DE3202487A1 - FUNGICIDAL PHENYL HYDRAZINE CARBOXYLATES, THEIR PRODUCTION AND USE - Google Patents

Description

32Q2A87

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O-O. EfEREN..MANUFACTURING AND USE

The present invention relates to compounds for controlling phytopathogenic fungi.

More specifically, the present invention relates to compounds of Formula I.

where R 1 is H, C 1, alkyl, halogen or C 1 -C 4 alkoxy, R 1 is C 1 -C 4 alkyl, halogen or C 1 -C 4 alkoxy, R _{3 is} H, C _{1 -C 4} alkyl or halogen, R 1 _{4 represents} C _1-4 alkyl,

R ₅ for C, ₄ alkyl, unsubstituted or substituted by halogen, CN or SCN,

and Rg for H; C, g-alkyl or Cp-g-alkenyl, unsubstituted or substituted by halogen; C2_ _ß alkynyl; C ~, cycloalkyl; C1-4 cycloalkyl-C1-4 alkyl; C ₂ _gEpoxyalkyl; Phenyl, Phenylene ^! or phenyl-Cp_ ₃ alkenyl in which the phenyl radical is unsubstituted or substituted by 1 to 3 substituents from the series C 1 -C 4 alkyl, C _1-4 alkOXy, halogen, NO ₂ , phenyl or phenoxy; C1-4 alkoxy-C1-4 alkyl; Cj_ ₄ alkylthio-C, ₄ alkyl; 2-furyl; 2-tetrahydrofuryl; halogenated 2-furyl; halogenated 2-tetrahydrofuryl; 1-imidazolylmethyl; 1-pyrrazolylmethyl; 2-tetrahydrofuryloxymethyl; 2-tetrahydropyranyloxymethyl.

If R ₁ , R _? or R ₃ is or contains an alkyl group (for example alkoxy), this is preferably C ₁ -alkyl, for example methyl, ethyl, jv-propyl or 2-propyl.

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If R _{1, R 2>} R ₃ , R ₅ and / or Rg is halogen, or contains ^ halogen means F, Cl, Br, I, preferably F, Cl or Br, more preferably Cl or Br, in particular Cl.

R- and R ₂ are preferably in the 2- and 6-position of the phenyl group to which they are attached.

R ₃ is preferably Cl or Br.

R. is preferably C, JUkyl, more preferably C, pAlkyl, especially CH _3.

When Rj- denotes substituted C1-6 -alkyl, it is preferably monosubstituted.

If R _{5 stands} for a C 1-4 alkyl group, it is preferably C, more preferably C 1-4 alkyl, in particular CH-.

Preferred C, _ _g alkyl significances of R are _ß Cp ^ alkyl, in particular C ₃ alkyl.

Preferred C ₂ _J \ lkenyl meanings of Rg are Co ^ alkenyl, in particular C ₃ alkenyl.

Preferred C _3-7 cycloalkyl meanings of Rg are C 1-6 cycloalkyl, especially C 1-4 cycloalkyl.

If Rg is halogenated 2-furyl, this is preferred monohalogenated, e.g. 5-chloro-2-furyl and 5-bromo-2-furyl.

If Rg is C-, haloalkyl, this is in particular C1-6 chloroalkyl or C1- bromoalkyl, for example CH ₂ Cl, CHgBr and C ₂ H ₅ CHBr.

If R _{ß is} halogenated 2-tetrahydrofuryl, this is preferably monohalogenated, in particular monochlorinated or monobrominated, such as, for example, 5-chloro-2-tetrahydrofuryl.

If R _{6 is} C,, alkoxy-Ci ^ alkyl, this is preferably C, _ ₃ -

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Al koxymethyl, in particular CH ₃ OCH ₂ and C ₂ H ₅ OCHP.

If R _{g is} C, .Alkylthio-C, ^ alkyl, this is preferably C ₁₃ -alkylthiomethyl, for example CH ₃ SCH _2,.

Rg is preferably C, g-alkyl, C ₂ _galkenyl, C ₃₇ cycloalkyl, Cj _ ^ - alkoxy-C, .alkyl, 2-furyl or 5-halo-2-furyl, particularly preferred is C _1-4 AlkOXy-C _1- ^ lkyl.

A preferred group of compounds are compounds of the formula Ia

R, ¹

N-COOR, ¹

^ö Ia

wherein R, ¹ and R ₂ ', independently of one another, are CH ₃ , Cl or Br, R ₃ ^{1 is} H, Cl, Br or CH ₃ ,
R _{5 is} ¹ C _1-4 alkyl

and R _{6 is} ¹ CH ₂ OCH ₃ , CH ₂ OC ₂ H ₅ , 2-furyl or 5-halo-2-furyl.

Particularly preferred meanings of R 'are CH ₉ OCH-, or CH ₉ OC ₉ Hj ..

The invention also relates to the preparation of the compounds of Formula I by N-alkylating a compound of Formula II

II

wherein R ₁ , R ₂ , R ₃ , R ₅ and R _{g have the} above meaning with the aid of an alkylating agent of the formula III

. R ₄ X ₁ in

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where R, has the above meaning,

X-j is a leaving group that is cleavable among the N-alkylation reaction conditions.

The N-alkylation according to the invention can be carried out analogously to known ones Procedures are carried out. Suitable alkylating agents are e.g. the corresponding alkyl halides, especially the alkyl iodides, Alkyl esters of sulfonic acids, e.g. methanesulfenic acid esters (Mesylates) or tosylates, or dialkyl sulfates, e.g. dimethyl sulfate. The compound of the formula II is expediently used as a salt, e.g. as N-alkali metal salt, especially as Na or K salt, which by reacting the corresponding compound of the formula II with a strong base, for example an alkali metal hydride, amide or alcoholate, in an inert under the reaction conditions Solvents such as a hydrocarbon such as toluene. Such salts are expediently heated, preferably to the reflux temperature manufactured. The N-alkylation according to the invention can then carried out by adding an alkylating agent to the reaction mixture which contains the compound of the formula II in salt form, such as, for example, C, alkyl iodide is added. The alkylating agent is preferred used in excess. The N-alkylation is expedient " with heating, e.g. at a temperature of 80 to 150 °.

The compounds of the formula I can be isolated from the reaction mixture in which it is formed, analogously to known methods.

The compounds of the formula II are new. You can by acylating the compounds of formula IV

NH-NH-COOR ₅ IV

wherein R ,, R ₂ , R ₃ and R _{5 have the} above meaning,

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by means of a compound of the formula V

O
R ₆ -CZ- V

where R _{ß has the} above meaning and

Z stands for halogen, in particular Cl, or OCORg, in which R _{ß has the} above meaning.

Suitable solvents for the acylation are, for example, hydrocarbons such as toluene or halogenated hydrocarbons such as chlorobenzene. The reaction is conveniently carried out at a reaction temperature from about 0 ° to about 120 °, for example at room temperature, optionally in the presence of a base such as triethylamine or Pyridine.

The compounds of the formula IV can be obtained by reacting the compounds of formula VI

NH-NH ₂ VI

where R ,, R _? and R- have the above meaning with compounds of the formula VII

O
X ₂ -C- OR ₅ VII

wherein R _{5 has the} above meaning and

X _{2 represents} halogen, in particular Cl, can be obtained.

The reaction is for example carried out at a temperature of about 0 ° to about 40 ⁰ C., conveniently at room temperature, in water or in an inert organic solvent under the reaction conditions, advantageously in the presence of a base, for example a

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organic amine or sodium bicarbonate.

The starting compounds described in the above processes and Reagents are known or can be prepared analogously to processes described here or to known processes.

The compounds of the formula I have a useful fungicidal effect, in particular against phytopathogenic fungi, especially against fungi from the class of the Oomycetes such as, inter alia, a significant fungicidal effect in the test against Phytophtora infestans in potatoes (test description see test A) and against Plasmopora vi * ti cola in vines (test description see test B) with test concentrations of 8 ppm to 125 ppm, e.g. 8 ppm, 32 ppm and 125 ppm. Representative compounds also show interesting activity against Pythium aphanidermatum after soil treatment with concentrations of 10 to 160 ppm, for example 32 and 125 ppm (see test C).

The compounds of formula I are essentially non-phytotoxic when the fungicidally effective dose is used in plants attacked by such fungi, and are of particular importance because of them -systemic, curative and eradicative effects (test D, E and F),

Test method A - fungicidal effect on Phytophthora infestan see p

Plant young potatoes planted in pots (in a 3 to 5 leaf stage) are sprayed to runoff with an aqueous spray suspension which contains 0.01% to 0.0008% (weight / volume) of a compound of the formula I, for example formulated according to formulation example I. Two hours later the treated plants are inoculated with a spore suspension of Phytophthora i nfestans (approx. 10 sporangia / ml), the treated plants are then transferred to a tent in which a 100% relative atmospheric humidity at an ambient temperature of 16 ° C prevails with a day length of 16 hours.

Control of the infestation is assessed by 4 to 5 days later

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Compare with untreated, but similarly oculated plants (for Test results with representative compounds: see in Table I below).

Test method B - fungicidal effect on Plasmopara viti cola

Young vine seedlings (in a 3 to 6 leaf stage) in pots are sprayed with an aqueous spray suspension containing 0.01% to 0.0008% (weight / volume) of a compound of the formula I, formulated for example according to formulation example I. Two hours later the plants treated in this way are inoculated with a suspension of about 10 sporangia / ml of spores of Plasmopara viticola and the plants treated in this way are then transferred to a tent in which a 100% relative atmospheric humidity and a temperature of 15 to 22 ° C prevails in daylight of 16 hours / day.

Disease control is 6 days after inoculation estimated by comparing the treated plants with untreated, similarly inoculated plants (for test results with representative compounds, see Table I).

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TABLE I : Fungicidal activity in % of the control

130-3917 O)

Test.A 32 8th Test B 32 8th - PPm 125 70 20th 125 70 30th • Compound 90 - (2) - 90 - - 1 50 - - 50 - - 2-3 100 40 20th - 100 60 2-6 80 - - 100 - - 2-14 50 - 50 - - 2-22 50 - - "- 70 50 35 70 70 20th 80 100 50 36 90 100 37

'' visual determinations, 100% is complete control of the Infestation and 0% is no control of the infestation.

(2) -: not checked

Test method C - soil treatment

Pythium aphanidermatum is cultivated in a sterile mixture of sand and corn flour (97: 3 V / V) to which water is added in a ratio of 1: 4 (V / V), for 4 days at 25 ° C. The fungus is then mixed with a semi-sterile mixture of peat and sand and then treated with a suspension containing the active substance in a concentration of 10 to 160 ppm (eg 10, 40 and 160 ppm calculated per volume of substrate). The substrate is placed in pots 5 cm in diameter in which cucumber seeds are sown. The pots are incubated at 24 ° C. and 60-70% relative humidity in an incubation room for 7 days, and the number of healthy plants that have emerged is compared with that in untreated, analogously inoculated comparative

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pots compared. The compound according to Example 1, used in Form of formulation example 1, gives a control of 90% with a test concentration of 125 ppm and 80% with a test concentration of 32 ppm. Tests analogous to test C with beets and sugar beets give comparable results.

Test Method D - Systemic Effect

Translocation in treated vine leaves. Cut vine leaves are sprayed with an aqueous suspension which contains 0.012% of a compound of the formula 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (composed according to formulation example I) treating only the lower half of these leaves. Two hours after the treatment, the whole leaf is inoculated with a spore suspension of Plasmopara v iticola , and then the leaves are incubated in a tent which has 100% atmospheric relative humidity under the conditions as described in test method B. Although only the lower half of the leaves were treated as described above, considerable control can be observed over the entire leaf surface. The same effect can also be observed over the entire leaf if only the upper half of the leaves was covered. This test method accordingly shows that the 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide (formulated according to formulation example I) is translocated both acro- and basipetal.

Test method E - Curative fungicidal effect against Plasmopara viticola

Young vine seedlings planted in pots (in a 3 to 6 leaf stage) are inoculated in the same way as according to test method B, except that the compound of the formula I 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidiny1 ) acetamide (formulated according to formulation example I) only takes place 3 days after the inoculation. The incubation conditions are the same as for test method B. The control of the disease is carried out in the same way as with the

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Test method B determined. With the test substance a sizable one becomes Control of fungicidal infection observed.

Test method F - Eradicative fungicidal effect against PTasmopara vi ti coIa. .

The procedure to determine this type of effect is in the test method E with the exception that the treatment is only carried out 6 days after the inoculation, when the spore formation is already visible on the lower leaf surface.

The control of the disease is 7 days after application of the spray liquid certainly. With e.g. 0.012% of the compound 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-oxazolidinyl) -acetamide (formulated according to formulation example I) will have a stopping effect on the already identified sporulating zones.

A particularly effective fungicidal activity is observed with the compounds of the formula Ia in which R, ¹ and R ₂ 'are CH ₃ , R ₃ ^{1 is} H, 3-Cl or 3-Br, R ₅ ^{1 is} CH ₃ and R _g ' stand for CH ₂ OCH _3.

The compounds of the formula I according to the invention are accordingly suitable for use as fungicides.

The invention therefore also relates to a method for combating phytopathogenic fungi, in particular the class of the Oomycetes in plants, seeds or in the soil with an amount of a compound of the formula I exhibiting a fungicidal effect.

Fungi of the class Oomycetes , against which the method according to the invention is particularly effective, are those of the order Phytophthora in crops such as potatoes, tomatoes and other types of vegetables, tobacco, citrus fruits, cocoa, apples, strawberries, and ornamental plants, for example Phytophthora infestans in potatoes and tomatoes;

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of the order Plasmopara in plants such as grapevines and sunflowers, e.g. Piasmopara viticola in grapevines.

of the order Peronospora in plants such as tobacco, for example Peronospora tabacina in tobacco;

of the order Pseudoperonospora in crops such as hops and cucumbers, for example Pseudoperonospora humuli in hops; of the order Bremia in crops such as lettuce, for example Bremialactucae in lettuce;

of the order Pythium , which causes rotting and rotting of the roots in a large number of plants, for example vegetables, sugar beets, ornamental plants and conifers, for example Pythium aphanidermaturn in sugar beet;

of the order Scelerospora in plants, such as in sorghum and maize, for example Sclerospora sorghis in sorghum.

When applying the inventive method, the amount to be used depends on various factors such as the type of to-control species of fungi, time and route of administration, and the amount and type of the compound used of the formula I.

In general, satisfactory results are obtained when im The habitat of the fungi, e.g. in crops or in the soil, are used in quantities of the order of 0.05 to 5 kg between 0.1 to 3 kg, in particular from 0.1 to 0.5 kg of one Compound of formula I per hectare of the treated site, where the procedure is repeated if necessary.

In the case of use as a dressing agent for treating seeds, satisfactory results are obtained when in a Amount from about 0.05 to 0.5, advantageously from about 0.1 to 0.3 g of a compound of the formula I is used per kilo of seed.

Depending on requirements, the compounds of the formula I can be used in combination with other pesticides, e.g. fungicides, bactericides,

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Insecticides, acaricides, herbicides or plant growth regulators, can be used to increase the effect or to expand the spectrum of action.

Fungicides which are particularly suitable for use in combination with the compounds of the formula I are one or several compounds from the range of copper fungicides, captan, folpet, mancozeb or maneb.

Examples of copper fungicides which are suitable for use in combination with compounds of the formula I are copper (II) carbonate, copper (II) calcium sulfate, copper (II) calcium oxychloride, tetra-copper (II) oxychloride, Bordeaux mixture, Burgundy Mixture, copper oxide, copper (II) hydroxide, copper (II) oxychloride or copper complexes, such as copper triethanolamine hydroxide of the formula [CuN (CH ₂ CH ₂ OH) ₃ XOH) ₂ , or bis (ethylenediamine) copper II- sulfate, as well as mixtures thereof, in particular copper oxide, copper (II) oxychloride, copper (11) hydroxide and a mixture of copper (II) calcium sulfate and copper (II) oxychloride.

"Captan", "Folpet", "Mancozeb" and "Maneb" are international ■ accepted names for protective fungicides that are effective against fungal diseases of the foliage. (Pesticide Manual, 5th Ed. By H. Martin and CR. Worthing, pages 76, 281, 328 and 329).

The compounds of formula I are expediently in the form of fungicides Compositions used in conjunction with agriculturally acceptable diluents. Such compositions also form part of the invention. In addition to a compound of the formula I, you can use other active ingredients as the active compound such as fungicides.

They can be used in both solid and liquid forms v / ground, e.g. in the form of a wettable powder, an emulsion concentrate, a water-dispersible suspension concentrate ("flowable"), a dust powder, a granulate, a depot form

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these forms containing the usual diluents. Such compositions can be prepared by customary methods, for example by mixing the active ingredients with a diluent and, if necessary, further formulation agents, such as, for example, surface-active substances. By diluents are meant liquid or solid, agriculturally acceptable materials which are suitable for bringing the active substance into a form that is easier or better to apply, or for diluting it to a useful or desired degree of effectiveness. Examples of such diluents are talc, kaolin, diatomaceous earth, xylene or water.

In particular, formulations which are used in the form of a spray such as water-dispersible concentrations or wettable powders, surface-active compounds such as Contain wetting or dispersing aids, e.g. the condensation product of formaldehyde with naphthalene sulfonate Alkyl aryl sulfonate, a lignin sulfonate, a fatty alkyl sulfate, an ethoxylated alkylphenol or an ethoxylated fatty alcohol.

In general, the formulations contain from 0.01 to 90 percent by weight Active ingredient, from 0 to 20% surfactants acceptable in a fungicide and 0.99 to 10% diluent, where the active substance consists either of at least one compound of the formula I or of mixtures of compounds of the formula I. with other active ingredients such as fungicides.

Concentrated forms of the compositions generally contain between about 2 and 80, mainly between about 5 and Weight percent of active ingredient. Use forms of formulations generally contain from 0.01 to 20, advantageously from 0.01 to 5 parts by weight of active ingredient.

The invention can be illustrated by the following example games, where the parts are parts by weight, the percentages are percentages by weight and the Temperatures are given in degrees Celsius.

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Formtilation Examples I - ' Wettable Powder

50 parts of methyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate are ground with 2 parts of lauryl sulfate, 3 parts of sodium! Igninsulfonate and 45 parts of finely ground kaolinite until the mean particle size is smaller than 5 microns. The wettable powder obtained in this way is diluted with water to a concentration between 0.01 to 5% of active substance before use. The spray liquid obtained in this way can be used both as a foliar spray and as a soaking spray on roots.

Formulation Examples 2 - Granules

On 94.5 parts of quartz sand in a rotary mixer, 0.5 part of a binder (a nonionic surfactant) is sprayed and the whole thing vigorously mixed. 5 parts of 1-methyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate in powder form are added and vigorous mixing is continued, a formulation in Granulate form is obtained with a particle size in the order of magnitude from 0.3 to 0.7 mm. The granules can be mixed with the soil near the plants to be treated. be applied.

Formulation examples 3 - Emulsions concentrate

25 parts of a compound of the formula I, for example the compound according to the following Example 1, 65 parts of acetone, 10 parts of the Reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate are mixed intensively until a homogeneous solution is obtained. The emulsion concentrate obtained in this way is before the Use diluted with water.

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End connection example 1

Methyl 1-methyl-2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate.

0.73 g of NaH and 7.82 g of methyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) hydrazine carboxylate in 100 ml of abs. Toluene is refluxed for 3 hours with stirring. The cooled reaction mixture is transferred to a pressure cylinder together with 9.52 g of CH ₃ I and heated to 110 ° for 20 hours. The reaction mixture is diluted with ether, washed with water, dried, evaporated and chromatographed over silica gel (chloroform / acetone 9: 1). The oily title compound crystallizes from diethyl ether / petroleum ether, melting point 72-74 °

Example 2

Analogously to Example 1, using the appropriate Compounds of the formula II and the alkyl iodides of the formula III, the obtained the following compounds (Table A). If the connection is noticed as OeI, it is characterized by the Rf value on Silica gel, with a), b), c), d), e) and f) being the flow agent used is, where a) n-hexane / ethyl acetate 1: 1, b) r ^ -hexane / ethyl acetate 1: 2, c) n-hexane / ethyl acetate 2: 1, d) n-hexane / ethyl acetate 1: 3, e) jfv-hexane / acetone 4: 1, f) chloroform / acetone 9: 1 and ^ g) diethyl ether represent.

TABLE A

130-3917

At-,
game *1 π ^R 3 ^aJ 3 * 5 • ^R 6 character
ization
Smp./Rf 2-1 2-CH ₃ η H κ / ^ 3
-CH ^ό
"^ CH ₃ -CH ₂ OCH ₃ 0.32 / f) 2-2 Il Il ti η -CHJCtT
^ * 3 η 0.18 / e) 2-3 Il η π - ^ 3 97-99 ° 2-5 Il ⁵ ~ ^αί 3 π -CH ₃ CH
OT ^J
^ CH ₃ . -CH ₂ OCiJ ₃ 0.24 / a) 2-6 ti H π α -CH ₃ "Φ 133-135 ° 2-7 It η π η π -ClJ ₂ OCH ₃ 0.2 / a) 2-8 Il Il η η π -CH ₂ OCH ₃ 0.24 / b) 2-9 U η η H It -CH ₂ (X ₂ H. 0.18 / a) 2-10 II Il η -C ₂ H ₅ Il 0.24 / a) 2-11 Il 11 π π Il -CH ₂ COi ₃ 0.25 / b) 2-12 Il 3-Cl η η π -CH ₂ CC ₂ H ₅ 0.25 / a) 2-13 π 4-Cl n CH ₃ π 110-112 ° 2-14 Il G-Ql ₃ π Il -CH ₂ OCH ₃ 0.18 / a) 2-15 2-C_H_
2 D 6-C ₂ H ₅ η η 0.35 / g)

*1 * 2 6-C ₂ H ₅ - 20th - ^R 5 130-3917 ^R 6 character
ization
Smp./Rf By S
play 2-C ₂ H ₅ 4-Cl Il ^R 4 CH ₃ -CH ₂ OC ₂ H ₅ O.28 / a) 2-16 η It η -3 η 103-110 ° 2-17 H η η ■ η π -9 0.31 / a) 2-18 Π ft Il η π -CH ₂ OCH ₃ O.24 / a) 2-19 If ti It -S ^H 5 H -CH ₂ OC ₂ H ₅ 0.34 / a) 2-20 It π K η η "Φ 109-111 ° 2-21 2-OCH ₃ H η ti Il -CH ₂ CGi ₃ 0.09 / a) 2-22 Il H η "^ ₃ η • φ 128-130 ° 2-23 It Π η η It -ς> 0.2 / d) 2-24 ft η It Il U - = «2-0 O.28 / a) 2-25 3-CF ₃ π η M. η -CH ₂ OCH ₃ 0.13 / a) 2-26 η η η π η • Φ 0.29 / a) 2-27 Il η η η π 0.21 / a) 2-28 ■ I η G-Cl It π -CH ₂ -Q 0.37 / a) 2-29 2-C1 4-Cl It π η -CH ₂ OCH ₃ 0.32 / a) 2-30 π π Il η It 162-165 ° 2-31 It K Il H « - <? 0.28 / a) 2-32 ti π Il Il 0.30 / c) 2-33 It

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130-3917

By S
play ^R l ^R 2 ^R 3 ^R 4 " ^R 5 • ^R 6 character
ization
Smp./Rf 2-34 2-CH ₃ 6-CH ₃ H CH ₃ CH ₃ CH ₂ CH ₂ CH ₃ O.33 / a) 2-35 2-CH3 5-CH ₃ H CH ₃ CH ₃ CH ₂ = CHCH ₃ . 87-90 ° 2-36 2-CH ₃ 3-Br 6-CH ₃ ^CH 3 CH ₃ CH = CHCH ₃ 0.18 / a) 2-37 2-CH ₃ 3-Br 6-CH ₃ CH ₃ CH ₃ CH ₂ OCH ₃ 0.22 / a) 2-38 2-CH 3-Br 6-CH ₃ CH ₃ CH ₃ CH ₂ CH ₂ CH ₃ 0.4 4 / b) 2-39 2-CH ₃ 6-CH ₃ H CH ₃ CH ₃ CH ₂ - (O) O.35 / a)

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Interconnections

Example A - Methyl 2- (2,6-dimethylphenyl) hydrazine carboxylate

To a solution of 34 g of 2,6-dimethylphenylhydrazine, 27.6 g of pyridine and 83 ml of water are 23.6 g of methyl chloroformate at room temperature added dropwise within 15 minutes. After adding 83 ml of water, the mixture is stirred for 3 hours at room temperature. The reaction mixture is mixed with ether, acidified with 2N HCl and the organic phase washed with water, dried and evaporated. The solid residue crystallizes from ether / petroleum ether, 80-81 °.

Example B - Methyl 2- (methoxyacetyl) -2- (2,6-dimethylphenyl) - • hydrazine carboxylate

To a solution of 16.9 g of methyl 2- (2,6-dimethylphenyl) hydrazine carboxylate in 115 ml of abs. Toluene, 10.4 g of methoxyacetic acid chloride are added dropwise over the course of 20 minutes. The suspension is stirred for 3 days at room temperature, then evaporated and the solid residue is crystallized from acetone / petroleum ether, melting point 171-172 °.

Claims (9)

SANDOZ-PATENT-GMBH -, K- Case 130-3917 Loerrach Claims ί \ .J compounds of the formula I wherein R ₁ is H, C ^ alkyl, halogen or C _1-4 A ^R 2 ^C l-4 ^{All <yl>} halogen or C ^ alkoxy, R ₃ is hydrogen, C, alkyl or halogen, ^R 4 ^is C _1-4 AIlCyI ₁ ^R 5 ^c i-4 ^{Alky1 is} unsubstituted or substituted by halogen, CN or SCN, and Rg H; C, g-alkyl or Cp-g-alkenyl is unsubstituted or substituted by halogen; C ₂ _g alkynyl; C _3-7 CyClOaIkyl; C ₃₇ cycloalkyl-C 1,., Alkyl; C ₂ _gEpoxyalkyl; Phenyl, phenyl-C, _3- alkyl or phenyl-C _2- ^ alkenyl in which the aromatic radical is unsubstituted or substituted by 1 to 3 substituents in the series consisting of C, ₄ alkyl, C, JUkoxy, halogen, NO ₂ , phenyl or Phenoxy; Cj _-4 alkoxy-C j_ ₄ alkyl; C ₁ _ ₄ A1 kyl thi 0-C _1- ^ l kyl; 2-furyl; 2-tetrahydrofuryl; halogenated 2-furyl; halogenated 2-tetrahydrofuryl; 1-imidazoylmethyl; 1-pyrrazolylmethyl; 2-tetrahydrofuryloxymethyl; 2-tetrahydropyranyloxymethyl. 2. A compound according to claim 1 of the formula Ia 3 2 ύ ι A δ / - 2 - 130-3917 Yes ^K 3 R ₀ ¹ H ² O wherein R. ¹ and R ^ ^{1 are} independently CH-, Cl or Br. R ₃ ^{1 is} H, Cl, Br or CH ₃ , R ₅ 'C _1-4 A
and R ₆ 'is CH ₂ OCH ₃ , CH ₂ OC ₂ H ₅ , 2-furyl or 5-halo-2-furyl. 3. A compound according to claim 2 wherein R, ¹ , R ~ ', R ₃ ¹ , R ₅ ¹ and R' a) CH ₃ , CH ₃ , H, CH ₃ and CH ₂ OCH ₃ ,
resp. b) CH ₃ , CH ₃ , 3-Cl, CH ₃ and CH ₂ OCH ₃ or respectively. c) are CH ₃ , CH ₃ , 3-Br, CH ₃ and CH ₂ OCH ₃ . 4. Process for the preparation of a compound of the formula I according to Claim 1, characterized in that a compound of the formula II II wherein R _{1, R 2} , R ₃ , R ₅ and Rg have the meaning given in claim 1, with an alkylating agent of the formula III R ₄ X ₁ III wherein R _{4 is} given in claim 1. Has meaning, and X, a group which can be split off under the conditions of an N-alkylation, is alkylated. 5. Fungicide characterized by a content of a compound of Formula I according to claim 1, - 3 - 130-3917 6. The use of a compound according to any one of claims 1 to as a fungicide. 7. The use according to claim 6 against fungi of the class of the Oomycetes. 8. The use according to claim 7 against fungi of the order Phytophthora . Plasmopara or Peronospora . 9. A method of combating fungi, characterized in that a fungicidally effective amount of a compound according to any one of claims 1 to 3 is applied to fungi or their habitat.