CA1067909A - Microbicides and plant growth regulators - Google Patents

Abstract

Abstract of the Disclosure Compounds of the formula I

Description

l~ '7~e~9 The present invention provides compounds of the formula 5 ~ C:l COOR~ (I) wherein Rl represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen~ R2 represents hydrogen, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen, R5 represents hydrogen, alkyl of 1 to 3 carbon atoms or halogen, R6 represents hydrogen or methyl, the total number -of carbon atoms in the substituents Rl, R2, R5 and R6 not exceeding 8, R3 re-presents hydrogen, me~hyl J or ethyl, and R4 represents alkyl of 1 to 6 carbon atoms, which is unsubstituted or substituted by cyano ~-CN) or rhodano (-SCN) alkenyl of 2 to 5 carbon atoms or cycloalkyl of 3 to 7 carbon atoms, a process for the manufacture of these compounds, fungicidal compositions containing , them and their use in combatting fungi.
Depending on the number of the indicated carbon atoms the following i groups are mentioned as examples of alkyl groups or as examples of alkyl moieties of alkoxy groups~ methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl5 sec. or tert, butyl as well as the pentyl or hexyl isomers. Examples ;~ of alkenyl radicals are vinyl, allyl, methallyl, butenyl, methylbutenyl and their isomers. Cycloalkyl radicals include cyclopropyl, cyclobutyl, cyclo-pentyl~, cyclohexyl and cycloheptyl. }lalogen is fluorine, chlorine, bro~ine or ~ iadine.
.
The compounds of the formula I possess for practical purposes a very favourable microb1cidal spectrl~ for the protection of cultivated plants.
Examples of cultlvated plants are: cerealsj maize, riceJ vegetablesJ sugar-.

~ 2 - ~ ~

~ 790~
be~t, soya, ground nuts, fruit treesJ ornamental plants, but principally vines, hops~ cucumber plants (cucumbers, marrows, melons), solanaceae, such as pota-toes~ tobacco and tomatoes, banana~ cocoa and rubber plants.
Employing the active substances of the formula I it is possible to destroy the fungi which occur in plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) and also to protect the parts of plants which grow later from at~ack by such fungi. The active substances act against the phytopathogenic fungi which belong to the following classes; ascomycetes (cryalphaceae); basidiomycetea, above all rust fungi (e,g. Puceinia graminis) fungi imperfecti ~e.g. moniliales, cercospara); but especially against the comycetes belonging to the class of the phycomycetes, e.g. phytophthora, peronospora, pseudoperonospora, pythium or plasmopara. In addition, the com-pounds of the formula I have a systemic action. They can also be used as seed-dressing agents for protecting seeds, fruit, tubers, kernels and plant cuttings from fungal infections as well as from phytopathogenic fungi which occur in ~he soil.
An interesting group of compounds comprises ~hose of the formula I wherein R4 represents alkenyl of 2 to 5 carbon atoms.
Preferred fungicides are ccmpounds of the formula I in which Rl represents methyl, R2 is in ortho-position to the amino group and represents methyl, ethyl or chlorine~ and R3, R4, R5 and R6 are as defined above.
Compounds of this group to be singled out for special mention on account of their action are those wherein R3 represents methyl, R4 represents alkyl of 1 to 4 carbon atoms, alkenyl of 3 to 4 carbon atoms or cycloalkyl radlcal of 3 to 6 carbon atoms and R5 and R6 are as defined above, the number of carbon atoms in the substituents Rl, R2, R5 and R6 not exceeding 4.
Another important subgroup of compounds comprises those of the ~0679~9 formula I whereln ~2 represents hydrogen, alkyl of 1 to 3 carbon atoms or halogen, the substituents R5 and R6 represent hydrogen and the substituents Rl, R3 and R4 are as defined in formula I.
- Preferred compounds within the above mentioned groups are those ; wherein R3 represents methyl.
According to the invention, t:he compounds of the formula I may be manufactured by acylation of a compound of the formula II

5 ~ NH / CH COOR3 1~ R6 R
;~ .
with a carboxylic acid of the formula III
HO-CO~R4 (III) or with the acid halide~ acid anhydride or ester.
According to the invention it is also possible to manufacture the ~ compounds of the formula I by con~erting the acyl anilide of the formula IV
., 1 R ~ NH-co-R4 ~IV) R6 `1-- .
R2 : .:
with butyl lithium or sodium hydride into the corresponding alkali salt, which is then reacted with a compound of the formula V

Hal-CHCOOR3 (V) to gi~e the desired end product, or else to react the acyl anilide of the ' " ' ~ l 1 r 4 r h~ ~
~ .

~'7~C1 9 formula IV with the compound of the formula V in the presence of an alkali carbonate (e.g, Na2CO3 or K2CO3) as proton acceptor, preferably with the addi-tion of catalytic amounts of alkali iodicle (e.g. potassium iodide).
In the formulae II, III, IV and V, the symbols Rl to R6 are as de-fined in formula I and Hal represents a halogen atom, preferably chlorine or bromine or another easily removable radical. The preferred acid halides are the acid chloride and acid bromide. The reac~ions can be carried out in the presence or absence of solvents or diluents which are inert to the reactants.
Examples of suitable solvents or diluents are: aliphatic or aromatic hydro-carbons, e.g. benzene, toluene, xylene, petroleum ether; halogenated hydro-carbons, e.g. chlorobenzene, methylene chloride~ ethylene chloride, chloro-form; ethers and ethereal compounds~ e.g. dialkyl ethers, dioxan, tetrahydro-furan; nitriles, e.g. acetonitrile; N,N-dialkylated amides, e.g. dimethyl formamide; dimethyl sulphoxide, ketones, e.g. methyl ethyl ketone, and mix-tures of such solvents.
The reaction temperatures are usually between 0~ and 180C, prefer-ably between 20C and 120C. It is often advantageous to use acid acceptors or condensation agents. Suitable examples are: tertiary amines, e.g. trialkyl-amines ~e.g. triethylamine), pyridine and pyridine bases, or inorganic bases, e.g. the oxides and hydroxides, hydrogen carbonates and carbonates of alkali metals and alkaline earth metals, as well as sodium acetate. Moreover, in the first manufacturing method, it is also possible to use a surplus of the respec-tive aniline derivative of the formula II as acid acceptor.
The process of manufacture which proceeds from compounds of the formula II can also be carried out without acid acceptors; in some instances it is expedient to pass through nitrogen in order to expel the hydrogen halide that has formed. In other instances it is very advantageous to use dimethyl . - 5 - ~

6~)9 formamide as reaction catalyst.
Particulars concerning the manufacture of the intermediates of the formula II can be learned from the general me~hods for the manufacture of aniline-alkane acid esters as described in the following publications:
J. Org. Chem. 30, 4101 ~1965)~ Tetrahedron 1967, 487;
Tetrahedron 1967, 493.
The compounds of the formula I contain an asymmetrical carbon atom and can be resolved into the optical antipodes in the customary manner. In this connection, the enanti~meric D-form has the more pronounced microbicidal ; action.
Within the scope of the invention, the use of compounds of the formula I in their D-configura~ion is accordingly preferred. These D-forms have a negative angle of rotation in ethanol or acetone.
The pure optical D~antipodes may be obtained by manufacturing the -racemic compound of the formula VI
R

~NH-Cil-C()OH tVI) R6 ~ ~ .

~ .' wherein Rl, R2, R5 and R6 have the meanings given in formula I, and then re-acting the compound of the formula VI in known manner with a nitrogen-contain-mg, optically active base to give the corresponding salt. The pure D-form is obtained stepwise by fractional crystallisation of the salt and subsequent liberation of the acid of the formula VI which is enriched with the optical D-antipode and, i~ appropriate, repeating (if necessary several times~ the salt - :10~;'7~0~3 formation, crystallisation and liberation of the c~-anilino-propionic acid of the formula VI. From this pure D-form it is then possible, if desired, to manufacture in known manner, for example in the presence of HCl or H2S0~, with methanol or ethanol the optical D-configuration of the ester falling under the formula II. A suitable optically active organic base is, for example, ~-phenylethylamine.
Instead of the fractional crystallisation, it is also possible to manufacture the enantiomeric D-form of the formula VII

Rl ~NH- `'CH - COoR3 (V l l ) by diazotising the amino group in the naturally occurring L-alanine in the presence of e.g. HCl or HBr and thereby replacing it by halogen accompanied by the splitting o~f of N2 and retention of the L-configuration~ then, if appropriate, effecting esterification with methanol or ethanol and subsequently reacting the ester with the aniline of the formula VIII

Rl ~ ~ (Vlll) R2 . ' whereby almos~ total inversion to the D-configurations of the formula VII
occurs ~J. Am. Chem. Soc. 76, 6065~. Irrespective of the cited optical iso-merism, an atropiso~erism is observed about the phenyl- N axis in those in-stances in which the phenyl ring is substituted at least in 2,6-position and ~ 7 ~"~ ! ' ' 1~6~9~9 at the same time unsymmetrically to this axis (i.e. also on account of the presence of additional substituents as the case may be). This phenomenon is occasioned by the steric hindrance of the radicals CH-CH3-COOR3 and -CO-R~ which are additionally introduced at the nit~ogen atom, Also irrespective of the optical isomerism, where R4 is alkenyl, cis/trans-isomerism can occur at the double bond.
Provided no synthesis with the object of isolating pure isomers is carried out, a product will normally occur as a mixture of two optical isomers, two atropisomers, two cis/trans-isomers or as a mixture of these 10 possible isomers. However, the basically better fungicidal action of the enantiomeric D-form (in comparison with the D,L-form or L-form~ is retained and is not noticeably affected by the atripisomerism or the cis/trans-isomer-sm.
The following Examples serve to illustrate the invention in more detail but do not limit it to what is described therein, Unless stated to the contrary, an active substance of the for~ula I, which can occur in optionally active form, is always to be understood as meaning the racemic ~ixture. The temperatures are given in degrees centigrade.
ample 1 Manufacture of ', .

3C~3 ICH3 N j ~compound 114) . C-CH=CH-CH3 C2H5 ll N-~l'-methoxycarbonyl-ethyl)-N-crotonyl-2,3-dimethyl-6-ethylaniline ~ 8 ~06~90~

a) A mixture of 100 g of 2,3-dimethyl-6-ethylaniline, 223 g of 2-bromo-propionic acid m~thyl ester and 84 g of NaHlC03 was stirred for 17 hours at 140C, then cooled, diluted with 300 ml of water and extracted with diethyl ether. The extract was washed with a small amount of water, dried over sodium sulphate, filtered and the ether evaporated. After the exc~ss

2-bromopropionic acid m~thyl ester had b~en distilled off, the crude product was distilled in a high vacuum; b.p. 88-90C/0.04 Torr.
b) A mixture of 17 g of the aster obtained according to a~, 10~4 g of crotonic chloride, 2 ml of dimethyl formamide and 150 ml of abs. toluene was refluxed for 1 hour. The solvent was evaporated off and the crude product distilled in vacuo; b.p, 128-129C/0.03 Torr.
The D-forms of both cis/trans-isomers (compounds 105 a and 105 b) are obtained by acylating the pure D-form of ~-~2,3-dimethyl-6-ethylanilino)-propionic acid methyl ester with crotonic acid or with one of the reactive derivatives thereof.
The other interm~diates are manufactured in a manner analogous to that of Examp~ la) e.g. the following compounds of the formula II~
~Rl in 2-position; R3=CH3 R6=H) Rl R ; ~Physical constant ._ _ . ._ - . _ CH3 6-CH3 Hb.p. 98/0.8 Torr CH3 6-C2H5 Hb.p. 88-90/O.OlTorr CH3 6-C2H55-CH3b.p. 96-99/0.03Torr CH3 6-CH33-CH3 145/9Torr CH3 6-CH34-CH3b.p. 88-90/0.04Torr CH3 6-C2H53~CH3b.p. 88-90/0.04Torr CH3 4-CH3 Hb.p. 95-100/0.02Torr CH3 5-CH3 Hb~p, 106-108/O lTorr ~ ~ .

~679~g ~ --R1 R2 R5 Physical constant . ' . _ _ , CH3 3-CH3 H b,p. 146/5Torr isoC3H7 H H b.p. 110/0,2Torr isoC3H7 6-isoC3H~ H b,p, 105/0.5Torr t.C4Hg H H b,p. 93/0.07Torr CH3 4-Cl H b,p. 125-127/0.07Torr CH3 6-Cl H b,p, 88-89/0.03Torr ; CH3 6-CH3 4-Br ~,p. 31.5~32,5 CH3 6-CH3 3-Br m.p. 46^47,5 F H H H b.p, 98/0,15Torr C1 H H b.p. 90-100/0.09Torr Br H H b.p. 110/O.OlTorr I H H b,p. 105/0.15Torr nC~HgO- H H b.p. 132/0.5Torr CH3 4~CH30- H b.p. 131~/0.5Torr CH3 4sec - H b.p. 138/0.15Torr C1 5- ~ H m.p. 51.5-54 1~ ..
. : .
as~ well as the compound C~3 NH-CH-COOC2H5 ~ b.p. 110-120/0.3 Torr :
: ., Example 2 Manufacture of CH3 C,~13 ~" ,CH - COOC}13 \ C-CH ~ l2 (compound 1) N-(l'methoxycarbonyl-ethyl)-N-cyclopropylcarbonyl-2,6-dimethylaniline.
51.8 g of d-(2,6-dimethylanilino)-propionic acid methyl ester in 200 ml of abs. toluene were treated with stirring at room temperature with 31.3 g of cyclo propanecarboxylic acid chloride in 50 ml of abs. toluene. After addition of 2 ml of dimethyl formamide the reaction mixture was re~luxed for 2 hours and the solvent and the excess of cyclopropanecarboxylic acid chloride then distilled off in vacuo. The residual oil was crystallized by scratching with the addition of petroleum ether. Compound 1 melted at 84~-87C after recrystallization from toluene/petroleu~ ether.
Ex~ple 5 Manuacture of CH3 , 3 N ~compound 2) C-Ci~=CH
CH ll 2

3 o N~ methoxycarbonyl-ethyl)-N-vinylcarbonyl;-2,6-dimethylaniline.
80.6 g of acrylic acid chloride in 150 ml of abs. toluene were added :11 Of~i7~09 dropwise with good stirring at 20C to 166 g of ~-(2,6-dime~hylanilino)-propionic aeid methyl ester and 70,4 g of pyridine in 600 ml of abs. toluene, The reaction mixture was stirred for 20 hours and the precipitated pyridine hydrochloride then filtered off. Th~ sol~ent ~Jas distilled off in vacuo and the residual oil fractionated in vacuo; b,p. 130~135C/0.01 Torr (compound 2).
The following compounds of the formula I can be manu~actured in this manner or by one of the methods indicated hereinbefore. i-Table I ~Rl in 2-position; R3=CH3; R5=R6=H) Comp. Rl ¦ R2 R4 Physical constant ~__ . __ _.__ _. ._ _ .
1 CH3 6-CH3 ~ m.p. 84-87 2 CH3 6-CH3 -CH=CH2 b.p. 130-135/0.01 Torr 3 CH3 6-CH3 -CH2_CH~CH3)2 b.p, 140/0.01 Torr

4 CH3 4-Cl -C(CH3)3 CH3 6-CH3 -C(CH3)3 m.p. 64-67 6 CH3 H C6Hl3(n) 7 CH3 6-CH3 -CH2SCN m.p, 101-103 .. __ _ ~ .__ . . _ __ r -- ¦
~ . ~ ' ~ - 12 ~
~.~1 .

9~5~

rable I cont'd ~Rl in 2- ~osition; R3=CH3 R5 = R6 = H) Comp Rl R2 4 Physical constant 8 CH36-C2H5 -C (CH3)3 9 Cl 5-C1 2 CN
CH36-CH3 -CH3 b.p. 108-110/0.03 Torr 11 CH36-CH3 -C2~l5 m.p, 78-80 12 CH36-CH3 -C3H7 ~n) m.p, 49-51 13 CH36-CH3 3 7 ~iso) m.p, 122-123 14 CH36-C2H5 -C3H7(iso) m.p. 93_95 CH36-CH3 6 13( ) b.p. 140-142/0.05 Torr 16 CH36-CH3 C4Hg(iso) b.p. 138-140/0.03 Torr 17 CH36-CH3 5 11 (n) b.p. 140tO.25 Torr 18 CH33-CH3 -C3H7(iso) b.p. 133jO.4 Torr 19 CH3;3-CH3 -ICH-C2H5 b.p. 136-142/0.03 Torr C2}15 ' , ', CH36-CH3 -IH~C2H5 m.p, 71-72 21 CH36-Cl -6H3 b.p. 123/0.07 Torr 22 CH36-Cl -C3H7tn) b.p. 170/0.04 Torr 23 CH36-Cl -fH-C2H5 m.p. 70-71 24 CH3 6-C2H5 C2HS b.p, 135-136/0.1 Torr CH3 6-Cl -C3H7(iso) m.p, 90-93 : : ' ~: : ~ "
:~ ____ .. ~.. _ ~ ~ -13- ~

~O~i~79~

_ _ _ __ _ _ ~
Comp. Rl R2 R4 Physical constan~
__ __._____ _7 : .-_~ _~
26 CH3 4-CH3_o 3~l7~iso) m.p. 96-98 27 isoC3H7 H 3 7~iso) m,p, 62-64 28 isoC3H7 H -CH-C2H5 m,p, 74_76 29 nC4Hg_O_ H -C3H7~iso) b,p, 152/0.05 Torr 4 9 H -ICH-C2H5 b.p, 145/0.05 Torr 31 isoC3H76-isoC3H7 -C3H7(iso) b,p, I33/0.1 Torr 32 isoC3H76_isoC3H7 -CH-C2H5 b.p. 147/0.03 Torr -33 isoC3H76-isoC3H7 5 11~ ) b.p, 143/0.03 Torr 34 CH3 4 CH3-_ -CH-C2H5 b.p, 154/0.6 Torr P H -C3H7(iso) b.p. 118-122/0.35 Torr-~36 F H C4Hg(is) b.p. 105/0.04 Torr 37 CH3 6-CH3 -CH=CH~CH3 m.p. 80-82 38 CH3 6-CH3 -CH=C(CH3)2 b.p. 118~0.07 Torr 39 CH3 6-G2H5 CH~CH_CH3 b.p. 130-132/0,05 Torr CH3 6-C2H5 _CH=C~CH3~2 b.p. 128/0.07 Torr 41 C2H5 6-C2H5 -CH=CH-CH3 b.p. 136-I38/0.04 Torr 42~ C2H5 6-C2H5 -CH=C(CH3)2 b.p. 135/0,07 Torr 43 CH3 H -CHoCH2 oil ~ ; _ _ ~ . ..
, ~
' "
14 _ ~ 0~'7909 .
CNOmp. Rl R2 R4 Physic~al constant . _. _ 44 CH3 H -CH=CH-CH3 b.p. 130/0.05 Torr C~13-O- H -CH=CH2 b.p. 138-139/0.02 Torr 46 CH3 5-CH3CH=CH-CH3 b.p. 122-123/0.05 Torr 47 CH3 5-CH3-CH=C(CH3)2 b.p. 147/0.09 Torr 48 CH3 6-Cl-CH=C(CH3)2 b.p. 141/0.03 Torr 49 CH3 6-Cl -CH=CH-CH3 m.p. 106-113 CH3 4-CH3-CH=C~CH3)2 b.p. 129-131/0.03 Torr 51 isoC3H7 H -CH=C(CH3)2 b.p. 129-131/0.03 Torr 52 CH3 6-CH3-CH2-CH=CH2 b.p. 143-145/0.04 Torr 53 CH3 4-CH3-O--CH=C~CH3)2 b.p. 148-150/0.1 Torr 54 isoC3H7 H -CH=CH-CH3 b.p. 142/0.3 Tsrr CH3 3-CH3-CH=C(CH3)2 b.p. 147/0.35 Torr 56 nC4Hg-O_ H -CH=C(CH3)2 b.p. 160/O.OS Torr 57 nC4}19~~ H -CH=CH-CH3 b.p. 157/0.05 Torr 58 1soC3H7 6-isoC3H7 -CH=CH-CH3 b.p. 140/0.1 Torr 59 isoC3H7 6-isoC3H7 -CH=C(CH3)2 b.p. 170/0.1 Torr 60. F H -CH=C(CH3)2 b.p. 125/0.3 Torr 61 F H -CH=CH=CH3 b.p. 126-131''/0.35~ Torr 62 Cl H -CH=C~CH3j2 b.p. 118-122/0.05 Torr 63 Br H -CH=C(CH3)2 b.p. 140/0.04 Torr 64 Br H -CH=CH-CH3 b.p. 138/0.04 Torr ~; 65 Cl H -CH=CH-CH3 b.p. 132/0.01 Torr : ~ . : ' '.
~' ~ . ' 7D```~

~ ' '. ' 067~0~

Comp; Rl - R-~ - ---R-- Physical constant .. _.__ 66 CH3 6-Cl ~ b.p.140-142 /0.04 Torr 67 CH3 4-CH3 ~ b.p.138-140 /0.05 Torr 68 CH3 5-CH3 ~ b.p.137-138 /0.07 Torr 69 C2H5 6-CH3 ~1 m.p.43 45 CH3 6-C2H5 ~1 m.p.71-76 71 CH3 4-CH3-0- --a m.p.82-83 72 C~13 3-CH3 --<1 b.p.142/0.03 Torr 73 CH ~
3 4-sec b.p.156/0.04 Torr 74 c4eHg. H ~ b.p. 150-152/0.1 Torr nC4Hg-O_ H ~1 b.p. 149-151/0.04 Torr 76 isoC3H7 H b.p. 135/0.03 Torr 77 isoC3H7 6-iso-C3H7 ~1 b.p. 138/0.03 Torr 78 ~ ~ F H ~ b.p. 125jO.03 Torr 79 Cl H ~ b.p. 140/0.06 Torr I H ~¦ b.p. 143/0.15 Torr 81 CH3 6-CH3 ~ m.p. 92-96 82 CH5 6-CH3 ~1 m.p. 116-121 83 CH3 ~ 6-Cl ~1 m.p.105-108~
~ ~ , ~ :' :
_ .

1~)t;'79V~

Comp. 1 R2 R4 Physical constant . .. _ . _ . , .. _ 84 C~13 6-CH3 ~ {~3 m.p. 138-140 CH3 6-Cl ~3 m.p. 129-130.5 86 CH3 6-C2H5 ~ im.p. 125-127 87 nC4~9-- H ~ m.p. 73-74.5 88 CH3 3-CH3 {~> m.p. 51-54 89 isoC3H7 H ~ b.p. 145/0.04 Torr c4eHt9. H ~ b.p. 152-155/0.06 Torr 91 CH3 4-CH3 i ~ m.p. S9-72 92 CH3 4-CH3-O- ~ wax-like 93 F H ~3 b.p. 132/0.05 Torr 94 ~ Br H ~ b.p. 135-145/0.05 Torr 1 Cl H ~ m.p. 102-104 96 : CH3 4-CH3 -CH2-SCN m.p. 68-72 - : 97 CH3 S-CH3 -CH2SCN m.p. 86-88 : ~^
; _ _ . . ~ ~ '~ ' "''','.
"' ~......

,,, ,..~,j - ~06'~909 TABLE I I
(Rl in 2-position; R = R = H) _ S ~ . . .
Comp. Rl R2 R3 R~ Physical constant . ,,", _ _ . . ~
98 CH3 6-Cl C2~l5 C~=C(CH3)2 b.p. 146-150 99 CH3 6-C1 C2H5 -CH=CH-CH3 m.p. 88-92 . _ ::
: ~ : : : :

:~

~Ot;~ 9 Table III (Rl in 2-position; R2 in 6-position; R3 = CH3) . . , ~ ~ ~
Comp Rl R2 R5 R6 R4 Physical constant _ _ .. . . _ ..
100 C~13 CH3 4-CH3 H -C3H7~n) m.p. 65-66.5 101 C2H5 CH3 3 CH3 H -CH=CH-CH3 b.p. 150-152/0.06 Torr 102 C2H5 CH3 3-CH3 H -C3H7~n) b.p. 143-145/0.03 Torr 103 CH3 CH3 3-CH3 H -CH=CH-CH3 b.p. 138-140/0.1 Torr 104 CH3 CH3 3-CH3 H -C3H7(n) b.p. 130-132/0.04 Torr 105 CH3 CH3 3-CH3 H _~ b.p. 130-132/0.04 Torr 10~ CH3 CH3 3-Br H -CH=CH-CH3 b.p. 155-160 107 CH3 C2H5 3-CH3 H -C3H7(n) 108 CH3 CH3 4-CH3 H -CH2-CH(CH3)2 109 C~13 CH3 3-CH3 H -CH2-CH(CH3) 110 CH3 CH3 3-CH3 5-CH3 -CH2cH(cH3)2 111 CH3 CH3 3-CH3 5-CH3 -C3H7(n) b.p. 174-177/0.04 Torr 112 CH3 CH3 3-CH3 5-CH3 CH=CH-CH3 b.p. 184-189/0.03 Torr 113 CH3 CH3 3-CH3 5-CH3 ~
114 CH3 C2H5 3-CH3 H -CH=CH-CH3 b.p. 128-129/0.03 Torr 115 CH3 CH3 4-CH3 H -CH=CH-CH3 b.p. 13g-I40/O.l Torr 116 c~l3 CH3 4-CH3 H ~ m.p. 88.5-89,5 117 CH3 CH3 4-Cl H C3H7(n) b.p. 147-149/0.03 Torr 118 c~l3 C1 4-Cl H ~3 b.p. 162-165/Oo02 Torr 119 C~l3 CH3 4-Br H --<:1 m.p. 122-123.S-120 CH3 CH3 4~C1 H -CH=CH-CH3 b.p. 152-154/0.04 Torr 121 CH3 CH3 4-CH3 H -CH2-CH=CH2 _ . __ _ ._ __ _ . .
.. , - 19 -~7 ~ ~ .

~0~;~79~)53 Table III con~'d ~Rl in 2-position; R2 in 6-position; R3 = CH3) Comp R2 R5 R R Physical constant 6 4 (~emperatures in C) _ . . _. _ _ _ _ _ ._ . .

122 C~13 CH3 3-CH3 H -cH2-cH=cH2 123 CH3 CH3 4-Cl H _~ b.p. 172-174/0.02 Tor 124 CH3 CH3 4-Br H -C}l=CH-CH3 m.p. 110-112 125 CH3 CH3 4-Br H 3H7(n)m.p. 102-105 126 CH3 Cl 4-Cl H 3H7~n)b.p. 189-193~/0.02 Tor 127 GH3 Cl 4-Br H ~

128 CH3 Cl 4-Br H C3H7(n)b.p. 187-190/0.03 Torr 129 CH3 Cl 4-Cl H -CH=CH-CH3b.p. 187-190/0.01 Tor 130 CH3 Cl 4-Br H-CH=CH-CH3 b.p. 193-195/0.02 Tor 131 iC3H7 _~ 4-Br ~-CH=CH-CH b.p. 154-158C/O.3 Tor The compounds of the formula I can be used with other suitable pesticides or active substances that promote plant growth in order to widen their spectr~un of activity. The compounds of the ormula I are used together with suitable car-riers and/or other add1tives. Suitable carriers and additives can be solid or liquid and correspond to t}le substances normally used in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, stickers, thickeners, binders or fer~ilisers. The amount of active substance in commercially useul compositions is between 0.1 and 90%.

' ' .

~067~

The compounds of the ~ormula I can be applied in the following forms (the percentages by weight in brackets denote the preferred amounts of active sub-stance~: solid forms: dusts and tracking agents ~up to 10%); granules; coated granules impregnated granules and homogeneous granules ~1 to 80%);
liquid forms:
a) active substance concentrates which are dispersible in water: wettable pow-ders and pastes (25-90% in the commercial pack, 0.01 to 15% in ready for use solution);
emulsion concentrates and concentrated solutions (10 to 50%; 0.01 to 15% as ready for use solution);
b) solutions (0.1 to 20%).
The active substances of the formula I can be formulated, for example, as follows:
Dusts: The following substances are used to manufacture a) 50% and b) a 2% dust:
a) 5 parts of active substance 95 parts of talcum;
95 parts of talcum;
b) 2 parts of active substance 1 part of highly disperse silicic acid 2097 parts of talcum.
The active substances a~e mixed with the carriers and ground and in this form can be processed to dusts for application.
Granules: The following substances are used to manufacture 5~ granules:
: ~ 5 parts of active substance ~ 0.25 part of epichlorohydrin : 0.25 part of cetyl polyglycol ether 3.50 parts of polyethylene glycol . .

9I parts of kaolin (particle size 0.3 - 0.8 mm).
.: ' : e. `,',.~ - 21 10~

The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylPne glycol and octyl poly~
glycol ether are added. The resultant so;Lution is sprayed on kaolin and ~he acetone is evaporated in vacuo. Such microgranules are advantageously used for combating soil fungi.
Wettable ~owders: The following constituents are used to manufacture a) a 70%, b) a 40%, c) and d) a 25% and e) a 10% wettable powder:
a) 70 parts of active substance

5 parts of sodium dibutyl naphthalsulphonate 103 parts of naphthalenesulphonic acid/phenolsulphonic acid/formalde-hyde condensate (3:2:1) 10 parts of kaolin 12 parts of Champagne chalk b) 40 parts o~ active substance 5 parts of sodium lignin sulphonate 1 part of sodium dibutylnaphthalenesulphonic acid 54 parts of silicic acid c) 25 parts of active substance 4.5 parts of calcium lignin sulphonate 1.9 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1) 1.5 parts of sodium dibutylnaphthalenesulphonate 19.5 parts of silicic acid 19.5 parts of Champagne chalk 28.1 parts of kaolin d) 25 parts of active substance Z.5 parts o~ isooctylphenoxy-polyethylene-ethanol 1.7 parts of a Champagne chaIk/hydroxyethyl cellulose mixture (1:1) ;8.3 parts of sodium alum mium sllicate 16.3 parts of kieselguhr ~106'7909 46 parts of kaolin ~) 10 par~s of active substance 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates 5 parts of naphthalenesulphonic acid/formaldehyde cond~nsate 82 parts of kaolin.
The active substances are intimately mixed in suitable mixers with the additives and ground in appropriate mills and coolers. Wettable powders of excellent wettability and Suspension powderare obtained. These wettable powders can be diluted with wa~er to give suspensions of desired concentration and can be used in particular for application to leaves.
Emulsifiable concentrates: The following substances are used to manufacture a 25% emulsifiable concentrate:
25 parts of active substance 2.5 parts of epoxidised vegetable oil 10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture 5 parts of dimethyl forma~ide 57.5 parts of xylene.
By diluting such concentrates with water it is possible to manu-facture emulsions o~ desired concentration which are especially suitable for application to leaves.
~ EXAMPLE 4 .
~ ~ Action against Phytophthora infestans on tomatoes.
.
la) Residual preventive_action 3-week old Solanum lycopersicum plants of the "Roter Gnom" variety ~were~spra-yed with a b:roth prepared from the-active -su~stance processed to a wettable powder and containing 0.06% of active substance, and after drying in-~fected with a zoospore suspension of Phytophthora infestans. They were then ~ 23 -...... , .. , ~ , . . . . .

~o~

kept for 6 days in a climatic charnber at 18 to 20 and high humidity crea~ed by a spray mist. After this time typical leaf specks appeared, the number and size of which served as criteria for evaluating the tested substance.
lb) Curative action:

-"Roter Gnom" tomato plants were sprayed when 3 weeks old wi~h azoospore suspension of the fungus and incubated in a climatic chamber at 18 to 20C and saturated humidity. The humidification was interrupte~ after 24 hours. After drying the plants were sprayed with a broth containing the active substance formulated as wettable powder in a concentration of 0.06%. After the spray coating had dried, thP plants were kept in the humid chamber for a further 4 days. Size and number of typical leaf specks which had appeared served as criteria for evaluating the effectiveness of the tested substances.
II) Preventive-systemic action The active substance is applied as wettable powder in a concentra-tion of 0.006% referred to the volume of the soil) to the surface of the soil containing 3 week old "Roter Gnom" tomatoes in pots. Three days later the underside of the leaves was sprayed with a zoospore suspension of Phytophthora infestans. The plants were then kept for 5 days in a spray chamber at 18~ to 20C and saturated humidity, after which time typical leaf specks form, The size and number of the specks serve as criterion for evaluating the effective-ness of the tested substance.
In the above three tests a reduction of attack to less than 20%
compared with infected but untreated control plants was achieved using e.g.
compounds Nos. 1, 2, 7, 12, 22, 37, 39, 49, 66, 81, 100, 103, 104, 105~ 111, 112, 114, 115 and 117.

.

, ~

EXAMPLE_S
Action against Plasmopara viticola (Bert. et Curt.~ (Be~l. et de Toni on vines a) Residual preventive action Vine cuttings of the variety "Chasselas" were reared in a greenhouse. Three plants in the 10 leaf stage were sprayed wi~h a broth prepared from the active substance and formulated as a wettable powder (0.06% active substance). After the coating layer had dried, the plants were infected on the underside of the leaves with a spore suspension of the fungus. The plants were subsequently kept for 8 days in a humid chamber, after which time symptoms of the disease were visible on the control plants. The number and size of the infected areas on the treated plants served as criteria for evaluating the effectiveness of the tested active substances.
b) Curative action Vine cuttings of the variety "Chasselas" were reared in a greenhouse and in-fected in the 10 lea stage on the underside of the leaves with a spore sus-pension of Plasmopara viticola. After they had been kept for 24 hours in a humid chamber, the plan~s were sprayed with a 0.06% active substance broth prepared from a wettable powder. The plants were then kept for a further 7 days in a h~lmid chamber, after which time symptons of disease were visible on the control plants. The si~e and number of the infected areas served as criteria for evaluating the effecti~eness of the tested substances. In both these tests a reduction of attack to less than 20% compared with infected but untreated control plants was achieved using e.g. compounds Nos. 1, 2, 7, 12 22, 37, 39, 49, 60, 81, 100, 103, 104, 105, 111, 112, 114, 115 and 117.

Act ~ inis on barley Residual protective action Barley plants c. 8 cm in height were sprayed wi~h a spray broth (0.02% active substance) prepared from a wettable powder. After 48 hours the treated plants f J ~ 25 - -1()tj'7~

were dusted with conidia of the fungus. The infected barley plants were stood in a greenhouse at ca. 22C and the fungus infection was evaluated after lO
days. Compounds Nos. 33, 34, 50, 56~ 579 58, 69, 73 and 74 and others ef-fected in this test a reduction of fungus inf0ction to 7 50% in comparison with infected but untreated control plants.

- : ~,r~

.

Claims (18)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compounds of the formula I

(I) wherein R1 represents alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halogen, R2 represents hydrogen, alkyl of 1 to 3 carbon atoms, al-koxy of 1 to 4 carbon atoms or halogen, R5 represents hydrogen, alkyl of 1 to 3 carbon atoms or halogen, R6 represents hydrogen or methyl, the total number of carbon atoms in the substituents R1, R2, R5 and R6 not exceeding 8, R3 represents hydrogen, methyl or ethyl, and R4 represents alkyl of 1 to 6 carbon atoms, which is unsubstituted or substituted by cyano or rhodano, or represents alkenyl of 2 to 5 carbon atoms or cycloalkyl of 3 to 7 carbon atoms.

2. Compounds of the formula I according to claim 1, wherein R1 represents methyl, R2 is in ortho-position to the amino group and represents methyl, ethyl or chlorine, and R4, R5 and R6 have the meanings assigned to them in claim 1.

3. Compounds of the formula I according to claim 2, wherein R3 represents methyl, R4 represents an alkyl, alkenyl or cycloalkyl radical of 2 to 4 carbon atoms and R5 and R6 have the indicated meanings, the total num-ber of carbon atoms in the substituents R1, R2, R5 and R6 not exceeding 4.

4. Compounds of the formula I according to claim 1, wherein R2 represents hydrogen, alkyl of 1 to 3 carbon atoms or halogen and the substi-tuents R5 and R6 represent hydrogen, and the substituents R1, R3 and R4 have the meanings assigned to them in formula I.

5. Compounds of the formula I according to claim 1, wherein R4 represents a cyanomethyl or a rhodanomethyl group.

6. N-(1'(methoxycarbonyl-ethyl)-N-rhodanoacetyl-2,6-dimethyl-aniline according to claim 1.

7. N-(1'-methoxycarbonyl-ethyl)-N-cyclopropanoyl-2,6-dimethyl-aniline according to claim 1.

8. N-(1'-methoxycarbonyl-ethyl)-N-acryloyl-2,6-dimethylaniline according to claim 1.

9. N-(1'-methoxycarbonyl-ethyl)-N-crotonoyl-2,6-dimethylaniline according to claim 1.

10. N-(1'-methoxycarbonyl-ethyl)-N-crotonoyl-2-methyl-6-ethyl-aniline according to claim 1.

11. N-(1'-methoxycarbonyl-ethyl)-N-cyclopropanoyl)-2-methyl-6-chloroaniline according to claim 1.

12. N-(1'-methoxycarbonyl-ethyl)-N-crotonoyl-2-methyl-6-chloro-aniline according to claim 1.

13. N-(1'-methoxycarbonyl-ethyl)-N-butyryl-2-methyl-6-chloroaniline according to claim 1.

14. N-(1'-methoxycarbonyl-ethyl)-N-(3"-methyl-butyryl)-2,6-dimethyl-aniline accordlng to claim 1.

15. The D-configuration of the compounds of the formula I accord-ing to claim 1.

16. A process for the manufacture of a compound of the formula I

of claim 1, wherein a compound of the formula II

(II) is acylated with a carboxylic acid of the formula III

or with the acid halide, acid anhydride, acid amide or ester thereof.

17. A process according to claim 16, wherein the acylation with the corresponding acid chloride or acid bromide is carried out in a tempera-ture range of 0°C to 180°C.

18. A method of combating phytopathogenic fungi on plants which comprises applying thereto, or to the locus thereof, a compound according to any one of claims 1 to 3.