CH644853A5 - BENZOXAZOLONE DERIVATIVES, METHOD FOR THEIR PRODUCTION AND PREPARATIONS THAT CONTAIN. - Google Patents

Description

The present invention relates to new benzoxazolone derivatives, to processes for their preparation, to fungicidal and bactericidal preparations which contain these derivatives, and to processes for controlling various fungi and bacteria using these new derivatives and preparations.

Certain benzoxazolone derivatives are known to be useful as fungicides and bactericides in agriculture and horticulture. For example, German Patent No. 1,023,627 describes the antifungal and antibacterial properties of some benzoxazolone derivatives whose benzene ring has a substituent such as 5-chloro, 5,6-or 5,7-dichloro or 4,5,7-trichloro, but no alkyl -bears substituents.

German Patent No. 1,147,007 describes the antimicrobial properties of 4,5,6,7-tetrachlorobenzoxazolone, while USSR Patent No. 355,008 mentions such properties of 4,5,6-trichlorobenzoxazolone.

Japanese Laid-Open No. 23519/65 also discloses the fungicidal and bactericidal properties of benzoxazolone derivatives of the formula:

r

—0

r

2nd

co-r in which Ri = R2 = Rj = H; Ri = Cl, R2 = R3 = H; R2 = Cl, Ri = R3 = H; Ri = R2 = CI, Ri = H; or Ri = R2 = R3 = Cl; and R4 denotes the phenyl group which is optionally substituted by halogen, nitro, lower alkyl or lower alkoxy.

In the effort to develop new benzoxazolone microbicides which have low toxicity and high safety and at the same time have high activity against a wide range of fungi and bacteria, a number of new benzoxazolone derivatives were produced and carefully investigated in the context of the present invention. The present invention therefore relates to new benzoxazolone derivatives which have not previously been described and which are very useful as fungicides and bactericides. The derivatives according to the present invention either carry at least one lower alkyl group and at least one halogen substituent in the benzene ring or are 5,6,7-trichloro derivatives. These new derivatives according to the present invention have significantly improved fungicidal and bactericidal properties compared to the known compounds 4,5,7-trichlorobenzo-xazolone and 4,5,6-trichlorobenzoxazolone, as is clear from the examples described later.

An object of the present invention is thus to provide new benzoxazolone derivatives which are useful as antifungal and antibacterial agents. Another object of the present invention is to provide processes for making these new benzoxazolone derivatives. Yet another object of the present invention is to obtain fungicidal or bactericidal preparations which contain these new derivatives as an active ingredient. Finally, another object of the present invention is to provide a method for combating fungi and bacteria using the new derivatives or the preparations which contain them.

The present invention relates to benzoxazo ion compounds of the general formula I.

c = 0

in which

X is a lower alkyl group with 1 to 4 carbon atoms, Y is a halogen atom,

m zero or an integer from 1 to 3,

n is an integer from 1 to 3, the sum of m + n being 2 to 4, provided that when m = 0, n is 3 and Yn is 5,6,7-trichlor, and R Represents hydrogen or an alkyl, alkylcarbonyl, haloalkylcarbonyl, alkyloxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, mono- or dialkylaminocarbonyl, alkyl-sulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group.

In general formula I, X is a lower alkyl group containing 1 to 4 carbon atoms, such as the methyl, ethyl, n-propyl, isopropyl or butyl group, of which the methyl group is preferred, and Y is a halogen atom, such as Bromine or preferably chlorine.

R can be an alkyl group, in particular with 1 to 4 carbon atoms, an alkylcarbonyl group, preferably with 2 to 4 carbon atoms, an alkylcarbonyl group

5

10th

IS

20th

25th

30th

35

40

45

50

55

60

65

644853

io

Haloalkylcarbonyl group, in particular a chloro (Ci-4) alkylcarbonyl group, an alkyloxycarbonyl group, in particular a (C1-4) alkyloxycarbonyl group, an alkenylcarbonyl group, preferably a (C2-4) alkenylcarbononyl group, an alkenyloxycarbonyl group, in particular “one (C2-4) alkenyloxycarbonyl group, a mono- or di-alkylaminocarbonyl group, in particular a mono- or di- (Ci-4) -alkylaminocarbonyl group, an alkylsulfonyl group, in particular a (Ci-4) -alkylsulfonyl group or the phenylsulfonyl group. R can also be an unsubstituted or optionally substituted benzoyl group, e.g. the methylbenzoyl and chlorobenzoyl groups, as well as an unsubstituted or substituted phenylaminocarbonyl group, e.g. a mono- or dichlorophenylamino-nocarbonyl group.

A preferred group comprises those compounds of formula I in which m = 0 and Yn represents 5,6,7-trichlor. Another preferred group of the new compounds are those of the formula I in which Xm represents the methyl, in particular the 7-methyl group and Yn dichloro, in particular 5,6-dichloro.

Specific examples of the compounds according to the invention are summarized in Table I below:

Table I 25

Table I (continued)

Connection structural formula no.

20th

c = o

30th

35

c = o c0ch-

c »0

c0c2h5

Melting point (° C)

171-172

161-162

Connection structural formula no.

c = o

Melting point (° C)

40

45

253-254

50

0 = 0

coc4h9

111-112

55

c-0

135-139 «»

c ~ 0

c0ch2c1

187-188

644853

Table I (continued)

Connection structural formula no.

Cl

Cl

Cl

10th

Cl

Table 1 (continued)

Melting joint structural formula point (° C) no.

Cl

Cl

10th

188-190 11

15

20th

198-200

35

40

157-159 45

50

\

60

C-0 163-164

65

c00ch,

Cl

\

i

/

I.

c0nhch-

c = 0

Cl

Cl

12

J

\

c = 0

Cl c0n (ch3) 2

Cl

13

o ero ci

Melting point (° C)

173-175

127-129

164-165

c0nh-

14

C-035-237

Cl

Cl

644853

Table I (continued)

Table I (continued)

Connection structural formula no.

Melting joint structural formula point (° C) no.

Melting point (° C)

Cl

Cl

15

O

C = 0

s02ch3

10th

19th

218-219

Cl

Cl

\

Cl c = 0

cooc3h7-iso

129-130

Cl

16

20th

20th

25th

197-198

30th

21st

35

c-0

Cl o

\

c = o

182-184

150-159

Cl

Cl

17th

Cl

Cl

Cl

18th

Cl c = o c00c2h5

c = o c00c3h7

45

99-100 22

50

55

60

104-105 23

65

ch-

c0ch,

Cs 0

c00c2h5

140-141

115-117

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Table I (continued)

Table I (continued)

Connection structural formula no.

Melting joint structural formula point (° C) no.

Melting point (° C)

24th

\

29

c = 0 254-257

10th

15

Cl o

c = 0 106-110

c2h5

coch2ci

25th

\

c

/

20th

30th

232-234

25th

30th

C-0 115-116

ch,

26

csro

Cl

27th

c = o c2h5

, n /

i h

/

35 31

93-94

40

45

32

126-130 50

Cl

O

\

c = 0

Cl

.N 'h ch-

O

c => 0

Cl ch-

251-252

122-123

Cl

28

O

c = 0

c2h5

N '

i c0ch,

60

101-103 33

ctlo 168-169

644853

Table I (continued)

Connection structural formula no.

34

c = o

COC ^ Hg-n

Table I (continued)

Schmeiz connection structural formula point (° C) no.

Melting point (° C)

54-56 38

15

CH.

Cl

Cro 170-172

Cl

H'

i

CONHCH.

20th

35

36

25th

165-166

39

30th

35

40

40

213-215

45

Cl

50

55

CH.

Cl

41

37

C ~ 0 135-138

Cl n «

I.

C00CH.

65

CH.

Cl

O

Cl o,

c = o

N S CH.

179-180

l

CON <

kCH.

CH.

Cl cso

150-152

CT

N

I.

CON

CH.

Cl

Cl '

C-O 221-222

Cl

CONH.

Cl

644853

Table I (continued)

Connection structural formula no.

42

c02ch3

Table I (continued)

Melting joint structural formula point (° C) no.

Melting point (° C)

10th

Cr; 0 199-200 46

15

c = 0 149-151

coocbl

43

20th

25th

191-193 47

30th

35

c = o

218-219

44

c = o

40

45 48

248-250

50

c ~ 0 136-138

: h3 ch3

ci

45

\

c = o c0ch-

55 60

133-135 49

65

Cl o

c -0 103-105

Cl ch3 coch3

644853

10th

Table I (continued)

Table I (continued)

Connection structural formula no.

Melting joint structural formula point (° C) no.

Melting point (° C)

50

cno 127-130 1 »

54

ch3 cooch3

15

c-0

262-264

20th

51

c_ 0 216-217 55

30th

C = -0 173-175

coch-

35

52

i-C

40

CcO

133-135 56

3 7

45

50

c = o

224-225

55

53

C = 0 150-152 57

65

c-0 158-159

c00ch,

coch.

11

644853

Table I (continued)

Connection structural formula no.

58

Table I (continued)

Melting joint structural formula point (° C) no.

Melting point (° C)

10th

c = o 236-239 62

15

C ~ 0 174-176

20th

59

CnO

30th

35

Cl

25 cl

134-136 63

O

C - 0 275-277

Cl

CH.

Cl

60

CHO 254-256 4S64

50

C-0

ch3 coch3

125-127

Cl

Cl

61

o ch n <

3 I 1

ci coch,

55

60

C ^ O 155-157 65

65

C ~ 0 288-289

644853

Table I (continued)

12

Table I (continued)

Connection structural formula no.

Melting joint structural formula point (° C) no.

Melting point (° C)

66

C ^ O

10th

142-144

69

15

c = 0 161-163

c0ch = ch,

67

68

20th

c-0

c-0

271-27225 Cl

70

30th

35

117-118

40

c = o c00ch2ch = ch2

96-98

The compounds of the invention can be prepared by the procedures outlined in Schemes A, B and C below, and some of these compounds 45 can be obtained according to Reaction Scheme D.

Scheme A

+ 0 = c

nhr

(II)

(III)

(I)

In the formulas I and II above, the symbols R, X, Y, m and n have the same meaning as defined above. The compounds of formula II, in which R is, for example, the acetyl group, can be obtained in high yield by acetylation of the corresponding orthoaminophenol, optionally substituted with lower alkyl, in a known manner and subsequent halogenation of the acetylation product with the required equivalent of a halogen. The compound thus obtained can be hydrolyzed, e.g. with dilute hydrochloric acid to make the appropriate

13

644 853

To give compound of formula II in which R represents hydrogen. This latter compound can be alkylated or acylated by any known method to give a variety of compounds of Formula II.

In the general formula III, A or B, which may be the same or different, denotes halogen, alkoxy, haloalkoxy, alkylthio or amino. The compounds of formula III include phosgene compounds such as phosgene and diphosgene (i.e. trichloromethyl chloroformate), halogen formates, halogen thiol formates, carboxylic acid diesters and urea.

According to Reaction Scheme A, it is generally assumed that the compounds of the formula I can be obtained in two stages, the compound HA or HB being eliminated after the reaction between the compound of the formula II and the compound of the formula III to form an intermediate which continues to react with the compound of formula III to allow further elimination of the formula HB or HA. Therefore, if a stable intermediate is formed, depending on the nature of the component of formula III used, this intermediate can be isolated and then cyclized to form the compound of formula I. Such stable intermediates can be formed in another method without requiring the reaction between the compound of formula II and the compound of formula III and subsequent cyclization to the compound of formula I.

The reaction between the compounds of formula II and III 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 III. Examples of suitable solvents include hydrocarbons, halogenated hydrocarbons, 5 ethers, esters, acid amides, alcohols and dimethyl sulfoxide, from which a suitable solvent is selected depending on the nature of the compound of the formula III. An acid binder can be used to ensure a smooth course of the reaction since some of the compound III fertilizers of Formula III can lead to the formation of an acid in the course of the reaction. Suitable acid binders for this purpose are organic amines, such as triethylamine and pyridine, and inorganic bases, such as potassium carbonate. The reaction can be carried out at room temperature, but it can be accomplished in a shorter time if it is carried out at elevated temperature.

After completion of the reaction, the compound of formula I obtained can be isolated and purified in a conventional manner. For example, if an acid binder was used, a salt or salts of the acid 20 binder which was precipitated in the reaction mixture could be filtered off and the solvent then evaporated from the filtrate to leave the compound of formula I. According to another method, water 25 and / or a suitable organic solvent, e.g. Benzene, chloroform, ether or tetrahydrofuran, are added to the reaction mixture in order to precipitate the desired compound of the formula I in a fractional manner.

Details of the process according to reaction scheme A 30 are described in the following Examples 1 to 4, 11 to 14 and 23.

Scheme B

Halogenie-runqsmi ttel

C = 0

(IV)

(V)

(I)

In the general formula IV, R, X and m have the same meaning as above, Z is a halogen atom and p represents 0, 1 or 2. The compounds of the formula IV can be prepared by the method described above in connection with reaction scheme A has been described. Examples of suitable halogenating agents (V) include halogens, such as chlorine or bromine, and also sulfuryl chloride alone and combinations of hydrohalic acid and an oxidizing agent, such as bleaching powder, potassium chlorate or manganese dioxide. .

The halogenation reaction according to Scheme B is usually carried out in a solvent and at an elevated temperature in order to accelerate the reaction in the case where the halogenation is carried out with a halogen such as chlorine or bromine or with sulphuryl chloride. The solvent which can be used in this case is e.g. Water, acetic acid or a halogenated hydrocarbon. If the halogenation is thus carried out using a combination of a hydrohalic acid such as hydrochloric acid or hydrobromic acid and an oxidizing agent such as bleaching powder, potassium chlorate or manganese dioxide, the compound of formula IV can be dissolved in the acid, whereupon the oxidizing agent as a powder or as a concentrated one aqueous solution is added. A solvent such as acetic acid can be used if necessary.

55 The presence of a catalyst, e.g. Iron, iron chloride, a phosphorus compound, aluminum chloride or antimony chloride, or ultraviolet radiation leads to the smooth course of the reaction according to scheme B.

After completion of the reaction, the compound of formula I obtained can be obtained directly by evaporating the solvent or possibly by adding water and / or a suitable organic solvent such as benzene, chloroform, ether or tetrahydrofuran for the purpose of fractional extraction.

Details of the procedure according to Reaction Scheme B are given in Examples 5, 6 and 15 to 17 below.

644853

14

Scheme C

C = 0

R D acid bi-demi ttel

(VI)

(VII)

(I)

In formula VI, X, Y, m and n have the same meaning as above. In formula VII, R is one of the groups listed above with the exception of hydrogen and D is halogen. When the group R to be introduced into the starting compound of the formula VI is an alkyl group, the reagent of the formula VII can be a dialkyl sulfate of the formula

RO.

RO

ÏSO2

in which R is an alkyl group.

Thus, compounds of formula VII can include alkyl halides, acyl halides, dialkyl sulfates, alkenoyl halides and alkenyl halide formates. These compounds can be prepared by known methods.

The reaction between the compound of formula VI and the compound of formula VII according to reaction scheme C 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 VII. Examples of suitable solvents include hydrocarbons, halogenated hydrocarbons, ethers, esters,

Peptones, acid amides, alcohols and dimethyl sulfoxide.

Suitable acid binders for this reaction include organic amines, such as triethylamine and pyridine, and 20 "inorganic bases, such as potassium carbonate. The reaction can be carried out at room temperature or at elevated temperature. The reaction time required, of course, depends on the nature of the compound of formula VII and The type of solvent, if any, and the reaction temperature used for 2 seconds, which can be reduced if the reaction is carried out in a polar organic solvent.

To obtain the compound of formula I formed after the reaction is complete, the reaction solution obtained can be filtered to remove a precipitated salt of the acid binder, and the filtrate can then be evaporated to leave the desired compound as a residue.

In certain cases, water and / or a suitable organic solvent, such as benzene, chloroform, ether or tetrahydrofuran, can be added to the reaction mixture to extract the desired compound of formula I.

Details of the process according to reaction scheme 40 C are given below in Examples 7 to 9.18 to 20 and 23.

Scheme D

C = 0 + R'NCO

C = 0

(VI)

(VIII)

(IX)

In formulas VIII and IX, R 'represents an alkyl group or an optionally substituted phenyl group. The process according to Scheme D is therefore suitable for the preparation of compounds of the formula I in which R represents alkylamino-carbonyl or optionally substituted phenylamino-carbonyl.

The reaction between the compounds of formulas VI and VIII can be carried out in the absence of a 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 VIII 60. The solvent to be used must be inert to the compound of formula VIII under the reaction conditions and includes e.g. Hydrocarbons, halogenated hydrocarbons, ethers, esters and ketones. If a small amount of an organic amine, 65 such as e.g. Triethylamine or pyridine, as a catalyst, the reaction is very smooth. The reaction can satisfactorily be carried out at room temperature or optionally at an elevated temperature.

15

644 853

The reaction time required depends on the nature of the compound of formula VIII and other reaction conditions, but the reaction can usually be completed in a relatively short time.

After completion of the reaction, the compound of formula I formed can be obtained from the reaction mixture by filtering off the crystals of the precipitated compound or by evaporating the solvent, depending on the case at hand.

The procedure according to Scheme D is described in detail in Examples 10 and 21.

The present invention therefore furthermore relates to processes for the preparation of a compound of the general formula I, as defined above,

(a) a compound of the general formula II

Presence of an acid binder with a compound of formula VII

RD

[VII]

- 5th

in which R represents the same as above, with the exception of hydrogen and D represents a halogen atom, or with a di-alkyl sulfate of the formula io RO-

RO '

SOa in which R represents an alkyl group, to form a compound of formula I in which R is other than hydrogen; or

(d) a compound of formula VI above with an isocyanate compound of formula VIII

20th

[II] R'NC = 0

[V III]

NHR

in which X, Y, m, n and R have the same meaning as above, with a carbonyl compound of the general formula III

0 = C;

-B

[IH]

in which A and B are identical or different and denote a halogen atom or an alkoxy, haloalkoxy, alkylthio or amino group;

(b) a compound of formula IV

C = 0

[IV]

in which X, n and R represent the same as above, Z represents a halogen atom and p represents 0, 1 or 2, halogenated to form a compound of formula I which carries one or more halogens on the benzene ring, the number of which is one than that of the halogens in the starting compound of the formula IV;

(c) a compound of formula VI

00

[VI]

in which X, Y, m and n mean the same as above, in which R 'represents alkyl or optionally substituted phenyl, to form a compound of formula I in which R represents a group -CONHR'.

The compounds of the present invention are highly effective against a large number of diseases caused by fungi or bacteria, such as;

30 Piricularia oryzae (mildew) for rice,

Pellicularia sasaki (sheath blight) in rice,

Cochiliobolus miyabeanus (brown spots) in rice, Xanthomonas oryzae (bacterial leaf damage / blight) in rice,

35 Alternaria kikuchiana (black spots) in pears, Glomerella cingulata (ripe red) in wine grapes,

Cladosporium fulvum (leaf mold) in tomatoes, Phytophthora infestans (late blight) in tomatoes,

Sclerotinia sclerotiorum (stem rot) in beans, 40 Sphaerotheca fuliginea (powdery mold) in cucumber, Fusarium oxysporum (fusarium wilt) in cucumber, Psendoperonospora cubensis (downy mold) in cucumber,

Colletotrichum lagenarium (anthracnose) in cucumbers, 45 Erwinia aroidea (soft red) in Chinese cabbage.

Some of the compounds of the invention are remarkably active in protecting seeds, e.g. against Gibberella fujikuroi (Bakanae disease) and Cochiiliobolus miyabeanus so with rice.

The compounds according to the invention are not only effective for combating diseases caused by fungi and bacteria, as mentioned above, in agriculture and horticulture, but also for regulating the growth of various fungi and bacteria which are capable of causing damage, e.g. of industrial materials. So these connections can e.g. successfully used to protect paints, wood, paper, pulp, textiles outside the textile industry, cosmetics, leather, ropes, plastics, rubbers and adhesives, which can be protected against destruction or damage that can be done without such an additive Fungi and bacteria would occur.

The compounds according to the invention can be used as such for fungicidal and bactericidal purposes, but they are advantageously processed into preparations which are used for these purposes. The present invention therefore also includes a fungicidal or bactericidal

644853

16

Preparation which contains as active ingredient a compound of general formula I, as defined above, together with a carrier for this active ingredient.

The invention further relates to a method for regulating the growth of fungi and bacteria for non-medical purposes, in particular in plants or industrial materials, which method involves the use of a compound of the general formula I on the surface to be protected or at the location of the plant which has already been caused by fungi or is infected with bacteria or is to be protected from such an infection.

For the purposes described above, the compounds according to the invention are preferably used in the form of a preparation, the type of preparation depending on the particular intended use.

The preparations may be in the form of dusting powders or granules which contain the active ingredient and a solid thinner or carrier, e.g. Kaolin, ben-tonite, kieselguhr, dolomite, calcium carbonate, talc,

Chalk, powdered magnesium oxide, fuller's earth, gypsum, Hewitt earth or diatomaceous earth. Preparations for the treatment of seeds (seed) can e.g. contain an aid for the adhesion of the preparation to the good, for example a mineral oil.

The preparations can also be in the form of dispersible powders or granules which contain a wetting agent in order to facilitate the dispersion of the powders or granules in liquids, which preparations can also contain fillers and suspending agents.

Aqueous dispersions or emulsions can be prepared by dissolving the active ingredient (s) in an organic solvent, which may contain wetting agents, dispersing agents or emulsifiers, and then adding the mixture to water, which in turn may also contain wetting agents, dispersing agents or emulsifiers. Suitable solvents of this type are dimethyl sulfoxide, dimethylformamide, formamide and aliphatic alcohols.

Preparations which should be used as sprays can also be in the form of erosols, the preparation being in a container in the presence of a propellant, e.g. Fluorotrichloromethane or dichlorodifluoromethane, is kept under pressure.

By adding suitable additives, e.g. Additives to improve the distribution, the adhesion and the resistance to rain on the treated surface, the different preparations can be better equipped for corresponding applications. The active ingredient can be used as a mixture with fertilizers (e.g. nitrogen or phosphorus containing fertilizers).

The preparations can also be in the form of liquid products for use as immersion baths or sprays, which are usually aqueous dispersions or emulsions which contain the active ingredient in the presence of one or more wetting agents, dispersing agents, emulsifying agents or suspending agents. These agents can be cationic, anionic or non-ionic.

Suitable cationic agents are quaternary ammonium compounds, e.g. Cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts or aliphatic monoesters of sulfuric acid (e.g. sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butylnaphthalenesulfonate, and a mixture of sodium diisopropyl and propyl naphthalenesulfonates). Suitable non-ionic

Agents are condensation products of ethylene oxide with fatty alcohols, such as oleyl alcohol or cetylaic alcohol, or with alkylphenols, such as octylphenol, nonylphenol and octyl-cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of these partial esters with ethylene oxide and also the lecithins. Suitable suspending agents are hydrophilic colloids (e.g. polyvinyl pyrrolidone and sodium carboxymethyl cellulose) as well as vegetable gums (e.g. acacia and tragacanth).

The preparations for use as aqueous dispersions or emulsions are usually supplied in the form of a concentrate which contains a high proportion of active ingredient, these concentrates being diluted with water before use. These concentrates should often be able to withstand storage for a long time and to be diluted with water after such storage to form aqueous preparations which remain homogeneous for a sufficient period of time to allow use with conventional spray devices. The concentrates can advantageously contain 10 to 95 percent by weight, usually 25 to 60 percent by weight, of active ingredients. After dilution to form aqueous preparations, these diluted preparations may contain various amounts of active ingredients depending on the purpose, but aqueous preparations containing 1 x 10 5 to 10% by weight of active ingredient can be used.

If the preparations according to the invention are in the form of dusting powders or granules, they are generally applied as such to the plants to be treated in an amount of 2 to 4 kg per 10 ares (or in an amount of 10 to 1000 g of active ingredient per 10 ares) applied. When the preparation is used in the form of a wettable powder, an emulsifiable concentrate or a flowable preparation, it is usually diluted with water before use to give an active ingredient concentration of 10 to 5000 ppm. The diluted preparation is usually applied to the plants in an amount of 50 to 300 liters per 10 ares. For the treatment of other surfaces, a diluted preparation which contains 10 to 5000 ppm of active ingredient is generally used, the concentration in each case being able to vary within wide limits.

The preparations according to the invention can also contain one or more compounds which have biological activity, e.g. other known fungicides, bactericides, plant growth regulators, herbicides and insecticides. In particular, it has been found that some of the compounds have a marked synergistic effect when used together with certain known fungicides, e.g. results from the results in Example 47.

Examples of fungicides and bactericides which can be used in a mixture with the compounds according to the invention are the following:

Carbamate fungicides, e.g. 3,3-ethylene-bis- (tetrahydro-4,6-dimethyl-2H-l, 3,5-thiadiazine-2-thione), zinc or manganese-ethylene-bis- (dithiocarbamate), bis- (dimethyldithio- carbamoyl) disulfide, zinc propylene bis (dithiocarbamate), bis (dimethyldithiocarbamoyl) ethylene diamine; Nickel dimethyldithiocarbamate, methyl 1 - (butyl-carbamoyl) -2-benzimidazole carbamate, 1,2-bis (3-methoxy-carbonyl-2-thioureido) benzene, l-isopropylcarbamoyl-3- (3,5-dichloro -phenyl) -hydantoin, potassium N-hydroxymethyl-N-methyldithiocarbamate and 5-methyl-10-butoxycarbonylamino-

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

10,11 -dehydrodibenzo- (b, f) -azepine; Pyridine fungicides, e.g. Zinc bis (l-hydroxy-2 (lH) pyridine ethionate and

2-pyridine-thiol-l-oxide sodium salt; phosphorus-containing fungicides, such as 0.0-diisopropyl-S-benzylphosphorthioat and

0-ethyl-S, S-diphenyldithiophosphate; Phthalimide fungicides, e.g. N- (2,6-diethylphenyl) phthalimide and N- (2,6-diethylphenyl) -4-methylphthalimide; Dicarboxyimide fungicides, e.g. N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyimide and N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboxyimide; Oxathine fungicides, e.g. 5,6-dihydro-2-methyl-l, 4-oxathine-3-carboxanilido-4,4-dioxide and 5,6-dihydro-2-methyl-1,4-oxathine-3-carboxanilide; Naphthoquinone fungicide, e.g. 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) benzothiazole;

3-hydroxy-5-methylisooxazole; N-2,3-dichlorophenyl-trachlorophthalic acid; 5-ethoxy-3-trichloromethyl-1 -2,4-thiadiazole; 2,4-dichloro-6- (0-chloroaniline) -1,3,5-triazine; 2,3-dicyano-l, 4-dithioanthraquinone; Copper 8-quinoline; Polyoxin; "Varidamycin"; Cycloheximide; Iron methane arsonate; Diisopropyl-l, 3-dithiolane-2-iridene malonate; 3-allyl-oxy-l, 2-benzoisothiazole-l, l-dioxide; "Kasugamycin"; "Bla-sticidin-S"; 4,5,6-7 tetrachiophthalide; 3- (3,5-dichlorophenyl) -5-ethenyl-5-methyloxazolizine-2,4-dione; N- (3,5-dichlorophenyl) -l, 2-dimethylcyclopropane-l, 2-dicarboxyimide; S-n-butyl-5'-para-t-butylbenzyl-N-3-pyridyldithiocarbonylimidate; 4-chlorophenoxy-3,3-dimethyl-1 -

(1 H, 1,3,4-triazol-1-yl) -2-butanone; Methyl D, L-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alalinate; N-propyl-2- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1 carboxamide; N- (3,5-dichlorophenyl) succinimide; Tetrachloroisophthalonetril; 2-dimethylamino-4-methyl-5-n-butyl-6-hydroxypyrimidine; 2,6-dichloro-4-nitroaniline; 3-methyl-4-chlorobenzothiazol-2-one; 1,2,5,6-tetrahydro-4H-pyrrolo- [3,2,1 -i, j] -quinolin-2-one; 3'-isopropoxy-2-methylbenzanilide; l- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxoran-2-ylmethyl] -1 H, 1,2,4-triazole; 1,2-benzisothiazolin-3-one; basic copper chloride; basic copper sulfate; N'-dichlorofluoromethyl-thio-N, N-dimethyl-N-phenylsulfamide; Ethyl N- (3-dimethylamino-propyl) thiocarbamate hydrochloride; "Piomycin"; S, S-6-methylquinoxaline-2,3-diyldithiocarbonate; Zinc and mainly dizinc bis (dimethyldithiocarbamate) ethylene bis (dithiocarbamate).

Examples of plant growth regulators and herbicides which can be used together with the compounds according to the invention include, for example, the following:

Isourea compounds, e.g. N-methoxy-car-bonyl-N'-4-methylphenylcarbamoyl-ethylisourea and

1- (4-chlorophenylcarbamoyl) -3-ethoxycarvonyl-2-methyl-isourea; another type of growth regulator, such as sodium naphthalene acetate, 1,2-dihydropyridazine-3,6-dione and "gibberellins"; Triazine herbicides, such as

2-methylthio-4,6-bis-ethylamino-1,3,5-triazine, 2-chloro-4,6-bis-ethylamino-l, 3,5-triazine, 2-methoxy-4-ethylamino-6- isopropylamino-l, 3,5-triazine; 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-methylthio-4,6-bis- (isopropylamino) -s-triazine and 2-methylthio-4-ethyIamino-6-isopropylamino-s- triazine; Phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid and methyl, ethyl and butyl esters thereof, 2-chloro-4-methylphenoxyacetic acid;

4-chloro-2-methylphenoxyacetic acid and ethyl 2-methyl-4-chlorophenoxybutylate; Diphenyl ether herbicides, such as 2,4,6-trichlorophenyl-4'-nitrophenyl ether, 2,4-dichlorophenyl-4'-

17 644 853

nitrophenyl ether and 3,5-dimethylphenyl-4'-nitrophenyl ether; Urea herbicides, such as 3- (3,4-dichlorophenyl) -1-methoxy-l-methylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and 3- (4-chlorophenyl) -5 1, 1-dimethyl urea; Carbamate herbicides such as 3-methoxy-carbonylaminophenyl-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 l-cyclohexyl-3,5-propylene-lo uracil; Thiol carbamate herbicides such as S- (4-chlorobenzyl) -N, N-diethylthiocarbamate, S-ethyl-N-cyclohexyl-N-ethyl-thiocarbamate and S-ethyl-hexahydro-lH-azepine-l-carbothioate and S -Ethyl-N, N-di-n-propyl-thiocarbamate; Pyridium herbicides such as l, l'-dimethyl-4,4'-bis-pyridinium-is dichloride; phosphoric herbicides, such as N- (phosphonomethyl) glycine; Aniline herbicides such as a, a, a-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine, 4- (methylsulfonyI) -2,6-dinitro-N, N-dipropylaniline and N3, N3 -Diethyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine; Acid anilide herbicide, such as 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetoa-nilide, 2-chloro-2', 6'-diethyl-N- (methoxymethyl) -acetoanilide, and 3,4-dichloropropionanilide; Pyrazole herbicides such as 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-hydroxypyrazole and 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5- (p-toluenesulfonyl-25 oxy ) -pyrazole; 5-tert-butyl-3- (2,4-dichloro-5-isopropoxy-phenyl) -l, 3,4-oxadiazolin-2-one; 2- [N-isopropyl-N- (4-chlorophenyl) carbamoyl] -4-chloro-5-methyl-4-isooxazolin-3-one; 3-isopropylbenzo-2-thia-1,3-diazionon- (4) -2,4-dioxide and 3- (2-methylphenoxy) pyridazine.

30th

Examples of insecticides which can be mixed together with the compounds according to the invention include:

35 phosphorus-containing insecticides, such as 0.0-diethyl-0- (2-isopropyl-4-methyl-6-pyrimidinyl) phosphorothioate, 0.0-diethyl S-2 - [(ethylthio) ethyl] phosphorodithioate , 0,0-Dimethyl-0- (3-methyl-4-nitrophenyl) thiophosphate, 0.0-Dimethyl-S- (N-methylcarbamoylmethyl) -phosphordi-40 thioate, 0.0-Dimethyl-S- (N -methyl-N-formylcarbamoyl-methyl) -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-trichloroethylphosphonate, 45 0.0-diethyl 0- (5-phenyl-3-isooxazolyl) phosphorothioate, 0.0-dimethyl-0- (2,5-dichloro-4-bromophenyl) phosphorus -thioate, 0.0-dimethyl-0- (3-methyl-4-methylmercapto-phenyl) -thiophosphate, O-ethyl-op-cyano-phenyl-phenyl-phosphorothioate, 0.0-dimethyl-S- (l, 2-di-carboethoxy-50 ethyl) phosphorodithioate, 2-chloro (2,4,5-tri-chlorophenyl) vinyl dimethyl phosphate, 2-chloro-1 - (2,4-dichlorophenyl) vinyl dimethyl phosphate, 0, 0-dimethyl-Ó-p-cyano-phenyl phosphorothioate, 2,2-dichlorovinyl I-dimethyl phosphate, 0.0-diethyl-0-2,4-dichlorophenyl phosphorothioate, 55 ethyl mercaptophenyl acetate - 0.0-dimethyl phosphorodithioate, S- [ (6-chloro-2-oxo-3-benzooxazolinyl) methyl] -0.0-diethylphosphorodithioate, 2-chloro-1, - (2,4-dichlorophenyl) vinyldiethyl phosphate, 0.0-diethyl-0- (3rd -oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate, 0.0-dimethyl-S- (1-methyl-60 2-ethylsulfinyl) -ät ethyl phosphorothiolate, 0.0-dimethyl-S-phthalimidomethyl-phosphorodithioate, 0.0-diethyl-S- (N-ethoxycarbonyl-N-methylcarbamoyl-methyl) -phosphorodithioate, 0.0-dimethyl-S- [2-methoxy -l, 3,4-thiadiahol-5- (4H) -onyl- (4) -methyl] -dithiophosphate, 65 2-methoxy-4H-l, 3,2-benzooxaphosphorine-2-sulfide, 0.0-diethyl -0- (3,5,6-trichloro-2-pyridyl) phosphorothioate, 0-ethyl-0-2,4-dichlorophenylthionobenzene phosphonate, S- [4,6-diamino-s-triazine-2- yl-methyl] -0,0-dimethyl-phos-

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phordithioate, O-ethyl-op-nitrophenyl-phenyl-phosphorothioate, 0, S-dimethyl-N-acetyl-phosphoramidothioate, 2-diethylamino-6-methyl-pyrimidin-4-yl-di-ethyl-phosphorothionate, 2-diethylamino-6- methylpyrimidin-4-yl-dimethylphosphorothionate, Q, 0-diethyl-0-N- (methyl-sufinyl) -phenyl-phosphorothioate, 0-ethyl-S-propyl-0-2,4-di-chlorophenyl-phosphorodithioate and cis-3- (Dimethoxyphos-phinoxy) -N-methyl-cis-croton amide; Carbamate insecticides, such as 1-naphthyl-N-methylcarbamate, S-methyl-N- [methylcar-bamoyIoxy] thioacetoimidate, m-tolymethylcarbamate, 3,4-xylyl-methylcarbamate, 3,5-xylyl-methylcarbamate, 2-sec .-Butylphenyl-N-methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate, 2-isopropoxy-phenyl-N-methylcarbamate, 1,3-bis (carbamoylthio) -2- (N, N -dimethylamino) propane hydrochloride and 2-diethylamino-6-methylpyridmidin-4-yl-dimethylcarbamate; and other insecticides such as N, N-dimethyl-N '- (2-methyl-4-chlorophenyl) formanidine hydrochloride, nicotine sulfate, "mite mycin", 6-methyl-2,3-quinoxalinedithiocyclinic S, S -Di-thiocarbonate, 2,4-dinitro-6-sec-butylphenyl-dimethyl-acrylate, l, l-bis- (p-chlorophenyl) -2,2,2-trichloroethanol, 2- (p-tert.- Butylphenoxy) isopropyl-2'-chloroethylsulfite, azoxy-benzene, di- (p-chlorophenyl) -cyclopropylcarbinol, di- [tri- (2,2-dimethyl-2-phenyl-ethyl) -tin] -oxide, 1 - (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea and S-tricyclohexyltin-0.0-di-isopropylphosphorodithioate.

The present invention is explained in more detail below with reference to the examples, to which the invention is not restricted, however, in these examples all percentages and parts relate to the weight.

example 1

Preparation of Compound No. 1 from Table I [Scheme A]

21.3 g of 2-amino-4,5,6-trichlorophenol, 27.6 g of anhydrous potassium carbonate and 150 ml of toluene were introduced into a 300 ml round-bottomed flask and 9.9 g of phosgene slowly with stirring and with cooling with an ice water bath introduced into the mixture. The mixture obtained was then heated under reflux for 1 hour and the reaction solution was then cooled and poured into a 500 ml separating funnel. 150 ml of tetrahydrofuran and 150 ml of water were added to the funnel and the organic layer was then separated, dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated to remove the solvent, leaving yellowish white crystals. The crystals were recrystallized from a mixture of methanol and acetone to give 22.7 g of 5,6,7-trichlorobenzoxazolone in the form of white crystals with a melting point of 253 to 254 ° C.

Example 2

Preparation of Compound No. 1 [Scheme A] 21.3 g of 2-amino-4,5,6-trichlorophenyol, 27.6 g of anhydrous potassium carbonate and 150 ml of ethyl acetate were placed in a 300 ml round bottom flask with a solution of 9. 9 g of diphosgene (trichloromethyl chloroformate) in 50 ml of ethyl acetate are added dropwise with stirring and with cooling in an ice water bath. The mixture obtained was heated under reflux for 1 hour and the reaction solution was then cooled and suction filtered to remove insoluble salts. The filtrate was evaporated to dryness under reduced pressure and gave yellowish-white crystals which were recrystallized from methanol / acetone and gave 19.6 g of 5,6,7-trichlorobenzoxazolone in the form of white crystals of melting point 253 to 254 ° C.

Example 3

Preparation of Compound No. 1 [Scheme A]

18.1 g of 2-ethoxycarbonylaminophenol (made from 2-aminophenol and ethyl chloroformate) was dissolved in 200 ml of acetic acid, and 23.4 g of chlorine gas was introduced into the solution at a temperature of 80 to 90 ° C. The reaction solution thus obtained was cooled and evaporated to remove acetic acid, whereby 27.9 g of yellow crystals of 2-ethoxycarbonylamino-4,5,6-trichlorophenol of melting point 190 to 193 ° C. were obtained.

The crystals were charged together with 45 ml of dimethylformamide and 0.5 g of anhydrous carbonate in a 200 ml round-bottomed flask and the mixture was heated to 140 ° C. for 4 hours with stirring. After the resulting solution was cooled, 100 ml of water was added to precipitate crystals, which were then filtered off with suction and air-dried for 2 hours, whereby pale yellow crystals were obtained. Recrystallization from methanol / acetone gave 19.1 g of white crystals of 5,6,7-trichlorobenzoxazolone with a melting point of 253 to 254 ° C.

Example 4

Preparation of Compound No. 3 in Table I [Scheme A]

10.9 g of O-aminophenol and 100 ml of acetic acid were placed in a 300 ml round-bottomed flask, and 10.2 g of acetic anhydride were added while cooling with ice water. The mixture was heated at 60 ° C for 1 hour to complete the reaction, which resulted in the formation of 2-acetaminophenol. 23.4 g of chlorine gas were then introduced into the reaction mixture at a temperature of 80 to 90 ° C. and the reaction solution obtained was cooled and evaporated under reduced pressure, 24.9 g of yellow crystals of 2-acetamino-4,5,6-trichlorophenol were obtained, which melted at 200 ° C with decomposition.

The crystals were placed in a 300 ml round bottom flask, to which 150 ml of tetrahydrofuran and then 9.6 g of sodium hydride (50% suspension in oil) were added. 9.9 g of phosgene was then introduced into the mixture with ice-water cooling and the resulting mixture was kept in motion at room temperature for 1 hour. The reaction solution was placed in a 500 ml separatory funnel, in which 150 ml of benzene and 150 ml of water were added, whereupon the organic solution was separated, dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated to remove the solvent, leaving yellow crystals. The crystals were recrystallized from a mixture of hexane and acetone to give 25.2 g of N-acetyl-5,6,7-trichlorobenzoxazolone in the form of white crystals with a melting point of 171 to 172 ° C.

Example 5

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-bottomed flask and the mixture was heated to 80 to 90 ° C, after which 7.8 g of chlorine gas was introduced. The reaction solution was concentrated by evaporating the acetic acid to give yellow crystals. The recrystallization from methanol / acetone led to 23.4 g of white crystals of 5,6,7-trichlorobenzoxazolone with a melting point of 253 to 254 ° C.

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-bottomed flask and mixed with 16.5 g of sulfuryl chloride at room temperature18

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puts. The mixture was then heated to reflux temperature for 2 hours, and the reaction solution obtained was evaporated under reduced pressure, leaving yellow crystals. Recrystallization from hexane / acetone gave 26.6 g of white crystals of N-acetyl-5,6,7-trichlorobenzoxazolone with a melting point of 171 to 172 ° C.

Example 7

Preparation of Compound No. 2 in Table I [Scheme C] 4.8 g of 5,6,7-trichlorobenzoxazolone, 2.8 g of anhydrous potassium carbonate, 2.5 g of dimethyl sulfate and 50 ml of acetone were placed in a 100 ml round bottom flask and the contents of the flask were heated under reflux for 2 hours. The reaction solution was then evaporated under reduced pressure and the residue was taken up in 50 ml of water. The solution was filtered to give brown crystals which were recrystallized from acetone to give 4.8 g of yellow crystals of N-methyl-5,6,7-trichlorobenzoxazolone with a melting point of 135 to 139 ° C.

Example 8

Preparation of Compound No. 7 in Table I [Scheme C] 4.8 g of 5,6,7-trichlorobenzoxazolone, 2.0 g of triethylamine and 50 ml of acetone were introduced into a 100 ml round-bottomed flask in which 2.8 g Benzoyl chloride was added dropwise with ice water cooling and stirring. After the addition was completed, the obtained mixture was heated under reflux for 1 hour to complete the reaction, whereupon the reaction solution was allowed to cool and was filtered to remove the precipitated salts. The filtrate was evaporated, leaving white crystals which were recrystallized from hexane / acetone and 6.5 g of white crystals of N-benzoyl-5,6,7-trichlorobenzoxazolone with a melting point of 188 to 190 ° C. were obtained.

Example 9

Preparation of Compound No. 10 in Table I [Scheme C] Using the same procedure as described in Example 8, but replacing the benzoyl chloride with 1.9 g of methol chloroformate, 5.7 g of N-methoxycarbonyl-5,6,7-trichlorobenzoxazolone was obtained obtained as yellowish-white crystals with a melting point of 163 to 164 ° C.

Example 10

Preparation of Compound No. 14 in Table I [Scheme D] 4.8 g of 5,6,7-trichlorobenzoxazoline, 3.8 g of 3,5-dichlorophenyl isocyanate, 50 ml of acetone and 3 drops of triethylamine were placed in a 100 ml - Fill the round bottom flask and keep the mixture in motion at room temperature for 1 hour. The precipitate which separated out was filtered off and gave 7.7 g of light yellow crystals, which were identified as N-3,5-dichlorophenylcarbamoyl-5,6,7-trichlorobenzoxazolone with a melting point of 235 to 237 ° C.

Example 11

Preparation of Compound No. 25 in Table I [Scheme A] The procedure of Example 1 was repeated starting with 15.8 g of 2-amino-4-chloro-6-methylphenol instead of 2-amino-4,5,6- trichlorophenol. The recrystallization of the crude brown crystals obtained from hexane / acetone gave 15.6 g of 5-chloro-7-methylbenzoxazolone as yellowish brown crystals of melting point 232 to 234 ° C.

Example 12

Preparation of Compound No. 67 [Scheme A]

The procedure of Example 2 was repeated starting with 21.2 g of 2-amino-3,5-dimethyl-4,6-dichlorophenol instead of the 2-amino-4,5,6-trichlorophenol. In this way, 20.9 g of 4,6-dimethyl-5,7-dichlorobenzoxazolone were obtained as pale yellow crystals with a melting point of 271 ° to 272 ° C.

Example 13

Preparation of Compound No. 1 [Scheme A]

In a 100 ml round bottom flask were placed 23.0 g of 2-ethoxycar-bonylamino-4-methyl-5-chlorophenol (made from 2-amino-4-methyl-5-chlorophenyol and ethyl chloroformate), 50 ml of dimethylformamide and 0.5 g of anhydrous potassium carbonate were added and the mixture was heated to 140 ° C. with stirring for 4 hours. The reaction mixture obtained was cooled and poured into 100 ml of water, whereby crystals were separated out, which were collected on a suction filter and dried in air at 80 ° C. for 2 hours to give yellow crystals. The recrystallization of these crystals from methanol gave 15.6 g of pale yellow crystals of 5-methyl-6-chlorobenzoxazolone with a melting point of 182 to 184 ° C.

Example 14

Preparation of Compound No. 52 in Table I [Scheme A]

According to the procedure described in Example 4

24.5 g of N-acetyl-5-isopropyl-6,7-dichlorobenzoxazolone in the form of yellowish brown crystals (melting point 133 to 135 ° C) from 15.1 g of 2-amino-4-isopropylphenol over a brown oil (25.7 g) obtained from 2-acetamino-4-isopropyl-5,6-dichlorophenol.

Example 15

Preparation of Compound No. 31 in Table I [Scheme B] The procedure of Example 5 was repeated, but using 18.4 g of 5-chloro-7-methylbenzoxazolone instead of 5,7-dichlorobenzoxazolone to make 20.7 g of 5 , 6-dichloro-7-methylbenzo-xazolone in the form of pink crystals with a melting point of 251 to 252 ° C.

Example 16

Preparation of Compound No. 54 [Scheme B]

18.4 g of 5-chloro-7-methyl-benzoxazolone and 150 ml of acetic acid were placed in a 300 ml round bottom flask and the mixture was added dropwise with a solution of 17.6 g of bromine in 30 ml of acetic acid. The resulting mixture was heated to 95 ° C and kept at this temperature for 4 hours. The reaction solution was then cooled to room temperature and concentrated by evaporating the acetic acid to give reddish brown crystals which were recrystallized from methanol / acetone and 22.3 g of 5-chloro-6-bromo-7-methylbenzoxazolone as brown crystals of melting point 262 to Resulted in 264 ° C.

Example 17

Preparation of Compound No. 64 [Scheme B]

The procedure of Example 6 was repeated, but using 26.0 g of N-acetyl-4-methyl-5,7-dichlorobenzoxazolone instead of N-acetyl-5,7-dichlorobenzoxazolone, whereby

23.6 g of the corresponding 5,6,7-trichloro derivative were obtained in the form of white crystals with a melting point of 125 to 127 ° C.

Example 18

Preparation of Compound No. 32 in Table I [Scheme C]

The procedure of Example 7 was repeated, but using 4.4 g of 5,6-dichloro-7-methylbenzoxazolone instead of 5,6,7-trichlorobenzoxazolone, 3.9 g of N-methyl-5,6-dichloro-7- methylbenzoxazolone as pink crystals of melting point 122 to 123 ° C were obtained.

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Example 19

Preparation of Compound No. 35 in Table I [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-bottomed flask in which 2.0 g of triethylamine were then added dropwise with ice-water cooling and stirring was added. After the addition was completed, the resulting mixture was heated under reflux for 1 hour to complete the reaction, whereupon the reaction solution was allowed to cool and filtered to remove the precipitated salts. The filtrate was evaporated to dryness to give yellowish-white crystals which were recrystallized from acetone and 5.5 g of white crystals of N-benzoyl-5,6-dichloro-7-methylbenzoxazolone with a melting point of 165 to 166 ° C surrendered.

Example 20

Preparation of Compound No. 37 [Scheme C]

According to the process described in Example 9, but starting from 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 4.6 g of N-methoxycarbonyl-5,6-dichloro-7-methyl-benzoxazolone in the form of pink crystals were added obtained a melting point of 135 to 138 ° C.

Example 21

Preparation of Compound No. 41 [Scheme D]

According to the procedure of Example 10, but starting from 4.4 g of 5,6-dichloro-7-methylbenzoxazolone, 7.4 g of N-3,5-dichlorophenylcarbamoyl-5,6-dichloro-7-methylbenzoxazolone in the form of pink crystals of melting point 221 to 222 ° C obtained.

Example 22

Preparation of Compound No. 69 [Scheme A]

The procedure of Example 1 was repeated, but the 2-amino-4,5,6-trichlorophenol was replaced by 22.6 g of 3-chloro-6-acryl-oylamino-2,4-xylenol (from 3-chloro-6-amino -2,4-xylenol and acryloyl chloride produced) replaced.

The recrystallization of the crude yellow crystals obtained from acetone gave 20.4 g of yellowish-white crystals of N-acryloyl-5,7-dimethyl-6-chlorobenzoxazolone with a melting point of 161 to 163 ° C.

Example 23

Preparation of Compound No. 70 [Scheme C]

Following the same procedure as described in Example 19, 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-allyloxycarbonyl-5,6,7 were obtained -trichIorbenzoxa-zolon obtained as light yellow crystals with a melting point of 96 to 98 ° C.

Example 24 Emulsifiable concentrate

An emulsifiable concentrate containing 20% of the active ingredient was prepared by uniformly mixing the ingredients below and stirring the mixture until all the ingredients were dissolved.

Compound No. 10

Dimethylformamide

Xylene

Polyoxyethylene alkyl aryl ether

Similar emulsifiable concentrates containing 20% of Compound No. 36 or No. 69 as an active ingredient were prepared in the same manner.

Example 25

Oily preparation

An oily preparation was produced by mixing 10 parts of Compound No. 1 and 90 parts of ethyl cellosolve (2-ethoxyethanol) and stirring the mixture until these components were dissolved.

Example 26

Flowable preparation io A flowable preparation which contained 40% of the active ingredient was prepared by uniformly mixing the following ingredients:

Compound No. 4 (ground to a particle size below 10 µ i5) 40 parts

Lauryl sulfate 2 parts

Sodium alkyl naphthalene sulfonate 2 parts

Hydroxypropyl cellulose 1 part

Water 55 parts

20th

Similar flowable preparations containing 20% of Compound No. 32 or No. 70 as an active ingredient were obtained in the same way.

25 Example 27

Water-dispersible powder preparation A water-dispersible powder was prepared by uniformly mixing the components below and then grinding the resulting mixture:

Compound No. 3 polyoxyethylene alkyl aryl ether calcium lignosulfonate 35 diatomaceous earth

20 parts 5 parts 3 parts 72 parts

Similar water dispersible powders containing 20% of Compound No. 48 or No. 69 as an active ingredient were prepared in the same manner.

40

Example 28

Dusting powder formulation A scattering powder was prepared by uniformly mixing the following components and grinding the mixture obtained:

Compound No. 5

finely powdered silicic acid anhydride

Calcium stearate

volume

talc

3 parts 0.5 parts 0.5 parts 50 parts 46 parts

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20 parts 30 parts 35 parts 15 parts

Similar scatter powders containing 3% of Compound No. 53 or No. 70 as an active ingredient were prepared in the same manner.

Example 29

Granular preparation

A preparation in the form of bodies was made by uniformly mixing the components below and then granulating the mixture in the presence of added water. The resulting mixture was dried and passed through a sieve to obtain the desired grain size.

65 Compound No. 6 calcium lignosulfonate bentonite clay

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Similar granular preparations containing 5% of Compound No. 24 or No. 70 as an active ingredient were obtained in the same manner.

Example 30 Wetting powder preparation

A wettable powder was prepared by uniformly mixing the ingredients below and grinding the mixture:

Compound No. 10

20 parts

N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide

Polyoxyethylene alkyl aryl ether

Calcium lignosulfonate

Diatomaceous earth

20 parts 5 parts 3 parts is 52 parts

Example 31

In this example, the benzoxazolone derivatives according to the invention were investigated against a number of diseases of plants caused by fungi or bacteria.

A:

20th

The tests were carried out according to the 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, which contained an acetone solution of the required concentration of the active ingredient, was inoculated with the aid of a platinum loop with a spore suspension which had been obtained by adding sterilized water to the test microorganisms, which were grown on an inclined agar from the same medium as in the test vessel had been. The further incubation of the vaccinated medium was carried out for 48 hours at 24 ° C. for fungi and at 28 ° C. for bacteria. The growth of the microorganisms was then observed and the minimum inhibitory concentration (MIC, (ig / ml) of the investigated derivatives was determined.

The results obtained are summarized in Table II below. In the following tables, controls A, B, C, and D mean the use of the following active compounds described in the references cited:

D:

[DT-PS 1.023.627]

[DT-PS 1.147.008]

[JP-AS 23519/65]

[JP-AS 23519/65]

644853

22

Table II

Disease and Plant Compound No. in Table I, MIC (jig / ml)

123456789

Fussarium oxysporum (cucumber)

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

<5

<5

<5

Cladosporium fulvum (tomato)

<2.5

<5

<2.5

<2.5

<5

<2.5

<5

<5

<5

Gibberella fujikuori (rice)

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

Glomerella eingulata (vine)

<1.25

<2.5

<2.5

<2.5

<2.5

<2.5

<5

<5

<5

Alternaria kikuchiana (pear)

<5

<5

<5

<5

<5

<5

<5

<5

<10

Piricularia oryzae (rice)

<1.25

<1.25

<1.25

<1.25

<1.25

<1.25

<2.5

<5

<5

Cochliobolus miyabeanus (rice)

<2.5

<2.5

<1.25

<1.25

<2.5

<1.25

<2.5

<2.5

<5

Erwinia aroidea (Chinese cabbage)

<2.5

<5

<5

<5

<5

<5

<10

<20

<20

Pseudomonas lachrymans (cucumber)

<10

<10

<10

<10

<10

<10

<20

<20

<20

Xanthomonas oryzae (rice)

<10

<10

<10

<10

<10

<10

<20

<20

<20

Table II (continued)

Disease and Plant Compound No. in Table I, MIC (µg / ml)

10 11 12! 3 14 15 16 17

Fussarium oxysporum (cucumber)

<2.5

<2.5

<5

<5

<5

<2.5

<5

<2.5

Cladosporium fulvum (tomato)

<2.5

<2.5

<2.5

<5

<5

<2.5

<5

<2.5

Gibberella fujikuori (rice)

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

<2.5

Glomerella eingulata (vine)

<2.6

<2.5

<5

<5

<5

<2.5

<2.5

<2.5

Alternaria kikuchiana (pear)

<5

<5

<5

<5

<5

<5

<5

<5

Piricularia oryzae (rice)

<1.25

<1.25

<2.5

<2.5

<2.5

<1.25

<2.5

<1.25

Cochliobolus miyabeanus (rice)

<1.25

<1.25

<5

<5

<5

<1.25

<5

<1.25

Erwinia aroidea (Chinese cabbage)

<2.5

<5

<10

<10

<10

<2.5

<10

<5

Pseudomonas lachrymans (cucumber) <10

<5

<10

<10

<10

<5

<10

<10

Xanthomonas oryzae (rice)

<10

<5

<20

<10

<5

<10

<10

<10

1

Table II (continued)

Disease and plant

Compound No. in Table I, MIC (µg / ml)

18th

19th

69

70

A

B

c

D

Fusarium oxysporum (cucumber)

<2.5

<2.5

<2.5

<2.5

<20

<20

<20

<20

Cladosporium fulvum (tomato)

<2.5

<5

<2.5

<5

<20

<20

<20

<20

Gibberella fujikuori (rice)

<2.5

<2.5

<2.5

<2.5

<20

<20

<20

<20

Glomerella eingulata (vine)

<2.5

<2.5

<1.25

<2.5

<20

<20

<20

<20

Alternaria kikuchiana (pear)

<5

<5

<5

<5

<40

<40

<40

<40

Piricularia oryzae (rice)

<1.25

<1.25

<1.25

<1.25

<20

<20

<20

<20

Cochliobolus miyabeanus (rice)

<1.25

<1.25

<2.5

<2.5

<20

<20

<20

<20

Erwinia aroidea (Chinese cabbage)

<20

<10

<10

<10

<160

<80

<160

<80

Pseudomonas lachrymans (cucumber) <10

<20

<10

<10

<160

<80

<160

<80

Xanthomonas oryzae (rice)

<10

<10

<10

<10

<40

<40

<40

<40

This example shows the fungicidal activity of the benzoxazolone derivatives against Piricularia aryzae (powdery mildew on rice).

A water-dispersible powder preparation, prepared as described in Example 27, was diluted with water to obtain test preparations containing the required concentrations of active ingredient. The test preparation was applied to seedlings of aquatic rice ("Asahi" variety, three-leaf stage) which had been grown in soil culture in unglazed porcelain pots of 9 cm in diameter in a greenhouse. A 60 day after application, the treated seedlings were infected by spraying with a spore suspension of Piricularia oryzae and incubation was carried out in a humid chamber with a relative humidity of 95 to 100% and a temperature of 24 to 25 ° C. Five 65 days after infection, the number of mildew lesions per leaf on the three-leaf seedling was determined and the disease control was calculated using the following equation:

23 644 853

v r ,, number of lesions in treated plants,

Disease control (%) = (1 - - ,, r ... - - -) x 100

Number of lesions on untreated plants

The disease control is an average of the

5

Table III (continued)

Results of the investigations, which are repeated in two

Phytotoxicity lungs for each concentration of the active ingredient

Connection no.

Concentration disease

for »nmi hf» kämnf? ina. The phytotoxicity to rice

planting was also done visually according to the following classification

68

200

94

0

rated:

10 69

200

100

0

70

200

100

0

rating

Extent of phytotoxicity

Control A

200

52

1

Control B

200

63

2nd

5

serious injury

15 control C

200

30th

1

4th

severe damage

Control D

200

30th

1

3rd

moderate damage

IBP (control) '

* 480

75

0

2nd

slight damage

Untreated

0

1

weak injury

0

no damage

20th

° /

\

The test results are summarized in Table III below

* IBP: (i _

C "H_ o 7

0) 7P-SCH2_ /

O)

set.

\

/

Table III

25th

Example 33

Connection no.

Concentration disease

Phytotoxicity

This example illustrates the effectiveness of the new Benz

(ppm)

combat (%)

oxazolone derivatives against Cochliobolus miyabeanus (leaf spotted

30 disease in rice).

1

200

100

0

The examinations were carried out according to the same procedure

2nd

200

78

0

performed as in Example 32, but the rice seedlings in

3rd

200

100

0

Four-leaf stage with a spore suspension from Cochlio

4th

200

98

0

bolus miyabeanus vaccinated.

5

200

94

0

35 The results obtained are shown in Table IV below

6

200

98

0

compiled:

7

200

98

0

8th

200

100

0

Table IV

9

200

96

0

10th

200

100

0

40 connection no.

Concentration disease

Phytotoxicity

11

200

100

0

(ppm)

control (%)

12

200

92

0

13

200

86

0

1

500

100

0

14

200

82

0

2nd

500

85

1

15

200

98

0

45 3

500

100

0

16

200

98

0

4th

500

98

0

17th

200

100

0

5

500

96

0

18th

200

100

0

6

500

100

0

19th

200

100

0

7

500

94

0

20th

200

84

0

50 8

500

92

0

22

200

92

0

9

500

88

0

23

200

96

0

10th

500

100

0

27th

200

82

0

11

500

98

0

30th

200

98

0

12

500

94

1

31

200

88

0

55 13

500

90

0

33

200

98

0

14

500

92

1

36

200

98

0

15

500

86

0

37

200

100

0

16

500

83

0

38

200

100

1

17th

500

100

0

41

200

98

1

60 18

500

100

0

46

200

92

0

19th

500

100

0

47

200

98

0

20th

500

100

0

50

200

98

0

21st

500

98

0

53

200

100

0

22

500

82

0

61

200

100

0

65 23

500

96

0

62

200

100

0

24th

500

76

0

64

200

98

0

25th

500

76

0

66

200

96

0

26

500

72

0

644 853

24th

Table IV (continued)

Table IV (continued)

Connection no.

Concentration (ppm)

Disease control (%)

Phytotoxicity

27th

500

88

0

28

500

80

0

29

500

92

0

30th

'500

88

0

31

500

100

0

32

500

96

0

33

500

100

0

34

500

94

0

35

500

96

0

36

500

100

0

37

500

100

0

38

500

98

0

39

500

100

0

40

500

96

0

41

500

100

0

42

500

98

0

43

500

98

0

44

500

96

0

45

500

88

0

46

500

98

0

47

500

98

0

48

500

76

0

49

500

72

0

50

500

98

0

51

500

82

0

52

500

76

0

53

500

88

0

54

500

94

0

55

500

98

0

56

500

73

0

57

500

88

0

58

500

98

0

59

500

100

0

60

500

98

0

61

500

96

0

62

500

100

0

63

500

76

0

64

500

82

0

65

500

80

0

66

500

100

0

67

500

72

0

68

500

100

0

69

500

100

0

70

500

100

0

Control A Control B Control C 5 Control D Triazine * (Control)

25th

30th

500 500 500 500

500

32 54 25 30

93

3rd

4th

1

2nd

Untreated

: Triazine:

20th

Example 34

In this example, the active compounds were tested for their activity against Sclerotinia sclerotiorum (falling sickness in bush beans) according to the following method:

A water-dispersible powder preparation, prepared as described in Example 27, was diluted with water to obtain test preparations which contained the required concentrations of active ingredient. The test preparations were applied to seedlings of bush beans (variety "Taisho Kintoki") in the two-leaf stage, which seedlings had been grown in soil culture in pots of unglazed porcelain of 9 cm diameter in a 35 greenhouse. The amount was 10 ml of the preparation per pot. A day later, each leaf of the two correct leaves was inoculated with a piece of fungal agar obtained by drilling the edge of a colony of Sclerotinia scle-40 rotiorum fungus with a 5 mm cork borer; this mushroom had been incubated in a potato dextrose agar medium at 20 ° C for 2 days. The vaccinated seedlings were then kept in a wet room at 20 ° C for 3 days to allow the disease to develop. The length of the overturning lesion was then measured using a caliper gauge and the disease control calculated using the following equation:

Disease control (%) = (1 -

Length of the lesion in treated plants Length of the lesion in untreated plants

-) x 100

The disease control value is an average of the results of the tests, which were repeated in two replicates at each concentration of the active ingredient. The phytotoxicity for bush beans was assessed visually after the same evaluation as in Example 32.

The results are summarized in Table V below:

Table V

Table V (continued)

Connection no.

Concentration (ppm)

500 500

Disease control (%)

100

Phytotoxicity

5

500

86

0

6

500

94

1

10th

500

100

0

17th

500

89

0

19th

500

85

0

Control A

500

43

3rd

Control B

500

48

4th

Control C

500

26

2nd

Control D

500

20th

2nd

CNA * (control) 500

72

0

Untreated

-

0

-

25th

644 853

: CNA:

Table V (continued) Cl

Ammonium sulfate, 6 g calcium superphosphate and 1.5 g potassium chloride) sown in plant sections of 30 x 60 x 10 cm. The sections were kept at 28 ° C in a greenhouse for growth.

20 days after sowing (in the three-leaf stage), the extent of the disease on the seedlings was determined visually according to the following evaluation:

rating

Degree of disease weakly strong

Example 35

This example shows the fungicidal activity of some of the moderately new benzoxazolone derivatives for protecting the seeds against Cochliovolus miyabeanus (leaf spot disease in rice).

10 g of rice seeds ("Asaminori" variety) infected with the disease were packed in a "Saron" mesh bag and placed in a 50 ml beaker in which they were diluted at 15 ° C for 24 hours Preparation was immersed, which was added in the same amount as that of the rice seeds and was prepared as described in Example 34. The seeds were then removed from the preparation and immersed in deionized water at 15 ° C for 5 days, after which they were allowed to sprout at 30 ° C for 24 hours. The rice seeds were then ground from black volcanic ash (incorporating 4.5 g

Disease was found only on very small parts of the primary leaf or in leaf discs

Primary leaf almost completely turned brown and killed together with brown lesions on the primary and secondary real leaves markedly weak growth of the seedlings, which were bent and stained brown with death.

The percentage of infestation (level of infestation) was determined from the seedlings which were rated as "severe" or "moderate" and the sperm protection (or sperm disinfection) strength was calculated according to the following equation:

Seed protection strength in percent = (1 -

Infestation strength in treated plants Infestation strength in untreated plants

-) x 100

The seed protection strength is an average of the results of the tests, which were carried out in two repetitions at each concentration of active ingredient. The phytotoxicity on rice plants was determined visually according to the same rating system as given in Example 32.

The results are summarized in Table VI below:

Table VI

Compound no

(ppm) (%)

Example 36

The benzoxazolone derivatives were tested for their protective effect against Gibberella fujikuroi (Bakanae disease in rice).

4o The test procedure used was the same as described in Example 35, but the rice seeds (variety «Reimei») which were naturally infected with the disease were used and the visual determination was carried out 26 days after sowing (in the four-leaf stage).

45 The results are summarized in Table VII below:

1

500

98

1

3rd

500

97

0

10th

500

96

0

11

500

98

0

14

500

92

0

Control A

500

63

2nd

Control B

500

72

3rd

Control C

500

40

1

Control D

500

40

1

TMTD *

(Control)

2000

70

0

Untreated

-

0

0

* TMTD: (CH3) zNC-S-S-CN (CH3) 2

Table VII

Connection no.

Concentration (ppm)

Seed protection strength phytotoxicity

(° 0)

1

500

98

1

3rd

500

100

0

10th

500

98

0

11

500

96

1

14

500

88

0

17th

500

90

0

18th

500

88

0

19th

500

92

0

Control A

500

47

0

Control B

500

52

3rd

"Benomyl" *

(Control)

500

98

0

Untreated - 0

644853

26

* "Benomyl":

Table VII (continued)

NHCOOCH.

CONHC4Hg-n

Example 37

In this example, the benzoxazolone derivatives were tested for their activity against Phytophthora infestans (leaf blight / late blight in tomatoes).

Dilute suspensions of a wettable powder containing the required concentrations of active ingredient were prepared as described in Example 34. The test suspension was applied in a quantity of 10 ml per pot to young seedlings of tomatoes (variety "Sekaiichi") s in the three-leaf stage. These seedlings had been grown in soil culture in unglazed porcelain pots of 9 cm in diameter in a greenhouse. Spores of Phytophthora infestans, which had been produced on potato tubers, were suspended in sterilized io water to give a spore concentration at which 20 to 30 spores were visible at a glance under a microscope with a 150-fold magnification.

One day after the treatment of the tomato seedlings, the leaves were inoculated with drops of the spore suspension and the seedlings were then kept in a moist room at 20 ° C. to allow the disease to develop. 3 days later the seedlings were removed from the room and the number of attacked leaves counted. The percentage of leaves attacked and disease control were calculated according to the following equations:

Percentage of leaves attacked

Number of attacked leaves Number of vaccinated leaves x 100

Disease control (%) = (1 -

Percentage of leaves attacked in treated plants Percentage of leaves attacked in untreated plants

■) x 100

The phytotoxicity to tomato plants was also determined using the same rating system as described in Example 32. The results are summarized in Table VIII below:

Table VIII

Connection no.

Concentration disease

Phytotoxicity

(ppm)

control (%)

1

500

100

0

3rd

500

92

0

4th

500

97

0

6

500

99

0

7

500

94

0

10th

500

98

0

11

500

88

0

13

500

99

0

14

500

99

0

15

500

96

0

18th

500

97

0

19th

500

99

0

20th

500

98

0

21st

500

96

0

24th

500

97

0

30th

500

94

0

31

500

98

0

33

500

94

0

36

500

99

0

37

500

100

0

38

500

100

0

41

500

100

0

42

500

98

0

47

500

96

0

50

500

100

0

51

500

98

0

56

500

98

0

59

500

98

0

45

50

55

60

500

98

0

61

500

90

0

62

500

100

0

67

500

92

0

68

500

98

0

Control A

500

0

0

Control B

500

0

0

Control C

500

0

0

Control D

500

0

0

"Maneb" *

(Control)

500

87

0

Untreated

-

0

-

: «Maneb»:

CHzNHCS-

I.

CH2HNCS '

II

S

; Mn

Example 38

This example illustrates the effectiveness of the new derivatives against Sphaerotheca fuliginea (powdery mildew in cucumbers).

60 The diluted preparation, prepared as in Example 37, was applied in an amount of 10 ml per pot to cucumber seedlings (variety "Sagamihanjiro") in the single-leaf stage, which were grown in soil culture in pots of unglazed porcelain of 9 cm diameter in a greenhouse 65 were. The following day, the seedlings were vaccinated by spraying them with a spore suspension of Sphaerotheca fuliginea. 10 days after vaccination, the percentage of damaged area was on the seedlings

27 644 853

determined and the disease control calculated according to the following equation:

, n /., ,, Percentage of damaged area in treated plants Disease control (%) = (l - Percentage of damaged area in untreated plants J X 100

The phytotoxicity was evaluated in the same manner as in the previous examples. The results are summarized in Table IX:

Table IX

Connection no.

concentration

(ppm)

Disease control (%)

Phytotoxicity

1

200

92

0

4th

200

95

0

5

200

92

0

8th

200

90

0

9

200

90

0

10th

200

96

0

11

200

92

0

18th

200

90

0

19th

200

98

0

22

200

82

0

29

200

85

0

33

200

92

0

36

200

96

0

40

200

94

0

45

200

100

0

47

200

98

0

52

200

100

0

55

200

100

0

58

200

100

0

59

200

100

0 1

60

200

100

0

61

200

100

0

63

200

97

0

64

200

100

0

65

200

99

0

66

200

100

0

69

200

100

0

70

200

100

0

Control A

200

20th

1

Control B

200

10th

1

Control C

200

10th

1

Control D

200

13

1

"Dimethirimol" *

(Control)

200

95

0

Untreated

-

0

-

* "Dimethirimol":

Example 39

The benzoxazolone derivatives were tested against pseudoperonospora cubensis (downy mildew in cucumbers).

The diluted preparation, which was prepared as in Example 37, was applied in an amount of 10 ml per pot to the black sides of the leaves of young cucumber seedlings (variety "Sagamihanjiro") at the single-leaf stage. These seedlings had been grown by soil culture in unglazed pots 9 cm in diameter in a greenhouse. Spores of Pseudoperonospora cubensis, which had been produced on cucumber leaves in an environment suitable for the development of the disease, were brushed in deionized water containing 50 ppm "Tween 20" (brand name of polxoxyethylene sorbitan monolaurate, product of Kao Atlas Co.) to form an inoculum which gave a spore concentration at which 20 to 30 spores could be seen at a glance under a microscope with a magnification of 150 times.

One day after the treatment, the leaves of the cucumber seedlings on the treated lower surface were inoculated by spraying them with the inoculum. After the vaccination had ended, seedlings were first placed in a moist room at 20 ° C. and then kept in a greenhouse at 24 ° C. to enable the disease to develop. 6 days later, the seedlings were removed from the greenhouse and the percentage of damaged area per pot was determined. Disease control (%) was calculated according to the same equation as in Example 38, and phytotoxicity on cucumber plants was evaluated according to the same evaluation as in Example 32.

The test results are summarized in Table X:

Table X

Connection no.

Concentration (ppm)

Disease control (%)

Phytotoxicity

1

500

100

0

3rd

500

98

0

7

500

90

0

10th

500

100

0

11

500

95

0

13

500

100

0

14

500

100

0

18th

500

100

0

19th

500

100

0

20th

500

88

0

21st

500

96

0

23

500

99

0

31

500

98

0

33

500

100

0

37

500

100

0

44

500

92

0

45

500

98

0

46

500

100

0

47

500

94

0

50

500

100

0

51

500

100

0

52

500

98

0

53

500

100

0

55

500

96

0

60

500

96

0

15

20th

25th

30th

35

40

45

50

55

60

644853

28

Table X (continued)

Connection no.

concentration

Disease

Phytotoxicity

(ppm)

control (%)

61

500

100

0

62

500

100

0

63

500

100

0

68

500

99

0

69

500

100

0

70

500

100

0

Control A

500

20th

1

Control B

500

25th

1

Control C

500

30th

1

Control D

500

36

1

"Maneb"

(Control)

500

90

0

Untreated

-

0

-

Example 40

The benzoxazolone derivatives were tested for their effectiveness against Collectorichum lagenarium (anthracnose in cucumbers).

s The diluted preparation, prepared as in Example 37, was applied in a quantity of 10 ml per pot to the leaves of young cucumber seedlings (variety "Sagamihanjiro") at the single-leaf stage, which seedlings were grown in soil in unglazed pots of 9 cm in diameter in one Greenhouse had been grown. Spores of Collectotrichum lagenarium, prepared by incubating harbor meal agar medium at 24 ° C for 10 days, were suspended in stabilized water containing 50 ppm "Tween 20" to give a suspension with a 15 spore concentration, at which approximately 100 spores were visible at a glance under a microscope of 150 times magnification.

One day after the treatment, the treated leaves of the cucumber seedlings were inoculated by spraying with the 20 spore suspension mentioned. The seedlings were then treated in the same manner as in Example 39 and the disease control was calculated according to the following equation:

Disease control (%) = (1

Number of lesions in treated plants Number of lesions in untreated plants

-) x 100

The results are summarized in Table XI. Table XI

Connection no.

Concentration disease

; TPN:

Table XI (continued) Cl

Phytotoxicity

(ppm)

control (%)

1

500

100

0

3rd

500

98

0

7

500

96

0

10th

500

100

0

19th

500

100

0

21st

500

88

0

23

500

97

0

28

500

94

0

31

500

98

0

33

500

100

0

36

500

100

0

37

500

100

0

40

500

98

0

44

500

96

0

46

500

100

0

49

500

99

0

50

500

100

0

54

500

98

0

55

500

100

0

58

500

100

0

60

500

94

0

62

500

100

0

69

500

100

0

70

500

100

0

Control A

500

45

1

Control B

500

37

1

Control C

500

35

1

Control D

500

43

1

TPN * (control) 500

98

0

Untreated

-

0

-

35

45 Example 41

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

The diluted preparation, prepared as described in Example 37, was applied in an amount of 20 ml per three pots to young wheat seedlings (variety “Norin No. 61”) at the single-leaf stage, which were grown in a 9 cm diameter unglazed pots in one Greenhouse had been pulled. Uredosporus from Puccinia recondita, which had been produced on wheat leaves 55, were brushed in sterilized water, which contained 50 ppm «Tween 20», to give an inoculum of a spore suspension with a spore concentration, in which approx. 50 spores in one view under one Microscope of 150x magnification were visible.

60 1 day after the treatment, the wheat seedlings were vaccinated by spraying with the inoculum. After the vaccination had ended, the seedlings were first kept in a moist room at 20 ° C. overnight and then left in a greenhouse at 20 ° C. in order to enable the development of the disease. Ten days after vaccination, the number of fungal uredosors that developed the disease was counted per leaf and the disease control was calculated by the following equation:

29

644853

Disease control (%) = (1 -

Number of uredosori in treated plants Number of uredosori in untreated plants

-) x 100

The phytotoxicity to wheat plants was examined on the same rating scale as described in Example 32. The results are summarized in Table XII:

Table XII

Untreated

Table XII (continued) 0

Connection no.

concentration

Disease

Phytotoxicity

(ppm)

control (%)

1

200

100

0

3rd

200

92

0

8th

200

90

0

10th

200

100

0

19th

200

98

0

Control A

200

10th

1

Control B

200

5

0

Control C

200

10th

1

Control D

200

5

0

"Maneb"

(Control)

200

96

0

20th

25th

Example 42

Some of the benzoxazolone derivatives have been tested against Pellicu-laria sasaki (vaginal rot in rice).

The diluted preparation, prepared as in Example 37, was applied in an amount of 40 ml per three pots to rice seedlings in the six-leaf stage which had been grown by soil culture in unglazed pots of 9 cm in diameter in a greenhouse. The following day, the seedlings were infected with the fungal disease by covering the second leaf sheath with an agar disk, which was obtained through pores with a 5 mm diameter cork borer at the edge of the colony of Pellicularia sasaki fungus on potatoes -Sucrose agar medium had been incubated at 27 ° C for 48 hours. The vaccinated seedlings were kept in a humid chamber overnight. 4 days after the infection, the length of the lesion per strain was determined and the disease control was calculated according to the following equation:

Disease control (%) = (1 -

Length of lesions in treated plants Length of lesions in untreated plants

-) x 100

The test results are summarized in Table XIII.

Table XIII

Connection no.

Concentration (ppm)

Disease control (%)

69

500

100

70

500

90

Control A

500

15

Control B

500

0

Control C

500

10th

Control D

500

0

Validamycin

125

90

Untreated

Example 43

In this example, the benzoxazolone derivatives were tested for their effectiveness against fungi and bacteria, which are able to destroy industrial materials.

The tests were carried out according to the agar dilution method as described in Example 31, but the incubation was carried out at 28 ° C. for 3 days

Fungi and at 30 ° C for bacteria. The tests were carried out in two repetitions at each concentration of the active compound examined, and an average of the minimum inhibitory concentrations (MIC) was determined in this way.

The results are summarized in Table XIV below.

Table XIV

Test microorganism Compound No.MIC (µg / ml)

1 2 3 4 5 6 7 8

Escherichia coli

<

1.25

<5

<

1.25

<

1.25

<

2.5

<

1.25

<5

<5

Bacillus subtilis

<

1.25

<5

<

1.25

<

2.5

<

5

<

1.25

<5

<5

Alcalignes viscoluktis

<

1.15

<5

<

1.25

<

1.25

<

2.5

<

1.25

<5

<5

Pseudomonas aeruginosa

<

1.25

<10

<

5

<

5

<

5

<

5

<5

<10

Aspergillus niger

<

1.25

<10

<

1.25

<

2.5

<

2.5

<

2.5

<5

<10

Pénicillium citrinum

<

1.25

<5

<

1.25

<

2.5

<

2.5

<

1.25

<5

<5

Rhizopus nigricans

<

1.25

<10

<

2.5

<

2.5

<

5

<

2.5

<10

<10

Cladosporium herbarum

<

1.25

<5

<

1.25

<

1.25

<

2.5

<

1.25

<5

<5

Chaetomium globosum

<

1.25

<5

<

1.25

<

1.25

<

1.25

<

1.25

<10

<10

644853

30th

Table XIV (continued)

Test microorganism Compound No.MIC (µg / ml)

9

10th

11

12

13

14

15

Escherichia coli

<5

<1.25

<1.25

<2.5

<5

<5

<1.25

Bacillus subtilis

<5

<1.25

<2.5

<2.5

<5

<5

<2.5

Alcaligenes viscoluktis

<5

<1.25

<1.25

<1.25

<2.5

<5

<2.5

Pseudomonas aeruginosa

<10

<2.5

<2.5

<2.5

<5

<10

<2.5

Aspergillus niger

<5

<1.25

<1.25

<2.5

<5

<10

<5

Pénicillium citrinum

<5

<1.25

<1.25

<2.5

<5

<10

<2.5

Rhizopus nigricans

<10

<2.5

<1.25

<2.5

<5

<5

<2.5

Cladosporium herbarum

<10

<1.25

<1.25

<2.5

<10

<10

<2.5

Chaetomium globosum

<10

<2.5

<2.5

<5

<10

<10

<5

Table XIV (continued)

Test microorganism Compound No.MIC (µg / ml)

16 17 18 19 A B «Proxel» *

Escherichia coli

<5

<

1.25

<

5

<

1.25

<40

<20

<10

Bacillus subtilis

<5

<

1.25

<

1.25

<

1.25

<40

<40

<10

Alcaligenes viscoluktis

<5

<

5

<

5

<

1.25

<40

<20

<10

Pseudomonas aeruginosa

<5

<

5

<

5

<

5

<80

<40

<20

Aspergillus niger

<10

<

1.25

<

2.5

<

1.25

<80

<80

<20

Pénicillium citrinum

<5

<

1.25

<

2.5

<

1.25

<40

<40

<10

Rhizopus nigricans

<5

<

5

<

5

<

5

<160

<80

<20

Cladosporium herbarum

<5

<

1.25

<

2.5

<

1.25

<80

<40

<10

Cahetomium globosum

<5

<

5

<

5

<

2.5

<40

<40

<20

* «Proxel»

II

Example 44

This example illustrates the durability of paints containing benzoxazolone derivatives against fungal growth.

The tests were carried out according to the method of JIS Z-2911 as follows: A given amount of oil preparation, prepared as described in Example 25, was added to a white color based on a polyvinyl acetate emulsion, and the mixture obtained for 30 seconds stirred in a homogenizer to produce a color preparation in which a filter paper (“Toyo Filter Paper” No. 2) with a diameter of 12 cm was immersed. The paper was then removed from the color preparation and air dried, adjusting the amount of color deposited on the paper to achieve a dry color charge of 99 to 100% based on the weight of the filter paper. The dried paper was cut into a 3 cm diameter disk and the round sample obtained was then placed on the center of an agar plate medium in a Petri dish. Both the medium and the sample were inoculated by spraying with 1 ml each of a mixed spore suspension, which had been incubated separately on a potato dextrose agar medium by mixing equal amounts of spore suspensions of the three fungi (Aspergillus niger, Pénicillium lutenum and Trichoderma Tl) , were manufactured.

The petri dish was then sealed and kept in an incubator at 28 ° C for 1 week to allow the fungi to be incubated, after which the growth of the fungi on the sample was judged by rating 3.2 or 1 , in which:

so 3 means no mycelium growth on the surface of the sample,

2 indicates that the growth area of the mycelium does not exceed one third of the surface of the sample, and

1 indicates that the area of mycelial growth exceeds 55 thirds of the surface of the sample.

Table XV

Connection no.

1

Ratio of compound to ink solids content (%)

Mushroom resistance rating

1

0.15

3rd

3rd

0.15

3rd

10th

0.15

3rd

11

0.15

3rd

15

0.15

5

31

644853

Table XV (continued)

Connection no.

Ratio of compound to solid content of the paint (° -'o)

Mushroom resistance rating

Control A

0.15

2nd

Control B

0.15

2nd

"Proxel"

(Control)

0.15

2nd

TBTO * control

0.15

2nd

Untreated

-

1

* TBTO (applied in the form of an emulsion) (n-C4H9) 3SnO

Example 45

This example illustrates the sludge-fighting effect of the benzoxazolone derivatives.

A certain amount of routine water from the paper mill was put in a flask to which an aqueous solution of the compound to be examined was added in such an amount that a concentration of 10 ppm of the active ingredient in the routine water was obtained.

5 Before the addition of the preparation and 0.5, 1, 2, 4 and 8 hours after the addition of the preparation, bacterial colony counts in the routine water were carried out using the agar dilution plate method as follows: A sample of the routine water was sterilized with sodium chloride -io diluted solution and put 1 ml of the diluted solution in a Petri dish. A dissolved broth agar medium was poured in and mixed with the solution. After incubation in the plate at 30 ° C. for 2 days, the bacterial colony was counted using a colony counter and i5 the number of bacteria per milliliter of the routine water was calculated taking into account the multiplicity for the dilution with the sterilized saline solution.

The tests were carried out in two replications and an average number of bacteria 20 was determined. The results are summarized in Table XVI.

Table XVI

Connection no.

Bacteria per ml of routine water

Time between addition of the connection and evaluation (hours)

before the addition

0.5

1

1 5.1 xlO7 3.8 Xl02 6.2 xlO2 8.1 x 102 6.5 xlO2 5.7 xlO2

3 5.1 xlO7 4.0 xlO2 6.8 xlO2 8.0 xlO2 7.4xl02 6.3 xlO2

10 5.1 xlO7 4.1 xlO2 7.2 xlO2 9.6 xlO2 8.8 xlO2 7.5 xlO2

MBT * (control) 5.1 x 107 4.3 xlO3 1.2 xlO4 3.2 xlO4 1.2 xlO5 4.8 xlO6 «Proxel» **

(Control) 5.1 x 107 5.1 xlO2 9.1 xlO2 3.1 xlO3 7.1 xlO3 9.0 x 103

* MBT: methylene bisthiocyanate

** "Proxel": 1,2-benzisothiazolin-3-one

Example 46

This example shows the effectiveness of the benzoxazolone derivatives as a wood preservative.

A bar of Cryptmerica japonica (Japanese "Sugi") of about 15 cm in diameter and 60 cm in length, which had been dried to the point of fiber saturation, was sealed at the two end faces with a pepoxy resin which contained glass wool. An oil preparation, prepared as described in Example 25, was diluted with water to a concentration of 2% of the active ingredient and then pressed into the wood under a pressure of 15 kg / cm 2 for 3 hours. The wood was then air-dried to reduce its water content to atmospheric moisture. Samples measuring 2 x 2 x 1 cm were taken from the dried wood and from a bar of the same wood which had been treated with known wood preservatives. All of these samples were air dried for 2 weeks.

The samples were then exposed to the weather using an ultraviolet carbon arc weatherometer for a period of 2 months (corresponding to 6 years under natural environmental conditions); the samples were filled with an amount of 2100 ± 100 mm / minute of water under a hydraulic pressure of 1.0 kg / cm2 during

Watered 18 minutes after two hours of exposure to ultraviolet rays, and these operations were repeated alternately during the above two months. The samples were then dried and weighed at a temperature 45 of 60 ± 2 ° C for 48 hours (the dry weight is referred to as Wi).

The samples were then subjected to the preservation tests according to the method of JIS A 9302. In this test, the samples were infected with Coriolellus palustris or Coriolus versicolor, which had been grown at 26 ° C for 15 days on a sand medium containing 4% glucose, 0.3% clay and 1.5% malt extract. After incubation at 26 ° C for 90 days, the mycelia and other deposits were removed from the samples, which were then air-dried for 24 hours, then further dried at 60 ° C for 48 hours and finally weighed, the Dry weight is referred to as W2.

The weight loss of the samples was calculated according to the following 60 equation:

Weight loss (%) =

W1-W2 Wi x 100

The preservation effect (P.E.) was calculated according to the following equation:

P.E. = (1 -

Average weight loss in treated samples Average weight loss in untreated samples

-) x 100

644853

The test results are shown in Table XVII. Table XVII

Connection no.

P.E. value

1

100

3rd

98

10th

96

TBTO *

40

PCP-Na **

63

Creosote oil

95

* Tributyltin oxide

** Sodium pentachlorophenolate

Example 47

This example illustrates the synergistic effect that can be achieved by mixing certain compounds of the present invention with other known fungicides.

Wetting powder preparations containing Compound No. 10 and other fungicides and prepared as described in Example 30 were diluted with water to the required concentrations of active ingredients. Using the diluted preparations, the tests were carried out against Pseudoperonospora cubensis (cucumber), Sphaerotheca fuliginea (cucumber) and Sclerotinia sclerotiorum (bush bean) according to the methods described in Examples 39, 38 and 34 above, respectively.

As a reference, further studies were carried out in the same way using similar diluted preparations containing Compound No. 10 alone or other fungicides alone.

15 The 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.

20 The results of the tests with other known fungicides alone (B) and mixed fungicides (A 4- B) are summarized in Tables XVIII, IXX and XX below.

Table XVIII

Activity against Pseudoperonospora cubensis

Single fungicide (B)

Mixed fungicides

connection

concentration

Disease

concentration

Disease

(ppm)

control (%)

A + B

control (° / o)

N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide

25th

28

25 + 25

78

Tetrachloroisophthalonitrile

25th

35

25 + 25

86

Manganese ethylene bis (dithiocarbamate)

25th

38

25 + 25

87

Zinc complex of manganese ethylene bis (dithiocarbamate)

25th

32

25 + 25

84

Dizink bis (dimethyldithiocarbamate) ethylene bis

(dithiocarbamate)

25th

33

25 + 25

83

basic copper chloride

50 (like Cu)

29

25 + 50

85

basic copper sulfate

50 (like Cu)

24th

25 + 50

81

Copper 8-hydroxyquinolinate

50

28

25 + 50

78

Methyl-DL-N- (2,6-dimethylphenyl) -N- (2'-methoxy-

acetyl) alanilate

5

38

25 + 5

87

Ethyl N- (3-dimethylamino-propyl) thiocarbamate-

hydrochloride

10th

30th

25 + 10

80

Table IXX

Activity against Sphaerotheca fuliginea

Single fungicide (B)

Mixed fungicides

connection

concentration

Disease

concentration

Disease

(ppm)

control (%)

A + B

control (%)

1,2-bis (3-methoxycarbonyl) -2-thioureido) benzene

5

32

50 + 5

80

Methyl 1 - (n-butylcarbamoyl-2-benzimidazole carbamate

5

34

50 + 5

83

1 - [2- (2,4-dichlorophenyl) -4-ethyl-1,3-oxoran-2-yl) methyl]

1

40

50+ 1

88

-lH-l, 2,4-triazolpiomycin

10th

32

50+ 10

87

4-chlorophenoxy-3,3-dimethyl-1 - (1 H-1,3,4-triazol-1 -yl) -2-

butanone

1

34

50+ 1

81

S-n-butyl-S'-p-t-butylbenzyl-N-3-pyridyl-dithio-

carboximidate

1

40

50+ 1

87

N-Propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1 -

carboxamide

5

27th

50 + 5

78

2-dimethylamino-4-methyl-5-n-butyl-6-hydroxypyrimidine

5

26

50; + 5

74

6-methylguinoxaline-2,3-dithiocarbonate

5

28

50 + 5

84

33 644853

Table XX

Activity against Sclerotinia sclerotirum

Single fungicide (B)

Mixed fungicides

connection

concentration

Disease

concentration

Disease

(ppm)

control (%)

A + -B

control (%)

N'-dichlorofluoromethylthio-N, N-dimethyl-N'-

phenylsulfamide

50

26

50 + 50

77

2,6-dichloro-4-nitroaniline

50

26

50 + 50

79

N- (3,5-dichlorophenyl) -l, 2-dimethylcyclopropane-l, 2-

dicarboximide

12.5

40

50 + 12.5

89

3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-2,4-oxa-

zolidin-dione

12.5

36

50 + 12.5

85

l-isopropylcarbamoyl-3- (3,5-dichlorophenyl) hydantoin

12.5

38

50 + 12.5

87

Polyoxin

25th

32

50 + 25

82

N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboximide

25th

36

50 + 25

85

B

Claims (12)

644853 2nd PATENT CLAIMS 1. Benzoxazolone compounds of the general formula I = 0 Location or applied to the object, which are infected by fungi or bacteria or are to be protected from such an infection. 11. A process for the preparation of a compound of general formula 5 as defined in claim 1, characterized in that a compound of formula II X [II] in which X is a lower alkyl group with 1 to 4 carbon atoms, Y is a halogen atom, m zero or an integer from 1 to 3, n is an integer from 1 to 3 and the sum of m + n is an integer from 2 to 4, provided that when m = 0, n is 3 and Yn is 5,6,7-trichlor means and R represents hydrogen or an alkyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, mono- or dialkylaminocarbonyl, alkylsulfonyl, phenylsulfonyl or optionally substituted benzoyl or phenylaminocarbonyl group. 2. Compound according to claim 1, characterized in that m = 0 and Yn represents 5,6,7-trichlor. 3. A compound according to claim 1, characterized in that m = 1, X is methyl, n = 2 and each Y is chlorine. 4. A compound according to claim 3, characterized in that Xm means 7-methyl and Yn 5,6-dichloro. 5. A compound according to claim 1, characterized in that m = 0, Yn 5,6,7-trichlor and R represents an alkenylcarbonyl or alkenyloxycarbonyl group. 6. Compound according to claim 1, selected from the following group: 5,6,7-trichlorobenzoxazolone, N-acetyl-5,6,7-trichlorobenzoxazolone, N-methoxycarbonyl-5,6,7-trichlorobenzoxazolone, N- (3,5-dichlorophenylcarbamoyl) -5,6,7-trichlorobenzoxa- zolon, N-methanesulfonyl-5,6,7-trichlorobenzoxazolone, N-isopropoxycarbonyl-5,6,7-trichlorobenzoxazolone, 5,6-dichloro-7-methylbenzoxazolone, N-acetyl-5,6-dichloro-7-methylbenzoxazolone, N-methoxycarbonyl-5,6-dichloro-7-methylbenzoxazolone and N-Alyloxycarbonyl-5,6,7-trichlorobenzoxazolone. 7. Fungicidal and bactericidal preparation, characterized in that it contains as active ingredient a compound of general formula I, as defined in claim 1, together with a carrier for the active ingredient. 8. A preparation according to claim 7, in the form of a concentrate which contains 10 to 95 percent by weight of the active ingredient. 9. Preparation according to claim 7, in the form of a dilute composition which contains 1 x 105 to 10 wt.% Of the active ingredient. 10. A method for regulating the growth of fungi and bacteria on plants or objects, insofar as it is carried out outside the textile industry, characterized in that a compound of the formula I, as defined in claim 1, on the plant or its NHR in which X, Y, m, n and R have the same meaning as in claim 20, with a carbonyl compound of formula III 0 = C < 25th , A -B [HI] in which A and B, which are the same or different, represent a halogen atom or an alkoxy, haloalkoxy, alkylthio or amino group. 30 12. A process for the preparation of a compound of formula I as defined in claim 1, characterized in that a compound of formula IV = 0 [IV] 45 in which X, m and R have the same meaning as in claim 1, Z is a halogen atom and p is 0.1 or 2, halogenated to produce a compound of formula I which carries one or more halogen atoms in the benzene ring, the number of one is greater than the number of halogens in the starting compound of the formula IV, 13. A process for the preparation of a compound of the formula I in which R has the same meaning as in claim 1, with the exception of hydrogen and alkyl, characterized in that one Compound of 55 formula VI C = 0 [VI] in which X, Y, m and n have the same meaning as in patent 3rd 644 853 claim 1, in the presence of an acid binder with a compound of formula VII R D [VII] H implemented in which R has the same meaning as in claim 1, with the exception of hydrogen and alkyl and D represents a halogen atom, or that a compound of formula VI with an isocyanate compound of formula VIII R'NCO [VIII] in which R 'is alkyl or optionally substituted phenyl, to form a compound of formula I in which R is a group-CONHR'. 14. A process for the preparation of a compound of the formula I in which R is alkyl, characterized in that a compound of the formula VI, as defined in claim 13, with a dialkyl sulfate of the formula RCk J> S02 RO- ^ in which R represents an alkyl group or with a compound of the formula VII ' R 'D [VIP] in which R 'is alkyl and D is halogen.