SI7510893A8 - Process for preparing new anilides - Google Patents

Description

The present invention relates to a process for the preparation of novel anilides of formula I

in which they commemorate

R1 is an alkyl group of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen,

R 2 is hydrogen, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen,

R7 is hydrogen, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen,

R1 is hydrogen or methyl, wherein the total number of carbon atoms of the substituents R1, R2, R7 and R8 in the phenyl ring does not exceed 8, represent

X is a group -CH2- or -CH- in

I

CHj / ^R ”

Rj group -COOR 'or -CON.

\ _R ”.

wherein R ', R' and R '' independently of one another are hydrogen, methyl or ethyl, standing

Y for one of the groups

a) -S-C-NH2.H-Hal, in which Hal is an atom of haNH logene,

b) -O-R4,

c) -SR 'in which R 5 is optionally substituted by halogen atom alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms or optionally of halogen or alkyl of 1 up to 4 carbon atoms substituted benzyl or phenyl, or

Rs

d) -S-C-N II

R ₆ which is Rs and R, independently

With each other, alkyl having 1 to 4 carbon atoms, a process for the preparation of these compounds, as well as agents containing these compounds as active substances, and the use of these effective substances as microbicides.

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl as well as pentyl and hexyl, with their isomers, are to be understood as alkyl or allylic moieties of the alkoxyl group. Alkenyl e 3 to 6 carbon atoms, in particular allyl, methylalphyl and pentyl, should be mentioned. As alkynyl having 3 to 6 carbon atoms, mention is made in particular of prop-2-inyl: (ipropargyl) and but-2-inyl. .. ί

By halogen, which may also occur as a substituent in the hydrocarbon residues of R-t, is meant fluorine, chlorine, bromine or iodine.

We have now surprisingly found that the compounds of Formula I have, for practical purposes, a very favorable microbicidal spectrum for crop protection. For the purposes of the present invention, for example, as cultural plants, e.g. cereals, maize, rice, vegetables, sugar beet, soybeans, groundnuts, fruit trees, ornamental plants, and especially vines, hops, pumpkin plants (cucumbers, pumpkins, melons, watermelons), solanaceae, such as potatoes, tobacco lin tomatoes as well bananas, cocoa and natural rubber plants.

With the effective compounds of Formula I, the emerging fungus can be suppressed or destroyed on plants or plant parts (fruits, tubers, leaves, stems, tubers, roots) of these and related beneficial cultures, and these fungi can also be added to plant parts that grow later. Effective substances are effective against phytopathogenic fungi of Ascomycetes classes, e.g. Erysiphaceae, Basidiomvcotes, as chiefly ram, Fungi imperfecti, e.g. Moniliales, and in particular against the class of Phycomycetes belonging to Oomycetes, such as Phytophthora, Peronospora, Pseudoperonospora, Pythium or Plasmopara, - In addition, compounds of formula I have a systemic effect. They can further be used to treat seeds (fruits, tubers, grains) and plant seedlings for protection against fungal infections as well as against phytopallogenic fungi present in the soil.

As microbicides, preferred compounds of Formula I, in which R1 is methyl, stands for R? in the ortho position against the amine group and stands for methyl, ethyl or chlorine, represents -Χ-R, the -CH-COOR group

I

CH, or -CH-CON (R) (R '”) while they have

I ch ₃

Y, R7, R ", R ', R" and R' "indicated meaning.

These should be referred to as the group la compounds.

Of these compounds of group la, due to their effect, it is necessary to emphasize those in which, when | R7 is hydrogen, criterion, chlorine or bromine, Ra is hydrogen or methyl, R 'is methyl, R is hydrogen or methyl and R' is methyl or ethyl and in the calipers stands Y for one of the groups - 37 311 • -3 a ') -SC-NH2.HOI II

NH b ') -OR ₄ or c') -SR4, in which R4 is alkyl with 1 to 4 carbon atoms, allyl, chloroaryl, 3-methylallyl, propargyl, phenyl, 4-methylphenyl, 4-chlorophenyl, 2,4 -dichlorophenyl, 4-tert-butylphenyl, benzyl or 4-chlorobenzyl, d ') -SGN (R 5) (R 1), in which R 5 is S dich or methyl and R 1 is methyl.

These should be referred to as the group Ib of the compounds.

The microbicidally important group under this group Ib are those wherein R7 and R1 independently of one another are hydrogen, or methyl, R 'methyl, R' hydrogen, R '' methyl or ethyl, and in which Y stands for the group -OR4 or . -SIL in which R4 is methyl, ethyl, propyl, isopropyl, butyl, sec. butyl or tert .butyl.

These (refer to the group of Ic compounds.

The microbial ia important subgroup within Formula I is that of Formula Id

(Id) in which they represent

R1 alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or halogen,

R2 is hydrogen, alkyl of 1 to 3 carbon atoms or halogen,

X is a group -CH2- or -CH- and I

CHi

-S'C-NH2; H-Hal, in which Hal is the anion of halo

NH gene,

-S-R4 in which R1 represents alkyl of 1 to 6 carbon atoms or optionally halogen. or alkyl having from 1 to 4 carbon atoms substituted phenyl,

S

II

-S-C-N (Rs) (ID in which Rs and R1 independently of one another represent an alkyl radical of 1 to 4 carbon atoms.

A further group of preferred compounds for the regulation of plant growth are compounds of formula I in which R1 stands for methyl or ethyl, R2 stands in the ortho position against the amine group and stands for methyl, ethyl or chlorine, -Χ-R1 represents the group - CH2-CON (R) (R '' '), while Y stands for -SR' and Ri, R7, Ra, R 'and R' 'have the meanings indicated.

The regulation of plant growth should be understood first and foremost as a retardimo control of natural plant development, in particular the desirable reduction of plant size, especially height of growth. This decrease in growth is observed in mono- and dicotyledonous plants, especially in grasses, cereal crops, soybeans and ornamental plants.

The compounds of formula I are prepared either by the compound of formula II

R _7x J ΝΗ-Χ-Ft, / r ^R 2 (II) is acylated with a compound of formula III Hal'-CO-CH _r Y (III)

wherein in formulas II and III, residues R1 to R1, R7 and R1 and X have the meanings indicated in formula I, whereas Hal1 represents halogen, preferably chlorine or bromine.

Rj group -COOR 'or -CON

R ”

R 'in which R',

R ”and R” 'independently of one another are hydrogen, methyl or ethyl, and stands

Y for one of the groups

Metabolism can be carried out in the presence or absence of a substance in the reaction of inert solvents or diluents. For example, e.g. aliphatic or aromatic hydrocarbons, such as benzene, toluene, xylene, petroleum ether, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, - 37 311 - a

ethers and ester compounds, such as dialkylehri, dioxane, tetrahydrofuran, nitriles, such as acetonitrile, N, N-dialkylated amides, such as dimethsiformamide, anhydrous acetic acid, dimethylsulfoxide, ketones, such as methylethylketone, and mixtures of such solvents.

The reaction temperatures are between 0 and 180, preferably between 20 and 120 ° C. In many cases, it is advantageous to use acid or acid binding agents. condensing joints. As such, tertiary amines such as triacylamines, n, e.g. triethylamine, pyridine and pyridine bases, or inorganic bases such as oxides and hydroxides, hydrogen carbonates and carbonates of alkali and alkaline earth metals as well as sodium acetate. In addition, the excess (each of the aniline derivatives of Formula II) may serve as binding agents (acids in the first mode of operation).

The process of the invention can also be carried out without acid-binding agents, in some cases nitrogen conduction is accepted to expel the welded halogen. In other cases, the addition of dimethylformamide as a reaction catalyst is very advantageous.

The particulars of the preparation of intermediates of formula II can be summarized from the methods generally described in the preparation of anilinoalkanoic acid esters in J. Org. Chem. 30, 4101 (1965), Tetrahedron 1967, 487 and Tetrahedron 1967, 493.

Compounds of formula I in which X is a skuCH ₃ pin - * CH- contain an asymmetric carbon atom (*) and can be cleaved in the usual way into optical antipodes. The enantiomeric form D has a stronger microbicidal effect.

In the context of the invention, therefore, those compounds, their agents and their use, which relate to configuration D of Formula I are preferred. These forms D generally have a negative rotation angle when measured in ethanol or acetone.

For the preparation of pure optical antipodes, e.g. a racemic compound of formula VI

in which R 1, R 2, R 7 and R 5 are as defined in Formula I, and then in a manner known per se by means of an optically active base containing nitrogen, is converted to the uitrescent salt. By fractional crystallization of the salt, followed by the release of the Formula VI-enriched optical antipode D, optionally by repetition, including repeated repetition, of salt formation, crystallization and release of the α-anillinopropionic acid of the Formula VI. the steps are obtained in pure form D. From this, if desired, in a conventional manner, e.g. in the presence of hydrochloric or sulfuric acid, the optical configuration of the D ester underlying the formula II or the corresponding amine of the formula HN (R ”) (R”) of the formula III corresponding to an amide, preferably via an acid halide, is prepared with methanol or ethanol. As an optically active organic base, e.g. α-phenylethylamine.

Instead of fractional crystallization, the enantiomeric Form D of Formula VII can be prepared

also by having the amine group in natural L-alanitene in the presence of e.g. Hydrochloric acid or hydrobromide is diazotized, thereby exchanging with nitrogen and retention of the configuration to halogen, then optionally esterified with methanol or ethanol and then reacted with aniline of formula VIII

the predominantly inversion to the configurations D of formula VII (J. Am. Chem. Soc. 76, 6056). It is reasonable to prepare a foreign di amide of the formula R3-CON (R ”) (R '”). Independently of the cd of said optical isomerism, as a rule, atropisometry can be observed around the phenyl-N <axis in cases where the phenyl ring is substituted at least in the 2,6 position and at the same time asymmetrically against the axis of the axis, in the given example, also with the presence of other substituents. This phenomenon is conditioned by steric hindrance of the residues -X-Rj and -CO-CFhV introduced on the nitrogen atom.

Independently of said optical isomerism, in the case of R4 being alkenyl, the cis / trans isomorium may occur on the double bond.

- 37 311 -

Unless directional synthesis is carried out for isolation of the isosomer scavengers, the product is normally obtained as a mixture of two optical isomers, two atroPioisomers, two cis / trans isomers, or as a mixture of these possible isomers, a substantially more favorable fungicidal effect of the enantiomeric form D (compared to Form D, L or form L), but remains conserved and is not considered to be of significant value by the aitropotisomerism or isomers of cis / / trans.

The following examples are intended to provide a further explanation of the invention without limiting it. Temperature data refer to degrees Celsius. Unless otherwise stated, a racemic mixture is always intended to indicate an effective substance of formula I that may occur in optically active forms.

Example 1

Preparation

CH-COOCH (Compound No. 65)

C-CH_-O-CH _q ii z 3

N- (1'-Methoxycarbonyl-ethyl) -N-methoxyacetyl-23-dimethyl-6-ethylaniline

a) 100 g of 2,3-dimethyl-6-etilanlilina, 223 g of methyl 2-bromo _and p is _l ropionove acid and 84 g of sodium bicarbonate is stirred for 17 hours at 140 °, then cooled, diluted with 300 m'1 of water and extracted with diethyl ether. The extract was washed with a little water, dried over sodium sulfate, filtered and the ether evaporated. After distillation of excess 2-bromoproplic acid methyl ester, the product is distilled under high vacuum, boiling. 88 do

9075,3 Pa

b) 11 g in the sense of a) the ester obtained, 6.5 g of methoxyacetyl chloride, 2 ml of dimethylformamide and 250 ml of absolute toluene are stirred at room temperature for 3 hours and refluxed for 1 hour. After evaporation of the solvent, the crude was distilled in vacuo, boiling. 126 to 132710.7 However, if pure D-form of α- (2,3-dimethyl-6-ethylanilino) -prop (methyl acid acyl methyl ester is acylated with methoxyacetic acid or one of its reaction-capable derivatives, Form D of both otropoisomers (Compounds 65a and 65b).

In a manner analogous to example la), other intermediate products are prepared, for example, e.g. those of the formula Ha, with Ri in position 2, which are listed below.

R. r ₂ Rs -X-Rj Physical constant ch ₃ CHj H -CH (CHj) -COOCHj boil. 987107 Well CHj C; H ₅ H -CH (CHj) -COOCHj boiling point 88 to 9071.3 Pa CHj c ₂ h ₅ 5-CHj -CH (CHj) -COOCH _} boil. 96 to 9974 Pa CH CHj CHj 3-CHj -CH (CHj) -COOCHj boil. 8374 Pa 1457120 Well CHj CHj 4-CHj -CH (CHj) -COOCHj boil. 88 to 9075.3 Pa CHj c ₂ h ₅ 3-CHj -CH (CHj) -COOCHj boil. 88 to 90 ° / 5A Pa CHj H 4-CHj -CH (CHj) -COOCHj boil. 95 to 10072,7 Pa ' CHj H 5-CHj -CH (CHj) -COOCH ₃ boil. 106 to 108713.3 Pa CHj H 3-CH, -CH (CH3) -COOCH3 boil. 1467667 Well 4Z0C3H7 H H -CH (CH ₃ ) -COOCHj boil. 110726,7 Pa IZ0C3H7 1Z0C3H7 H -CH (CHj) -COOCH ₃ boil. 105767 Well terc.CjH? H H -CH (CHj) -COOCHj boil. 9379,3 Pa

- 37 311 -

Ri r ₂ Rs -X-Rj Physical constant CHj H 4-C1 -CH (CHj) -C00CHj boil. 125 to 12779.3 Pa CHj Cl H -CH (CHj) -C00CHj boil. 88 to 8974 Pa CHj. - CHj 4-Nr -CH (CHj) -C00CHj ' m.p. 31.5 to 32.5 ° CHj CHj 3-Nr -CH (CHj) -C00CHj m.p. 46 to 47.5 ° F H H -CH (CHj) -C00CHj boil. 98720 Well • Cl H H -CH (CHj) -C00CHj boil. 90 to 100712 Pa Nr H H -CH (CHj) -C00CHj boil. 110 ° l, 3 Pa CH ₃ CHj 4-J -CH (CHj) -C00CHj m.p. 81 to 83 ° J H H -CH (CHj) -C00CHj boil. 105720 Well 11C4H9O- H -CH (CHj) -C00CHj boil. 132767 Well CHj H 4-CH 2 O -CH (CHj) -C00CHj boil. 131767 Well ch ₃ H 4sec. C4HiO -CH (CHj) -C00CHj boil. 138720 Well Cl H • 5-CI -CH (CHj) -C00CHj m.p. 51.5 to 54 ° CHj c ₂ h ₅ H -CH (CH ₂ ) -CO ₃ NH ₂ boil. 155 to 157713.3 Pa CjH ₅ c ₂ h ₅ H -CH (CH3) -C0NH ₂ m.p. 71 to 73 ° C ₂ H _s c ₂ h ₅ H -ch ₂ -conh ₂ m.p. 103 to 106 ° C ₂ H _s C ₂ Hs H -ch ₂ -cooc ₂ h _s boil. 100 to 10375,3 Pa C ₂ H ₅ c ₂ h ₅ H -CH ₂ -C0N (CH ₂ ) ₂ waxy ch ₃ CHj H -CHrC0NH ₂ m.p. 89 to 91 ° ch ₃ CHj H -CH (CHj) -CONH ₂ m.p. 102 to 103 ° CHj CHj H -CH (CH3) -C0NHCH3 m.p. 75 to 76 ° CHj CHj H -CH (CHj) -CON (CHj) ₂ boil. 104 to 10872.7 Pa CjHs c ₂ h ₅ H -CHrCONHCHj m.p. 59 to 61.5 ° c ₂ h ₅ c ₂ h ₅ H -CH ₂ -C0NHC ₂ Hs m.p. 79 to 80 ° CHj CHj H -CHrCOOCHj boil. 155 to 160 ° 2666 Pa CHj Cl H -CH (CHj) -C00C ₂ H ₅ boil. 110 to 120740 Pa CHj c ₂ h ₅ H -CHrCOOCHj boil. 168 to 17174000 Pa CHj Cl H -CH (CHj) -CONHCHj m.p. 51 to 53 ' CHj Cl 4-J -CH (CHj) -COOCHj m.p. 118 to 122 ° CHj CHj 4-C1 -CH (CHj) -C00CHj m.p. 135 to 13772.7 Pa CHj c ₂ h ₅ 4-J -CH (CHj) -COOCHj m.p. 65 to 69 ° CHj c ₂ h ₅ 4-C1 -CH (CHj) -COOCHj boil. 142 to 14575.3 Pa CHj Cl 4-01 -CH (CHj) -C00CHj boil. 151 to 15374 Pa CHj Cl 4-Nr -CH (CH3) -C00CH, m.p. 82 to 85 ° CHj c ₂ h ₅ 4-Nr -CH (CHj) -COOCHj m.p. 52 to 54 °

- 37 311 -

Example 2

Preparation of the Optical Isomers of N- (1'methoxy-carbonylethyl) -N-methoxyacetyl-2,6-dimethylaniline of the formula

32.9 g (159 mmol) of (d) -a- (2,6-dimethylanilino) -propionic acid methyl ester is mixed with 19.35 g (182.5 mmol) of soda in 350 ml of toluene. Add to this with good stirring at 10 to 15 ° C

solution of 16.7 ml (182.5 mmol) of methoxyacetyl chloride in 50 ml of toluene.

Then the reaction mixture was stirred for 2 hours at 45'C. After cooling to room temperature, it is filtered, the filtrate is diluted with oeester and recovered to neutral. The residual oil after evaporation is fractionated in a high vacuum. 26.7 g of (D) -N- (1'-methoxycarbonyl-ethyl) -N-methoxyacetyl) -2,6-dimethylaniline are obtained as an oil [¢ 1¾ - - -57 ° ± Γ; c = 1.807% g / V in acetone.

In an analogous manner, 29.8 g of L-ester are obtained

17.2 g of (L) -N- (r-methoxy-carbonylethyl) -N- (methoxyacetyl) -2,6-dimethylaniline as an oil, [¢ 3¾ = + 57 ° - ± ± Γ; c = 2.883% g / V in acetone.

The optically active form of the α- (2,6-dimethylanilino) -propionic acid methyl ester used is obtained by digesting the diastereomer with α-phenethylamine, fractionating the crystallization of the salts, releasing the (D) - and (L) -salts and esterifying them with methanol.

? ^H 3- ·

I / CH-COOCH ₃ \ o-ch ₂ -oz ₁

Compound no. Ri Rj R7 Z, Physical constant 1 CHj 6-CHj H -CHj m.p. 67 to 68 ° C 2 CHj 6-CHj H -C2H5 boil. 130 to 13272.7 Pa 3 CHj 6-CHj H -n-CjHr boil. 133 to 140 ° / 4 Pa 4 CHj 6-CHj H -izoCjHi boil. 137 to 140 / 75.3 Pa 5 CHj 6-CHj H -se.CjH? vtrel. 141 to 14375.3 Pa 6 CHj 6-CHj H -n-CiH) boil. 145 to 14774 Pa 7 CHj 6-C2H5 H CHj boil. 138 to 13979.3 Pa 8 CHj 6-C ₂ H ₅ H -C2H5 boil. 140 to 14275.3 Pa 9 CHj 6-C2H5 H -izoCjH? boil. 14870,4 Torr 10 CHj 6-C2H5 H -Sec.CJH boil. 141 to 14476.7 Pa 11 CHj 6-C1 H -CHj m.p. 47 to 56 ° 12 CHj 6-C1 H -C2H5 boil. 148 to 15075.3 Pa 13 CHj 6-C1 H -izoCjH? boil. 147720 Well 14 CHj 6-C1 H -terc.C «H» 15 CHj 6-C1 H -sec.C4H9 boil. 153 to 15579.3 Pa 16 CHj 5-CHj H -izoCjH? boil. 147740 Well

 - 37 311 -

Compound no. R, ^R 2 R7 · Z, Physical constant L 17 c ₂ h ₅ 6-C2H5 H -ch ₃ boil. 142 to 14578 Pa ^: J8 c ₂ h ₅ 6-C2H5 H -isoC ₃ H7 boil. 152713,3 Pa • 19 ch ₃ 3-CH ₃ 6-CH ₃ -ch ₃ m.p. 58 to 68 ° * 20 ch ₃ 3-CHj 6-CH ₃ -c ₂ h ₅ 'hot. 140 to 14275.3 Pa 21 ch ₃ 3-CH ₃ 6-CH ₃ -nC ₃ H ₇ boil. 138 to 14078 Pa 22 ch ₃ 3-CHj 6-CH ₃ -isoC ₃ H7 incl. 140 to 142710.7 Pa • 23 ch ₃ 3-CH ₃ 6-CH ₃ -nC ₄ H9 boil. 147 to 14878 Pa 24 ch ₃ 3-CH ₃ 6-CH ₃ -sec.C ^ boil. 150 to 15278 Pa 25 ch ₃ 3-CH ₃ 6-CH ₃ -sec.CsHn boil. 159 to 16175.3 Pa .26 ch ₃ 4-CH ₃ 6-CH ₃ -ch ₃ m.p. 50 to 53 * '27 ch ₃ 4-CH ₃ 6-CH ₃ -CjHs boil. 148 to 151710.7 Pa 28 ch ₃ 4-CH ₃ 6-CH ₃ -isoC ₃ H7 boil. 149 to 15279.3 Pa 29 ch ₃ 4-CH ₃ 6-CHj -sec.C <H9 boil. 157 to 15975.3 Pa 30 ch ₃ 3-Nr 6-CHj -CHj boil. 20075,3 Pa 31 Gl 6-C1 H -CHj boil. 180 to 18271.3 Pa 32 F H H -isoC ₃ H7 boil. 13071,3 Pa 33 F H H - -sec.CJH boil. 130 to 137 * 75.3 Pa 34 Cl H H -isoC ₃ H7 boil. 13076,7 Pa 35 J H H -i7.0C.jH7 boil. 168740 Well - 36 CH ₃ 3-CHj H -ch ₃ boil. 14075,3 Pa 37 ch ₃ 3-CH ₃ 6-C2H5 -CHj boil. 126 to 132710.6 Pa 38 ch ₃ 4-sec.C4H9O H -isoC ₃ H7 boil. 175740 Well 39 CHj 6-CH ₃ H -CH2-CH-CH2 boil. 151 to 15375.3 Pa ⁴⁰ ch ₃ 6-CI U -CHrCH = CH ₂ boil. 162 to 16475.3 Pa 41 ch ₃ 6-C2H5 H -CH2-CH = CH ₂ boil. 150 to 15278 Pa 42 F H H -CH _r CH = CH 2 boil. 12976,7 Pa 43 ch ₃ 6-CH ₃ H -CHrC (CH ₃ ) = CH 2 boil. 158 to 16072.7 Pa 44 ch ₃ 6-CHj U -CtHs boil. 17575,3 Pa 45 ch ₃ 6-C2H5 H -CtHs boil. 178 to 18076.7 Pa 46 ch ₃ 3-CH ₃ 6-CH ₃ -c ₆ h ₃ boil. 182 to 18476.7 Pa 47 ch ₃ 4-CH ₃ 6-CH ₃ -c ₆ h ₅ boil. 187 to 18975.3 Pa 48 F H H -c ₆ h ₅ m.p. 37 to 40 ° 49 CH ₃ 6-CH ₃ H -C ₆ HjC1 ₂ (2,4) m.p. 101 to 104 ° 50 F H H -C ₆ HjCl2 (2,4) m.p. 133 to 136 ° 51 ch ₃ 6-CH, H -CHj-CtHs m.p. 81 to 86 ° 52 ch ₃ 3-CHj 6-CH ₃ -CH ₂ -CtH ₅ boil. 180 to 18274 Pa 53 ch ₃ 6-CH ₃ H -CH2-C6H4-CK4) boil. 187 to 18975.3 Pa

- 37 311 - '9

Compound no. Ri R ₂ r ₇ Z, Physical constant -, 54 CHj 3-CHj 6-CHj -CH (CH 2) -C = CH viscous oil 55 CHj 4-CHj 6-CHj -CH (CHj) -C ^ CH viscous oil 56 CH, 6-CHj H -CHrC ^ CH viscous Oil < 57 CH, 6-CHj H -CH2-C = CJ m.p. 58 to 60 ° 58 CH, 4-CI 6-CHj -CHj m.p. 87 to 90 °. 59 CH, 4-CI 6-CHj -sec.C ^ g m.p. 75 to 78 ° 60 CH ₃ 4-Nr 6-CHj -CHj m.p. 98 to 100 ° 61 ch ₃ 4-Nr 6-CHj -C2H5 m.p. 64 to 65.5 ° 62 CHj 4-Nr 6-CHj -CH 2 CH = CH ₂ m.p. 38.5 to 41 ° 63 CHj 4-Nr 6-CHj -sec.C <H9 m.p. 51 to 53.5 ° 64 CHj 4-Nr 6-CHj -CbH ₅ m.p. 110 to 111 ' 65 CHj 4-J 6-CHj -CHj m.p. 82 to 84 ° 66 CHj 4-CI 6-Ci -CHj m.p. 105 to 108 ° 67 CHj 4-Nr 6-C2H5 -CHj m.p. 87 to 90 ° 68 CHi 4-Nr 6-C2H5 -CHrCH = CH ₂ boil. 183 to 18572.7 Pa 69 CHj . 4-J 6-C2H5 -CHj boil. 192 to 19774 Well on analog way can let's prepare compounds with the following a formula in which Ri is in position 2.

Compound no. R. R2 R; R « -X-Rj Z2 Physical constant 70 CHj 6-CHj H H -CH-COOC2H5 1 CHj -CH, boil. 136 to 13872.7 Pa 71 CH, 6-CHj H H -ch-cooc ₂ h ₅ 1 CHj -CH2-GH5 boil. 178 to 18274 Pa 72 CHj 6-CHj H H -CH2-COOCH3 -se.CdH « boil. 162 to 16575.3 Pa 73 CHj 6-CHj H H -CH2-COOCH3 -c ₆ h ₅ m.p. 82 to 85 ° 74 CHj 6-C2H5 H H -CHrCOOCHj -c ₆ h ₅ m.p. 70 to 74 ° 75 CH, 6-CHj H H -CH2-COOCH3 -CiHjOh (2,4) m.p. 102 to 105 °, 76 CHj 6-C2H5 H H -CH2-COOCH3 -C6HjCl2 <2.4) m.p. 82 to 84 °

- 37 311 -

Compound Ri r ₂ r ₇ Rs -xr ₃ by ₂ Physical constant 77 c ₂ h ₅ 6-C ₂ H ₅ H H -CHj-COOCHj -C ₆ H ₃ CIX2,4) m.p. 82 to 85 ° 78 c ₂ h ₅ 6-C ₂ H ₅ H H -CHj-COOCH, -CH ₃ m.p. 50 to 52 ° 79 ch ₃ 3-CH, č-CH ₃ H -CH ₂ -COOCHj -CH ₃ oil 80 c ₂ h ₅ 6-C ₂ Hs H H -CH1-CONHCH, -isoC ₃ H ₂ m.p. 96 ° 81 c ₂ h ₅ 6-C ₂ Hs H H -CH ₂ -CONHC ₂ H ₅ -ch ₃ boil. 165 to 170740 Pa 82 c ₂ h ₅ 6-C ₂ H, H H -ch ₂ -conh ₂ -C ₆ H _s m.p. 147 to 148 ° 83 c ₂ h ₅ 6-C ₂ Hs H H -CH ₂ -CONHCH ₃ -CiHs m.p. 122 to 124 ° 84 CH ₃ 6-C ₂ H, H H -ch ₂ -conhch ₃ -c ₆ h ₅ m.p. 108 to 11Γ 85 ch ₃ 6-CH, H H -CHrCONHCH, -C ₆ H ₅ m.p. 122 to 124 ' 86 C ₂ H ₅ 6-C ₂ H ₅ H H -CHrCONH ₂ -C «H ₃ C1 ₂ (2,4) m.p. 162 to 164 ' 87 c ₂ h ₅ 6-C ₂ Hs H H -CHrCONHCH, -C ₆ H ₃ Cl2 <2.4) m.p. 167 to 169 ° 88 CjHs 6-C ₂ Hs H H -CHrCONHGHs -CoH ₃ Cl ₂ (2,4) m.p. 119 to 121 ' 89 ch ₃ 6-C ₂ H ₃ H H -CHrCONHCHj -C «H ₃ C1 ₂ (2,4) m.p. 137 to 141 ' 90 CHj 6-CH, H H -CHj-CONHCH, -C6H, C1 ₂ (2,4) m.p. 104 to 107 '

Compounds of the following formula are also prepared in an analogous manner in which R1 is in position 2.

xr ₃ /

^X CO-CH ₂

S-2

Compound no. Ri r ₂ r ₂ Ri -Χ-Rj Z, Physical constant 91 ch ₃ 6-CH, H H -CH (CH,) - COOCHj -CHrCeHs boil. 190 to 192720 Pa 92 ch ₃ 6-C ₂ H ₅ H H -CH (CHj) -COOCH ₃ -CHrC ₆ Hs boil. 194 to 197726,7 Pa 93 ch ₃ 6 Cl H H -CH (CH ₃ ) -COOCH ₃ -CHrC ₆ H5 boil. 215 to 22079.3 Pa 94 ch ₃ 3-CH, 6-CH, H -CH (CH,) - COOCHj -CHrCiHs boil. 188 to 19075.3 Pa 95 CHj 4-CH ₃ 6-CH ₃ H CH (CH ₃ ) -COOCH ₃ -CH ₂ -C ₆ Hs boil. 205 to 21074 Well 96 CHj 6-CH, H H -CH (CH,) - COOCH, -ch ₂ -c = ch ₂ 1 Cl boil. 185 to 195713.3 Pa 97 ch ₃ 6-CjHs H H -CHrCOOCH, -CH ₂ -C = CH ₂ 1 Cl boil. 187 to 190726.7 Pa 98 c ₂ h ₅ 6-C ₂ H ₅ H H -CHrCONHCHj -CH ₂ -C = CH ₂ m.p. 70 to 72 °

Cl - 37 311 -

Compound R! r ₂ R? R ₈ -Χ-Rj Zj Physical constant 99 C2H5 6-C2H5 H H -CH2-CONH2 -CH _r C = CH ₂ I m.p. 83 to 86 ° 100 ch ₃ 4-CHj 6-CHj H -CH (CHj) -COOCHj Cl -izoCjH? boil. 151 to 153713.3 Pa 101 CHj 5-CHj 6-C ₂ H ₅ H -CH (CHj) -COOCH ₃ -CHj boil. 134 to 13672.7 Pa 102 ch ₃ 3-Nr 6-CHj H. -CH (CHj) -COOCHj -CHj boil. 180 to 18278 Pa 103 CHj 4-CHj 6-CHj H -CH (CHj) -COOCHj -C ₆ H4-CH ₃ (3) m.p. 98 to 99 ° 104 CH, 4-CHj 6-CHj H -CH (CHj) -COOCHj -C «H5 m.p. 63.5 to 64.5 ° 105 CHj 4-CHj 6-CHj H -CH (CHj) -COOCHj -C ₆ H <C1 (4) m.p. 71 to 72.5 ° 106 CHj 3-CHj 6-CHj H -CH (CHj) -COOCHj -C «H _S 107 CHj 3-CHj 6-C2H5 H -CH (CHj) -COOCH ₃ -CHj m.p. 81 to 92 ° 108 CHj 4-CHj 6-CHj H -CH (CH ₃ ) -COOCHj -C2H5 m.p. 43 to 45.5 ' 109 CHj 4-Nr 6-CHj H -CH (CHj) -COOCHj -C2H5 boil. 175 to 17872.7 Pa 110 CHj 4-Nr 6-CHj H -CH {CHj) -COOCHj -iso-CjH7 boil. 180 to 18474 Pa 111 CHj 3-CHj 6-CHj H -CH (CHj) -COOCHj -C «H4-CHj (4) boil. 201 to 20375.3 Pa 112 CHj 4-Nr 6-CHj H -CH (CHj) -COOCHj -CHiCiHs brown oil 113 CHj 4-J 6-CHj H -CH (CHj) -COOCHj -C2H5 m.p. 105 to 107 ° 114 CHj 4-Nr 6-CHj H -CH (CHj) -COOCHj -C «H4-CHX4) m.p. 87 to 91 °

The following compounds of the following formula are also prepared in an analogous manner in which R1 is in position 2.

Sppjina no. R. R ₂ -XR _} Y Physical constant 115 CHj 6-CHj -CH (CHj) -COOCH ₃ -S-CH2 m.p. 65 to 67 ° 116 CHj 6-CHj -CH (CHj) -COOCHj -sc ₂ h ₅ m.p. 55.5 to 56 ° 117 CHj 6-CHj -CH (CHj) -COOCHj -S-nCjHj boil. 166 to 16975.3 Pa 118 CHj 6-CHj -CH (CH ₃ ) -COOCHj -S-isoCjH7 boil. 145 to 14872.7 Pa 119 CHj 6-C1 -CH (CHj) -COOCHj -S-isoCjH7 m.p. 81 to 95 ° 120 CHj 6-C1 -CH (CHj) -COOCHj -S-sec.C4H9 boil. 154 to 156712 Pa 121 CHj 6-CHj -CH (CHj) -COOCHj -S-sec.C4H9 boil. 172 to 174713.3 Pa

- 37 311 -

Compound Ri r ₂ -X-R, Y Physical constant 122 ch, 6-C ₂ H, -CH (CH,) - COOCH, -SC ₂ H ₅ boil. 162 to 164713.3 Pa 123 ch, 6-C ₂ H, -CH (CH,) - COOCH, -S-isoC, H7 boil. 152 to 15578 Pa 124 CH, 6-C ₂ H, -CH (CH,) - COOCH, -S-nC ₄ H ₉ boil. 197 to 19972.7 Pa ¹²⁵ ch ₃ 6-CH, -CH (CH,) - COOCH, -S-nC ₄ H9 boil. 172 to 174713.3 Pa 126 CH, d-CH, -CH (CH,) - COOCH, -sc ₆ h ₅ boil. 178 to 179710.7 Pa 127 ch ₃ 6-C1 -CH (CH,) - COOCH, -sc ₆ h ₅ m.p. 83 to 85 ° 128 ch ₃ '6-CH, -CH (CH,) - COOCH, -SC ₆ H ₄ C1 (3) m.p. 63 to 64 ° 129 CH, 6-C1 -CH (CH,) - COOCH, _ _s - <o> -CiCHj) , boiling. 210 to 21272.7 Pa 130 CH, 6-CH, -CH (CH,) - COOCH, -5- <O> -CH ₃ boil. 197 to 199712 Well 131 C ₂ H ₅ 6-C ₂ H ₅ CHrCOOCH, -S-CH, boil. 158 to 16076.7 Pa 132 CH, 6-C ₂ H _s -CH (CH,) COOCH, -S-CiH ₄ -CH, (4) boil. 210 to 212710,7 Pa 133 C ₂ H ₅ 6-C ₂ H _s -CH ₂ -CONHC ₂ H ₅ -S-CH, boil. 151 to 175713.3 Pa 134 CH, 6-CH, -CB (CH,) - COOCH, -S-tert.C «H <> boil. 145 to 14774 Pa 135 CH, 6-C1H5 -CH (CH,) COOCH, -sc * h ₅ boil. 191 to 193726.7 Pa 136 CH, 6-C ₂ H, -CH (CH,) COOCHj -S-GsH ₄ CI (3) m.p. 52 to 55 ' 137 CH, 6-C1 -CH (CH,) - COOCH, -S-CiH ₄ -CH, (4) boil. 202 to 205726,7 Pa 138 CH, 6-C1 -CH (CH,) - COOCH, -S-nC ₄ H9 m.p. 51 to 56 ° 139 CH, 6-C1 -CH (CH,) - COOCH, -SC ₂ Hs boil. 166 to 168710.7 Pa 140 CH, 6-C1 -CH (CH,) COOCH, -S-tert, C ₄ H ₉ boil. 138 to 141710.7 Pa 141 CH, 6-C ₂ H, -CH (CH,) COOCH, -S-sec.CiH) boil. 171 to 173713.3 Pa 142 CH, 6-C1 -CH (CH,) COOCH, -S-CiH ₄ Cl (3) m.p. 77 to 79 °

Compounds of formula I may be used with other suitable ipsticidal or plant growth-promoting agents to expand their effect spectrum.

The compounds of formula I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and excipients may be solid or liquid and may suit conventional substances, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting, adhesives, thickeners, agents, binders or fertilizers.

The content of the active substance in marketable agents ranges from 0.1 to 90%.

For the application, the compounds of Formula I may be present in the .processed forms listed below. In doing so, weight data. % in parentheses represent favorable amounts of the active substance.

Solid processed forms: pollinating and spreading agents (up to 10%), granules, coated gra. null impregnated granules and homogeneous granules (1 to 80%).

Liquid processed forms:

(a) water-dispersible concentrates of active substances:

spray powders (\ vettable ipowders) and pastes (25 to 90% in commercial packaging, 0.01 to 15% in ready-to-use solution), emulsion and dissolving concentrates (10 phonates up to 50%, 0.01 to 15% in solutions ready for use),

b) solutions (0.1 to 20%).

The active compounds of formula I of the present invention can be processed into the preparations listed below.

- 37 311

Pollination agent

The following substances are used to prepare a) 5% and b) 2% pollinator:

a) 5 parts of the active substance 95 parts of talc

b) 2 parts of the active substance part of the highly dispersed silica 97 parts of talc.

The active substances are mixed with carrier materials and ground and can be used in this form for apirying.

Granulate

For the preparation of 5 ^{O /} o granules, use the following substances:

parts of the active substance 0.25 parts of epichlorohydrin 0.25 parts of cetylpolyglycoleter 3.50 parts of polyethylene glycol 91 parts of kaolin (grain size 0.3 to 0.8 mm).

The active substance was mixed with epichlorohydrin and dissolved in 6 parts of aoetone, then poly was added. ethylene glycol and cetylpolyglycol ether. The solution thus obtained was sprayed onto kaolin and then the acetone was evaporated in vacuo. Such microgranules are advantageously used to suppress terrestrial fungi. Spray powder

The following ingredients are used to prepare a) 70%, b) 40% ncga, c and (d) 25%, and e) 10% spray powder:

a) 70 parts of the active substance parts of sodium dibutylnaphthalenesulfonate parts of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde 3: 2: 1 parts of kaolin 12 parts of champagne chalk

b) 40 parts of the active substance parts of the sodium salt of ligninsulfonic acid (vinegar line part of the sodium salt of dibutylnaphthalenesulfonic acid parts of silica

c) 25 parts of the active substance

4.5 parts of calcium ligninsulfonate

1.9 parts of champagne / hydroxyethylcellulose (1: 1)

1.5 parts of sodium dibutylnaphthalenesulfonate

19.5 parts of silica

19.5 pieces of champagne chalk

28.1 parts of kaolin

d) 25 parts of the active substance

2.5 parts of isooctylphenoxypolyloxyethylene ethanol

1.7 parts of champagne / hydroxyethyl acetate (1: 1)

8.3 parts of sodium aluminum silicate

16.5 parts of kieselguhr 46 parts of kaolin

e) 10 parts of the active substance are parts of a mixture of sodium salts of sulphates of saturated fatty alcohols of parts of the condensate of naphthalenesulfonic acid and of formaldehyde parts of kaolin.

The active substances in suitable mixers are closely mixed with additional substances and milled on suitable mills and cylinders. Spray powders are obtained with excellent wettability and hovering ability, which can be diluted with water in suspensions of any desired concentration and used especially for leaf application.

Emulsion concentrate

The following substances are used to prepare the 25% emulsifiable concentrate:

parts of the active substance

2.5 parts of epoxidized vegetable oil blend of allcylarylsulfonate and polyglycol ether fatty alcohol parts of dimethylformamide

57.5 parts of xylene.

These concentrates can be easily diluted with water. We prepare emulsions of any desired concentration, which are suitable especially for leaf application.

- 37 311 -

Example 4

Effect against Phytophthora infestans on Solanum lycopeirsiicum (tomatoes) la) Residual-preventive effect

Solanum lycopersicum (tomato) plants of the "Roter Gnom" type after 3 weeks of cultivation after spraying with 0.05% of the active substance (prepared from the active substance prepared as a spray powder) and infected by drying with Phytophfhora infestans zoospores . They then stay in an air-conditioned chamber at 18 to 20 ° for 6 days and the high humidity produced by artificial spray mist. After this time, characteristic leaf spots appear. Their number and size is a measure of the evaluation of sons tested.

lb) Curative effect

After 3 weeks of cultivation, the Roter Gnom tomato plants are sprayed with the head zoospore suspension and incubated in Ikabina at 18 to 20 ° and saturated humidity. The humidification is stopped after 24 hours. After drying, the plants are sprayed with a broth containing the active substance, prepared as a spray powder, at a concentration of 0.05%. After drying the spray coating, the plants are placed in a humid cabin for 4 days. The number and size of typical leaf blemishes produced after this time are a criterion for the evaluation of the substances tested.

II) PreventiveTsystemic effect

As a spray powder, the prepared active substance is placed at a concentration of 0.05% (relative to the volume of soil) on the soil surface of 3-week-old rotter-gnom tomato plants. After a 3-week waiting time, spray the underside of the leaves with a suspension of Phytoaphthora infestans zoospores. They are then held in a spray booth at 18 to 20 ° for 5 days and saturated with humidity. After this time, characteristic 'leaf spots' are formed, the number and size of which are the criteria for evaluating the substances tested.

In these three experiments, the compounds of formula I show a strong leaf fungicidal effect. In the application of compounds of the subgroup of formula Ia in which R 'stands for methyl, a fungal infection of less than 20% (mean values) is observed. With compounds no. 1, 2, 4, 5, 11, 18, 24, 28, 29, 33, 39, 118, 374, 378 and other fungal infections are almost completely suppressed (0 to 5%). With compounds no. 7, 9, 12, 16, 20, 30, 31, 32, 35, 36, 38, 44, 65, 97, 98, 120, 130, 155, 157, 158, 159, 168, 199, 204, 222, 259, 272, 281, 328, 331, 337, 350 and others at a concentration of effective substances only 0.02+ observed infection with PCD 20% (mean values).

EXAMPLE 5

Effect against Plasmopara viticola (Bert. Et Curt.) (Beri. Et DeToni) on Vine

a) Residual-preventive effect

In the greenhouse we raised seedlings of the vine species "Chasselas". In a 10-leaf stage, a spray of 0.05% of the active substance, prepared from the active substance, prepared as a spray powder was sprayed. After drying the spray coating, the plants on the underside of the leaf were uniformly infected with a fungal spore suspension. The plants were then kept in a humid chamber for 8 days. After this time, different symptoms of the disease appeared on the control plants. The number and size of infection sites on treated plants served as a criterion for evaluating the effectiveness of the test substances.

b) Curative effect

The seedlings of 'Chasselas' vines were grown in a greenhouse and in the 10 leaf stage at the underside of the leaves were infected with a suspension of Plasmopora viticola spores. After 24 h retention in a humid cabin, the plants were sprayed with a 0.05% active substance spray prepared from the Active Powder spray powder. The plants were then kept in a humid cabin for a further 7 days. After this time, the control plants showed symptoms of the disease. The number and size of infection sites on treated plants served as a criterion for evaluating the effectiveness of the test substances.

The compounds of formula I (in both experiments mainly showed good leaf fungicidal effects. With the compounds listed individually in Example 4, the fungal infection was reduced to below 20% throughout, in part, such as for example compounds 1, 2, 4, 5, 18, 28, 29, 30, 33, 118, infection almost did not occur (0 to 5%).

Example 6

Effect against Erysiphe graminis on Hordeum vulgare (barley) Residual protective effect

Around 8 cm tall barley plant is sprayed with a spray broth (0.05% of the active substance) prepared from the spray powder of the active substance. After 48 hours, the treated plants were irrigated with fungal conidia. Infected barley plants were placed in a greenhouse with 22 ° C linine after 10 days to evaluate the infection with the fungus.

Part of the compounds of formula I in this test show a reduction in head infection to below 20%.

The strong inhibition of growth was shown, in particular, by the effective compounds of formula I, in which -X-Rj is the formula X1O-N (R ") (R" ') defined for formula I and in which Y stands for -S-Rv

Claims (4)

PATENT APPLICATIONS 1. A process for the preparation of new general formula amnylides - 37 311 - Example 7 Effect against Pythium debaryanum on Beta vuigaris (sugar beets) a) Effect after ground application The fungus is cultured on sterile oat grains and added to a mixture of soil and sand. Put the infected soil into flower pots and sow sugar beet seeds. Immediately after sowing the soil, spray the test preparations as aqueous suspensions (20 ppm of the active substance relative to the volume of the soil) as a spray. The pots are then placed in a greenhouse at 20 to 24 ° C for 2 to 3 weeks. Keep the soil evenly moist with light water spraying. When evaluating the test, we determine the origin of sugar beet plants as well as the number of healthy and diseased plants. b) Effect after leaching application The fungus is cultured on sterile oat grains and added to a mixture of soil and sand. The contaminated soil is then placed in flower pots and sown with sugar beet seeds, which have been prepared as one test preparation by the puddle (1000 ppm of effective substance by weight of seed). Put the pots planted for 2 to 3 weeks in a greenhouse at 20 to 24 ° C. Soil is kept evenly moist by lightly spraying with water. The evaluation determines the origin of sugar beet plants as well as the number of healthy and diseased plants. After treatment with the effective compounds of Formula I, under test conditions a) and b), more than 85% of the sugar beet plants emerged and had a healthy appearance. In the untreated control, less than 20% of plants with partially diseased appearance emerged. Example 8 Inhibition of grass growth In an established outdoor meadow consisting of Lolium perenne, Poa pjratensiis and Festuca rubra grasses, the 3 m ² parcels are sprayed two days after the first mowing with aqueous preparations of the effective substance of Formula I. The amount of active substance used is calculated to be 5 kg. effective substances / ha. Leave the uncultivated plots in control. 6 weeks after application, determine the mean height of grass growth in cultivated and untreated plots. With the effective substances, the grass directly on the surface of the soil was evenly compact and had a healthy appearance. in which they appear R1 is C1-C4 alkyl, C1-Cralkoxy or halogen, R1 is hydrogen, C1-C6-alkyl, C1-Cralcoxd or halogen, R7 is hydrogen, C1-C3-alkyl or halogen, R e is hydrogen or methyl, wherein the total number of carbon atoms in the substituents R 1, R 2, R 7 and R 8 in the phenyl ring does not exceed 8; CH ₃ I X is -CHt- or -CH-, R ” R3 is -COOR 'or -COh ^, wherein X is _R. ' R ', R' and R '' independently of one another are hydrogen, methyl or ethyl and Y is O-R4 or -S-R4, wherein R4 is optionally substituted with C1-C6-alkyl, C3 -C6-alkenyl, C1-C4-alkenyl or, optionally, halogen or C1-C4-alkyl substituted benzyl or phenyl, as well as their optically active derivatives if X is -CHfCft), characterized in that the acid derivative of the general formula - 37 311 - in which Ki, R2, R7, R5 and X have the above meaning, is acalised with an acid halide of the formula Hal'-CO-OHrY (HI) where Y has the upper ppmen and Hal 'is halogen at a temperature of ambient temperature to the reflux temperature, in an organic solvent containing no hydroxyl groups, and optionally in the presence of an acid-binding agent, wherein the acid derivative of -formula (II), if X is -CH (CH 3) -, can be used in the racemic or optically active form. 2. A process according to claim 1, characterized in that, as the acid halide of formula (III), one uses 'in which Hal' stands for chlorine or bromine, Process according to claim 1, characterized in that: toluene is used as an inert solvent. The process of claim 1, wherein d: dime tilformamide is used as the acid-binding agent.