Means for controlling phytopathogenic fungi

(42) Date of commencement of the patent: 15. 7.1989 (45) Date of issue: 12. 2.1990 (51) Int.Cl.⁵

DD1N 43, ^ 76 // C070 263/26 (62) Excreted except for No 4160/80

<td>(30) Priority:</td><td>(73) Patent inmate:</td>

<td>16. 8.1979 G8 7928603 claims. 25. 4.1980 GB 8013721 claims. 25. 4.19C0 GB 8013720 claims. 25. 4.1900 GS 8013719 claims.</td><td>SAFDOZ-ERFIMXJNGEN ADMINISTRATIVE COMPANY MBH A-1235 VIENNA (AT).</td>

<td>(56) citations;</td><td></td>

<td>US-A-3884671 US-A-2902356</td><td></td>

(54) NUTS TO COMBAT PHYTOPATHOGENIC MUSHROOMS

QQ • Ή

O

C \

CO

ΙΛ

No. 389801

The invention relates to agents for controlling phytopathogenic fungi, characterized in that it contains as active ingredient a compound of the formula &lt;

in which R j is a radical of the formula

<img file="AT389801B_D0001.tif" />

(I).

Ry and Rg are independently (1-4C) -alkyl, halogen or (1-4C) -alkoxy,

Rg is hydrogen, (1-4C) -alkyl or halogen,

R 10 is (1-4C) alkoxy (1-4C) alkyl, (1-4C) alkylthio (1-4C) alkyl, 2-furyl, 2-tetrahydrofuryl, 1-imidazolylmethyl, 1-pyrrazolylmethyl, 2 Tetrahydrofuryloxymethyl, 2-tetrahydropyranyloxymethyl or halo (1-4C) alkyl and

Rj, R₄, Rj, Rg independently of one another denote hydrogen or (1-4C) -alkyl.

If each of the radicals Rg, R₄, Rj, Rg, Ry, Rg or Rg is an alkyl radical or contains an alkyl radical (eg in an alkoxy radical) which is mainly (1-3C) -alkyl, e.g. Methyl, ethyl, n-propyl or

1- Propyl. If Ry or Rg are each halogen, stands for F, CI, Br or I, mainly F, CI or Br, especially CI or Br or especially Ci. If Rg or Rjq is in each case halogen or halogen, they stand for F, Cl, Br or I, especially for F, Cl or Br, in particular for CI or Br.

Preferred halogenated 2-furyl radicals in the meaning of Rjq are monohalogenated 2-furyl radicals, eg. 5-chloro-2-fluoro and 5-bromo-2-furyl.

Preferred halogenated (1-4C) -alkyl radicals in the meaning of Rjq are chloro (1-4C) -alkyl or bnomo (1-4C) -alkyl, e.g. Chloromethyl, bromomethyl and C2HgCHBr-,

Preferred halogenated 2-terahydrofuryl radicals in the meaning of Rjq are monohalogenated

2- Tetrahydrofuryl, especially monochlorinated or monobrominated 2-Tetrahydrofurylreste, z. For example, 5-chloro-2-tetrahydrofuryl.

Preferred (1-4C) -alkoxy- (1-4C) -alkyl radicals in the meaning of Rjq are (1-3C) -alkoxymethyl, especially CH-jOC ^ - and C2H5-OCH2 '.

Preferred (1-4C) alkylthio (1-4C) alkyl radicals in the meaning of Rjq are (1-3C) -alkylliomethyl, for example ch₃s-ch.

Rjq particularly represents (1-4C) alkoxy- (1-4C) alkyl, 2-furyl or 5-halo-2-furyl.

In the event that one of the radicals R₃ or R₄ is (1-4C) -alkyl, the other is especially for

Hydrogen.

If one of the radicals Rj or Rg is (1-4C) -alkyl, the other radical is especially hydrogen.

A preferred group of active compounds of the formula I are compounds of the formula

-2Nr. 389801

<img file="AT389801B_D0002.tif" />

wherein R₁₀'' CHj-OCH ^, -CH2-OC2H5,2-furyl or 5-halo-2-furyl Ry and Rg 'independently of each other -CHp Cl or Br and R9 * are H, Cl, Br or -CHj, where R₇'and Rg' advantageously have the same meanings.

The compounds of the formula I can be obtained by reacting a compound of the formula

Ri-N

NH-C-G

<img file="AT389801B_D0003.tif" />

II

II.

<img file="AT389801B_D0004.tif" />

wherein Rp R₂, R4, Rj, Rg, and Rjq have the meanings given above and

Y is halogen, intramolecularly condensed

Y is advantageous for chlorine or bromine, especially for chlorine.

The intramolecular condensation can be carried out by methods known per se. The reaction is exothermic. The reaction may be carried out in an anhydrous medium using an ether such as dimethoxy fl uant as a solvent or a hydrocarbon such as toluene or another solvent which is inert under the reaction conditions

The reaction temperature is not critical and may be approximately between 0 ° and 100 ° C. Since the reaction is exothermic, the reaction is conveniently started at room temperature to allow the reaction temperature to rise gradually.

The reaction is conveniently carried out in the presence of an acid binding agent such as sodium hydride, sodium amide or a sodium alcoholate such as sodium ethylate. The intramolecular condensation can also be carried out in an aqueous organic two-phase system in the presence of an inorganic base, for. For example, sodium hydroxide and optionally with a catalytic amount of a PhasenUBERiagungskatalysators be performed.

The organic phase may suitably comprise any inert water immiscible solvent, such as hydrocarbons or halogenated hydrocarbons, e.g. As xylene, toluene. ortho-dichlorobenzene or dichloromethane.

Suitable phase transfer catalysts are ammonium compounds such as benzyltrimethylammonium bromide, quaternary phosphonium compounds such as benzyltriphenylphosphonium chloride and Crown^.'Äther, like 18-'Crown45.

The compounds of formula II are new. They can be obtained by acylation of a compound of the formula

II

Rj-NH-NH-C-G o _{B &lt;/}K_{6 X /}r₄

Ό-CCY

ΠΙ.

wherein Rp R3, R4, Rj, Rg and Y have the meanings given above, with a compound of formula

No. 389801 Ο

II • z

IV.

wherein Rjq has the meanings mentioned above and

Z is halogen, especially chlorine or -O-CO-Rjq. wherein R jq has the meanings given above, can be obtained.

Suitable solvents for this Acylierungsrcaktion hydrocarbons, such as toluene or halogenated hydrocarbons, such. For example, chlorobenzene. The reaction is conveniently carried out at temperatures from about 50 ° to about 100 ° C, e.g. B. performed at 80 ° C.

The compounds of formula ΙΠ can be prepared by reacting a compound of formula

Rj-NH-NHY

V, wherein Rj has the abovementioned meanings, with a compound of the formula

O

II xc-σ

<img file="AT389801B_D0005.tif" />

CCY

VI, wherein R₃, R4, R ^, Rg and Y have the meanings given above, and

X is halogen, especially chlorine.

This reaction may be carried out at a temperature of about 0 ° to 10 ° C in water or in an organic solvent which is inert under these reaction conditions, conveniently in the presence of a base, e.g. As an organic amine or Natriumhydrogencarbonai,

The starting compounds and reagents used in the methods described above are either known or, if not known, may be prepared according to the methods described herein or by methods known in the art.

The compositions according to the invention which contain compounds of the formula I as active component have a useful and excellent fungicidal activity, in particular against phytopathogenic fungi, especially against fungi from the class Oomycctcs as shown by a significant effect in the following tests:

Example 1:

<img file="AT389801B_D0006.tif" />

Young potato plants planted in pots (at a 3 to 5 leaf stage) are sprayed with an aqueous suspension containing 0.003% (w / v) of a compound of formula I, e.g. B. 2-Methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (Compounded according to the formulation in Example I) Two hours later, the treated plants are treated with a spore suspension of Inoculated Phytophthora infestans.

The treated plants are then transferred to a tent in which there is a 100% relative atmospheric humidity at an ambient temperature of 16 ° C and a day length of 16 hours

The fungicidal activity is determined 4 to 5 days later by comparing the treated plants with untreated but similarly inoculated plants.

While a considerable fungicidal infestation is observed during the control, the inventive minerals allow a significant inhibition of the infestation without any signs of phytotoxicity βfiisHiclli

<img file="AT389801B_D0007.tif" />

Young pot-planted vine seedlings (in a 3 to 6 stage of blue) are sprayed with an aqueous suspension containing 0.0008% (w / v) of a compound of formula I, e.g. B. 2-Methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxyzolidinyl) -acetamide (composed according to the formulation of Example I). Two hours later, the plants so treated are inoculated with a suspension of spores of Ibasmaprarviticola and the treated plants are then transferred to a tent in which 100% relative atmospheric humidity is maintained at a temperature of 15 to 22 ° C with a Tagcslänge of 16 hours.

The control of the disease is estimated for 6 days of inoculation by comparing the treated with the untreated similarly inoculated plants. While in control a handsome

-4Nr. 389801 fungicidal infestation is observed, the agents according to the invention allow a substantial inhibition of the infestation without signs of phytotoxicity.

Bsispi.gl3;

Young pot-planted vines (in a 3 to 6 stage of blue) are inoculated in the same manner as in Test Method B except that the compound of formula I is 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo). 3-oxazolididinyl) -acetamide (composed according to the formulation of Example I) is applied only 3 days after inoculation. The incubation conditions were the same as in the test method B. The curative effect is estimated in the same way as in Test Method B. While a considerable fungicidal attack is observed during the control, the agent according to the invention permits one. significant inhibition of infestation.

Example 4:

Eradicative action against Plasmopara viticola.

The method for determining the eradicative effect is as described in Test Method C, with the exception that the treatment is not performed until 6 days after the inoculation when sporulation on the lower leaf surface is already visible.

The eradicative effect was determined 7 days after the application of 0.012% of the compound 2-methoxy-N- (2,6-dimcthylphenyl) -N- (2-oxo-oxazolidinyl) -acctamide (composed according to the formulation of Example I). There is a clear eradicaüve effect on the already sporulating zones found.

P-cispisL5;

Translocation in treated leaves of Rcbc seedlings.

Any selected leaves of Rcbcnsämlingcn be sprayed with an aqueous suspension containing 0.012% of a compound of formula 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3oxazolidinyl) acctamide (composed according to the formulation of 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 viticola, and then the leaves are incubated in a tent having 100% atmospheric relative humidity, under the conditions described in Test Method B. Although only the lower half of the leaves has been treated as described above, considerable control can be observed throughout the leaf surface. The same effect can also be observed over the whole leaf if only the upper half of the leaves were inoculated. This test method thus shows that the 2-methoxy-N- (2,6-dimethyl-phenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide (composed according to the formulation in Example I) is distributed over the whole leaf, even if the spraying took place only at the base or even at the top of the leaf, (i.e. H. the agent is translocated both acroally and basipetally).

Example 6: (in vivo)

Pivudium ananidermatum is cultured 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 ingredient in a concentration of 10 to 160 ppm (e.g. B. 10.40 and 160 ppm calculated per volume of substrate). The substrate is placed in 5 cm diameter pots, 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 compared to untreated, analogously inoculated comparison plants. The compound of Example 1 used in the wettable powder formulation according to Formulation Example 1 gives complete control. Similar tests with beets and sugar beet give comparable results. ₍

A particularly effective fungicidal activity is found according to the tests listed above with agents containing one of the following compounds of formula Ia as active ingredient:

wherein R₂'-COCH₂-OC₂H5,

Ry and Rg 'are each -CHss and Rp' are hydrogen;

or wherein R₂'-CO- (2-furyl),

Ry and Rg'each part -CH₃ and Ry are hydrogen;

No. 389,801 or wherein R₂ -CO- (5-bromo-2-furyl),

R₇'and Rg' each -CH₃ and Rp 'are hydrogen;

or wherein R₂ -CO-CH₂-O-CH₃.

R and Rg * each represents CI and Rg 'represents hydrogen;

or wherein R₂-CO-CH₂-O-CH₃.

R₇'and Rg' each -CH₃ and Rg'3-Br and especially with the compound of formula Ia, wherein R₂ -CO-CH₂-O-CH₃.

R₇'and Rg' each -CH₃ and Rq 'is hydrogen.

The agents according to the invention are suitable for controlling phytopathogenic fungi, in particular the class of Oomycetes in plants, in seeds or in the soil.

Mushrooms of the class Oomvcctcs. against which the agents according to the invention are particularly effective, those of the genus Phytophthora in plants such as potatoes, tomatoes, tobacco, citrus, cocoa, gum, apples, strawberries, crops and ornamental plants, eg. B. Phytophthora infestans in potatoes and tomatoes;

in the genus Peronospora in plants such as tobacco, eg. B. Peronospora tabacina in tobacco;

in the genus Pseudopemosoora in plants, such as hops and cucumber, z. B. Pseudopcronospora humuli in hops;

in the Gattimg Breroia in plants, such as lettuce or salad, z. B. Breroia lactucae in lettuce; in the genus Pythium. which the rotting and decaying of the roots in a large number of

Causes crops, for example, in crops, sugar beets, ornamental plants and Nadclbäumen, z. B.

in the genus Sclcrosnora in plants such as sorghum and maize, e.g. B. Sclerospora sorghis in sorghum.

In the application, the amount of the agent to be used depends on various factors, such as the fungus species to be controlled, the time and application, and the amount and type of compound of formula I.

In general, satisfactory results are obtained when the agents are in place, e.g. B. in crops or in the soil in amounts which contain 0.05 to 5 kg, advantageously between 0.1 to 3 kg of a compound of formula I per hectare of surface to be treated.

In the case of a treatment in the preparation of seeds or seeds, eg. B. as a seed coat, satisfactory results are obtained when used in an amount of about 0.05 to 05, advantageously from about 0.1 to 0.3 g of a compound of formula I per kilo of seed.

Advantageously, the compositions according to the invention contain, in addition to a compound of the formula I, other fungicides which are active against phytopathogenic fungi against which the compounds of the formula I do not have sufficient activity.

Particularly suitable are agents which, in addition to a compound of the formula I (component a), contain an active constituent (component b) selected from one of the components:

bp a Kupferiungicid or a component b₂) 3alpha, 4,7,7alpha-tetrahydro-N- (trichloromethanesulphenyl) phthalimide or N (trichloromethanesulphenyl) phthalimide or bj) Mancozcb or Manch.

Examples of copper fungicides which are suitable for use as component (bj) are cupric carbonate, cupric calcium sulfate, cupric calcium chloride, tetracupric oxychloride, bordeaux mixture, burgundy mixture, cuprous oxy, copper ID. hydroxide, copper (II) oxychloride or also coupling complexes, such as copper triethanolamine hydroxide of the formula [CuN (CH₂CH₂OH)₃]-(OH)₂, or bis (ethylenediamine) copper (II) sulfate, and mixtures thereof, in particular copper oxide, copper (II) oxychloride, copper hydroxide and a mixture of copper (II) calcium sulfate and cupric oxychloride.

No. 389801

Mancozeb and Manch are internationally accepted names (Pesticide Manual, 5th ed. By H. Martin and

CR Worthing, pages 76, 281, 328 and 329). Mancozeb is an amorphous complex fungicide based on

Maneb andZineb. Some: manganese ethylene bis (dithiocarbamate)

Zincb: zinc ethylene bis (dithiocarbamate)

The preferred weight ratio of a component a) to a component b) is in a range from 1: 1 to 1:10, in particular 1: 2 to 1:10 and very particularly from 1: 2 to 1: 7.

The erfindungsgmäßen agents suitably contain agriculturally acceptable carriers or solvents or other Hilfsmiuel. Such compositions resp. Formulations also form part of the invention.

They can be used in both solid and liquid forms, e.g. B. in the form of a wettable powder, an emulsified concentration, a water-dispersible suspension concentration (flowable), a dust powder, granules, a depot form which gradually releases the activity of the active compound, which formula may contain the usual carriers , as well as solvents and / or other auxiliaries. Such compositions may be ascertained by conventional methods.

The formulations according to the invention which comprise components a) and b) can be obtained, for example, by mixing these two components a) and b), mainly with a carrier and other ingredients customary in the formulations.

In particular, formulations which are used in the form of a spray, such as. Water-dispersible or wettable powders, may contain surface-active compounds as wetting or dispersing agents, e.g. Example, the condensation product of formaldehyde with naphthalene sulfate, 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 of active substance, said active substance consisting of either at least one compound of formula I or mixtures of compounds of formula I, if desired, with other active ingredients, such as fungicides, for. B. a component b), as described above.

Concentrated forms of the compositions generally contain between about 2 and 80, principally between about 5 and 70 percent by weight of active. Liquid formulations of formulations generally contain from 0.01 to 20, preferably from 0.01 to 5 parts by weight of active ingredient.

The invention is illustrated by the following examples, wherein parts are parts by weight, percentages by weight and temperatures are in degrees Centigrade.

Fommylationbcispicl 1

Wettable powder.

Parts 2-Mcthoxy-N- (2,6-dimethyl-phenyl) -N- (2-oxo-3-oxazolidinyl) -acetamide are milled with 2 parts of lauryl sulfate, 3 parts of sodium lignosulfonate, 45 parts of finely ground kaolinite until the middle Particle size is less than 5 microns. The wettable powder thus obtained is diluted before use with water to a concentration between 0.01 to 5% of active substance. The spray liquid thus obtained can be used both as a foliar spray and as a root penetration spray.

Formulation Example 2

granules

On 49.5 parts of quartz sand in a Roticrmischer 0.5 parts of a binder (a nichtionischcs surfactant) are sprayed on and mixed vigorously. 5 Parts of 2-methoxy-N- (2,6-dimcthylphenol) -N- (2-oxo-3oxazolidinyl) -acctamide in powder form are added and vigorous mixing is continued to give a granular formulation having a particle size on the order of 0.3 to 0.7 mm. The granules can be entered into the soil near plants to be treated.

Formulation Examples 3 to 6

Wettable powders.

<td></td><td colspan="4">percentages by weight</td>

<td>example</td><td>3</td><td>4</td><td>5</td><td>6</td>

<td>Component a) ü)</td><td>12.65</td><td>6.25</td><td>12.5</td><td>6.25</td>

<td>Copper-o-oxychloride (- 56% copper)</td><td>47</td><td>47</td><td></td><td></td>

<td>Copper oxide (~ 88% copper)</td><td></td><td></td><td>29</td><td>29</td>

<td>sodium lauryl sulfate</td><td>1</td><td>1</td><td>1</td><td>1</td>

<td>lignin sulfonate</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>kaolin</td><td>29.5</td><td>35.75</td><td>-..... 39 ^,.,</td><td>45.75</td>

No. 389801 (1) e.g. For example, 2-methoxy-N- (2,6-dimcthylphenyl) -N- (2-oxo-3-oxazolidinyl) acetamide.

All components of the formulations are mixed, ground and remixed according to known methods.

Formulas 7 to 9

Wettable powders.

<td></td><td colspan="3">percentages by weight</td>

<td>example</td><td>7</td><td>8th</td><td>9</td>

<td>Component a) ^</td><td>25</td><td>12.5</td><td>6/25</td>

<td>Component b)₂</td><td>50</td><td>50</td><td>50</td>

<td>Natriumoleoylmethyltaurid</td><td>2</td><td>2</td><td>2</td>

<td>Condensation product of sodium alkylnaphthalene</td><td></td><td></td><td></td>

<td>sulfonate and formaldehyde</td><td>5</td><td>5</td><td>5</td>

<td>silica gel</td><td>5</td><td>5</td><td>5</td>

<td>kaolin</td><td>13</td><td>25.5</td><td>31.75</td>

(1) z. 2-methoxy-N- (2,6-dimethylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamine. ,

(2) z. B. N- (trichloromethanesulphenyl) phthalimide.

All components of the formulations were mixed, ground and mixed again by known methods

Formulation Examples 10 to 1?

Wettable powders.

<td></td><td colspan="3">percentages by weight</td>

<td>Examples</td><td>10</td><td>11</td><td>12</td>

<td>Component a) ^</td><td>25</td><td>12.5</td><td>6.25</td>

<td>Component b)₃</td><td>50</td><td>50</td><td>50</td>

<td>sodium lauryl sulfate</td><td>1</td><td>1</td><td>1</td>

<td>lignin sulfonate</td><td>4</td><td>4</td><td>4</td>

<td>silica gel</td><td>5</td><td>5</td><td>5</td>

<td>kaolin</td><td>15</td><td>27.5</td><td>33.75</td>

(1) z. 2-methoxy-N- (2,6-dimcthylphenyl) -N- (2-oxo-3-oxazolidinyl) -acetamind.

(2) z. B. Mancozeb.

The formulations are obtained by mixing the components, then grinding the mixture and remixing, all operations being carried out by known methods.

Hrstellungsvorschrift 1:

2-methoxy-N- (2,6-dimcthylphenyl) -N- (2-oxo-3-oxazolinidyl) -aceiamid.

11.8 g (0.037 mol) of 2-chloroethyl 2- (methoxy-acetyl) -2- (2,6-dimethylphenyl) -hydrazinecarboxylate are added portionwise at room temperature to a suspension consisting of 2.0 g of sodium hydride (in the form of an approx 55% mineral oil) and 100 ml of absolute toluene under a nitrogen atmosphere. The reaction temperature increases with this addition up to 40 °. After completion of the addition, the mixture is stirred for 30 minutes without cooling and then cooled to 10 ° C. The unreacted sodium hydride is then destroyed with ethanol, the resulting solution is washed with water and washed with MgSO 4₄ dried and the solvent removed in vacuo. The residue left as the Tilelverbindung which is recrystallized from ethanol. The colorless title compound is obtained in crystal form with a melting point of 103 ° to 104 °.

No. 389801

Manufacturing instructions la:

2-Chlorüthyl2- (mcthoxyacctyl) -2- (2₁6-dimcthylphcnyl) -hydrazincarboxylat.

The starting compound used in Preparation 1 can be obtained as follows:

A mixture consisting of 14.7 g (0.06 mol) of 2-chloroethyl 2- (2,6-dimcthylphcnyl) -hydrazinecarboxylate and 16.2 g (0.1 mol) of methoxy-acetic anhydride [(CH 2 -OCO 2 CO ^ O] are dissolved in 1 ml of absolute toluene

After cooling, the solution is washed with water, then with a 5% aqueous NaCOy solution and then again with Wrsser. The solution is mixed with MgSO4₄ dried and then the solvent removed in vacuo, the Titelvcrbindung is obtained according to Preparation Procedure la.

2-Chloroethyl 2- (2,6-dimcthylphenyl) -hydrazinecarboxylate.

To a mixture consisting of 127 g (0.935 mol) of 2,6-dimethylphenylhydrazine, 102.5 g (1.3 mol) of pyridine and 400 ml of water is added at 0 ° to 5 '133.5 g (0.935 mol) of chloroformic acid Beta-chloroethyl ester added. After completion of the addition, the mixture is stirred at room temperature for 2 hours, the precipitate formed is filtered off with water and dried. The title compound thus obtained is recrystallized from toluene to give colorless crystals which melt at 74-75 °.

A preferred alternative method of production regulations 1, 1a and 1b can be carried out as follows:

ÜCRjl, gllnnss.yotsglirift2:

2-methoxy-N- (2,6-dimcthylphenyl) -N- (2-oxo-3-oxa7.olidinyl) -acciamid.

A mixture of 236.1 g (0.75 mol) of 2-chloroethyl 2-methoxyacetyl 2- (2,6-dimethylphenyl) hydrazinecarboxylate, 375 ml of xylene and 187 ml of water are stirred while cooling from the outside; To this mixture is added in portions 82.5 ml (0.82 mol) of an aqueous solution of sodium hydroxide (containing approximately 0.4 g NaOH per ml) and keeping the internal reaction temperature at approximately 20 °. After complete addition, the mixture is stirred for 1 hour at 20 ° and for 2 hours at 0 °. The residue is filtered off, washed with 150 ml of water and dried; the weakly colored solid title compound having a melting point of 102 ° to 103 ° is obtained.

feglhinEsyQrschriflJb;

2-chloroethyl 2- (mcthyloxyacetyl) -2- (2,6-dimcthyl-phenyl) -hydrazinecarboxylate,

A mixture consisting of 200 g (0.825 mol) of 2-chloroethyl 2- (2,6-dimethylphcnyl) hydrazinecarboxylate and 500 ml of xylene, is heated to 80 ° and heated to 80 ° to a solution of 2-methoxy-acctylchlorid in 250 ml of xylene [prepared by treating 73.5 g (0.826 mol) of 2-methoxyacetic acid dissolved in 250 ml of xylene with 107.1 g (0.9 mol) of thionyl chloride at 80 ° for 2 hours]. The mixture is heated for 30 minutes at 80 ° and then worked up the product according to the instructions in preparation la

Pre-setting procedure 2b

2-ChIoräthyl-2- (2,6-dimethylphenyl) -hydrazincarboxylat.

A mixture consisting of 17.7 g (0.1 mol) of 2,6-dimethylcancylhydrazine hydrochloride, 21.2 g (0.2 mol) of sodium carbonate in 50 ml of water and 50 ml of xylene is stirred at room temperature for 30 minutes and then cooled to 5 °. 14.3 g (0.1 mol) of 2-chloroethylchloramecanoate are then added over one hour, keeping the temperature at 5 °. The mixture is stirred at 5 ° for an additional hour and added at the end of 100 ml of water. The precipitate thus formed is filtered off, washed with water and dried. The work-up is carried out according to the instructions in Preparation Specification Ib.

In a similar manner as described in the addition formulas 1 and 2, the following compounds of the formula I can be prepared.

No. 389801

<td>No.</td><td>^R3</td><td>^R4</td><td>^r5</td><td>^R6</td><td>^R7</td><td>^r8th</td><td>^r9</td><td>^Ri0</td><td>melting point (O °</td>

<td>3</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₉OC_?H &lt;;</td><td>62-4</td>

<td>4</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>CI</td><td>H</td><td>ch₂och₃</td><td>99-100</td>

<td>5</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>'Ö</td><td>190-1</td>

<td>6</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-C1</td><td>ch₂och₃</td><td>107-9</td>

<td>7</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂SCH,</td><td>113-5</td>

<td>8th</td><td>H</td><td>H</td><td>H</td><td>H</td><td>€ H₃</td><td>ch₃</td><td>H</td><td>ch₂ci</td><td>134-6</td>

<td>9</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>CI</td><td>H</td><td>CH2C1</td><td>135-6</td>

<td>10</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>CI</td><td>H</td><td>Ό</td><td>166-7</td>

<td>11</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂SC₄H₉(N)</td><td>oil</td>

<td>12</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>CI</td><td>H</td><td>CH₂SC₄H₉(N)</td><td>oil</td>

<td>13</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch-c₂H₅1 He</td><td>123-4</td>

<td>14</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>ch-ch₃1 CI</td><td>147-8</td>

<td>15</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂br</td><td>143-4</td>

<td>16</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>'Π'^8th'</td><td>119-20</td>

<td>17</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CI</td><td>CI</td><td>H</td><td>ch₂och₃</td><td>107-9</td>

<td>18</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CI</td><td>CI</td><td>H</td><td>ch₂ci</td><td>142-4</td>

<td>19</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CI</td><td>CI</td><td>H</td><td>'Ö</td><td>173-4</td>

<td>20</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>^CH2^N3</td><td>139-41</td>

<td>21</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-CH₃</td><td>ch₂och₃</td><td>oil</td>

<td>22</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>^C2^H5</td><td>H</td><td>ch₂ci</td><td>oil</td>

<td>23</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-C1</td><td>ch₂gch₃</td><td>90-2</td>

<td>24</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Br</td><td>ch₂och₃</td><td>96-7</td>

<td>25</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Br</td><td>ch₂ci</td><td>182-3</td>

<td>26</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>3-Br</td><td>ö</td><td>145-8</td>

<td>27</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>br</td><td>4-CH₃</td><td>CH, OCH,</td><td>125-6</td>

<td>28</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>br</td><td>4-CH₃</td><td>ch₂ci</td><td>124-6</td>

<td>29</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>sr</td><td>4 &lt;H₃</td><td>tu</td><td>193-4</td>

1Λ

No. 389801

<td>No.</td><td>^R3</td><td>r₄</td><td>^R5</td><td>^R6</td><td>^R7</td><td>^r8th</td><td>^R9</td><td>^R10</td><td>melting point (° C)</td>

<td>30</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>choch₃1 ch₃</td><td>904</td>

<td>31</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>Ό</td><td>149-52</td>

<td>32</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-CI</td><td>ch₂ci</td><td>resin</td>

<td>33</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-C1</td><td>Ώ</td><td>164-5</td>

<td>34</td><td>H</td><td>H</td><td>H</td><td>H</td><td>c₂H₅</td><td>^C2^H5</td><td>H</td><td>ch₂och₃</td><td>109-12</td>

<td>35</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>CH₂OC₃H₇(N)</td><td>oil</td>

<td>36</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td rowspan="2">ch₂och₃</td><td>107-8</td>

<td>37</td><td>H</td><td>H</td><td>CH-s</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>79-80</td>

<td>38</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>H</td><td>Z = rN^CH2^NkJ</td><td>56</td>

<td>39</td><td>H</td><td>H</td><td>H</td><td>H</td><td>c₂H₅</td><td>c₂H₅</td><td>H</td><td>Ώ</td><td>1424</td>

<td>40</td><td>H</td><td>H</td><td>H</td><td>H</td><td>c₂H₅</td><td>c₂H₅</td><td>H</td><td>ch₂ci</td><td>88-9</td>

<td>41</td><td>H</td><td>H</td><td>H</td><td>H</td><td>br</td><td>br</td><td>H</td><td>ch₂och₃</td><td>150-2</td>

<td>42</td><td>H</td><td>H</td><td>H</td><td>H</td><td>CI</td><td>CI</td><td>4-CI</td><td>ch₂och₃</td><td>128-9</td>

<td>43</td><td>H</td><td>H</td><td>H</td><td>H</td><td>^C2^H5</td><td>^C2^H5</td><td>4-CI</td><td>CH, OCH,</td><td>114-6</td>

<td>44</td><td>H</td><td>H</td><td>H</td><td>H</td><td>br</td><td>CI</td><td>4-CH₃</td><td>CH, OCH,</td><td>1314</td>

<td>45</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>C₂H₅</td><td>H</td><td>ch₂cch₃</td><td>96-8</td>

<td>46</td><td>H</td><td>H</td><td>H</td><td>H</td><td>ch₃</td><td>ch₃</td><td>4-Br</td><td>ch₂och₃</td><td>137-8</td>

No. 389801