DE2201063C3 - 1,2,4-Triazole derivatives, process for their preparation and their use as fungicides - Google Patents

Description

I.
R ^l -O-C-Y-R ³

R ²

(D

in which R ^{1 stands} for the phenyl group which can optionally be substituted by halogen atoms, by nitro, trifluoromethyl, alkyl with up to 6 carbon atoms, alkoxy with up to 4 carbon atoms and ortho or para phenyl groups, R ² represents a hydrogen atom, an alkyl group with up to 4 carbon atoms or a phenyl group, R ³ door represents an alkyl group with up to 4 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, a phenyl or 4-chlorophenyl group and Y represents a keto group or their customary functional derivatives, as well as their salts.

2. Process for the preparation of 1,2,4-triazole derivatives or their salts, characterized in that in a manner known per se

a) Halogen ether ketones of the general formula II

Shark

R ¹ —O — C — Y — R ³
R ²

(N)

in which R ¹ , R ² , R ³ and Y have the meaning given in claim 1 and Hal stands for a halogen atom, or reacts with 1,2,4-triazole, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent
b) compounds of the general formula III

OR ¹

R ¹ -O-C-Y-R ³
R ²

(IH)

in which R ¹ , R ² , R ³ and Y have the meaning given in claim 1, with 1,2,4-triazole hydrochloride, optionally in the presence of a diluent and optionally in the presence of an acidic catalyst, and reacted by this process compounds obtained optionally prepares the salts.

3. Use of 1,2,4-triazole derivatives according to Claim 1 for combating phytopathogenic fungi.

The invention relates to 1,2,4-triazole derivatives and their salts, processes for their production and their use as fungicides.

It has already become known that n-dodecylguanidine acetate is effective as a fungicide and has protective and noticeably curative properties (See U.S. Patent 2,425,341). As the compatibility of this compound with some types of fruit however, if it is small, it can only be used in the pre-flowering period.

It has also become known that 1-trityl

1,2,4-triazole is fungicidal (see Swiss U.S. Patent 4,888,713). However, its effect is at low application rates and concentrations are not always entirely satisfactory.

It has been found that the 1,2,4-triazole derivatives of the general formula I according to the invention

([N

R ¹ - C - Y - R ³
R ²

in which R ^{1 stands} for the phenyl group which can optionally be substituted by halogen atoms, by nitro, trifluoromethyl, alkyl with up to 6 carbon atoms, alkoxy with up to 4 carbon atoms and ortho- or para-phenyl groups, R ² for a Hydrogen atom, for an alkyl group with up to 4 carbon atoms or for a phenyl group, R ³ for an alkyl group with up to 4 carbon atoms, a cycloalkyl group with 5 to 6 carbon atoms, a phenyl or 4-chlorophenyl group and Y for a Keto group or their customary functional derivatives, and their salts have excellent fungicidal properties against phytopathogenic fungi.

It has also been found that 1,2,4-triazole derivatives can be used of the formula (I) or the salts thereof, if one is used in a manner known per se

a) Halogen ether ketones of the general formula II

Shark

R ¹ -O-C-Y-R ³
R ²

(II)

in which R ¹ , R ² , R ³ and Y have the meaning given above and Hal stands for a halogen atom, reacts with 1,2,4-triazole, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or
b) compounds of the general formula III

OR ¹

R ¹ —Ο — C — Υ — R ³

R ²

(III)

in which R ¹ , R ² , R ³ and Y have the abovementioned meaning, with 1,2,4-triazole hydrochloride, optionally in the presence of a diluent

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and optionally in the presence of an acidic catalyst, and from the according to this process compounds obtained optionally prepares the salts

Surprisingly, the 1,2,4-triazole derivatives according to the invention and their salts show a considerable amount higher fungicidal effect than the n-dodecyl-guanidine acetate known from the prior art and -Trityl-1,2,4-triazoI, which is the closest active ingredients are of the same type of effect. The substances according to the invention are thus an enrichment of the Technology.

Uses manto-bromo-tu- (2,6-dichloro-phenoxy) -acetophenone and 1,2,4-triazole as starting materials, the course of the reaction can be indicated by the following equation are reproduced (process stage a):

Br

O — CH-CO-

N-

-HBr

Use 1-bis (2,4-dichloro-phenoxy) -1-phenyl-3-dimethyl-butan-2-one and 1,2,4-triazole hydrochloride as starting materials, the course of the reaction can be represented by the following equation (process variant b):

Cl- / I-O-C-CO-C (CH ₃ J ₃

^ = Y I

N-

Cl

(I NH ⁶¹ Cl ο
H

-Cl

OH

Cl Cl ^e '

In the compounds according to the invention and thus also in the corresponding starting compounds, R ^{1 represents} a phenyl radical which is optionally substituted in the manner indicated; as substituents are preferably: fluorine, chlorine or bromine atoms, nitro groups, straight-chain or branched alkyl groups with 1 to 6, in particular 1 to 4 carbon atoms, alkoxy groups with 1 to 4, in particular 1 to 2 carbon atoms and the trifluoromethyl radical, furthermore the o- or p-linked phenyl radical as a substituent in question. R ² represents a hydrogen atom, a straight-chain or branched alkyl radical having 1 to 4 carbon atoms or a phenyl radical.

A grouping of a functional keto group Y is preferably the carbonyl group, which may optionally be in the hydrated form —C (OH) ₂ - or the ketal group —C (OR) ₂ -, where R is an alkyl'-est with preferably 1 or 2 carbon atoms means.

In the formula (II), Hai preferably represents a chlorine or bromine atom.

Examples of the compounds of the formula (II) which can be used according to the invention are specifically called:

55

60 1 -Bromo-1 -phenoxy-SS-dimethyl-butan ^ -one,

1 -Bromo-1 - ^

butan-2-one,

1 -Bromo-1 - (3-chlorophenoxy) -3,3-dimethylbutan-2-one,

1 -Brom-1 - (^

butan-2-one,

1 -Bromo-1 - (2,6-dichlorophenoxy) -3,3-dimethylbutan-2-one,

1 -Bromo-1 - (2,5-dichlorophenoxy) -3,3-dimethylbutan-2-one,

1 -Bromo-1 - (4-methoxyphenoxy) -3,3-dimethylbutan-2-one.

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1 -Bromo-1 - (2-methylphenoxy) -3,3-dimethylbutan-2-one,

1 -Bromo-1 (2,3-dichlorophenoxy) -3,3-diniethylbutan-2-one,

1 -Bromo-1 - (4-bromophenoxy) -3.3-dimethylbutan-2-one,

l-bromo-1- (4-fluorophenoxy) -3,3-dimethyI-butan-2-one,

1 -Bromo-1 - (2,4,6-trichlorophenoxy) -3,3-dimethylbutan-2-one,

1 -Bromo-1 - (4-tert-butyl-phenoxy) -3,3-dimethyl-butan-2-one,

1 -Bromo-1 - (4-isopropyl-phenoxy) -3,3-dimethyl-butan-2-one,

l-bromo-l- (2-methyl-4-chlorophenoxy) -3,3-dimethyl-butan-2-one,

1 -Bromo-1 - (4-trifluoromethylphenoxy) -3,3-dimethyl-butan-2-one,

1 -Bromo-1 - (4-nitrophenoxy) -

3,3-dimethyJ-butan-2-one,

1 -Bromo-1 - (2-nitrophenoxy) -

3,3-dimethyl-butan-2-one,

i -Bromo-1 - (p-diphenoxy) -3,3-dimethylbutan-2-one,

1 -Bromo-1 -io-diphenoxy) -3,3-dimethylbutan-2-one.

co-bromo-co-phenoxy-acetophenone,

ai-bromo-co - ^ - chlorphenoxyJ-acetophenon, tu-bromo-w- (3-chlorophenoxy) -acetophenone, (o-bromo-a) - (2,4-dichlorophenoxy) -acetophenone, cu-bromo-oj-H-methylphenoxyJ-acetophenon, oj-chloro-w- (2-chloro-4-methyl-phenoxy) -acetophenone,

cu-chloro-o) - (2-methyl-4-chloro-phenoxy) -acetophenone,

fu-bromo-tu ^ -methyl-phenoxyl-acetophenon, i «-Chlor-cu- (2,4-dichlorophenoxy) -4-chloroacetophenone,

w-bromo-tu- (2,6-dichlorophenoxy) acetophenone.

Some of the halogen compounds of the formula (II) used as starting materials are known as yet unknown compounds of the formula (II) can be prepared by known processes, by z. B. Compounds of the formula

The starting materials for process variant b) are generally defined by formula (III). What has already been said above applies to the radicals R ¹ , R ² and R ^3.

Specific examples of the compounds of the formula (III) which can be used according to the invention are called:

1 - phenyl-1,1-bis-phenoxy-

3,3-dimethyl-butan-2-one,
l-phenyl-l, l-bis- (4-chlorophenoxy) -

3,3-dimethyl-butan-2-one,

1 - phenyl-1,1-bis- (3-chlorophenoxy) -

3,3-dimethyl-butan-2-one,

1 - phenyl-1,1-bis- (2,4-chlorophenoxy) -3,3-dimethyl-butan-2-one,

l-phenyl-l, l-bis (4-methoxyphenoxy) -

3,3-dimethyl-butan-2-one,

l-phenyl-l, l-bis (4-methylphenoxy) -

3,3-dimethyl-butan-2-one.
w-phenyl - (//, w-bis-phenoxy-acetophenon.

w-phenyl-ü ', (u-bis- (4-chlorophenoxy) -

acetophenone,

("-Methyl-t / ^ oj-bis-phenoxy-acetophenon.

o "-Methyl-oj, (" - bis (4-chlorophenoxy) -acetophenone.

<»- methyl-w, (u-bis- (2,4-dichlorophenoxy (-

acetophenone,

w-methyl-oj, w-bis- (2,6-dichlorophenoxy) -

acetophenone.
(u-Ethyl- «i, i« -bis- (4-chlorophenoxy) -

acetophenone,

2-bis-phenoxy-butan-3-one.

The used as starting materials of the formula (III) Some ketals are known. Those not yet known can be prepared by customary processes (cf. J. Chem. Soc. [London] [1970]. 3. pp. 462 to 464, Liebigs Ann. Chem. 735 [1970], 145 to 157). Furthermore, these ketals can by Reformatzky synthesis or Grignard synthesis, which lead to an aralkyl ketone continues by bromination on the carbon atom adjacent to the keto group and through Implementation of the resulting dibromoketone with an alcoholate or phenolate can be prepared according to the following two formula schemes:

R ¹ -OH

(IV)

Hai-C-CO-R ³ R ²

Formula scheme

in which R ^{1 has} the meaning given in formula (I), with a halo ketone of the formula

(V)

55

in which R ² and R ^{3 have} the meaning given in formula (I) and Hal is a halogen atom, preferably chlorine and bromine, is reacted. The still remaining active hydrogen atom is then exchanged for halogen in the usual way and the keto group is optionally converted into a functional derivative.

The!, 2,4-triazole still used as starting material for process variant a) is generally + 2Br,

- 2HBr

R ² —CH ₂ -ZnCl + Cl- C - R- '

Il

R ² -CH ₂ -CR ³
Br O

I Il

R ² -C C -C R ³

Br
R ¹
O

R ¹ - O - C - CO - R- ¹

+ 2R ¹ ONa

- 2NaBr

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Formula scheme 2

R ² - CH ₂ MgCl + N = CR ¹

+ Η, Ο Il

- NH ₃ R ² CH ₂ -CR ¹ + 2Br ₂ Br O
Il
f> 2 c γ * ρ3
Ix V_ ^ Ix
Br - 2HBr OR ¹
R ¹ —O — C — CO — R ³
R ² + 2R ¹ ONa - 2NaBr

As salts of the 1,2,4-triazole compounds of the formula (I) those with physiologically acceptable acids may be mentioned as preferred. Examples of such acids are the hydrohalic acids, such as. B. the chlorine and hydrobromic acid, especially hydrochloric acid, furthermore the phosphoric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as B. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, Salicylic acid, sorbic acid, lactic acid, 1,5-naphthaundisulphonic acid.

In process a) (reaction of the halogen derivatives of the formula (II)) come with as diluents 1,2,4-triazole), preferably polar organic solvents in question. These include preferably nitriles, such as acetonitrile; Sulfoxides such as dimethyl sulfoxide; Formamides such as dimethylformamide; Ketones such as acetone; Ethers such as diethyl ether and tetrahydrofuran; Nitroalkanes such as nitromethane and unsymmetrical chlorinated hydrocarbons such as methylene chloride and chloroform.

The reaction (process a) is carried out in the presence of an acid binder. Preferably used a corresponding excess of 1,2,4-triazole. However, you can also do all the rest Add commonly used organic acid binders, such as lower tertiary alkylamines or Aralkylamines, e.g. B. triethylamine or dimethylbenzylamine.

The reaction temperatures can be varied over a wide range in process a). In general, one works between about 20 to about 150 ^° C., preferably at 80 to 120 ^° C.

When carrying out the method according to the invention a) one sets preferably about 1 mole of 1,2,4-triazole to 1 mole of the compound of the formula (II) and about 1 mole of acid binder.

To isolate the compounds of the formula (I), the solvent is evaporated off in vacuo and the residue taken up with an organic solvent. A water extraction follows to remove the 1,2,4-triazolyl hydrochloride which is also formed and evaporating the solution to dryness. The base is made from the residue Recrystallize the salt by treating it with the appropriate acid according to the usual methods won.

As a diluent in process b) (reaction of compounds of the formula (III) with 1,2,4-triazole hydrochloride) can be high-boiling polar ones organic solvents can be used. These preferably include sulfoxides such as dimethyl sulfoxide. Formamides such as dimethylformamide, ethers such as dioxane or dibutyl ether. Implementation after Process b) is, however, preferably carried out without a solvent, d. H. made in the melt.

It can be useful when carrying out process b) to facilitate the cleavage of alcohol or phenol acidic catalysts, such as. B. hydrochloric acid or p-toluenesulfonic acid to add.

The reaction temperatures can be varied over a wide range in process b).

In general, the reaction is preferably carried out between about 8l) and about 250 ⁰ C, between 120 and 200 ° C, particularly 140-190 ⁰ C. In the presence of a solvent is carried out conveniently at the boiling point of the respective solvent.

When carrying out the method according to the invention b) about 1 mole of 1,2,4-triazole hydrochloride is added to 1 mole of the compound of the formula (III) and in some cases about 0.01 to 0.1 moles of catalyst.

To isolate the compounds of the formula (I), the reaction mixture is taken up in water, this partially going into solution; the suspension is neutralized with alkali or alkali carbonate and with organic solvents that are not very miscible with water, e.g. B. methylene chloride extracted. the organic phase is dried and the solvent is distilled off. The obtained solid or oily The residue is purified by recrystallization

The compounds of the formula (I) obtained according to processes a) and b) can be converted into functional derivatives (of the keto group) and / or into their salts by the customary methods.
The following are specifically mentioned as new active ingredients that can be prepared by processes a) and b):

<»- (!, 2,4-TriazoI -] - yl) -cu-phenoxy-

acetophenone,

<ii- { 1,2,4-Triazol-1 -yl) -to- (4-chlorophenoxy) -acetophenone,

«I- (1,2,4-Triazol-1-yO-cu-O-chlorophenoxy) -

acetophenone,

ω- {1,2,4-triazol-1 -yl) -cu- (2,4-chlorophenoxy) -

acetophenone,
oi- (1,2,4-triazol-1 -yl) -to- (2,4-dichlorophenoxy) -

acetophenone,

eo- (1,2,4-triazol-l-yl) - (u- (2,4-dichlorophenoxy) -

4-chloro-acetophenone,

«Hl, 2,4-Triazol-l-yl) -a) - (2,6-dichlorophenoxy) -acetophenone,

(o- (l, 2,4-triazol-l -yl) - co- (4-methox yphenoxy) -

acetophenone,

cu- (1,2,4-triazol-l-yl) -a> - {4-methylphenoxy) -

acetophenone,
o> - {1,2,4-Triazol-l-yl) -ai- (2-methylphenoxy) -

acetophenone,

(o-Methyl-eu- (1,2,4-triazol-l -yl) -a> - (4-chloro-

phenoxy) acetophenone,

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ίο

(D- phenyl-f /) - (1,2,4-triazol-1-yl) - <»- (2,4-dichlorophenoxy) acetophenone, « ι- phenyl-oi- (1,2,4- triazol-1 -yl) -w- (2,5-dichlorophenoxy) acetophenone, 1 - (1,2,4-triazol-1 -yl) -1 - (2,4-dichlorophenoxy) propan-2-one ,

2- (1,2,4-triazol-1-yl) -2-phenoxy-butan-3-one, 2- (1,2,4-Triazol-1-yl) -2- (4-chlorophenoxy) -butan-3-one,

2- (1,2,4-triazol-1-yl) -2- (4-fluorophenoxy) -butan-3-one,

2- (1,2,4-Triazol-1 -yl) -2- (2,4-dichlorophenoxy) -butan-3-one,

1 - (1,2,4-Triazol-1-yl) -1 - (2,4-dichlorophenoxy) -3-methyl-butan-2-one, 2- (1,2,4-triazol-1-yl) -2- (4-chlorophenoxy) -4-methyl-pentan-3-one, 2- (1,2,4-Triazol-1-yl) -2- (2,4-dichlorophenoxy) -4-methyI-pentan-3-one, I - (1,2,4-triazol-1-yl) -1 - (4-chlorophenoxy) -3,3-dimethyl-butan-2-one, I - (1,2,4-triazol-1-yl) -1 - (2,4-dichlorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (2,5-dichlorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (2,6-dichlorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (2,4,6-trichlorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-Triazol-1-yl) -1 - (2-chlorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (4-bromophenoxy) -3,3-dimethyl-butan-2-one, J - (1,2,4-Triazol-1-yl) -1 - (4-fluorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-Triazol-1-yl) -1 - (4-methylphenoxy) -3,3-di methyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (4-methoxyphenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-Triazol-1 -yl) -1 - (4-tert-butylphenoxy) -3,3-dimethyl butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (4-isopropylphenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (2-methyl-4-chlorophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (4-trifluoromethylphenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-Triazol-1-yl) -1 - (4-nitrophenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (2-nitro phenoxy) -3,3-dimethyl-butan-2-one, 1 - (1,2,4-triazol-1-yl) -1 - (p-diphenoxy) -3,3-dimethyl-butan-2-one, Hl, 2,4-triazol-l-yl) -l- (o-diphenoxy) -3,3-dimethyl-butan-2-one, 2- (l, 2,4-triazol-l-yl) -2-phenoxy-4,4-dimethylpentan-3-one,

2- (1,2,4-triazol-1-yl) -2- (4-fluorophenoxy) -4,4-dimethyl-pentan-3-one, 2- (1,2,4-triazol-1-yi ) -2- {2,4-dichlorophenoxy) -4,4-dimethyl-pentan-3-one, l-phenyl-l- (l, 2,4-triazol-l-yl) -l-phenoxy-3, 3-dimethyl-butan-2-one, 1 - phenyl-1 - (1,2,4-triazol-1 -yl) -1 - (4-fluorophenoxy) -3,3-dimethyl-butan-2-one, l-phenyl-l- (lA4-triazol-l-yl) -H2,4-dichlorophenoxy) -3,3-dimethyl-butan-2-one, 2- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenoxy) -I -cyclohexyl-ethan-1-one,
2- (1,2,4-Triazol-1 -yl) -2- (2,4-dichlorophenoxy) -I -cyclopentyl-ethan-1-one,

2- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenoxy) -3-cyclohexyl-propan-3-one.

The following are particularly effective substances:

1 - (1,2,4-Triazol-1-y I) -1 - (4-chlorophenoxy) -3,3-dimethyl-butan-2-one and its hydrochloride as well

I - (1,2,4-Triazol-1-yl) -1 - (2,4-dichlorophenoxy) -3,3-dimethyl-butan-2-one and its hydrochloride.

The active ingredients according to the invention have a strong fungitoxic effect. Harm you Cultivated plants in the concentrations necessary for combating fungi do not and have one low toxicity to warm blooded animals. They are because of their low odor and their good tolerance not uncomfortable for the human skin to handle. For these reasons, they are for use suitable as a plant protection agent for combating fungi. Fungitoxic agents in crop protection are used to combat Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

The active ingredients according to the invention have a very broad spectrum of activity and can be used are used against parasitic fungi that attack above-ground parts of plants or plants from the ground attack as well as seed-transmitting pathogens.

They are particularly effective against parasitic fungi on parts of plants above ground, such as Phytophthora species, Erysiphe species, Peronospora species and Venturia species, also against Piricularia and Pellicularia species, e.g. B. against the pathogen apple powdery mildew (Podosphaera leucotricha), apple scab (Fusicladium dendriticum) and wheat stone brandy (Tilletia tritici). It should be particularly emphasized that the active ingredients according to the invention not only develop a protective effect, but also have a curative effect, i.e. when used after contamination with the spores of the fungus. Furthermore it is on the systemic effect of the substances to point out. In this way it is possible to protect plants against fungal attack if you have the active ingredient on the The soil and the roots are supplied to the above-ground parts of the plant. As a pesticide you can use the substances according to the invention for soil treatment, for seed treatment and for treating above ground Plant parts are used.

The active compounds according to the invention can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, pastes and granulates. These are done in a well known manner produced, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants. In the case of using Water as an extender can be, for. B. organic solvents can also be used as high-pressure solvents. The following essentially suitable liquid solvents are: aromatics, such as xylene, toluene, benzene

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or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or Paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as Dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or Carriers are liquids that are meant which are at normal temperature and under normal pressure are gaseous, e.g. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic minerals such as highly dispersed silicic acid, aluminum oxide and Silicates; as emulsifiers: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, and aryl sulfonates; as a dispersant: e.g. B. Lignin sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations as a mixture with other known ones Active ingredients are present, such as fungicides, insecticides, acaricides, nematicides, herbicides, protective substances against bird damage, growth substances, plant nutrients and soil structure improvers.

The formulations generally contain between 1 and 95 percent by weight of active ingredient, preferably between 5 and 90.

The active ingredients can be used as such, in the form of their formulations or those derived therefrom Diluting prepared application forms, such as ready-to-use solutions, emulsions, suspensions, Powders, pastes and granules can be used. It is used in the usual way, e.g. by watering, spraying, spraying, dusting, scattering, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

When used as foliar fungicides, the active ingredient concentrations in the use forms can be varied in a larger area. They are generally between 0.1 and 0.00001 percent by weight, preferably between 0.05 and 0.00001.

In the treatment of seeds, amounts of active compound of 0.01 to 50 g per kilogram are generally used Seed, preferably 0.01 to 5 g, is required.

For soil treatment, amounts of active ingredient from 1 to 1000 g per obm buoys, preferably from 10 to 200 g, required.

The various possible uses are shown in the following examples:

given amount of water, which contains the additives mentioned.

Young cucumber plants with around three leaves are sprayed with the spray liquid up to Dripping wetness. The cucumber plants remain in the greenhouse to dry for 24 hours. Then will dusted them for inoculation with conidia of the fungus Erysiphe cichoreacearum. The plants are subsequently at 23-24 ° C and about 75%

ίο relative humidity set up in the greenhouse. After 12 days, the infestation of the cucumber plants is a percentage of the untreated, but also inoculated Control plants determined. 0% means no infestation, 100% means that the infestation is the same

! 5 is high as with the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Table A.
Erysiphe test

Active ingredient

Infection in% of the infestation of the untreated control at an active ingredient concentration of

0.00019%

0.00009%

known:

According to the invention (the
Reference numbers
on the compounds specified in the preparation examples)

₅ o (D (38)

16
19th

37 25

continuation

Example A.
Erysiphe test

Solvent: 4.7 parts by weight acetone.
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.
Water: 95 parts by weight.

The amount of active substance necessary for the desired concentration of active substance in the spray liquid is mixed with the specified amount of solvent and dilute the concentrate with the (2)

(4)

(5)

(17)

(37)

(70)

at an active ingredient concentration of

0.000125%

21
41
0
50
10
37

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Example B Podosphaera test (apple powdery mildew) / Protective

Solvent: 4.7 parts by weight acetone. Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

Water: 95 parts by weight.

The amount of active ingredient necessary for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dilute the concentrate with the specified Amount of water that contains the additives mentioned.

Young apple seedlings, which are in the 4-6 leaf stage, are sprayed with the spray liquid until they are dripping wet. The plants remain in the greenhouse for 24 hours at 20 ^° C. and a relative atmospheric humidity of 70%. They are then inoculated by dusting them with conidia of the apple powdery mildew pathogen (Podosphaera leucotricha Salm.) And placed in a greenhouse at a temperature of 21-23 ° C and a relative humidity of approx. 70%.

10 days after the inoculation, the seedlings are infected in% of the untreated, but likewise inoculated control plants determined.

0% means no infestation, 100% means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Table B.
Podospharea test / protective

Active ingredient

Infestation in% of the infestation of the untreated control

at an active ingredient concentration of

0.00078%

0.00039%

Trityl-triazole (known, 52
Formula see table A)

continuation

28
26th

61

26 39

at an active ingredient concentration of

0.00062%

continuation

0
24
16
26th

at an active ingredient concentration of

0.0005% 0.00025%

Example C
Fusicladium test (apple scab) / Protective

Solvent: 4.7 parts by weight acetone.

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

Water: 95 parts by weight.

ίο Mix the one for the desired concentration of active ingredient Amount of active ingredient required in the spray liquid with the specified amount of solvent and dilutes the concentrate with the specified amount of water, which contains the additives mentioned contains.

Young apple seedlings, which are in the 4-6 leaf stage, are sprayed with the spray liquid until they are dripping wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative atmospheric humidity of 70%. Subsequently, they are (Fusicladium dendriticum Fuck.) With an aqueous conidia suspension of the apple scab, and incubated in a humid chamber at 18-20 ⁰ C and 100% relative humidity for 18 hours.

The plants are then returned to the greenhouse for 14 days.

15 days after the inoculation, the Seedlings determined in% of the untreated, but also inoculated control plants.

0% means no infestation, 100% means that the infestation is just as high as in the control plants. Active ingredients, active ingredient concentrations and results are shown in the following table:

Table C.
Fusicladium test / protective

Active ingredient

Infestation in% of the infestation of the
untreated control

with an active ingredient concentration
from

0.025% 0.00156%

Trityl-triazole (known
Formula see table A)

(D

(H)
(38)

11th 26th

continuation

at an active ingredient concentration
from

0.0025%

48

(2)
(17)
(19)
(20)

22 Ol 063

Continuation!

(48)
(49)

hci of an active ingredient concentration win

19th 45 14th

Example D I-'usicladium-Tcst (Apple Schorfl / Curativ

Solvent: 4.7 parts by weight acetone. Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

Water: 95 parts by weight.

The active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the specified amount of solvent and dilute the concentrate with the appropriate

given amount of water, which the said to sät / c contains.

Young apple seedlings c. which is in the 4 - 6-Blattstadiurr are located, with an aqueous Konidiensuspen sense of the apple scab pathogen (Fusicladium dendriticurr Fuckcl) and inoculated for 18 hours Humid chamber at 18-20 C and 1 (X)% relative: humidity incubated. The plants are coming then into the greenhouse. They dry off.

After a reasonable dwell time, dif plants are treated with the spray liquid which is in the upper specified manner was made, splashed to runoff. Then the planters come again in the greenhouse.

15 days after the inoculation, the attack on the apple seedlings is determined as a percentage of the untreated but also inoculated control plants. O ⁰ X means no infestation, 100% means that the infestation is just as high as in the case of the control plants

Active ingredients, active ingredient concentrations, the dwell / eil between inoculation and spraying and the results are shown in the table below emerged.

Table D.
Fusicladium test / curative

Active ingredient

Vcrwcilzcil in hours

Infestation in% of Infestation of the unbchandcltcn control with an active ingredient concentration tration of 0.025%

NH

C ₁₂ H ₂₅ NH-C ^ CHjCOOH 42 1 (1) NH ₂ (known) 42 2 (8th) 42 1 (19) 42 0 (34) 42 7th (38) 42 0

Example E. Erysiphc test / systemic

Solvent: 4.7 parts by weight acetone. Dispersant: 0.3 part by weight of alkylaryl polyglycol ether.

Water: 95 parts by weight.

Mix the concentration required for the desired active substance Required amount of active substance in the casting liquid with the specified amount of solvent and dilutes the concentrate with the specified amount of water, which contains the additives mentioned contains.

Cucumber plants grown in standard soil grow three times in the 1 2-leaf stage within one week with 20 ecm of the pouring liquid in the specified active ingredient concentration, based on 100 ecm of soil poured.

The plants treated in this way become after treatment with conidia of the fungus Erysiphe cicho raccarum inoculated. Then the plants are zen at 23 24 C and a relative humidity

ds of 70% placed in the greenhouse. After 12 days the percentage of infestation on the cucumber plants is that of the untreated. but also inoculated control plants determined.

709 665/22 i

22 Ol 063

0% means no infestation, 100% means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Table F.
Fusicladium-Tesl systemic

Table E.
Erysiphe test / systemic

Active ingredient

Infestation in "u of the infestation untreated control

in the case of an active ingredient kun / enlralion from

0.003 ";

0.0015 ".,

Active ingredient

(I)
(17)

Infestation in% of the infestation of the untreated control

at an active ingredient concentration from

0.003%

0.0025 "/ ,,

continuation

0 0

0 0

in the case of an active substance formation from

0.0025 ".

Example F
Fusicladium-Tcst / systemic

Solvent: 4.7 parts by weight acetone.
Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether.

Water: 95 parts by weight.

Mix the concentration required for the desired active substance Amount of active ingredient required in the casting liquid with the specified amount of solvent and dilutes the concentrate with the specified amount of water, which contains the additives mentioned contains.

Apple seedlings grown in standard soil become at the 3 4-leaf stage once within a week with 20 ecm of the pouring liquid in the specified active ingredient concentration, based on 100 ecm of soil, poured.

The plants treated in this way are treated with an aqueous conidia suspension of Fusicladium dentriticum Fuck, inoculated and In a fire chamber at 18-20 C for 18 hours and 100% relative humidity. The plants are then reinserted for 14 days Glasshouse.

15 days after the inoculation, the Seedlings determined in% of the untreated, but also inoculated control plants. Means 0% no infestation, 100% means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Example G

Pellicularia test

Solvent: 1.9 parts by weight of dimethylformamide.

Dispersant: 0.1 part by weight of alkylaryl polyglycol ether.

Water: 98 parts by weight.

Other additives: parts by weight.

} o Mix the concentration required for the desired active substance Amount of active ingredient required in the spray liquid with the specified amount of solvent and the dispersant and dilutes the concentrate with the specified amount of water.

.vs The spray liquid is sprayed about 30 3 week old rice plants to dripping wet. The plants remain in one until they dry out Greenhouse at temperatures of 22 to 24 C and a relative humidity of about 70%. After that the plants are infected with a culture of Pellicularia sasakii grown on malt agar and at 28 to 30 C and 100% relative humidity.

In the plants infected with Pellicularia sasakii

the infestation is after 5-8 days on the leaf sheaths in relation to the untreated, but infected Control determined. 0% means no infestation, 100% means that the infestation is exactly as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table:

Table G
Pcllicularia test

Active ingredient

Infestation in% of the infestation of the untreated control

at an active ingredient concentration from

Trityl-triazole (known.
Formula see table A)

(D
(38)

(1.05%

KK)

0 0

0.025%

50

25th

22 Ol 063

Example H

Sprout cultivation test / powdery mildew / protective (leaf-destroying mycosis)

To produce an appropriate preparation of active ingredient, 0.25 part by weight of active ingredient is used in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier (alkyl aryl polyglycol ether) and adds 975 parts by weight of water. The concentrate is diluted with water to the desired level Final concentration of the spray mixture.

To test for protective effectiveness, the single-leaved young barley plants of the variety are sprayed Blackbird with the active ingredient preparation is dewy. After drying, the barley plants are dusted with Spores of Arysiphe graminis var.hordei.

To test for curative effectiveness, proceed in the same way, but in reverse order before. The single-leaf young barley plants are treated with the preparation of the active compound 48 hours after inoculation if the infection is already manifest.

After 6 days of residence time of the plants at a temperature of 21 to 22 "C and an air humidity 80 to 90% of the population of the plants with powdery mildew pustules is evaluated. The degree of infestation is expressed as a percentage of the infection of the untreated control plants. Where 0% means no infestation and 100% the same degree of infestation as in the untreated control. The active ingredient is the more effective, the lower the powdery mildew infestation.

Active ingredients, active ingredient concentrations in the spray mixture and degrees of infestation are based on the following Table shows:

Table H.
Sprout treatment test / grain flour / protective concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for curative effectiveness, the same procedure is followed, but in reverse order how to test for protective effectiveness. The treatment of single-leaved young barley plants with the active ingredient preparation takes place 48 hours after the inoculation, if the infection is already is manifest.

ίο After 6 days 'dwell time of the plants at a temperature of 21 to 22 ^r' C and a humidity of 80 to 90% to evaluate the trimming of the plants from with mildew pustules. The degree of infection is expressed as a percentage of the infection of the untreated control plants. 0% means no infection and 100% means the same degree of infection as in the case of the untreated control. The lower the powdery mildew infestation, the more effective the active ingredient.

Active ingredients, active ingredient concentrations in the spray mixture and degrees of infestation are based on the following Table shows:

Table J
Sprout treatment test / cereal mildew / curative

Active ingredients Active ingredient infestation in "/" the

concentration of untreated in the spray control broth in Cicw .-%

Untreated 100

Trityl-triazole (known, 0.01 50.0

Formula see table A)

(6) 0.01 21.3

(39) 0.01 10.0

(48) 0.01 25.0

(68) 0.01 12.5

(70) 0.01 0.0

0.001 0.0

0, (X) I 12.5

(87) 0.01 0.0

Example J

Sprout treatment test / cereal mildew / curative (leaf-destroying mycosis)

For the production of an appropriate active ingredient preparation take 0.25 parts by weight of active ingredient in 25 parts by weight of dimethylformamide and 0.06 parts by weight Emulsifier alkyl aryl polyglycol ether and adds 975 parts by weight of water. The con-

Active ingredients Active ingredient Fell in "A, the concentration untreated in the injection control briihe in weight- '! Untreated 100 Trityl-triazole 0.025 100 (known, formula 0.01 100 see table A) 0.005 100 (6) 0.025 0.0 (48) 0.025 0.0 0.01 0.0 0.005 17.5 (68) 0.025 0.0 (70) 0.025 0.0 0.01 0.0 0.005 0.0 (87) 0.025 0.0 Example K

Powdery mildew test (Erysiphe graminis var. Hordei) / systemic

(fungal cereal sprout disease)

The active ingredients are used as powdered seed treatment agents. They are made by stretching the respective active ingredient with a mixture of equal parts by weight Talc and kieselguhr to a finely powdered mixture with the desired active ingredient concentration. For seed treatment, barley seeds with the quenched active ingredient are shaken in a sealed container Glass bottle. The seeds are sown with 3 χ 12 seeds in flower pots 2 cm deep in a mixture from one volume part of Fruhstorfer unit earth and one volume part of quartz sand. The germination and emergence take place under favorable conditions in the greenhouse. 7 days after sowing if the When barley plants have developed their first leaf, they are filled with fresh spores of Erysiphe graminis

22 Ol

var. hordei pollinated and at 21 to 22 C and 80 to 90% rel. Humidity and 16-hour exposure cultivated. The typical powdery mildew pustules form on the leaves within 6 days.

The degree of infestation is expressed as a percentage of the infestation of the untreated control plant. So 0% means no infestation and 100% the same degree of infestation as in the case of the untreated Kortrolle. The lower the powdery mildew, the more effective the active ingredient.

Active ingredients, active ingredient concentration in the seed treatment agent as well as its application rate and the percentage of powdery mildew infestation are based on the following Table shows:

Table K

Barley powdery mildew test (Erysiphe graminis var. Hordei | < systemic

Active ingredients Active ingredient Pickling agent Infestation in "Ό concentra expense- the un tion in pickling amount in treated medium in g / kg of seeds control Weight% Unheated _ - HO Trityl-triazole 25th 10 88.8 (known, For 25th 4th 100 mel see Table A) (6) 25th 10 0.0 (68) 25th 4th 0.0 (70) 25th 10 0.0 25th 4th 0.0 10 2 0.0 1 2 0.0 B e i s ρ i el 1 ^ O-CH-CO-C (CH ₃ ) j

The starting product is manufactured as follows:

Br

-O - CH- CO ((CH.,) J

to 2,4-dichloro-phenolate-sodium, which is made from 32.6 g (0.2 mol) 2,4-dichlorophenol and 4.6 g (0.2 mol) sodium is prepared in 130 ml of absolute alcohol, 35.8 g (0.2 mol) of a-bromo-pinacolone in 50 ml Dripped ethyl acetate and heated to boiling overnight.

The sodium bromide formed is then filtered off with suction while hot, the filtrate is distilled in vacuo and

the solid residue recrystallized from a little ligroin.

38 g (73% of theory) of l- (2.4-dichloro-

phenoxy) -3,3-dimethyl-butan-2-one of melting point

20 65 C.

To 26.1 g (0.1 mol) of 1- (2,4-dichlorophenoxy) -3,3-dimethyl-butan-2-one 6 ml (0.11 Moll bromine) are added and the mixture is refluxed at 140 ° C. for 1 hour. The oily residue obtained is taken up with petroleum ether, whereupon it crystallizes: the test residue is suctioned off and washed thoroughly.

30 g (89% of theory) 1-bromine are obtained - (2,4-dichlorophenoxy) -3-dimethyl-butan-2-one of melting point 70 ° C

Preparation of the hydrochloride 1 - (1.2.4-Triazol-1 -yl l · 1 - (2.4 - dichlorophenoxy) - 3,3 - dimethyl - butan - 2 - one are suspended in anhydrous ether and mixed with ethereal hydrochloric acid Solution 1. The ether is distilled off in vacuo and the residue that remains is recrystallized from isopropanol.

The l- (1,2,4-triazol-1-yl) -l- (2,4-dichlorophenoxy) -3-dimethyl-butan-2-one hydrochloride obtained shows

a melting point of 153 ° C.

Example 2 CI- / ~~ VO-CH-CO-C (CH ₃ I ₃ · HCl

^

11.2 g (0.033 mol) of 1-bromo-1- (2,4-dichlorophenoxy) -3,3-dimethyl-butan-2-one and 9.9 g (0.15 mole) 1,2,4-triazole are dissolved in 80 ml of acetonitrile and refluxed for 48 hours. After that the solvent Distilled off in vacuo, the residue taken up in 150 ml of water and the aqueous solution three times extracted with 40 ml of methylene chloride each time. The organic phase is then used twice Washed 150 ml of water each time, dried over sodium sulfate and distilled.

The oil obtained as a residue is fractionally recrystallized from a little ether, initially 1 g of a product with a melting point of 145 ° C., which was not identified as a by-product, was obtained and then 7.6 g (70% of theory) 1 - (1,2,4-triazol-1-yl) -1 - (2,4-dichlorophenoxy) -3.3-dimethyl-butan-2-one with a melting point of 65 ° C.

17.7 g (0.05 mol) 1,1-bis (4-chlorophenoxy) -3,3-dimethyl-butan-2-one are intimately mixed with 5.9 g (0.055 mol) of 1,2,4-triazole hydrochloride, within one hour heated to 220 ° C and at this temperature Leave for 30 minutes; the split off 4-chlorophenol comes to the boil.

After cooling, 100 ml of 10% sodium hydroxide solution are added, which is covered with 2C0 ml of ether would. The ether phase is separated, three times with 30 ml of 5% sodium hydroxide solution each time and twice with each Washed 50 ml of water. After drying over sodium sulfate, the solvent is reduced in vacuo distilled off. The oily residue is taken up with 100 ml of anhydrous ether and added to this solution Introduced 0.055 mol of hydrogen chloride. This creates a precipitate, which after standing overnight is filtered off and washed with ether.

22 Ol 063

7.3 g (46% of theory) of I- (1,2,4-triuzole-I) are obtained -yl) -1 - (4-chlorophynoxy) -3,3-dimethyl-bulan-2-one hydrochloride from melting point 103 to 105 C.

The starting compound l, l-bis (4-chlorophenoxy) -3.3-dimethyl-butan-2-one is made as follows:

6.5 g (0.2 mol) of 80% sodium hydride are suspended in K) OmI anhydrous acetonitrile, und.bei Room temperature is 27 g (0.21 mol) of 4-chlorophenol in 50 ml of acetonitrile with stirring and cooling added dropwise.

After the evolution of hydrogen has ceased, a further 27 g (0.105 mol) of IJ-dibromoO ^ -dimcthylbulan-2-one are added (Manufactured according to Organic Synthesis 10, p. 12) added with stirring and cooling. Then slowly heat to the boil! and refluxed for 12 hours.

After cooling, the solvent is distilled off in vacuo and the residue is boiled with it hot ethyl acetate, add activated charcoal, filter, boil again briefly and distill the solution initially in a vacuum, after the solvent has passed over in a high vacuum.

54 g (76.5% of theory) of 1,1-bis (4-chlorophenoxy) -3,3-dimethyl-butan-2-one are obtained from the boiling point Kp.o.i 150'C. The viscous oil continues to solidify some time.

Example 3

N-

(IN

NVl /

O-CH-CO

18.0 g (0.05 mol) <..- bromine- <..- (2,6-dichlorophenoxy) -acetophenone and 15 g (0.22 moles) of 1,2,4-triazole become dissolved in 120 ml of acetonitrile and refluxed for 48 hours. After distilling off the solvent the residue is taken up in 400 ml of water in vacuo. This aqueous solution is extracted with methylene chloride as described and the organic phase is washed twice with 100 ml of water each time, then dried over sodium sulfate and the solvent is distilled off in vacuo. The oily residue obtained crystallizes at Heating with ether.

After recrystallization from ethylene chloride, 7 g (40% of theory) </ i- (1,2,4-triazol-1-yl) - in - (2,6 - dichlorophenoxy) - acetophenone with a melting point of 166 "C.

The <»- bromine) - {2,6-dichlorophenoxy) -acetophenone used as starting material is made by condensation of 2,6-dichlorophenol with m-chloroacetophenone and bromination of the resulting m- (2,6-dichlorophenoxy) acetophenone made in the usual way and has a melting point of 58 "C.

Example 4

(CH ₃ J ₃ C

39 g (0.12 mol) of 1-bromo-H4-tert-butylphenoxy) -3,3-dimethyl-butan-2-one and 24 g (0.35 mol) 1,2,4-triazole are dissolved in 240 ml acetonitrile and 24 hours heated to boiling under reflux. The solvent is then distilled off in vacuo, the Ice water is added to the residue and the mixture is extracted three times with 40 ml of methylene chloride each time. After detaching the organic phase is washed twice with 200 ml of water each time, over sodium sulfate

ίο dried and the solvent is distilled off in vacuo.

The residue is recrystallized from ligroin. 26 g (69% of theory) of I- (1,2,4-triazole-1) are obtained - yl) -1 - (4-tert-butylphenoxy) -3,3-dimethyl-butan-2-one with a melting point of 115 "C.

The i-bromine-1 used as the starting material - (4 - tert - butylphenoxy) - 3,3 - dimethyl - butan - 2 - one (Melting point 50 ° C) is by condensation of p-tert-butyl-phenol with A-bromopinacol-2-one and then Obtained bromination.

Example 5

N-η H N

CI- <f VOC- C-C (CH ₃ ) ₃

19.0 g (0.05 mol) of 1-bromo-1-phenyl-H4-chlorophenoxy) -3,3-dimethy] -butan-2-one are dissolved in 120 ml of acetonitrile, then 12 g (0.175 mol) of 1,2,4-triazole added and the solution heated under reflux for 12 hours. After distilling off the solvent 200 ml of ice water are added in vacuo. The mixture is then used four times 50 ml of methylene chloride each time extracted, the organic phase separated and three times with 50 ml of water each time washed. It is dried and the solvent is distilled off in vacuo. The oily residue is recrystallized from ligroin.

5.3 g (29% of theory) 1-phenyl-1 - (4 - chlorophenoxy) -1 - (1,2,4-triazol -1-yl) -3,3-dimethyl-butan-2- are obtained on from melting point 130 ⁰ C.

The starting material l-phenyl-l- (4-chlorophenoxy) -3,3-dimethyl-butan-2-one is made as follows:

From 38 g (0.3 mol) of benzyl chloride and 7.3 g (0.3 mol) of magnesium in 300 ml of anhydrous ether, the Grignard connection established. For this purpose, 21 g (0.25MoI) pivalonitrile in 100 ml anhydrous ether was added dropwise and refluxed for 3 hours.

After cooling, the reaction mixture is poured into 1.5 liters of ice water, the ether phase is separated off, discarded and the aqueous phase stirred on the water bath for 2 hours. The mixture increases gradually take on an oily consistency. The oil is extracted several times with 250 ml of methylene chloride, the organic phase washed with water, dried and subjected to vacuum distillation.

22 Ol 063

This gives 40.5 g (92% of theory) 1-phenyl-3,3-dimethyl-butan-2-one with a boiling point of bp, _K H6 to 88 "C.

17.6 g (0.1 mol) of 1-phenyl-.VVdimethyl-butan-2-one are dissolved in 100 ml of carbon tetrachloride, plus 5 ml (0.1 mol) of bromine with stirring and reflux added dropwise and heated to boiling for an hour. After cooling and distilling off the solvent 25.4 g of 1-bromo-phenyl-3,3-dimethyl-butan-2-one are obtained in quantitative yield from melting point 38-42 "C.

A solution of 25.4 g (0.1 mol) of I-bromo-1-phenyl-

3,3-dimethyl-butan-2-one in 50 ml of Hssigester is at the boiling point to a solution of 12.85 g (0.1 mol) 4-chlorophenyl and 2.3 g (0.1 mol) sodium in KK) ml Ethanol dripped. After refluxing for 12 hours, the precipitated sodium bromide is filtered off while hot. The filtrate is distilled in vacuo and the remaining solid residue of ligroin recrystallized 20.2 g (67% of theory) 1-phenyl-1 - (4-chlorophenoxy) -3,3-dimethyl-butan-2-one are obtained with a melting point of 103 C.

The compounds listed in Table I below are prepared analogously.

Table I.

Tl
IN

R ¹ - Ο — C — Υ — R ^J R ²

Example R ¹

R-

R ¹ melting point. (. '

CO

CO

65 to 70 viscous oil

Cl

CO

101 to 104

C (CH ₃ J ₃ CO

110

C (CH ₃ J ₃ CO

186

C (CH ₃ J ₃ CO

110

C (CH ₃ I ₃

C (CH ₃ J ₃ CO

CO

89 to 92

Bp 0.3 torr / 160

continuation

Example R ¹

K ²

28

Melting point, C.

CH,

CH (CH ₃ J ₂ -

17 O ₂ N-

18 F ₁ C-19

25 Cl-

H H H

H H H H

// V

CH,

CH ₃

CH ₃

C (CH,).,
C (CH ₃ J ₃
C (CH,).,

C (CH ₃ ).,
C (CHj).,
C (CHj) ₃

QCHj) ₃

C (CH ₃ ).,
C (CH ₃ J ₃
QCHj) ₃
CH ₃

CO CO CO

CO CO CO CO

80 76 94 to

129

106

105 to

70 to

CO Hydrochloride: 120 CO viscous oil CO viscous oil CO 125 to 131

CO

viscous oil

Cl-

CH,

CH,

CO

CO

CH (CH ₃ J ₂ CO

viscous oil viscous oil 115

CH ₃

CH (CH ₃ J ₂ CO

viscous oil

continuation

Example R ¹

Cl

Cl

CI

CH ₃ CH ₃

CH ₃

Cl

Cl

Cl

Cl

Cl

CI

R ² ! <■ '

CH ₃ CH (CH ₃ J ₂ CO

CO

CO

CO

HC (CH ₃ ) j CO

HC (CH ₃ J ₃ CO

HC (CH ₃ I ₃ CO

<^^ C (CH ₃ J ₃ CO

HC (CHj) ₃

CH ₃

CO

CO

CO

HC (CH ₃ J ₃ CO

HC (CH ₃ I ₃ CO

30th

Melting point. ("

viscous oil

98

102

viscous oil

62

ρ ,,., (Fp. 76)

po (fp. 71)

Hydrochloride

75

Hydrochloride 78-81

Hydrochloride

142 to

114

CH ₃

continuation

Example R ¹ No.

43 CI

CH ₃

44 Cl

CH,

CI

CF,

CF ₃

H ₇ N-

O ₇ N-

// X

Cl Cl

49 cl

Cl

Cl Cl

5>

Cl

K- R '

HC (CH ₃ ) ₃

H. C (CH ₃ J ₃

32

. C (CH ₃ J ₃ CO

HC (CH ₃ J ₃ CO

HC (CH ₃ J ₃ CO

HC (CH ₃ J ₃ CO

C (CH ₃ J ₃ CO

HC (CH ₃ J ₃ C (OH) ₂

HC (CH ₃ ) ₃ CO

CO

HC (CH ₃ J ₃ CO

HC (CH ₃ J ₃ CO

CO

Schmcl / punk

88 to

101

135 to 13)

74 to

122 to

C (CH ₃ J ₃ C = NOH

206

65 to

94 to

87

74

125

continuation R- 22 Ol 063 Y I.
34 I. 33 Bcispid R ¹
No. H CO I. 55 Cl - <\ ~~ Y- R- ' Melting point. C "|
ϊ Cl C (CH ₃ J ₃ 82 to 84 I. O ₂ N H CO I. 56 \ / ~ CH ₃ H QCH ₃ ,., CO 154 I. ₅₇ HO ₂ ^ Jy. I. Cl H C (CH ₃ ), CO f
100 to 104 58 CI - <^ V H CO 59 Cl ^ \ Jy ^ - H C (CH ₃ )., CO Sulfate 141 60 Π— <ζ ~ \ - H C (CH ₃ )., CO Nitrate 140Zs. 61 Cl- / V- C (CH ₃ J ₃ 1,5-naphthalene
disulfonate 270-273
Zs. Cl H C (CH ₃ J ₃ CO Nitrate 129 133 62 Cl - <^ V- \
Cl H C (CH ₃ J ₃ CO Sulphate 145-148 63 Cl- ^ Λ— Cl H C (CH ₃ J ₃ CO 1,5-naphthalene
disulfonate 250 Zs. 64 o _2N _ </ "\ v_ H CO 65 O ₂ NO H C (CH ₃ J ₃ CO Hydrochloride
126-130 66 O ₂ N- / V- H QCH ₃ J ₃ CO Sulfate 169-170 67 O ₂ N - / V- H C (CH ₃ )., C = NOH Nitrate 140-141 68 Cl - <^ ~ V- C (CH ₃ )., 1,5-naphthalene
disulfonate 255 Zs. C (CH ₃ J ₃ 194 to 205

22 Ol 063

36

continuation

Example K ¹

No.

69

70

72 73

! 74

76

77

78

79

80 81

82

Cl

Cl

9-

CH,

Br

NO ₂

K-

H H

H H H

H H

C (CH ₃ I ₃ CO

C (CH ₃ I ₃ CO

C (CH ₃ I ₃ CO

C (CH ₃ I ₃ CO

C (CH ₃ I ₃ CO

C (CH ₃ I ₃ CO

C (CH ₃ J ₃ CO

CO

C (CH ₃ J ₃ CO

QCH ₃ J ₃

QCH ₃ I ₃

C (CH ₃ I ₃
C (CH ₃ I ₃

CO

co

co co

Schrncl / punkl. C.

C (CH ₃ I ₃ CO

Hydrochloric! 150 to

107 to

Hydrochloride 142 bis

70 to

73 to

79 to

90 to

110 to

107

145 to

Tris-phosphate 124 bis

Citrate 101 to sorbinate 99 to

Methyl sulfonate oil

37

continuation

Example R "

87 Cl

H
H
H

C (CH,)., C (CHj) ₃ C (CH ₃ ).,

C (CH ₃ ).,

co co co

38

Melting point. C.

Hydrochloride 143 bis

Sulphate 128 to Nilral 130 to

Bis-phosphate 89 bis

204

Claims (1)

22 Ol 063 claims: 1. 1,2,4-triazole derivatives of the general formula I. N- Il N