FI61478B - VAEXTFUNGICIDA N- (1'-METOXY- OCH ETOXICARBONYL-ETHYL) -N-ACYL-ANILIN DERIVATIVES - Google Patents

Description

ΓβΙ rt1v ADVERTISING PUBLICATION

Ma LJ ('UTLÄGGININCSSKRIFT 61478 (45) Patent iscd'J,' lat (51) Kv.ik.Vci.3 o 07 e 103/46, 121/00. 161/03 // A 01 N 37/46, 47 / 00 ENGLISH — FI N LAND (21) Pttunttlhtkuimi »- Pttantans6knlng 750923 (22) Htktmltpllv * - Anseknlngtdtg 26.03-75 (23) Starting point —Glltlghtttdtg 26.03.75 (41) Become slipped

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Patent and registration authorities in the United Kingdom and the United States of America J · υ4 ·

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Ο7.Ο3.75 Switzerland-Switzerland (CH) U998 / 7U, 2906/75 (71) Ciba-Geigy AG, CH-U002 Basel, Switzerland-Switzerland (CH) (72) Adolf Hubele, Magden, Switzerland-Switzerland (CH) ) (7 ^) Oy Jalo Ant-Wuorinen Ab (5 ^) Plant fungicidal W- (1'-methoxy- and ethoxycarbonyl-ethyl) -N-acyl-aniline derivatives - Växtfungicida N- (1'-methoxy-och-ethoxycarbonyl-ethyl) This invention relates to plant fungicidal N-acylaniline derivatives of the formula CH 3 C 1 -C 2 wherein C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen, R 2 hydrogen, C 1 -C 6 alkyl -alkyl, C 1 -C 4 -alkoxy or halogen,

R 9 is hydrogen, C 1 -C 6 alkyl or halogen,

Rg is hydrogen or methyl, wherein the total number of C atoms of the phenyl ring substituents R1, R2> Rg and Rg does not exceed 8, R3 is methyl or ethyl, and C1-C8-alkyl optionally substituted by cyano (-CN) or rhodano (-SCN) , C 2 -C 8 alkenyl or C 8 -C 8 cycloalkyl.

'l f 2 ¢ 1478

As alkyl or alkyl part of an alkoxy group, the following groups are meant depending on the number of carbon atoms in each case: methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert. butyl and pentyl and hexyl isomers. Alkenyl residues which may be mentioned are, in particular, vinyl, allyl, methallyl, butenyl, methylbutenyl and their isomers, while cycloalkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Halogen means fluorine, chlorine, bromine or iodine.

German application 2,212,268 states in general terms that N-haloacylated anilinoalkanecarboxylic acid esters have a selective herbicidal action. However, only a few N-haloacetylated 2,6-di-alkyl-anilinoacetic acids and their esters have been named and found to have herbicidal activity. It does not mention any microbicidal, in particular phytosanitary, effect.

It has now surprisingly been found that compounds with a clearly different structure of the formula I have a very advantageous spectrum of plant fungicides for the protection of useful plants for practical purposes. Within the scope of this invention, useful crops include, for example, cereals, corn, rice, vegetables, sugar beet, soybeans, peanuts, fruit trees, ornamentals, but above all vines, hops, cucumbers (cucumber, pumpkin, melons), moths, solanacee and as well as banana, cocoa and natural rubber crops.

The active compounds of the formula I can be used to prevent or eradicate fungi present in plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of such and closely related useful crops, so that subsequently growing plant parts are also protected against such fungi. The active ingredients are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphaceae); Basidiomycetes, such as 61478 3 above all rust fungi; Fungi imperfecti (e.g. Moniliales); above all, however, in particular, the Phycomycetes class includes Oomycetes such as Phytophtora, Peronaspora, Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of the formula I have a systemic effect. They can also be used as pickling agents for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect them against fungal infections and against phytopathogenic fungi present in the soil.

Preferred microbicides are compounds of the formula I in which methyl represents, R 2 is in the ortho position to the amino group and represents methyl, ethyl or chlorine, and R 9, R 6, R 8 and R 8 have the same meaning as above. These are called compound group Ia.

Of these compounds of formula Ia, mention may be made, by virtue of their activity, of compounds in which R1 represents an alkyl, alkenyl or cycloalkyl radical having 2 to U carbon atoms and R8 and R8 have the same meaning as above, the substituents R1, R25 of the phenyl ring being The total number of C atoms in Rg and Rg does not exceed 4.

Another important subgroup are those compounds of formula I in which R 2 represents hydrogen, C 1 -C 6 alkyl or halogen and the substituents R 9 and R 8 are hydrogen, while the substituents R 1, R 8 and R 4 have the same meaning as in formula I.

For certain uses, e.g. as pickling agents or against fungi, preference is given to compounds of the formula I or of subgroup Ia in which R1 represents a cyanomethyl or Roda nomine group.

U

ft * ^ · '* 4 61478

The compounds of formula I are prepared, for example, by acylation of a compound

Ri I? H3 ch - COOR3 λΦ / NH w 11 R6 r2 with a carboxylic acid of formula

ho-co-r4 III

or its acid halide, acid anhydride or ester, in individual cases also its acid amide (re-amidation).

Alternatively, compounds of formula I may also be prepared starting from acyl anilides of formula

Rs J

nh-co-r4 iv

Rr 6 R2 and convert them with butyllithium or sodium hydride to the corresponding alkali salt, which is then reacted with a compound of formula? H3 v

Hal-CH-C00R3 is obtained from the desired end product, or acylanilides of formula IV, by reacting them with a compound of formula V in the presence of an alkali carbonate (such as sodium carbonate or potassium carbonate) as a proton acceptor, preferably by adding catalytic amounts of alkali iodide (such as KJ).

In formulas II, III, IV and V, R 1 is as defined in formula I, while "Hai" means a halogen atom, preferably chlorine or bromine, or some other easily cleavable residue. The phrase "acid halide" preferably means acid chloride or acid bromide.

The reactions may be carried out in solvents or diluents which are inert to the reaction components, or without these substances.

H * 1 # ·., Rt 61478

D

Examples which may be mentioned are: Aliphatic or aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform; ethers and ether-like compounds such as dialkyl ether, dioxane, tetrahydrofuran; nitriles such as acetonitrile; N, N-dialkylated amides such as dimethylformamide; anhydrous acetic acid, dimethyl sulfoxide, ketones such as methyl ethyl ketone, and mixtures of such solvents.

Reaction temperatures are 0-180 ° C, preferably 20-12 ° C. In many cases, it is preferable to use acid-binding agents or condensing agents. Suitable such are tertiary amines, such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases, such as alkali and alkaline earth metal oxides and hydroxides, bicarbonates, and carbonates, and sodium acetate. In addition, an excess of the aniline derivative of the formula II used in each case can be used as the acid-binding agent.

The production process starting from the starting materials of the formula II can also be carried out without an acid-binding agent, in which case it is advantageous in some cases to pass nitrogen through the mixture to displace the hydrogen halide formed. In other cases, it is highly preferred to add dimethylformamide as a reaction catalyst.

The details for the preparation of intermediates of formula II correspond to those generally described for the preparation of anilino-alkanoic acid esters in the following publications: J. Or g. Chem. 30, 41 01 (1965),

Tetrahedron 1967, 487,

Tetrahedron, 1967, 493,

The compounds of formula I have an asymmetric carbon atom and can be cleaved into optical antipodes in a conventional manner. In this case, the enantiomeric D-form has a stronger microbicidal effect.

In the context of the invention, those compounds having the D-configuration of the formula I are preferred. These D-forms generally have a negative rotation angle when measured in ethanol or acetone.

‘V t ** 6 61478

To prepare pure optical D-antipodes, e.g. a racemic compound of formula R1 Γ3 is prepared

KMJ / -NH-CH-COOH VI

R6 r2 where R- | , R 2) R c, and R 8 are as defined in formula I and this is then reacted in a manner known per se with an N-containing optically active base to give the corresponding salt. Fractional crystallization of the salt followed by liberation of the acid of formula VI enriched with an optical D-antipode and optionally repeating (also multiplying) the salt formation, crystallization and liberation of the α-anilinopropionic acid of formula VI periodically gives pure Form D. From this, the optical D-configuration of the ester of formula II can then be prepared in a conventional manner, e.g. in the presence of HCl or H 2 SO 4, with methanol or ethanol, if desired.

Suitable optically active organic bases are, for example, α-phenylethylamine.

Instead of fractional crystallization, the enantiomeric form D of the formula ΐ R y-1 CH3 - nh- + ch-coor3 VI1 r6 i "7 R2 can also be prepared by diazotizing the amino group in naturally occurring N-alanine with e.g. HCl or HBr. in the presence of and thus replaced by halogen while cleaving N2 and maintaining the L-configuration, then optionally esterified with methanol or ethanol and then reacted with aniline of the formula 7 61 4 7 8 v £) V -nh2 VI11 where there is mainly an inversion to the D-configuration of formula VII (J. Am. Chem. Soc. Soc. 60, 6056) Irrespective of said optical isomerism, Atrop isomerism relative to the phenyl-N <axis is generally observed in those cases where the phenyl ring is substituted at least at the 2,6-position and at the same time asymmetrically with respect to this axis (possibly also in the presence of additional substituents). This is also due to the steric hindrance of the residues CKo -CH-COOR "C0R4 attached to the N atom. agarose.

In addition, regardless of the above-mentioned optical isomerism, a cis-trans isomer relative to the double bond may be present in the case of alkenyl.

If no determined synthesis is carried out to isolate the pure isomers, the product is generally obtained as a mixture of two optical isomers, two atropisomers, two cis, trans isomers or a mixture of these possible isomers. However, the in principle more favorable fungicidal effect of the enantiomeric form D (compared to the D, L form or L form) remains unchanged and is not significantly affected by the Atrop isomer or the cis / trans isomer.

The following examples further illustrate the invention without, however, limiting it. Temperatures are given in degrees Celsius.

Unless otherwise stated, the active ingredient of the formula I, which may be present in optically active form, is in each case a racemic mixture.

Example 1:

The compound ru CH3 CHa 73

I I 3 I

1 -1 CH-COOCH 9 -N> sx (Compound No. 105) '-f C-CH = CH-CH 3 C 2 H 50 O · ··' * prepared -crotonoyl-2,3-dimethyl-6-ethylaniline (a) 100 g of 2,3-dimethyl-6-ethylaniline, 223 g of 2-bromopropionic acid methyl ester and 84 g of sodium hydrogen carbonate are stirred for 17 hours at 140 °, cooled, diluted to 300 ml. with water and extracted with diethyl ether. The extract is washed with a small amount of water, dried over sodium sulfate, filtered and the ether is evaporated. After distilling off the excess 2-bromopropionic acid methyl ester, the crude product was distilled under high vacuum; bp 88-90 ° / 0.04 torr.

(b) 17 g of the ester obtained in (a), 10.4 g of crotonic acid chloride, 2 ml of dimethylformamide and 150 ml of abs. toluene was heated at reflux for 1 hour. After evaporation of the solvent, the crude product was distilled in vacuo, b.p. 1 2 8-1 29 ° / 0.03 torr.

If the pure D-form of α-C (2,3-dimethyl-6-ethylanilino) -propionic acid methyl ester is acylated with crotonic acid or a reactive derivative thereof, the D-forms of both cis-trans isomers are obtained (compounds 105a and 105b).

Corresponding to Example 1a), other intermediates were also prepared, e.g. the following compounds of formula II: (R 1 is in the 2-position, R 2 is in the 6-position, R 2 is CH 3, R 8 is H).

R-ι Ro Rr Physical Constants CH ^ H k.p. 98 ° / 0.8 Torria CH3 C2H5 H b.p. 88-90 ° / 0.01 Torria CH3 C2H5 5_CH3 b.p. 96-99 ° / 0.03 Torria C ^ 3 CH3 3-CH3 b.p. 83 ° / 0.03 Torria; 145 ° / 9 Torria CH3 CH3 4-CH3 b.p. 88-90 ° / 0.04 Torria

Vl. '· · *. j, * 61 478 9 R-R „Re physical 1 ^ ^ Constants CH3 C2H5 3-CH3 b.p. 88-90 ° / 0.04 Torria CH3 H 4-CH3 b.p. 95-100 ° / 0.02 Torria CH3 H 5-CH3 b.p. 106-108 ° / 0.1 Torria CH3 H 3-CH3 b.p. 146 ° / 5 Torria isoC3H ^ H H b.p. 110 ° / 0.2 Torria isoC3Hy isoC3Hy H k.p. 105 ° / 0.5 Torria t.C4H9 H H b.p. 93 ° / 0.07 Torria CH3 H 4-Cl b.p. 125-127 ° / 0.07 Torria CH3 Cl H b.p. 88-89 ° / 0.03 Torria CH3 CH3 4-Br S.p. 31.5-32.5 ° CH 3 CH 3 3-Br S.p. 46-47.5 ° F H H.p.-98 ° / 0.15 Torria

Cl H H k.p. 90-100 ° / 0.09 Torria

Br H H k.p. 110 ° / 0.01 Torria J H H k.p. 105 ° / 0.15 Torria nC ^ HgO- H H k.p. 132 ° / 0.5 Torria CH3 H 4-CH30- b.p. 131 ° / 0.5 Torria CH ~ H 4sec.- k.p. 138 ° / 0.15 Torria c4h9o- C1 H 5-Cl S.p. 51.5-54 ° and the compound: CH 2 -N 2 O 3 ((R) - NH-CH-C 2 Cl 2 k.p. 110-120 ° / 0.3 Torria

Cl '«' V f <t!> R.

10 61478

Example 2:

compound

CH, I

_ ^ “Ch-cooch3 \ C ^) / - II 'CH9 (Compound No. 1)

\ C C XC-CH 2 I

X CH- |! Preparation of (- [* - methoxycarbonyl-ethyl) -N-cyclopropylcarbonyl-2,6-dimethylaniline to 51.8 g of α- (2,6-dimethylanilino) -propionic acid methyl ester in 200 ml of abs. toluene was added with stirring at room temperature 31.3 g of cyclopropanecarboxylic acid chloride in 50 ml of abs. toluene. 2 ml of dimethylformamide were added, followed by refluxing for 2 hours, and the solvent and excess cyclopropanecarboxylic acid chloride were distilled off in vacuo. Trituration with a small amount of petroleum ether caused the residual oil to crystallize. After recrystallization from toluene-petroleum ether, compound no. 1 melted at 8U-87 °.

Example 3:

Preparation of CH3 * | H3, - (^ CH-C00CH3 \ O / —N \ i compound # 2) - [(NvC-CH = CH2 ch3 ä) N- (1'-methoxycarbonyl-ethyl) -N-vinylcarbonyl- 2,6-dimethylaniline to 166 g of α- (2,6-dimethylanilino) -propionic acid methyl ester and 70 .mu.g of pyridine in 600 ml of abs. toluene was added dropwise while carefully stirring at 20 ° 80.6 g of acrylic acid chloride in 150 ml of abs. toluene. After stirring for 20 hours at room temperature, the separated pyridine hydrochloride was filtered off, the solvent was distilled off in vacuo and the residual oil “M ·; <61478 11 was purified in vacuo; bp 1 30-1 35 ° / 0.01 towers (compound 2).

In this or any of the above ways, the following compounds of formula I were prepared.

Table I (is in 2-asenia, R 3 = CH 6, P 2 and R 8 = F).

t> π o Physical Constants

Yhd.no. R1 K2 K4 1 CH3 6 "CH3 m.p. 84-87 ° 2 CH2-6-CH3 -CH-CH2 m.p. 130-135 ° / O.Oltorria 3 CH3 6-CH2-CH2-CH (CH3 ) 2 kp 140 ° / 01.01 towers 4 CH3 6-CH3 -C (CH3) 3 mp 64-67 ° 5 CH3 6-CH3 -CH2SCN mp 101-103 ° 6 CH3 6-CH3 -CH3 kp 108-110 ° / 0.03 towers 7 CH3 6-CH3 -C2H5 mp 78 80 ° '8 CH3 6_CH3 -C3H2 (n) mp 49 · 51 ° 9 CII3 6-CH3 -C3H7 (iso ) mp 122-123 ° 10 CH 3 6 -C 2 H 5 -C 3 H 7 (iso) mp 93-95 ° 11 CH 3 6 -CH 3 -C 6 H 7 (n) k * P · 140-142 ° / 0, 05.towers 12 CH3 6-CH3 -C ^ Hg (iso) k * P · 138-140 ° / 0.03 atoms 12 CH3 6-CH3 -C ^ H ^^ Cn) kp 140 ° / 0.25 towers 14 CH3 3- CH3 -C3H7 (iso) bp 133 ° / 0.4 towers 15, CH3 3-CH3 -CH-C2H5 bp 136-142 ° / 0.03 towers

r f, I

f '·' c2h5 61478 12

Yhd.no. R 1 R 2 R 2 Physical Constants 16 CH 3 6 -CH 3 -CH-C 2 H 5 m.p. 71-72 ° c2h5 17 CH3 6-Cl -CK3 b.p. 123 ° / 0.07 torr 18 CH 3 6 -Cl -C 3 H 2 (n) b.p. 170 ° / 0.04 torr 19 CH3 6-Cl -CH-C2H5 m.p. 70-71 ° C2h5 20 CH3 6-C2H3 -CH-C2H3 b.p. 135-136 ° / 0.100 CH2 6 -Cl -C3H7 (iso) m.p. 90-93 ° 22 CH 3 4-CH 3 -O · -C 3 H 2 (iso) m.p. 96-98 ° 23 isoC3H? H -C 3 H 2 (iso) m.p. 62-64 ° 24 isoC 3 H 7 H -CH-C 2 H 5 m.p. 74-76 ° C> 5 25 nC ^ Hg-O-! H -C 3 H 7 (iso) k.p. 152 ° / 0.05 torr 2 6 nC, Hn-0-! H -CH-COH, b.p. 145 ° / 05.05 torria 4 9 i I 2 5! C2H5 27 isoC3H76-isoC3 -C3H._ (iso) b.p. 133 ° / 0.1 torr 28 isoC3H7 jo-isoC3 -CH-C2H. bp 147 ° / 0.03 torr II ^ <5 29 isoC3H7 6-iso (^ H7 -C5H1] L (n) bp 143 ° / 0.03 torr 30 CH ~ 4-CH - Oi -CH-C ° / 0.6 torr

i H

C2H5 31 F H -C3H7 (iso) b.p. 118-122 ° / 0.35 torr 32 F II -C4H9 (iso) b.p. 105 ° / 0.04 torr 33 CH3 d-CH3 -CH = CH-CH3 m.p. 80-82 ° 34 CH 3 5-CH 3 -CH = C (CH 3) 2 k.p. 118 ° / 0.07 torr 35 CH3 5 "C2H5" CH = CH-CH3 kp 130-132 ° / 0.05 torr 36 CH3 5-C2H5 -CH = C (CH3) 2 kp 128 ° / 0.07 torr 37 C01U 6-COH, - CH = CH-CH- mp 136-138 ° / 0.04 torr 2 0 2 5 3 wyr 614 7 8 13 | ί

Yhd.no. j ^ 2 | _ ^ 4 Physical Constants 38 | C2H5 b-C2H5 -CH = C (CH3) 2 k.p. 135 ° / 0.07 torria! ί 39 CH3 H -CH = CH2 ol3y 40 CH-! h -CH = CH-CH0 k.p. 130 ° / 0.05 towers O j | ! 41 CH3-0- | H | -CH = CH2 k.p. 138-139 ° /0.02 towers 42 CH3 5-CH3 -CH = CH-CH3 b.p. 122-123 ° / 0.05 torr 43 CH3 p_CH3 -CH = C (CH3) 2 k.p. 147 ° / 09.09 towers 44 CH3 b-Cl -CH = C (CH3) 2 k.p. 141 ° / 0.03 torr 45 CH- 6-Cl -CH = CH-CH ~ m.p. 106-113 ° 3 I 3 46 CH3 fr-CH3 -CH = C (CH3) 2 k.p. 129-131 ° / 0.03 torr 47 isoC3H7 | H -CH = C (CH3) 2 k.p. 129-131 ° /0.03 'torr 48 CH3 6-CH3 -CH2-CH = CH2' b.p. 14-3-145 ° / 0.04 torr 49 CH 2 Cl 2 -O- -CH = C (CH 2) 0 k.p. 148-150 ° / 0.1 torr

3 j 3 3 L

50 lisoC-H-, 1H-CH = CH-CH ~ k.p. 142 ° / 0.3 torria 3 7 * 3 j 51! CH3 3-CH3 -CH = C (CH3) 2 k.p. 147 ° / 0.35 torr 52 · jnC4H9-0- | H -CH = C (CH3) 2 k.p. 160 ° / 0.05 torr 53 nCAH9-0-! H -CH = CH-CH3 k.p. 157 ° / 0.05 torr 54 isoC3H /: 6-iso ^ -CH = CH-CH3 b.p. 170 ° / 0.1 torrra 56 F H -CH = C (CH3) 2 k.p. 125 ° /0.3 torr 57 F H -CHCH-CH3 b.p. 126-131 ° / 0.35 torr 58 Cl H -CH = C (CH3) 2 k.p. 118-122 ° / 0.05 torr 59 Br H -CH = C (CH3) 2 k.p. 140 ° / 0.04 torr 60 Br H -CH = CH-CH3 b.p. 138 ° / 0.04 torr 51 Cl H -CH = CH-CH3 b.p. 132 ° / 0.01 torr 62 CH3 6-Cl <3 I k.p.140-142 ° / 0.04 torr 6 3 ClI3 4-CH3 <1 j k.p. 138-140 ° / 0.05 torr 64 CH 5-CHo k «P · 137 -138 ° /0.07 torr.

14 614 7 8

Yhd.no. l Physical Constants 65 j C2H5 6-C2H5 - <] m.p. 43-45 ° 66 CH 3 6-C 2 H 5 and m.p. 71-76 ° 67 CH3 4-CH3-O- - <^ J, m.p. 82-83 ° 68 ch3; 3-ch3 <jk.p. 142 ° / 03.03 torr 69 CH3 | 4-sec. bp 156 ° / 0.04 torr

C4H9- ° "N

70 ^ ert.C ^ HJ H - ^ 1 k.p. 150-152 ° / 0. ltorria 71 aC ^ Hg-O- H k.p. 149-151 ° / 0.04 torr 72 LsoC3H7 H - ^ j k.p. 135 ° / 0.03 tons 73 LsoC3H7 in 6> Cp7 - ^ J k.p. 138 ° / 0.03 torr 74 F j H - ^ J k.p. 125 ° / 0.03 torr 75 Cl j H k.p. 140 ° /0.06 torr 76 j J j H - ^ J k.p. 143 ° / 0.15 tons 77 CH3 6-CH3 m.p. 92-96 ° 78 CH 3 6-CH 3 -CD m.p. 116-121 ° 79 CH, 6-Cl-Γ7] m.p. 105-108 ° C mm 80 CH3 6-CH3 H4 m.p. 138-140 ° 81 CH 3 6-Cl H 2 m.p. 129-130.5 ° S # · J., Is 61478

I I

Combined No. I R, R „I R, Physical Constants ί 1 2 i 4 I ^ 82 I CH3 6-C2H5 m.p. 125-127 °! I .—.

83 nC ^ Hg-O-j H I - ^ Hy sul. p73-74.5 '84 CH3 3-CH3 - ^ ~ Hy * sul. p51-54 ° 85 isoC3H7 H —k.p. 145 ° / 0.04 torr 86 terLC ^ g! H _ ^ H ~ ^ k.p. 152-155 ° / 0.06 torr 87 CH3 4-ch3 I m.p. 69-72 ° 88 CH3 4-CH3-0- waxy r 89 F I H - ^ k .p. 132 ° / 0.05 torria in 90 Br! Η / 5Λ. bp 135-145 ° / 0.05 torria i I "/1 / 'ί ^ 91 Cl S Η _ / ηΛ m.p. 102-104 ° 92 CH3 4-CH3 -CH2-SCN m.p. 68-72 ° 93 CH3 5-CH3 - CH2SCN m.p. 86-88 ° V> 0.

16 61 478

According to Examples 1-3 or any of the other methods mentioned above, the following compounds of formula I are also prepared:

Table u (R ^ is in the 2-position · ia r i - H) YHd. R R R r physical

Nr. ^ 34 Constants 94 6-C1 C2H5 -CH = C (CH3) 2 k.p. 146-150 ° 95 CH 3 6 -Cl C 2 H 5 -CH = CH-CH 3 S.p. 88-92 °

According to Examples 1-3 or any of the other methods mentioned above, the following compounds of formula I are also prepared:

Table III (R 1 is in the 2-position; r is in the 6-position; R = CH) 2 3 3

Tr ": R1 I R2 | R5 I R6 [* 4 I

96 CH3 CH3 4-CH3 H -C3H7 (n) S.p. 65-66.5 ° 97 C2H. CH- 3-CH- H -CH «= CH-CH, m.p. 150-152 ° / JJJ 0.06 Torria 98 C2H5 CH- p-CH- H -C-H7 (n) mp 143-145 ° / JJJ '0.03 Torria 99 CH- CH- 3-CHq H -CH « CH-CH- kp 138-140 ° / JJ 0.1 Torria 100 CH- CH- 3-CH- H -C-H7 (n) kp 130-132 ° / JJJ '0.04 Torria 101 CH CH, 3-CH, H <1 kp130 -132 ° / JJJ 0.04 Torria 102 CH3 CH3 3-Br H -CH-CH-CH3 kp 155-160 ° 103 CH-CH-3-CH-5-CH- -C-H- (n) mp 174-177 ° / 0 J J 33 / 0.04 Torria

17 6 1 4 7, C

Comp. R- R2 Rr R / physical

No. ·> Constants 104 CH- CH- 3-CH- 5-CH- -CH = CH-CH- k.p. 184-189 ° 0.03 Torria 105 CH- CH, 3-CH- Η i -CH-CH-CH- kp128-129 ° / 0.03 Torria 106 CH3 CH3 4-CH3 H -CH = CH-CH- mp138-140 ° / ^ <0.1 Torr 107 CH3 CH3 4-CH3 H "\ | S. p.88.5-89.5 ° 108 CH3 C2H5 4-Br H - <^ 1 kp 174-176 ° / ^ 0.1 Torria 109 CH- CH- 4-Br H -C, H- (n) kp145-146 ° / * * 0.03 Torria 110 CH3 CH- 4-Br H -CH = CH-CH- kp 173-175 ° / 0.08 Torria 111 Cl Br 4-Br H -CH = CH-CH- kp 145-150 ° / 0.05 Torria 112 F Br 4-Br H -CH = CH-CH 2 kp141- 146 ° / 0.03 Torria 113 CH- CH- 4-C1 H -C-H7 (n) mp 147-149 ° (J '0.03 Torria 114 CH3 Cl 4-C1 H ~ 1 mp 162-165 °). xi 0.02 Torria 115 CH3 CH3 4-Br H "\ j S .p. 122-123.5 ° 116 CH3 CH3 4-Cl H -CH = CH-CH3 b.p. 152-154 ° / .. 0.04 Torria 117 CH- CH- 4-C1 H ~ \ Ί k.p. 172-174 ° / 0.02 Torria 118 CH3 CH.3 4-Br H -CH = CH-CH3 S.p. 110-112 ° 119 CH3 CH3 4-Br H -C3H7 (n) mp102-105 ° 120 CH3 Cl 4 -Cl H -CH 2 (n) mp 189-193 ° / 0.02 Torria 121 CH3 Cl 4-Br H -C ^ H? (N) 'kp 187-190 ° / 0.03 Torria 122 CH3 Cl 4 -Cl H -CH = CH-CH- kp187-190 ° / J 0.01 Torria 123 CH- Cl 4-Br H -CH-CH-CH- kp 193-195 ° / J 0.02 Torria 124 C3H2 (0C3H2 (i) 4-Br H -C5Hn (n) M.p. 102-105 ° 125 CH- (i) C-H7 (i) 4-Br H - <m.p. 147-151 ° / '^ 0.1 Torr 126 CH (i) CH- (i) 4-Br H - CH-CH-CH- mp 154-158 ° / -3 1 0.3 Torr y .

1 8 61478

The compounds of the formula I can be mixed with other suitable pesticides or plant growth promoters in order to broaden their spectrum of action.

The compounds of the formula I can be used as such or in combination with suitable carriers and / or other additives. Suitable strains or additives may be solid or liquid and correspond to those commonly used in the art of preparation, e.g. they may be natural or regenerated minerals, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.

The active ingredient content is 0.1-90% in commercial substances.

For use, the compounds of formula I may take the following forms of treatment (in which case the percentages by weight in parentheses denote the preferred amounts of active ingredient):

Solid applications: Granules, dust granules, coating granules, impregnation granules and homogeneous granules (1-80%) of dust and dispersants (up to 10%); liquid forms of treatment: (a) Water-dispersible concentrates: wettable powders and pastes (25-90% in commercial packaging, 0.01-15% in ready-to-use solution); emulsion and solvent concentrates (10-50%; 0.01-15% in ready-to-use solution); b) Solutions (0.1-20%); The active ingredients of the formula I of the present invention can be formulated, for example, as follows: Dusting agent: a) The following substances were used to prepare 5% and b) 2% dusting agent: a) 5 parts of active ingredient 95 parts of talc; b) 2 parts active ingredient 1 part highly dispersed silicic acid, 97 parts of talc;

The active ingredients are mixed and ground with carriers and can be used in this form for dusting.

Ψ 19 f · 'tl f:

Granulate: The following substances are used to prepare 5% granulate: 5 parts of active ingredient 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol 91 parts of kaolin (grain size 0.3 to 0.8 mm).

Your active ingredient is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto the kaolin and then the acetone is evaporated off under vacuum. Such a microgranulate is preferably used to control soil fungi.

Spraying powder: a) 70%, b) 40%, c) and d) 25%, e) 10% spraying The following ingredients are used to prepare the powder: a) 70 parts of active ingredient 5 parts of sodium dibutyl naphthyl sulfonate, 3 parts naphthalenesulfonic acid phenolsulfonic acid formaldehyde condensate 3: 2: 1, 10 parts kaolin 12 parts Champagne chalk; b) 40 parts of active ingredient 5 parts of lignin sulphonic acid sodium salt, 1 part of dibutylnaphthalenesulphonic acid sodium salt, 54 parts of silicic acid, c) 25 parts of active substance 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk / 1 sodium hydroxase ethylcellulose -dibutyl naphthalene sulfonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin; d) 25 parts of active ingredient 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk / hydroxyethylcellulose mixture (1: 1), 8.3 parts of sodium aluminum silicate, 16.5 parts of diatomaceous earth, 46 parts of kaolin; e) 20 parts of active ingredient 3 parts of a mixture of sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid / formaldehyde condensate, 82 parts of kaolin;

The active ingredients are thoroughly mixed with the additives in suitable mixers and ground in suitable mills and rollers. An spray powder is obtained which has excellent wettability and fluidity and which can be diluted with water to suspensions of the desired concentration in each case and which can be used in particular for application to leaves.

Emulsifiable concentrates: The following substances are used to prepare a 25% emulsifiable concentrate: 25 parts of active ingredient 2.5 parts of epoxidized vegetable oil, 10 parts of alkylarylsulfonate / fatty alcohol-polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylol.

Such concentrates are obtained by diluting with water emulsions of the desired concentration, which are particularly suitable for application to leaves.

Example U:

Effect against Phytophtora infestans in Solanum lycopersicum _ (= tomato) _ la) Residual inhibitory effect

Seedlings of Solanum lycopersicum, species "Roter Gnoro", are infected three weeks after being sprayed with porridge containing 0.06% of active substance (prepared from the active ingredient formed as spray powder) and, after drying, with a flocking sprout suspension of Phytophtora infestans. They are then kept for 6 days in an air-conditioning chamber at 18-20 ° and high humidity maintained by artificial spray mist. After this time, typical spots appear on the leaves. Their number and size are considered as a basis for evaluating the tested substance.

lb) Healing effect

Tomato seedlings of the species 'Roter Gnom' are sprayed, after three weeks of cultivation, with a fungal sprouting suspension and incubated in a chamber at 18 to 20 ° C and saturated humidity. Irrigation is stopped after 21 hours. After drying, the seedlings are sprayed with porridge, containing syringes of the active ingredient formulated as a powder at a concentration of 0.06% After drying the sprayed material, the seedlings are again exposed to humidity for four days, after which the number and size of typical leaf spots appear as a basis for evaluating the effectiveness of the tested substances.

II) Preventive-systemic effect

The active ingredient, formulated as a spray powder, is applied at a concentration of 0.006% (based on soil volume) to the soil surface of 3-week-old potted tomato seedlings "Roter Gnom". After a waiting period of three days, a flocking sprout suspension of Phytophtora infestans is sprayed on the underside of the leaves of the plants. They are then kept for 5 days in a spray chamber at 18-20 ° and saturated humidity. After this time, typical leaf spots are formed, the number and size of which are used to evaluate the efficacy of the test substances.

In these three experiments, the compounds no. 1, 2, S, 8, 18, 33, 35, 45, 62, 77, 96, 99, 100, 101, 103, 104, 105, 106, 108, 109 and 113 for a fungal infection value of less than 20% compared to untreated but infected control seedlings.

Example 5:

Effect against Plasmopara viticola (Bert. Et Curt.) (Berl. Et DeToni) in the vine ___ a) Residual inhibitory effect

In the greenhouse are grown wine cuttings, species "Chasselas". In the 10-leaf stage, three taints are injected with a porridge made of the active ingredient formulated as a powder (0.05% of the active ingredient). After drying the sprayed substance, the seedlings are evenly adhered to the underside of the leaves with a spore suspension of the fungus. The seedlings are then kept for 8 days in a humid chamber. After this time, there were clear symptoms in the control seedlings. The number and size of sites of infection in the treated seedlings were used as a basis for evaluating the efficacy of the test substances.

(b) Healing effect

Wine cuttings, species "Chasselas", were grown in a greenhouse -.S. · * '*' - ΛΓν · '22 f. 14 7 8 and infected in a 10-leaf stage with a spore suspension of Plasmopara viticola from the underside of the leaves. After 24 hours at humidity, the seedlings were sprayed with 0.05% active ingredient porridge prepared from active ingredient spray powder. Thereafter, the seedlings were further kept for 7 days in a humid chamber. After this time, symptoms appeared in control seedlings. The number and size of sites of infection in the treated seedlings were used as a basis for evaluating the efficacy of the test substances.

In both experiments, compounds 1, 2, 5, 6, 7, 9, 18, 33, 35, 36, 44, 45, 62, 77, 78, 96, 99, 100, 101, 106, 107 and 117 inhibit fungal infection. , which is less than 20% compared to untreated but infected control seedlings.

Example 6:

Effect against Erysiphe graminis in Hördeum vulgare (barley)

Residual protection effect

Barley seedlings about 8 cm high are sprayed with an active ingredient spray powder (0.02% active ingredient). After 48 hours, the treated seedlings are pollinated with fungal conidia. Infected barley seedlings are kept in a greenhouse at about 22 °; and fungal infection is determined after 10 days.

Compounds no. 29, 30, 46, 52, 54, 65, 69, 70, and 125 reduced fungal infection by <20% in this experiment compared to untreated but infected control seedlings.

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