 5 - 22 -. i *

EXAMPLE 6 Preparation of Compound No. 3 (Scheme B) 24.6 g of N-acetyl-5,7-dichlorobenzoxazolone and 150 ml of chloroform were placed in a 300 ml round bottom, to which was then added 16.5 g of sufuryl chloride at room temperature. The mixture was heated to reflux for two hours and the reaction solution thus obtained was evaporated under reduced pressure to leave yellow crystals. Recrystallization from hexane / acetone gave 26.6 g of white crystals of N-acetyl-5,6,7-trichlorobenzoxazolone, mp. 171-172 ° C,

Example VII

Preparation of Compound No. 2 of Table A (Scheme C) 4.8 g of 5,6,7-trichlorobenzoxazolone, 2.8 g of anhydrous potassium 15 carbonate, 2.5 g of dimethyl sulfate and 50 ml of acetone were placed in a 100 ml round bottom and refluxed for 2 hours, then the reaction solution was evaporated under reduced pressure and the residue was taken up in 50 ml of water. The solution was filtered to give yellow-brown crystals, which were recrystallized from acetone, giving 4.8 g of yellow crystals of N-methyl-5,6,7-trichlorobenzoxazolone, mp 135-139 ° C, were obtained.

Example VIII

Preparation of Compound No. 7 of Table A (Scheme C) 4.8 g of 5,6,7-trichlorobenzoxazolone, 2.0 g of triethylamine and 50 ml of acetone were placed in a 100 ml round bottom, followed by stirring and cooling dropwise 2.8 g with ice-water. Benzoyl chloride was added. After the addition was complete, the resulting mixture was heated under reflux for one hour to effect the reaction, then the reaction solution was allowed to cool and filtered to remove the precipitated salts. The filtrate was evaporated, leaving white crystals which were recrystallized from hexane / acetone to yield 6.5 g of white crystals of N-benzoyl-5,6,7-trichlorobenzoxazolone with m.p.

188-190 ° C were obtained.

Example IX

Preparation of Compound No. 10 of Table A (Scheme C)

According to the same method as described in Example 81 0 0 39 5 - 23 - VIII, except that the benzoyl chloride was replaced by 1.9 g of methyl chloroformate, 5.7 g of N-methoxycarbonyl-5,6,7-trichlorobenzoxazolone were formed as yellowish white crystals with m.p. 163-164 ° C.

5 Example X

Preparation of Compound No. 14 of Table A (Scheme D) 4.8 g of 5,6,7-trichlorobenzoxazolone, 3.8 g of 3,5-dichlorophenyl isocyanate, 50 ml of acetone and three drops of triethylamine were placed in a 100 ml round bottom and the mixture was stirred at room temperature for 10 hours. The precipitate was filtered off, yielding 7.7 g of pale yellow crystals, which were identified as N-3,5-dichlorophenylcarbamoyl-5,6,7-trichlorobenzoxazolone with mp 235-237 ° C.

Example XI

15 Preparation of Compound No. 25 of Table A (Scheme A)

The procedure of Example I was repeated, starting from 15.8 g of 2-amino-4-chloro-6-methylphenol instead of the 2-amino-4,5,6-trichlorophenol. Recrystallization of crude brown crystals from hexane / acetone gave 15.6 g of 5-chloro-7-methyl-20-benzoxazolone as yellow-brown crystals, mp 232-234 ° C.

Example XII Preparation of Compound No. 67 (Scheme A)

The procedure of Example II was repeated starting from 21.2 g of 2-amino-3,5-dimethyl-4,6-dichlorophenol in place of the 2-amino-4,5,6-trichlorophenol. Thus, 20.9 g 4,6-dimethyl-5,7-dichlorobenzoxazolone obtained as pale crystals of mp 271-272 ° C.

Example XIII Preparation of Compound No. 1 (Scheme A) In a 100 ml round bottom, 23.0 g of 2-ethoxycarbonyl-amino-4-methyl-5-chlorophenol prepared from 2-amino-4-methyl-chlorophenol and ethyl chloroformate), 50 ml of dimethylformamide and 0.5 g of anhydrous potassium carbonate and the mixture was heated to 140 ° C with stirring for 4 hours. The resulting reaction mixture was cooled and poured into 100 ml of water to separate crystals, which were collected by suction filtration and then air dried at 80 ° C for 2 hours to yield yellow crystals. Recrystallization thereof from methanol gave 15.6 g of pale yellow crystals of 5-methyl-6-chlorobenzoxazolone with m.p. 182-184 ° C.

Example XIV

Preparation of Compound No. 52 of Table A (Scheme A). By the method described in Example IV, 24.5 g of N-acetyl-5-isopropyl-6,7-dichlorobenzoxazolone were obtained in the form of yellow-brown crystals (mp. 133). -135 ° C) prepared from 15.1 g of 2-amino-4-isopropylphenol via a brown oil (25.7 g) of 2-acetamino-4-isopropyl-5,6-dichlorophenol.

Example XV

Preparation of compound no. 31 of Table A (Scheme B)

The method of Example V was repeated, but 18.4 g of 5-chloro-7-methylbenzoxazolone were used instead of 5,7-dichlorobenzoxazolone to give 20.7 g of 5,6-dichloro-7-15 methylbenzoxazolone as red crystals mp 25l-252 ° C.

Example XVI Preparation of compound No. 54 (scheme B) 18.4 g of 5-chloro-7-methylbenzoxazolone and 150 ml of acetic acid were placed in a 200 ml round bottom and the mixture was added dropwise with a solution of 17.6 g of bromine 30 ml of acetic acid were added. The resulting mixture was heated to 95 ° C and stirred at that temperature for 4 hours. Then the reaction solution was cooled to room temperature and concentrated by evaporation of the acetic acid to give red-brown crystals which were recrystallized from methanol / acetone to give 22.3 g of 5-chloro-6-bromo-7-methylbenzoxazolone as brown crystals, mp 262-264 ° C.

Example XVII

Preparation of Compound No. 64 (Scheme B)

The method of Example VI was repeated but 26.0 g of N-acetyl-4-methyl-5,7-dichlorobenzoxazolone were used in place of N-acetyl-5,7-dichlorobenzoxazolone to give 23.6 g of the corresponding 5 6,7-trichloro derivative was obtained in the form of white crystals, mp 125-127 ° C.

Example XVIII

Preparation of compound No. 32 of Table A (Scheme C) 8 1 0 0 39 5 - 25 -

Preparation of compound No. 32 of Table A (Scheme C)

The procedure of Example VII was repeated, but 4.4 g of 5,6-dichloro-7-methylbenzoxazolone were used instead of 5,6,7-trichlorobenzoxazolone to give 3.9 g of N-methyl-5,6-di-5 Chloro-7-methylbenzoxazolone was obtained as red crystals, mp 122-223 ° C.

Example XIX

Preparation of Compound 35 of Table A (Scheme C) 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 2.8 g of benzoyl chloride and 50 ml of acetone were placed in a 100 ml round bottom to which 2 0 g of triethylamine were added with stirring and cooling with ice-water. After the addition was complete, the resulting mixture was refluxed for one hour to effect the reaction, then the reaction mixture was allowed to cool and filtered to Remove precipitated salts. The filtrate was evaporated to leave yellowish-white crystals, which were recrystallized from acetone, yielding 5.5 g of white crystals of N-benzoyl-5,6-dichloro-7-methylbenzoxazolone, mp 165-20 166 °. C were obtained.

Example XX Preparation of Compound No. 37 (Scheme C)

Following the method described in Example IX, but .7 starting from 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 4.6 g of N-methoxycarbonyl-5,6-dichloro-7-methylbenzoxazolone were obtained in the form of pink crystals with mp. 135-138 ° C.

Example XXI Preparation of Compound No. 41 (Scheme D)

According to the method as in Example X, but starting from 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 7.4 g of N-3,5-dichlorophenylcarbamoyl-5,6-dichloro-7- methylbenz-oxazolone obtained as pink crystals, mp 221-222 ° C.

Example XXII Preparation of Compound No. 69 (Scheme A) The method of Example 1 was repeated, but replacing the 2-amino-4,5,6-trichlorophenol with 22.6 g of 3-chloro-6-acrvloylamino- 2,4-xylenol (prepared from 3-chloro-6-amino-2,4-xylenol and acryloyl chloride). Recrystallization of raw yellow crystals from acetone gave 20.4 g of yellow white crystals of 8 1 0 0 39 5 '' - - 26 - N-acryloyl-5,7-dimethyl-6-chlorobenzoxazolone with a melting point. of 161-163 ° C.

Example XXIII Preparation of Compound No. 70 (Scheme C).

By the same method as described in Example XIX, but using 23.9 g of 5,6,7-trichlorobenzoxazolone, 12.0 g of allyl chloroformate and 10.1 g of triethylamine, 27.4 g of N-allyloxycarbony 1 -5,6,7-trichlorobenzoxazolone obtained in the form of pale yellow crystals, mp 96-98 ° C.

10 Example XXIV

Emulsifiable concentrate formulation

An emulsifiable concentrate containing 20% active ingredient was prepared by homogeneously mixing the below ingredients and stirring the mixture well until all ingredients had dissolved.

share

Compound No. 10 20

Dimethylformamide · 30

Xylene 35 20 Polyoxyethylene alkylaryl ether 15

In the same manner as mentioned above, corresponding emulsifiable concentrates containing 20% of compound No. 36 or No. 69 as an active ingredient were prepared.

Example XXV 25 Oil formulation

An oil formulation was prepared by mixing 10 parts of compound No. 1 and 90 parts of ethyl cellosolve (2-ethoxyethanol) and stirring the mixture until the ingredients were dissolved.

Example XXVI 30 Liquid formulation

A liquid formulation with 40% active ingredient. was prepared by homogeneously mixing the following ingredients together: parts 35 Compound No. 4 (ground to a particle size below 10 μπι) 40

Lauryl sulfate 2

Sodium alkyl naphthalene sulfonate 2

Hydroxypropyl cellulose 1 8100395 - 27 - r

Via ter 55

Such liquid formulations containing 20% of compound No. 32 or No. 70 as the active ingredient were prepared in the same manner as described above.

5 Example XXVII

Water-dispersible powder formulation A water-dispersible powder was prepared by uniformly mixing the ingredients listed below and then grinding the mixture.

10 Share

Connection No. 20

Polyoxyethylene alkylaryl ether '5

Calcium lignosulfate 3

Kieselguhr 72 Such water-dispersible powders containing 20% of compound No. 48 or No. 69 as active ingredient were prepared in the same manner as described above.

Example XXVIII Dusting powder formulation. A dusting powder was prepared by the methods listed below. evenly mix ingredients and grind the resulting mixture.

Share

Compound No. 5 3 25 Fine silica 0.5

Calcium stearate 0.5

Clay 50

Talk 46

Such dusting powders with 3% of compound No. 53 or No.

70 as an active ingredient were prepared in the same manner as described above.

Example XXIX Granular formulation

A granular composition was prepared by uniformly mixing the ingredients listed below and then granulating the mixture in the presence of water. The resulting mixture was dried and passed through a sieve to obtain the desired grain size,

8 1 0 0 39 S

- 28 - * *. Share

Connection No. 6 5

Calcium lignosulfonate 1

Bentonite 30 5 Clay 64

Such granular formulations containing 5% of compound No. 24 or No. 70 as the active ingredient were prepared in the same manner as described above.

Example XXX 10 wettable powder formulation

A wettable powder was prepared by uniformly mixing the ingredients listed below and grinding the resulting mixture.

Parts 15 Compound No. 10 20 N-trichloromethylthio-4-cyclohexene-1,2-dicarbonimide 20

Polyoxyethylene alkylaryl ether 5

Calcium lignosulfonate 3 20 Kieselguhr 52

Example XXXI

In this example, the benzoxazolone derivatives of the invention were tested against various fungal and bacterial diseases of plants. The tests were performed according to standard agar dilution method. The culture medium used was potato dextrose agar medium (pH 5.8) for fungi and broth agar medium (pH 7.0) for bacteria. The medium containing an acetone solution of the required concentration of active ingredient was inoculated with using a platinum loop with a spore suspension obtained by adding sterilized water to test ant organisms incubated on a disc of the medium in a test tube. Further incubation on the inoculated medium for 48 hours at 24 ° C. for 35 fungi and at 28 ° C for bacteria. Afterwards, the growth of the ant organism was examined and the minimum inhibitory concentration (MIC, µg / ml) of the tested derivatives was determined.

The test results are shown in Table B below.

In the following Tables, controls A, B, C, and D.

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Example XXXIX

This example shows the fungicidal activity of the benz-oxazolone derivatives against Piricularia oryzae (blastomycosis on rice).

A water-dispersible powder formulation, prepared as described in Example XXVII, was diluted with water to prepare test formulations containing the required concentrations of active ingredient. The test formulation was applied to aqueous rice cuttings C & sahi (10). three-leaf stage) which were grown on soil in pcrcelijne.pafeferv.rTe £: a 9cm "Mfldéin" line in a greenhouse. One day after application, the treated cuttings were inoculated by spraying with a spore suspension of Piricularia oryzae and incubated in a humid chamber with a relative humidity of 95-100% and a temperature of 24-25 ° C. Five days after inoculation, the number of breaks per leaf in the three-leaf stage was counted and the disease control was calculated with the following equation:

Number of fractures in 20 Disease control <%, - (1 -) * 100 untreated groups

Disease control is an average value of the results of the tests performed in two replicates 25 at each active ingredient concentration. Phytotoxicity for rice plants was also assessed visually with the following grading:

Grade Degree of Phytotoxicity 5 Severe Damage 30 4 Strong Damage 3 Moderate Damage 2 Slight Damage 1 Minor Damage 0 No Damage 35 The test results are shown in Table C below.

8 1 0 0 39 5 'f. «Ε - 34 -

Table C

Compound Concentration Disease control Phytotoxicity No. (dpra) (%) 1 200 100 0 5 2 200 78 0 3 200 1 * 00 0 4 200 98 0 5 200 94 0 6 200 98 0 10 7 200 98 0 8 200 100 0 9 200 96. 0 10 200 100 0 11 200 100 0 15 12 200 92 0.

13 200 86 0 14 200 82 0 15 200 98 0 16 200 98 0 20 17 200 100 O '18 200 100 0 19 200 100 0 20 200 84 0 22 200 92 0 25 23 200 96 0 27 200 82 0 30 200 98 0 31 200 88 0 33 200 98 0 30 36 200 98 0 37 200 100 0 38 200 100 1 41 200 98 1 46 200 92 0 35 47 200 98 0 50 200 98 0 53 200 100 0 61 200 100 0 62 200 100 0 81 0 0 39 5 - 35 -

Table C {continued)

Compound Concentration Disease Control Phytotoxicity No. _ (ppm) _ (_%) _ _ 64 200 98 0 5 66 200 96 0 68 200 94 0 69 200 100 0 70 200 100 0

Control A 200 52 1 10 Control B '200 63 .2

Control C 200 30 1

Check D 200 30. 1 IBP ((check) * _480_75_0_ 15 Untreated 0 IBP: formula 11.

Example xxxill

This example shows the action of the benzoxazolone derivatives against Cochliobolus miyabeanus (brown spot on rice). The tests were performed according to the same method as in Example XXXII, except that rice cuttings in the four-leaf stage were inoculated with a spore suspension of Cochliobolus miyabeanus.

The results are recorded in Table D.

Table D

Compound Concentration Disease Control Phytotoxicity No. (ppm) (%) 1 500 100 0 2 500 85 1 30 3 500 100 - 0 4 500 98 0 5 500 96 0 6 500 100 0 7 500 94 0 35 8 500 92 0 9 500 88 0 10 500 100 0 11 500 98 0 8 100 395 - 36 -

Table B (continued)

Compound Concentration Disease Control Phytotoxicity No. (ppm) (%) 12 500 94 1 5 13 500 90 0 14 500 92 1 15 500 86 0 16 500 83 0 17 500 100 0 10 18 500 100 0 19 500 100 0 20 500 100. 0 21 500 98 0 22 500 82 0 15 23 500 96 0 24 500 76 0 25 500 76 0 26 500 72 - 0 27 500 88 0 20 28 500 80 0 29 500 92 0 30 500 88 0 31 500 100 0 32 500 .. 96 0 25 33 500 1Ό0 0 34 500 94 0 35 500 96 0 36 500 100 0 37 500 100 0 30 38 500 98 0 39 500 100 0 40 500 '96 0 41 500 100 0 42 500 98 0 35 43 500 98 0 44 500 96 0 45 500 88 0 46 500 98 0 47 500 98 0 40 48 500 76 0 8 1 0 0 39 5 - 37 -.

* r t

Table D (continued)

Compound Concentration Sickness Control Phytotoxicity No. _ (ppm) _ (%) _ __ 49 500 72 0 5 50 500 98 0 51 500 82 0 52 500 76 0 53 500 88 0 54 500 94 0 10 55 500. 98 0 56 500 73 0 57 500 88 0 58 500 98 '0 59 500 100 0 15 60 500 98 0 61 500 96 0 62 500 100 0 63 500 76 0 64 500 82 0 20 65 500 80 0 66 500 100 0 67 500 72 0 68 500 100 0 69 500 100 0 25 70_500_100_0_

Control A 500 32 3

Control B 500 54 4

Control C 500 25 1

Control D 500 30 2 30 Triazine * 500 93 0 (Control) ........

Untreated - 0 -

Triazine = formula 12

Example XXXIV

In this example, the active compounds were tested for Sclerotinia sclerotiorum (stem rotting in green beans) using the technique below.

A water-dispersible powder formulation, prepared in the manner described in Example XXVII, was mixed with water 81 0 0 39 5 - 38 - "- * 1". _ '. diluted to prepare test formulations with the required concentrations of active ingredient. The test formulation: was applied to seedlings of green beans ("Taisho Kin. toki" variety) in the two true leaves stage, which had been ground in porcelain pots with a diameter of 9 cm in a greenhouse. The application amount was 10 ml formulation per pot. A day later, each leaf of the two true leaves was inoculated in the middle with a piece of fungi-infected agar obtained by using a cork drill 10 of 5mm out the edge of the Sclerotiriia sclerotiorum fungus colony, which was incubated in potato dextrose agar for two days at 20 ° C. The seedlings inoculated were then kept in a humid chamber at 20 ° C for three days to treat the disease The length of the stem rot fractures was then measured with a caliper and disease control was calculated by the following equation:

Length of fractures in treated groups 20 Disease control (%) = (l - = -z - r -——— r—) x 100 v Length of fractures m 'untreated groups

Disease control is an average value of the results of the tests performed in two replica 25 for each concentration of the active ingredient. Phyto-toxicity to green beans was assessed visually according to the same grade as in Example XXXII.

The results are reported in Table E below.

Table E

30 Compound Concentration Disease Control Phytotoxicity No. _ (ppm) _ (%) 1 500 100 1 3 500 88 0 5 500 86 0 35 6 500 94 1 10 500 100 0 17 500 89 0 19_500_85 0 _

Control A 500 43 3 40 Control B 500 48 4

Control C 500 26 2

Control D 500 20 2 8 1 0 0 3 9 5 '- * 4.

- 39 -. . Table E (continued)

Compound Concentration Disease Control Ft Toxicity No. (ppm) _ (%) __ CNA * 500 72 0 5 (Control)

Untreated 0 * CNA = formula 13

Example XXXV

This example shows the fungicidal activity of some benzoxazolone derivatives as seed coat against Cochliobolus miyabeanus (brown spots on rice).

10 g of rice seeds (Asaminori "variety), which were infected by the disease, were packed in a Saron net bag and placed in a 50 ml beaker, in which they were immersed in a diluted formulation (prepared as described in Example XXXIV) which was added in the same amount as that of the rice seeds. The seeds were then removed from the formulation and immersed in deionized water at 15 ° C for 5 days and then germinated at 30 ° C for 24 hours. The rice seeds that were sprouted were sown on a black volcanic ash bottom (in which -5.5 g of ammonium sulfate, 6 g of calcium superphosphate and 1.5 g of potassium chloride) in plant pads (30 x 60 x 10 cm). The cushions were then stored in a greenhouse at 28 ° C to grow.

Twenty days after sowing (in the three-leaf stage), a visual assessment was made of the extent to which the disease had affected the seedlings in each treated group expressed in the following grade:

Grading Degree of disease attack. Slight Disease attack is only observed in a very small part of the primary leaf or in the leaf shaft.

Moderate Primary leaf has become almost brown and almost dead, as well as brown lesions on the primary and secondary true leaves.

Violent Remarkably poor growth of the seedlings, which are bent and have a brown color under dying.

8100395. ~ * 1 - 40 -

The percent disease attack (degree of infection) was determined from all seedlings rated as "heavy" and "moderate" and the degree of seed coat (or seed detection) was calculated using the following equation 5 Degree of infection in

Degree of seed coat (%) = (1 - treated groups, 100 3 Degree of infection in untreated groups

The degree of seed coatings is an average value of the 10 results of the tests, which were carried out in two replicas for each concentration of the active ingredient. The phytotoxicity for the rice plants was visually assessed with the same grade as in Example XXXII.

The results are reported in Table F below

Table F

Compound Concentration Degree of Phytotoxicity No. (ppm) seed coat _ (%) _. 1 500 98 1 20 3 500 97 0 10 500 96 0 11 500 98 0 14 500 92 0

Control A 500 63 2 25 Control B 500 72 3

Control C 500 40 1

Control D 500 40 1 TMTD * 2000 70 0 (Control) 30 Untreated 0 0 STMTD = formula 14

Example XXXVI

The benzoxazolone derivatives were tested for their seed-coating activity against Gibberella fujikuroi (Bakanae disease on rice).

The test procedure used was the same as described in Example XXXV, except that rice seeds ("Reimei" strain) that were naturally infected by the disease were used and that visual assessment was made 26 days after seeding (in the four-bladed stage).

81 0 0 39 5. . - 41 - *., The results are shown in Table G below.

Table G

Compound Concentration Degree of Phytotoxicity No. (ppm) seed coat 5 _ _ (%) _ 1 500 98 1 3 500 100 0 10 500 98 0 11 500 96 1 10 14 500 88 0 17 500 90 0 18 500 88 0 19 500 92 '0

Control A 500 47 0 15 Control B 500 52 3

Benomyl * 500 98 0 (Control)

Untreated 0 * Benomyl = formula 15

Example XXXVII

In this example, the benzoxazolone derivatives were tested against Phtyophthora infestans (note mildew for tomatoes).

Dilute suspensions of a wettable powder containing the required concentrations of active ingredient were prepared as described in Example XXXIV. The test suspension was applied in an amount of 10 ml per pot to young seedlings of the tomato plant ("Sekai-ichi" variety) at the stage with three true leaves grown in soil in porcelain pots with one diameter. 30 cm in a greenhouse. Traces of Phytophthora infestans grown on potato tubers were suspended in sterilized water to a spore concentration, with 20-30 spores observable under one microscope at 150 times magnification with one storage.

35 One day after application, the leaves of the toma seedlings were inoculated with drops of the spore suspension and the seedlings were then kept at 20 ° C in a humid chamber to allow the disease to develop. Three days later, the seedlings were removed from the chamber and the number of affected leaves was counted. 81 0 0 39 5 "4 * - 42 - number of affected leaves. The percentage of affected leaves and the disease control were calculated from the equations below:

Percentage affected _ Number of affected leaves χ 1qq 5 leaves Number of inoculated leaves% affected leaves of

Disease management ina (%) = (1 - treat £ lde? ΓΟβΡ? Η_) x χ00

see xteneneersing ^ U% affected leaves of} x iUU

untreated groups 10 Phytotoxicity to tomato plants was also assessed with the same grade as recorded in Example XXXII. Results are recorded in Table H below.

Table H

Compound Concentration Disease control Phytotoxicity 15 _no. _ (ppm) _ (% _) _ _ 1 500 100 0 3 500 92 0 4 500 97 0 6 500 99 0 20 7 500 94 0 10 500 98 0 11 500 88 0 13 500 99 0 14 500 99 0 25 15 500 96 0 18 500 97 0 19 500 99 0 20 500 98 0 21 500 -96 0 30 24 500. 97 0 30 500 94 0 31 500 98 0 33 500 94 0 36 500 99 0 35 37 500 100 0 38 500 100 0 41 500 100 0 42 500 98 0 47 500 96 0 40 50 500 100 0 51 500 98 0 8100395 - 43 -

Table H (continued)

Compound Concentration Disease Control Phytotoxicity No. (ppm) _ (%) _ _ 56 500 98 0 5 59 500 98 0 60 500 98 0 61 500 90 0 62 500 100 0 67 500 92 0 10 68 500 98 0

Control A 500 0 0

Control B 500 0 0

Control C 500 0 0

Control D 500 0 0 15 Maneb * 500 87 0 (Control)

Untreated 0 ate

Maneb = formula 16

Example XXXVIII

This example shows the action of the derivatives against Sphaerotheca fuliginea (powdery mildew on cucumbers).

The diluted formulation, prepared as in Example XXXVII, was applied in an amount of 10 ml per pot to one-25 leaf stage cucumber seedlings ("Sagamihanjiro" variety) grown in soil in porcelain pots with a diameter of 9 cm in a greenhouse. The next day, the seedlings were inoculated by spraying with a spore suspension of Sphaerotheca fuliginea. Ten days after inoculation, the percentage of lesion areas on the seedling-30 and disease control were determined from the equation below:

Percentage of lesions in

Disease control (%) -, l - Sggggjg-gggfBg-> * 100 35 untreated groups

The results are recorded in Table J below.

Table J

Compound Concentration Disease Control Phytotoxicity No. _ (ppm) _ (%) _ _ 40 1 200 92 0 4 200 95 0 8 1 0 0 39 5 - 44 - i j

Table J (continued)

Compound Concentration Disease Control Phytotoxicity No. (ppm) _ {%) _ ___ 5 200 92 0 5 8 200 90 0 9 200 90 0 10 200 96 0 11 200 92 0 18 200 90 0 10 19 200 98 0 22 200 82 0 29 200 85 0 33 200 92 0 36 200 96 0 15 40 200 94 0 45 200 100 0 47 200 98 0 52 200 100 0 55 200 100 0 20 58 200 100 0 59 200 100 0 60 200 100 0 61 200 100 0 63 200 97 0 25 64 200 100 0 65 200 99 0 66 200 100 0 69 200 100 0 70 200 100 0 30 Control A 200 20 1

Control B 200 10 1

Control C 200 10 1

Control D 200 13 1

Dimethirimol * 200 95 0 35 (Control)

Untreated - 0 - sk

Dimethirimol = Formula 17

Example XXXIX

The benzoxazolone derivatives were tested against Pseudopero-8100395-45 nospora cubensis (downy mildew on cucumber).

The diluted formulation, prepared as in Example XXXVII, was applied in an amount of 10 ml per jar to the underside of the leaves of young cucumber seedlings ("Sagamihanjiro" variety) at the true leaf stage grown in the soil were in porcelain pots with a diameter of 9 cm in a greenhouse. Traces of Pseudoperonospora cubensis, the products obtained on cucumber leaves in a disease development environment, were brushed in deionized water, 50 ppm Tween 20 ( trade name for polyoxyethylene sorbitan monolaurate, Kao Atlas Co.), thereby obtaining an inoculum having a spore concentration, with 20-30 spores visible in one storage under a microscope at 150 times magnification.

One day after application, the leaves of the cucumber seedlings were inoculated on their treated bottom by spraying with the inoculum. After the inoculation was completed, the seedlings were first placed in a humid chamber at 20 ° C and then in a greenhouse at 24 ° C to develop the disease. Six days later, the seedlings were removed from the greenhouse and assessed for the percent lesion area per pot. Disease control (%) was calculated using the equation reported in Example XXXVIII and the phytotoxicity was assessed with the same grading as in Example XXXII.

The test results are shown in Table K below,

Table K.

Compound Concentration Disease Control Phytotoxicity No. (ppm) _ (% _) _ _ 1 500 100 0 30 3 500 98 0 7 500 90 0 10 500 100 0 11 500 95 0 13 500 100 0 35 14 500 100 0 18 500 100 0 19 500 100 0 20 500 88 0 21 500 96 0 40 23 500 99 0 8 100 395 - 46 -

Table K (continued)

Compound Concentration Disease Control Phytotoxicity No. (ppm) _ (_%) _ · _ 31 500 98 0 5 33 500 100 0 37 500 100 0 44 500 '92 0 45 500 98 0 46 500 100 0 10 47 500 94 0 50 500 100 0 51 500 100, 0 52 500 98 0 53 500 100 0 15 55 500 96 0 60 500 96 0 • 61 500 100 0 62 500 100 0 63 500 100 0 20 68 500 99 0 69 500 100 0 70 500 100 0

Control A 500 20 1

Control B 500 .25 1 25 Control C 500 30. 1

Control D 500 36 1

Maneb 500 90 0 (Control)

Untreated 0

30 Example XL

The benzoxazolone derivatives were tested against Collectotrichiumlagenarium (cucumber anthracnose).

The diluted formulation, prepared as in Example XXXVII, was applied in an amount of 10 ml per jar to the 35 leaves of young cucumber seedlings ("Sagamihanjiro" variety) at the single leaf stage grown in porcelain soil pots with a diameter of 9 cm in a greenhouse. Traces of Collectotrichum layersarium, obtained by incubation - on an oatmeal agar medium for 10 da-40 gene at 24 ° C, were suspended in sterilized water, 8100395 - 47 - at 50 ppm Tween 20 contains, to provide a suspension having a spore concentration, with about 100 spores visible in one storage under a microscope at 150 times magnification.

One day after application, the treated leaves of the cucumber seedlings were inoculated by spraying with the above spore suspension. The seedlings thus inoculated were then treated in the same manner as in Example XXXIX and the disease control was calculated using the equation below:

Number of lesions in

Disease control, *, - (1 -> * 100 untreated groups) The results are shown in Table L below.

Table L

Compound Concentration Disease Control Phytotoxicity No. (ppm) _ (% _) _ _ 1 500 100 0 20 3 500 98 0 7 500 96 0 10 500 100 0 19 500 100 0 21 500 88 0 25 23 500 97 0 28 500 94 0 31 500 98 0 33 500 100 0 36 500 100 0 30 37 500 100 0 40 500 98 0 44 500 96 0 46 500 100 0 49 500 99 0 35 50 500 100 0 54 500 98 0 55 500 100 0 58 500 100 0 60 500 94 0 40 62 500 100 0 69 500 100 0 70 500 100 0 81 0 0 39 5 - 48 -. . Table L (continued)

Compound Concentration Disease Control Phytotoxicity No. _ (ppm) _ (_% _) _ _

Control A 500 45 1 5 Control B 500 37 1

Control C 500 35 1

Control D 500 43 1 TPN * 500 98 0 (Control) 10 Untreated - 0 * TPN = formula 18

Example XL'I

This example shows the action of the benzoxazolone derivatives against Puccinia recondita (leaf rust in wheat).

The diluted formulation, prepared according to Example XXXVII, was applied in an amount of 20 ml per three pots to young wheat seedlings ("Norin No.61" variety) at the stage of real leaf grown in soil in porcelain pots with a diameter of 9 cm in a greenhouse.

20 Uredosorus of Puccinia recondita, which had been formed on wheat leaves, was brushed in sterilized water containing 50 ppm Tween 20 to provide an inoculum of a spore suspension having a spore concentration, with approximately 50 spores discernible in one storage below 25 a microscope with a magnification of 150 times.

One day after application, the wheat seedlings were inoculated by spraying with the inoculum. After the inoculation was completed, the seedlings were first kept overnight at 20 ° C in a humid chamber and then transferred to a greenhouse at 20 ° C to develop the disease. Ten days after inoculation, the number of fungus uredosori caused by the disease per leaf was counted and the disease control; was calculated with the equation:

Number of uredosori per 35 ". , ^ "Treated group c,"

Disease control (%) = (1 f ^ - 5-r-- x 100 3 Number of uredosori per untreated group

Phytotoxicity to wheat plants was assessed using the same grade as recorded in Example XXXII. Results are reported in Table M below.

8 1 0 0 3 9 5 - 49 -

Table Μ

Compound Concentration Disease Control Phytotoxicity No. _ (ppm) _ [% _) _ _ 1 200 100 0 53 200 92 0 8 200 90 0 10 200 100 0 19 200 98 0

Control A 200 10 1 10 Control B 200 5 0

Control C 200 10 1

Control D 200 5. 0

Maneb 200 96 0 (Control) 15 Untreated 0 -

Example XLII

Some benzoxazolone derivatives were tested against Pellicu-laria sasaki (leafy mildew on rice).

The diluted formulation, prepared as in Example XXXVII, was applied in an amount of 40 ml per three pots, to six-leaf stage rice seedlings grown in soil in porcelain pots of 9 cm diameter in a greenhouse. The following day, inoculation of the seedlings with the fungus disease was carried out by applying an agar disk to the second leaf sheath obtained by drilling the edge of a colony of Pellicularia sasaki fungus with a 5 mm diameter cork drill. , which was incubated on potato-sucrose agar medium at 27 ° C for 48 hours. The inoculated seedlings were then stored overnight in a humid chamber overnight. Four days after infection, the length of the lesions per stem was determined and disease control was calculated using the equation below:

Lesion length 35 Disease control (%) = (1 - in treated ... groups ^ Lesion length m untreated groups

The test results are shown in Table N below.

8100395 - 50 -

Table N

Compound No. Concentration (ppm) Sickness Control (%) 69 500 100 70 500 90 5 Control A 500 15

Control B 500 0

Control C 500 10

Check D500 0

Validamycin 125 90 10 (Control)

Untreated - 0

Example XLIII

In this example, the benzoxazolone derivatives were tested against fungi and bacteria capable of attacking industrial materials.

The tests were performed according to the agar dilution method, as described in Example XXXI, but the incubation was performed for 28 days at 28 ° C for fungi and at 30 ° C bacteria. The tests were performed in two replicates at each concentration of the active compound tested and mean value of minimum inhibitory concentrations. :) (MIC) was determined.

The results are reported in Table O below.

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Example XLIV

This example shows resistance to fungi growth for paints containing the benzoxazolone derivatives.

The tests were performed according to the method of 5 JIS Z-2911 in the following manner: a certain amount of oil formulation, prepared as in Example XXV, was added to a white paint based on a polyvinyl acetate emulsion and the resulting mixture was kept for 30 sec. stirred in a homogenizer to prepare a paint formulation into which a filter paper ("Toyo Filter Paper" No. 2) of 12 cm diameter was inserted. The paper was then removed from the paint formulation and dried on the air, if the amount of paint deposited on the paper was adjusted to obtain a dry paint loading of 99-100% based on the weight of the filter paper. The dried paper was then cut to a diameter of 3 cm to obtain a circular sample, which was then pasted on the center of an agar plate medium in a petri dish. Both the medium and the sample were each inoculated by spraying with 1 ml each of a mixed spore suspension prepared by mixing equal amounts of respective spore suspensions of the three fungi (Aspergillus: niger, Penicillium lutenum and Trichoderma Tl ), which were incubated separately on potato dextrose agar medium.

The petri dish was then covered and kept in a incubator at 28 ° C for one week in order to allow incubation of the fungi, after which the growth of the fungi on the sample was assessed with grade 3, 2 or 1, in which: 3 indicates that no mycell growth has occurred on the surface of the sample, 2 indicates that the area of mycell growth has not exceeded one third of the surface of the sample, 1 indicates that the surface of mycells growth exceeds one third of the surface of the sample.

Table P

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15 Example XLV

This example shows the mucus-regulating action of the benzoxazolone compounds.

An amount of plain water from a paper mill was placed in a flask, to which an aqueous solution of the compound to be tested was added to a concentration of 10 ppm active ingredient in the plain water. Before adding the formulation and 0.5 At 1, 2, 4 and 8 hours after the addition of the formulation, bacterial colony counts in the ordinary water were determined with the agar plate diluted.

Method in the following manner: a sample of the ordinary water was diluted with sterilized saline and 1 ml of the diluted solution was placed in a petri dish. A dissolved broth agar medium was poured in and mixed with the diluted solution. After incubating in the plate at 30 ° C for 2 days, the bacterial colony was counted using a colony counter and the bacterial count per ral of plain water was calculated, taking into account the dilution factor with the sterilized saline. The tests were performed in two replicates and an average bacterial count was determined. The results are shown in Table R.

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Example * XLVI

This example demonstrates the effectiveness of the benzoxazolone derivatives as wood preservatives.

A block of Cryptmerica japonica (Japanese "Sugi") with a diameter of about 15 cm and a length of 60 cm, which had dried to its fiber saturation point, was sealed on both transverse ends with an epoxy resin containing glass wool. An oil formulation, prepared as in Example XXV, was diluted with water to a concentration of 2% active ingredient and then injected under pressure of 15 kg / cm for 3 hours into the wood. Then the wood was air dried to determine its water content. to atmospheric humidity. Samples measuring 2 x 2 x 1 cm were taken from the dried wood and from a block of wood of the same kind treated with known wood preservatives as controls, and all samples were subjected to two weeks air dried.

These samples were then exposed to imitation weather conditions using an ultraviolet 35 carbon arc weather gauge over a two month period (equivalent to six years under natural weather conditions); the samples were n.1. watered at a rate of 2100-100 mm / min. under a hydraulic pressure of 1.0 kg / cm for 18 min. after 2 hours of irradiation with ultraviolet light and these operations were repeated in this order during this period. The samples 8 1 0 0 39 5 - 56 - - . . then dried at a temperature of 60-2 ° C for 48 hours and weighed (the dry weight is recorded as Wj).

The samples were then subjected to preservation tests according to the method of JIS A 9302. In this test 5, the samples were inoculated with Coriolellus palustris and Coriolus versicolor grown at 26 ° C for 15 days on a sand medium containing 4% glucose, 0.3% peptone and 1.5% malt extract. After incubation for 90 days at 26 ° C, the mycelia and other deposits were removed from the samples, then air-dried for 24 hours, then at 48 hours 60 ° C were dried and weighed (the dry weight is recorded as W2).

The weight loss of the samples is calculated by the equation: W - W

15 Weight loss (%) = —-- x 100 W1

The preservation efficiency (P.E.) is obtained from the equation below:

Average weight loss _ n _ in treated groups. inn 20. . v Average weight loss x in untreated groups

The test results are recorded in Table S.

Table S

Compound No. P.E.value 25 1 100 3 98 10 96 TBTO * 40 PCP-Na ** 63 30 Creosote Oil 95 ^ Tributyltin Oxide

Sodium pentachlorophenolate

Example XLVII

This example demonstrates the synergistic effect obtained by mixing a given compound of the invention with other known fungicides.

Wettable powder formulations containing Compound No. 10 and other fungicides prepared as described in Example XXX were diluted with water to the required concentration of active ingredients. The tests were carried out. Den using the diluted formulations performed against Pseudoperonospora cubensis (cucumber), Sphaerotheca fuliginea (cucumber) and Sclerotinia sclerotiorum (sper-5 beans) according to the methods mentioned herein, in Examples XXXIX, XXXVIII and XXXIV, respectively.

For comparison, tests were also performed in the same manner using such dilute formulations containing only Compound No. 10 or other fungicides airborne.

Concentration and disease control of compound No. 10 alone (A) were 25 ppm and 26% for Pseudoperonospora cubensis, 50 ppm and 24% for Sphaerotheca fuliginea and 50 ppm and 26% for Sclerotinia sclerotiorum.

The results of tests with other fungicides alone (B) and mixed fungicides (A + B) are summarized in Tables U, V and V below.

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Claims (2)

A benzoxazolone compound of formula 2, wherein X is a short chain alkyl group; Y is a halogen atom; m = 0, 1 # 2 or 3, n = 1, 2 or 3 and the sum of m + n = 2, 3 or 4, and 5 Yn can be a 5,6,7-trichloro group; and R is a hydrogen atom or an alkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, mono- or di-alkylaminocarbonyl, alkylsulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group 10. 2. Benzoxazolone compound according to claim 1, characterized in that. k that m ί 0 and Yn eeri is 5,6,7-trichloro group. 3. Benzoxazolone compound according to claim 1, characterized in that m = 1 /. X = methyl, n = s »2 and each Y is chlorine. Benzoxazolone compound according to claim 3, characterized in that Xm is a 7-methyl group and Yn = 5,6-dichloro. 5. Benzoxazolone compound according to claim 1, characterized in that m = 0; Yn is a 5,6,7-trichloro group and R is an alkenylcarbonyl or alkenyloxycarbonyl group. 6. Benzoxazolone compound according to claim 1, characterized in that it is 5,6,7-trichlorobenzoxazolone; N-acetyl-5,6,7-trichlorobenzoxazolone; N-methoxycarbonyl-5.6.7-trichlorobenzoxazolone; N- (3,5-dichlorophenylcarbamoyl) - 5.6.7-trichlorobenzoxazolone; N-methanesulfonyl-5,6,7-trichlorobenzoxazolone; N-isopropoxycarbonyl-5,6,7-trichlorobenzoxoxazolone; 5,6-dichloro-7-methylbenzoxazolone; N-acetyl-5,6-30 dichloro-7-methylbenzoxazolone; N-methoxycarbonyl-5,6-dichloro-7-methylbenzoxazolone or N-allyloxycarbonyl-5,6,7-trichlorobenzoxazolone is 7, Fungicide or bactericidal preparation for non-medical purposes, characterized in that it is active component contains a compound of formula 2, wherein X is a short chain alkyl group; Y is a halogen atom; m = ί 0, 1, 2 or 3; n = 1, 2 or 3; and the sum of m + n = 2, 3 or 4, and Yn are a 5,6,7-trichloro group ka.n; and R a hydrogen 8 1 0 0 3 9 5 - 62 - *? Atom or an alkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkenylcarbonyl, mono or di-alkylaminocarbonyl, alkylsulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group, in appropriate or non-dilute form. Preparation according to claim 7, characterized in that it is a concentrate of 10-95% by weight. contains active ingredient. Preparation according to claim 7, characterized in that it consists of a dilute formulation with 1 x 10-5 to 10% by weight of active ingredient. 10. A method of controlling the growth of fungi and bacteria on a plant or an industrial material, characterized in that a compound of formula 2, wherein X is a short chain alkyl group? Y is a halogen atom; m = 0, 1, 2 or 3? n = 1, 2 or 3; and m + n = 2, 3 or 4, and Yn can be a 5,6,7-trichloro group? and R is a hydrogen atom or an alkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, mono or di-alkylaminocarbonyl, alkylsulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group or yields the plant on the plant the site of the plant which is infected or is likely to be infected by the fungi and / or bacteria. 11. Process for preparing a new benzoxazolone compound, characterized in that a compound of formula 2, wherein X is a short chain alkyl group; Y is a halogen atom? m = 0, 1, 2 or 3; n = 1, 2 or 3? and the sum of m + n = 2, 3 or 4, and Yn can be a 5,6,7-trichloro group? and R is a hydrogen atom, or an alkyl, alkyl-carbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, mono- or di-alkylaminocarbonyl, alkylsulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group), in that one is prepared by compound of formula 3, wherein X, Y, m, n and R have the above meaning, react with a compound of formula 4, wherein A and B are the same or different and 8 1 0 0 3 9 5 - 63 - * #. -. each independently a halogen atom or an alkoxy, haloalkoxy, alkylthio or amino group, or b) a compound of formula 5 wherein X, m and R have the above meaning, Z is a halogen atom and p = 0, 5. or 2 halogenates to give a compound of the formula II which contains in the benzene ring a halogen atom more than the benzene ring of the starting compound of the formula 5; or c) a compound of formula 7, wherein X, Y, m and n have the above meaning, is reacted in the presence of an acid binding agent with a compound of formula 8, wherein R has the above meaning and D has a halogen, or with a dialkyl sulfate, wherein the alkyl group is R 1, to form a compound of formula 2, wherein 15 is not hydrogen; or d) reacting a compound of formula 7 with an isocyanate compound of formula 9, wherein R 'is an alkyl, or optionally substituted phenyl group to form a compound of formula 2, wherein R is -CONHR' group. 8100395 1 J • * * ^ ° ÊC> - '· ”-' l§Oc · 0 Yn Yn CONHR '7 9 10 ï / r \ (i - c3h70) 2 p - sch2 - / Q) 11 Cl M-jo) Cl 12 13 ï! , rr ^ rv. (CH3) 2MC - s - S - CN (CH3) 2 () -NHCOOCH3 CONHC4Hg-n '14 15 · n-C4H9 ch3 -s ToT o ^ hncs ^^ CH-HNCS' ^ T 2 .11 C1. 'n (ch, k SI 32 Cl N. / CN ToT ci ^ Y ^ ci CN 8 1 0 0 3 9 5 ie HOKKO CHEMICAL INDUSTRY CO., LTD H *> «# 1 0'N \ co * 2 * 3 GO - R4 1 v Xm Xm., 'For "· <. · =" 1 - * ferv. "·! & V Yn R 3 4 2 Xm Xm 0 • ί / Γ \ 1 n. _,, Halounerinas - λ (^ "" Ν> C = Ο b IPXN / i ^ a ^ / • zp It 'γη l 5 6 2, * Xn ^ (acid binding | W |' X. c φ £ > - * = »- ^ ®L> - ° Yn h Yn l 7 8 2 HOKKO CHEMICAL INDUSTRY CO., LTD. 8100395