DD149600A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to novel fungicidal compositions containing as active ingredient at least one substituted N-alkyl-acetanilide of general formula I in which R & exp1! forhydrogen, alkyl, halogen, alkoxyalkyl or alkylthioalkyl, R & exp2! for hydrogen, alkyl, alkoxyalkyl or alkylthioalkyl, R & exp3! for hydrogen, alkyl, alkoxyalkyl or alkylhioalkyl, R & exp4! for hydrogen, alkyl or alkoxyalkyl, R & exp5! phenyl, R & exp6! for hydrogen, alkyl, halogen or unsubstituted phenyl, R & exp7! for hydrogen, alkyl, halogen or substituted phenyl, R & exp8! for furyl, tetrahydrofuryl, thiophenyl Alkyl substituted isoxolyl, optionally alkyl substituted by cyano or thiocyano, alkenyl and alkynyl, dihaloalkyl, and the groupings -CH & ind 2! -Az, CH & ind 2! -OR & exp9 !, - CH & ind2! -SR & exp9 !, - OR & exp9 !, - SR & exp9 !, - CH & ind2! -OSO & ind2! R & exp9 !, - COOR & exp9 !, and formula wherein R & exp9! For substituted alkyl, alkenyl, alkynyl or alkoxyalkyl and Ar for pyrazo-1-yl, 1,2, 4-triazol-1-yl and imidazol-1-yl.

Description

Berlin, 11.8.1980 57 039/18

219759 - * -

Field of application of the invention

The present invention relates to the use of novel substituted N-allyl-acetanilides as fungicides,

Character! Gtik of the known technical Lögungen

It has already been disclosed that haloacetanilides, such as N-chloroacetyl-N- (2,6-dialkylphenyl) -alanine or -glycine alkyl esters, can be successfully used to combat fungal plant diseases (see DT-OS No. 2 350 944 or US Pat. No. 3,780,090). However, their action is not always completely satisfactory, especially at low application rates and concentrations, in particular also in the control of Phytophthora species.

Object of the invention

The aim of the invention is to show new fungicides which can be used in agriculture for controlling fungal plant diseases.

Explanation of the essence of the invention

The invention has for its object to provide new fungicides with good application properties, such as low application rates and concentrations.

There have now been the new substituted N-ailyl-acetanilides

R ⁶

R ⁷ (D.

the general formula R * R I CH I - C R ² R ¹ II 0 R ³ R ³

in which

R ^{1 is} hydrogen, alkyl, halogen, alkoxy

"alkyl or alkylthioalkyl,

R ^{2 is} hydrogen, alkyl, alkoxyalkyl or alkylthioalkyl,

R ^{3 is} hydrogen, alkyl, alkoxyalkyl or alkylthioalkyl,

R * represents hydrogen, alkyl or alkoxyalkyl,

R ^{5 is} hydrogen, alkyl, halogen or optionally substituted phenyl,

R ^{6 is} hydrogen, alkyl, halogen or ge

optionally substituted phenyl,

R ^{7 is} hydrogen, alkyl, halogen or optionally substituted phenyl,

Le A 19 517

\ 97 5 9 -3- 11.8.1980

57 039/18

R ^{8 is} furyl, tetrahydrofuryl, thiophenyl,

tetrahydrothiophenyl; optionally substituted by alkyl isoxazolyl; optionally cyano or thiocyano substituted alkyl, alkenyl and alkynyl; dihaloalkyl; as well as the groupings

-CH ₂ -Az, -CH ₂ -OR ⁹ , -CH ₂ -SR ⁹ , -OR ⁹ , -SR ⁹ , -CH ₂ -OSO ₂ R ⁹ , -COOR ⁹ and -CH ₂ -O- (T \ stands, where

R is optionally substituted alkyl, alkenyl, alkynyl or alkoxyalkyl and

Az is pyrazol-1-yl, 1,2,4-triazol-1-yl and imidazol-1-yl,

found.

The compounds of the formula (I) may optionally be present in the two geometric isomers eis and trans; they are predominantly mixtures of the two. The use of all isomers and the mixtures is claimed according to the invention.

4-11.8.1980

57 039 /

The substituted IT-allyl-acetanilides of the formula (I) are obtained if one

a) H-allyl-anilines of the formula

_ "j> 5, 1

in which

1 7

R to R have the abovementioned meaning,

with acid chlorides or bromides or anhydrides of the formula

R ⁸ - C - Cl (Br) (purple),

It

or*

(R ⁸ ^ CO) ₅ O 0

in which

2197 59 -5-

R ^{8 has} the meaning given above,

in the presence of a diluent and optionally in the presence of an acid binder, or

b) Anilides of the formula

V "

(IV)

sC .. / ^N r _ approx

R ³

in which

R ¹ , R ² , R ³ and R ^{8 have} the abovementioned meaning

with allyl halides of the formula

Hai - CH - C = C (V)

^X R ⁷

in which

R ⁴ to R ^{7 have} the abovementioned meaning

Hai is chlorine or bromine,

in the presence of an acid binder and optionally in the presence of an organic diluent or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, or

Le A 19 517

5 '9

- 6 - c) aldehydes or ketones of the formula

(VI)

in which

R ¹ to R ⁵ and R ^{8 have} the abovementioned meaning,

with phosphine alkylene of the formula

/ ^R6 e G / ^R6

(Q ₆ H ₅ ) ₃ P = C <> (C ₆ H ₅ I ₃ P - C (VII)

^X R ⁷ R ⁷

in which

R ⁶ and R ^{7 have} the abovementioned meaning, if appropriate in the presence of a diluent.

Individual compounds of formula (i) can also be obtained by

d) N-propargyl-acetanilides of the formula

CH - C = C - R ⁷

(VIII)

in which

Le A 19 517

2 t 97 5 9

R ¹ to * R *, - 7 -

R ⁷ and R ⁸ are as defined above,

with hydrogen in the presence of a catalyst and optionally in the presence of a polar solvent selectively hydrogenated, or

e) N-propargyl-acetanilides of the formula

R ² . No- R ¹ R * N N R * C = C - R ⁷ (VIII) % - R ⁸ R ³ ' J Γ R ⁸ in which one the R ¹ to meaning R ⁷ and above specified to have,

with halogens or hydrohalides of the formula

X-Y (IX)

- in which

X is hydrogen or halogen

and Y is halogen,

in the presence of a catalyst and optionally in the presence of a solvent, or

Le A 19 517

P "(ft

-B-

f) Halogenacetanllide the formula

C-CH, - Hal '

(X)

in which

R ¹ to R ^{7 have} the abovementioned meaning and

Hai ^{1 represents} chlorine, bromine or iodine

with compounds of the formula

BR ¹⁰ (XI)

in which

B is hydrogen or an alkali

metal stands and

R ^{10 is} Az and the grouping is -OR ⁹ or -SR ₉ ,

in the presence of a diluent and optionally in the presence of an acid binder, or

g) substituted N-allyl-hydroxyacetanilides of the formula

  R6

II /

CH - C - ρ - N R? (XII)

^X C - CH ₂ OH OH ^z

Le A 19 517

219759

- 9 - 'in which

R ¹ to R ⁷ 'have the abovementioned meaning,

(α) optionally after activation by means of alkali metal with halides of the formula

R ¹¹ - Hai '(ΧΪΙΙ)

in which

Hai ^{1 has} the meaning given above and

R ^{11 is} the radical R ⁹ and the group -SO ₂ -R ⁹ , where R ^{9 is} the abovementioned Be

has meaning

in the presence of an organic diluent and optionally in the presence of an acid binder or in an aqueous-organic Zweiphasensysten in the presence of a phase transfer catalyst, or

(ß) with dihydropyran of the formula

(XIV)

in the presence of a diluent and optionally in the presence of a catalyst, or

h) hydroxyacetanilides der.Formel-

Le A 19 517

(XV) R ³

21 97 ^ 9 - ¹⁰ ~ 11.8.1980

57 939/18

in which 1 3

R to R have the abovementioned meaning,

optionally after activation by means of alkali metal with allyl halides of the formula

R ⁴ I R ¹ r5 Hal - CH -I in which R ⁴ to and Hal the

_R 6

have the meaning given above,

if appropriate in the presence of an acid binder and in the presence of an organic diluent or in an aqueous-organic two-phase system in the presence of a Pliasentransferkatalysators _e implements

Surprisingly, the novel substituted N-allyl-acetanilides of the formula (I) show a better fungicidal activity, in particular against Phytophthora species, than the N-chloroacetyl-N- (2,6-dialkylphenyl) alanine known from the prior art. or -glycine alkyl esters, which are chemically and functionally obvious compounds * The new substances thus enrich the technology »

21 97 5 9 -11- 11.8.1980

57 039/18

The novel substituted N-allyl-acetanilides are generally defined by the formula (I). In this formula

R 3 and R 5 preferably denote hydrogen and straight-chain or branched alkyl, alkoxy or alkylthioalkyl having in each case 1 to 4 carbon atoms in the alkyl moiety. R furthermore preferably represents halogen, in particular fluorine, chlorine or bromine is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms as \ Tie ^A lkoxyalkyl having 1 to 4 carbon atoms in each alkyl part. B? is preferably hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, halogen and optionally substituted by halogen, alkyl R 1 and R 5 preferably represent hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, halogen and phenyl which is optionally substituted by halogen, alkyl having 1 to 4 carbon atoms or nitro Puryl, tetrahydrofuryl, thiophenyl, tetrahydro-thio-phenyl, for gegeb optionally substituted by methyl or ethyl isoxazolyl and optionally substituted by cyano or thiocyano-substituted alkyl with 1 to 4 and alkenyl and alkynyl each having 2 to 4 carbon atoms; further preferably for dihaloalkyl having 1 to 2 carbon atoms, wherein the halogen atoms are preferably fluorine and chlorine may be mentioned, and for the groupings -CH ₂ -Az, -CH ₂ -OR ⁹ , -CH ₂ -SR ⁹ , -OR ⁹ , -COOR ⁹ and - (^)

Az is preferably pyrazol-1-yl, 1,2,4-tri

azol-1-yl and imidazol-1-yl. R is preferably optionally halogen, in particular fluorine, chlorine and bromine, C _yan0 and. Thiocyano substituted alkyl of 1 to 4 and alkenyl and alkynyl each having 2 to 4 carbon atoms in each alkyl moiety.

1 €.

Very particular preference is given to those substituted N-allyl-acetanilides of the formula (i) in which R ¹ , R ² and R ^{3 are} hydrogen, methyl, ethyl, isopropyl, sec-butyl, tert-butyl, methoxymethyl, ethoxymethyl and Methylthiomethyl; R ^{1 is} also chlorine or bromine; R ^{4 is} hydrogen, methyl, ethyl, methoxymethyl or ethoxymethyl; R ⁵ , R ⁶ and R ^{7 are} hydrogen, methyl, ethyl, phenyl, fluorine, bromine, chlorine or iodine; and R ^{8 is} 2-furyl, 2-thienyl, 2-tetrahydrofuryl, 5-methylisoxazol-3-yl, methoxymethyl, ethoxymethyl ,. Allyloxymethyl, propargyl oxymethyl, ethoxymethoxymethyl, methylmercaptomethyl, methoxy, ethoxy, methylmercapto, methylsulfonyloxymethyl, methoxycarbonyl, ethoxycarbonyl, dichloromethyl, pyrazol-1-yl-methyl, imidazol-1-yl-methyl, 1, 2, A-triazol-1-yl methyl and tetrahydropyran-2-yl-oxy-methyl.

Specifically, in addition to the compounds mentioned in the preparation examples, the following compounds of the general formula (I) may be mentioned:

R ⁵ ' R ³ , R ¹ R * I R ⁵ I : C ' -CH ₂ (I) R ² " H , CH S -CH ₂ 6-CH ₃ H R * / NC - I! O R ⁸ R ⁷ -CH ₂ R ⁸ R ¹ 6-CH ₃ H H R ⁵ R ⁶ H -CH ₂ -Q CH ₃ 6-CH ₃ H H H H H -CH ₂ -O CH ₃ 6-CH ₃ ^H H H H H -0-C H CH ₃ 6-CH ₃ H H H- H · H -O-CH ₂ -OC ₂ H ₅ CH ₃ 6-CH ₃ H H H H CH ₃ 19 517 H H ' H H CH ₃ H H Le A

21 975.9

R ² R ³

- 13 -

R ⁵ R ⁶ R ⁷

CH ₃ 6-CHj H

-D

CH ₃ 6-CHj H H H H H H ₂ -S-Cn ₃ ^ I CH ₃ 6-CH ₃ H H H H H -CHCl ₂ CH ₃ 6-CH ₃ H H H H H -COOCH ₃ CHj 6-CH ₃ H H H H H -CH ₂ OSO ₂ CH ₃ CHj 6-CH ₃ H H CH ₃ H H / N =] -CH ₂ -N _ I VlI I KT -CH ₂ SCH ₃ CHj 6-CH ₃ H H CH ₃ H H / NI -CH ₂ -N ^ J -CH ₂ SC ₂ H ₅ CHj 6-CH ₃ H H CH ₃ H H / = N -CH ₂ -N ^ J -CHCl ₂ CH ₃ 6-CHj H H CH ₃ H H -CH ₂ OC ₂ H ₅ -COOCH ₃ CH ₃ 6-CH ₃ H H CH ₃ H H -CH ₂ OCH ₂ OC ₂ H ₅ -CH ₂ OSO ₂ CH ₃ CH ₃ 6-CH ₃ H H CH ₃ H H -cu _z o- (~ y CH ₃ 6-CH ₃ H H CH ₃ H H CH ₃ 6-CH ₃ H H CH ₃ H H - CH ₃ 6-CH ₃ H H CH ₃ H H - CH ₃ 6-CH ₃ ' H H CH ₃ H H CH ₃ 6-CH ₃ H H CH ₃ H H CH ₃ 6-CH ₃ H H CH ₃ H H CHj 6-CH ₃ H H CH ₃ H H CH ₃ 6-CHj H H CH ₃ H H

Le A 19 517

CH,

1 97

¹ R ² R ³ • R * H - 14 - _R 6 H R ⁸ -U CH ₃ 6-CH ₃ H CH ₃ H H H -CH ₂ OCH ₃ NJ CH ₃ 6-CHs H CH ₃ H H H -CH ₂ -, ζ CH ₃ 6-CH ₃ H CH ₃ H H , H H H i N = -CH ₂ -N _ -CH ₂ -N ^ I ₂ -OC ₂ H ₅ CH ₃ CH ₃ 6-CH ₃ 6-CH ₃ H H , CH ₃ CH ₃ H H H H -CH ₂ OC ₂ Hj CH ₃ 6-CH ₃ H CH ₃ H H * H -CH ₂ -O-CP CH ₃ 6-CH ₃ H CH ₃ H

• Η

CH ₃ 6 -CH ₃ H

CH ₃

CH ₅

-CH ₂ O

ο- /

CH ₃ 6-CH ₃ H CH ₃ H H H - CH ₃ 6-CH ₃ H CH ₃ H H H - CH ₃ 6-CH ₃ H CH ₃ H H H CH ₅ 6-CH ₃ H CH ₃ H H H CH ₃ 6-CH ₃ H CH ₃ H H H CH ₃ 6-CH ₃ H CH ₃ H H H CH ₃ 6-CH ₃ H CH ₃ H H H -CH ₂ SCH ₃ -Ch ₂ SC ₂ Hj -CHCl ₂ -COOCH ₃ -CH ₂ OSO ₂ CH ₃

Le A 1.9 517

5

R ² R ³ R ^ R5 - 15 - R ⁷ R ¹ 6-CH ₃ H H H R ⁶ H CH ₃ ' .6-CH ₃ H H H CH ₃ H CH ₃ 6-CH ₃ H H H CH ₃ H CH ₃ 6-CH ₃ H H H CH ₃ H CH ₃ CH ₃ 6-CH ₃ H H H H CH ₃ 6-CH ₃ H H H CH ₃ H CH ₃ 6-CH ₃ H H H CH ₃ H CHj 6-CH ₃ H H H CH ₃ H CHj CH ₃

R ⁸

-CH ₂ OCH ₃

/ N = -CH ₂ -N

^ N • N = -CH, -N

-CH, -N

-CH ₂ OC ₂ H ₅ -CH ₂ -O-CH ₂ -OC ₂ H ₅

-CH ₉ 0-

CH ₃ 6-CH ₃ H H H CH ₃ H - CH ₃ 6-CH ₃ H H H CH ₃ , H - CH ₃ 6-CH ₃ H H H CH ₃ H - CH ₃ 6-CH ₃ H H H CH ₃ H CH ₃ 6-CH ₃ H H H CH ₃ H CH ₃ 6-CH ₃ . H H H CH ₃ H CH ₃ 6-CH ₃ H H H CH ₃ H CH ₃ 6-CH ₃ H H H CH ₃ H -CH ₂ SCH ₃ -CH ₂ SC ₂ H ₅ -CHCl ₂ -COOCH ₃ -CH ₂ CSO ₂ CH ₃

Le A 19 517

R ² sy ι 97 p 9 R ⁵ - 16 - R7 R ⁸ -U U- 6-CH ₃ </ H R ⁶ H -CH ₂ OCH ₃ 6-CH ₃ H CH ₃ H - ^cH * -C U- R ¹ 6-CHj R ³ R * H CH ₃ H N = CH ₃ H CH ₃ CH ₃ -CH ₂ -N _ CH ₅ 6-CHj H CH ₃ H H CHj H CHj CH ₃ -CH ₂ SCH ₃ 6-CH ₃ H H -CH ₂ SC ₂ H ^ CH ₃ 6-CH ₃ H CH ₃ H CH ₃ H / = N -CHCl ₂ 6-CH ₃ H CH ₃ H " ^CH2 " ^N \ = J -COOCK ₃ CH ₃ 6-CHj H CH ₃ H CH ₃ H -CH ₂ OC ₂ H ₅ -CH ₂ OSO ₂ ( CH ₃ 6-CHj H. CHj H CHj H -CH ₂ -O-CH ₂ -OC ₂ H ₅ UH ₃ CH ₃ 6-CH ₃ H CHj H CiI ₃ H -CH ₂ O- (N CHj 6-CH ₃ H qHJ Ή CH ₃ H - CH ₃ 6-CH ₃ H CH ₃ H CH ₃ H - CH ₃ 6-CH ₃ H CH ₃ H CH ₃ H - CH ₃ 6-CH ₃ H CH ₃ H CH ₃ H CH ₃ 6-CHj H CH ₃ H CH ₃ H CH ₃ 6-CH ₃ H CH ₃ H CH ₃ H CH ₃ H CH ₃ CH ₅ CH ₃ H CH ₃ CH ₃ H CH ₃

Le A 19 517

R ¹ 2 R ² 1 9 R ³ 75 • R * 9 R ⁵ - 17 - R ^e R ' CH ₃ 6-CH ₃ H H Cl (H) H (Cl) H CH ₃ 6-CH ₃ H H Cl (H) H (Cl) H CH ₃ 6-CH ₃ ^ H H Cl (H) H (Cl) H CH ₃ 6-CH ₃ H H Cl (H) H (Cl) ν H CH ₃ 6-CH ₃ H H Cl (H) \ H (Cl) H CH ₃ 6-CH ₃ H H Cl (H) H (Cl) H CH ₃ 6-CH ₃ H H Cl (H) H (Cl) H CH ₃ 6-CH ₃ H H Cl (H) H (Cl) H CH ₃ 6-CH ₃ H H Cl (H) H (Cl) H CH ₃ 6-CHj H H Cl (H) H (Cl) H

CH, 6-CH,

CHj 6-CHj H H CHj 6-CHj H H CH ₃ 6-CHj H H CH ₃ 6-CH ₃ H H CH ₃ 6-CH ₃ H H

Cl (H) H (Cl) H

Cl (H) H (Cl) H

Cl (H) H (Cl) H

Cl (H) H (Cl) H

Cl (H) H (Cl) H

Cl (H) H (Cl) H

R ^e

-CH ₂ OCH ₃

-CH ₂ -NI _ ^N -CH ₂ -rf _

-CH ₂ -N ^

-CH ₂ OC ₂ H ₅

-CH ₂ -O-CH ₂ -OC ₂ H ₅

-CH ₂ OQ

-CH ₂ SCH ₃ -CH ₂ SC ₂ H ₅ -CHCl ₂ -COOCH ₃ -CH ₂ OSO ₂ CH ₃

Le A 19 517

R ² R ³

R ⁵

- 18 R ⁶ R ⁸

CH ₃ 6-CHj H CH ₃ Cl (H) H (Cl) H

CH ₃ 6-CHj H CH ₃ Cl (H) H (Cl) H

CH ₃ 6-CHj H CH ₃ Cl (H) H (Cl) H

CH ₃ 6 -CH ₃ H CH ₃ Cl (H) H (Cl) H

CH ₃ 6 -CH ₃ H CH ₃ Cl (H) H (Cl) H

CH ₃ Cl (H) H (Cl) H CH ₃ Cl (H) H (Cl) H

CH ₃ Cl (H) H (Cl) H

CH ₃ 6-CHj H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H CH ₃ 6-CH ₃ H

CiI ₃

Cl (H) H (Cl) H

CH ₃ Cl (H) H (Cl) H

CH ₃ Cl (H) H (Cl) H

Cl (H) H (Cl) HI ₅ Cl (H) H (Cl) H

CH, 6-CH,

CH ₃

CH _n

CH ₃ Cl (H) H (Cl) H

CH ₃ Cl (H) H (Cl) H

CH ₃ Cl (H) H (Cl) H -CH ₂ OCH ₃ -CH ₂ -NI

-CH, -rf

-CH, -N

-CH ₂ OC ₂ H ₅ -CH ₅ -O-CHo -OC ₂ H.

₂ H ₅

-CH ₂ O

-O

-CH ₂ SCH ₃ -CH ₂ SC ₂ H ₅ -CHCl ₂ OOCCh ₃ -CH ₂ OSO ₂ CH ₃

Le A 19 517

219759

R ¹ R ² R ³ R * R ⁵ - 19 - R ⁶ R7 R ⁸ U CH ₃ 6-CH ₃ H H H Cl Cl U CH ₃ 6-CH ₃ H H H. Cl Cl CH ₃ 6-CH ₃ H H H Cl Cl Φ a * / N = -CH ₂ -N CH ₃ 6-CH ₃ H H H Cl Cl N = -CH ₂ -li CH ₃ 6-CH ₃ H H H Cl Cl -CH ₂ SCH ₃ CHj 6-CH ₃ H H H Cl Cl -CH ₂ SC ₂ H ₅ CHj 6-CHj Η- H H Cl Cl -CH ₂ -N ^ J -CHCl ₂ CH ₃ 6-CHj H H H Cl Cl -CH ₂ OC ₂ H ₅ -COOCHj CH ₃ 6-CHj H H H Cl Cl -CH ₂ -O-CH ₂ -OC ₂ H ₅ -CH ₂ OSO ₂ CH ₃ CH ₃ ⁶ "CH ₃ H H H Cl Cl -CH ₂ OQ CH ₃ 6-CH ₃ H H H Cl Cl - CH ₃ 6-CH ₃ H H H Cl Cl - CH ₃ 6-CH ₃ ,H H H Cl Cl - CH ₃ 6-CH ₃ H H H Cl Cl CH ₃ 6-CH ₃ H H H Cl Cl

Le A 19 517

R2 R ³ R * R ⁵ - 20 - R ⁷ R ⁸ -U ^ S * ^ :H. R ¹ 6-CH ₃ H CH ₃ H R ⁶ Cl -CH ₂ -I ^ _ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl -CH ₂ -tf _ -CK ₂ -N ^ j CH ₃ 6-CH ₃ H CH ₃ H Cl , Cl -CH ₂ OC ₂ H ₅ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl -CH ₂ -O-CH ₂ -OC ₂ H ₅ CH ₃ 6-CH ₃ H CH ₃ H Cl , Cl -CH ₂ OQ -CH ₂ SCH ₃ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl - -CH ₂ SC ₂ H ₅ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl - -CHCl ₂ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl - -COOCH ₃ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl -CH ₂ OSO ₂ CH ₃ 6-CH ₃ H CH ₃ H Cl Cl CH ₃ 6-CH ₃ H CH ₃ H Cl. Cl CH ₃ 6-CH ₃ H CH ₃ H Cl Cl CH ₃ 6-CH ₃ H CH ₃ H Cl Cl. CH ₅ 6-CH ₃ H CH ₃ H Cl Cl CH ₃ 6-CH ₃ H CH ₃ H Cl Cl CH ₃ Cl

Le A 19 517

R ¹ R ² R ³

R ⁵

- 21 -

R ⁸

CH ₃ 6-CHj H HH Cl

CHj 6-CHj HH H Cl

CH ₃ 6 -CH ₃ HH H Cl

CH ₃ 6 -CH ₃ HH H Cl

CH ₃ 6 -CH ₃ HH H Cl

CH ₃ 6 -CH ₃ HHH Cl

CH ₃ 6 -CH ₃ HHH Cl

CH ₃ 6 -CH ₃ HH H Cl

CH ₃ 6 -CH ₃ HH H Cl

CH ₃ 6 -CH ₃ HH H Cl

CH,

CH ₃ -CH ₂ CH ₃

CH ₃ CH ₃

CH ₃

CH ₃ CH ₃ CH,

^ N

-N = CH ₂ -N

CH, -CH ₂ -N.

/ = N

-CH ₂ OC ₂ H ₅

-CH ₂ -O-CH ₂ -OC ₂ H ₅

-CH ₂

O-Q

-O

CH ₃ 6-CH ₃ H H H Cl CH ₃ -CH ₂ SCH ₃ CHj 6-CH ₃ H H H Cl CH ₃ -CH ₂ SC ₂ H ₅ CH ₃ 6-CH ₃ -H H H Cl CH ₃ -CHCl ₂ CH ₃ 6-CHj H H H Cl CHj -COOCH ₃ CH ₃ 6-CH ₃ H H H Cl CHj -CH ₂ OSO ₂ CH ₃

Le A 19 517

R ¹

R ² R ³

R ⁵

- 22 -

R ⁶

R ⁷

R ⁸

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃

CH ₃

CH ₃ CH ₃

CH ₃ CH ₃

CH ₃

CH ₃

'CH ₅

CH,

H H

H H H

Cl Cl Cl

CH,

Cl CH ₃ -CH ₂ -r

rf

Cl CH ₃ -CH ₂ -1

/ = - N Cl CH ₃ -CH ₂ -N __ |

CH ₃ -CH ₂ OC ₂ H ₅

CH ₃ -CH ₂ -0-CH ₂ -OC ₂ H ₃

ΓΗ ΓΗ Ο / ~ λ

V /

CH ₃ CH ₃ CH ₃

CH ₃ 6-CH ₃ H CH ₃ H Cl CH ₃ -CH ₂ SCH ₃ CH ₃ 6-CH ₃ H CH ₃ H Cl CH ₃ -CH ₂ SC ₂ H ₅ CH ₃ 6-CH ₃ , H CH ₃ H Cl CH ₃ -CHCl ₂ CH ₃ 6-CH ₃ H CH ₃ H Cl CH ₃ -COOCH ₃ CH ₃ 6-CH ₃ H CH ₃ H Cl CH, -CH, OSO, CH

Le A .19 517

R ¹ 2 R ² 1 9 R ³ . 759 R * R = 23 - R ⁶ · R ⁷ R ^e 6-C ₂ H ₅ H H H H H CH ₃ 6-C ₂ H ₃ H H H H H • Ο CH ₃ 6-C ₂ H ₅ H H H H H CH ₃ 6-C ₂ H ₅ H H H .H H CH ₃ .6-C ₂ H ₅ H H H H H -CH ₂ OCH ₃ CH ₃ 6-C ₂ H ₃ H H H H H / N =) -CH ₂ -NI \ ZN CH ₃ 6-C ₂ H ₅ H H H H H / N = -CH ₂ -N CH ₃ 6-C ₂ H ₅ H- H H H H CH ₃ 6-C ₂ H ₅ H H H H H -CH ₂ OC ₂ H ₅ CH ₃ 6-C ₂ H ₅ H H H H H -CH ₂ OSO ₂ CH ₃ CH ₃ 6-C ₂ H ₅ H H H H H -CHCl ₂ CH ₃ -COOCH ₃ ~ \ O / -CH ₂ SCH ₃ -CH ₂ -0Λ

Le A 19 517

R ¹

R ²

"CH, 6-C ₅ H

 2 "3

CH,

- 24 -

R ⁶ R ⁷

CHj 6-C ₂ H ₅ H CH ₃ H H  Η -CH ₂ pCHj ~ λ CHj 6-C ₂ H ₅ H CH ₃ H H H CHj 6-C ₂ H ₅ H CH ₃ H H H / N = I -CH ₂ -NI Well CH ₃ 6-C ₂ H ₅ H CH ₃ H H H , N = -CH ₂ -N CH ₃ 6-C ₂ H ₅ H CH ₃ H H H CH ₃ 6-C ₂ H ₅ H CH ₃ H H H -CH ₂ OC ₂ H ₅ CH ₃ 6-C ₂ H ₅ H " CH ₃ H H H -CH ₂ OSO ₂ CH ₃ CH ₃ 6-C ₂ H ₅ H CH ₃ H H H -CHCl ₂ CH ₃ 6-C ₂ H ₅ H CH ₃ H H H -COOCH ₃ CHj 6-C ₂ H ₅ H CH ₃ H H H -CH ₂ S ^ H ₃ -CH ₂ -0 \

Le A 19 517

219759

R ¹ R ² R ³ R * R5 25 - _R6 . R ' R ⁸ 6-C ₂ H ₅ H. H CH ₃ H H CH ₃ 6-C ₂ H ₅ H ' H CH ₃ • H H "Μ CH ₃ 6-C ₂ H ₅ H H CH ₃ H H CH ₃ 6-C ₂ H ₅ H H CH ₃ H H CH ₃ 6-C ₂ H ₅ H H CH ₃ H H -CH ₂ pCHj CH ₃ 6-C ₂ H ₅ H H CH ₃ H H -CH ₂ -NI CH ₃ 6-C ₂ H ₅ H H CH ₃ H H / N = -CH ₂ -N CH ₃ 6-C ₂ H ₅ H H CH ₃ H. H CH ₃ 6-C ₂ H ₅ H H CH ₃ H H -CH ₂ OC ₂ H ₅ CH ₃ 6-C ₂ H ₅ H H CH ₃ H H -CH ₂ OSO ₂ CH ₃ CH ₃ 6-C ₂ H ₅ H H CH ₃ H H -CHCl ₂ CH ₃ -COOCH ₃ -UJ -CH ₂ SCH ₃ -CH ₂ -θ /

Le A 19 517

R ¹

- 26 -

R ^5, R ⁶ ·

CH ₃ 6-C ₂ H ₅ H CH ₃ 6-C ₂ H ₅ H

CH ₃ 6-C ₂ H ₅ H

H H

H H

R ⁸

Cl H

Cl H -CH ₂ OCH ₃

Cl H -CH ₅

-N I \ ZN

CH ₃ 6-C ₂ H ₅ H H H Cl H , / N- CH ₂ -N -ν CH ₃ 6-C ₂ H ₅ H H H Cl H CH ₃ 6-C ₂ H ₅ H H H Cl H -CH ₂ OC ₂ K ₅ CH ₃ DC ₂ H ₅ H H H Cl H -CH ₂ OSO ₂ CH CH ₃ 6-C ₂ H ₅ H H H Cl H -CHCl ₂ CH ₃ 6-C ₂ H ₅ H H H Cl H -COOCH ₃ CH ₃ 6-C ₂ H ₅ H H H Cl H -Q CH ₃ 6-C ₂ H ₅ H H H Cl H -CH ₂ SCH ₃ -CH ₂ -θ /

Le A 19 517

R ¹ R ² R ³ R * R ⁵ 27 - R ⁶ , R ⁷ R ⁸ 6-C ₂ H ₅ H H H H H C ₂ H ₅ 6-C ₂ H ₅ H H H H H -U C ₂ H ₅ 6-C ₂ H ₅ H H H H H -CH ₂ OCH ₃ C ₂ H ₅ 6-C ₂ H ₅ H H H H H / N = I -CH ₂ -NIN ^ N C ₂ H ₅ 6-C ₂ H ₅ H H H , H H / N = I -CH ₂ -N C ₂ H ₅ 6-C ₂ H ₅ H H H H H -CH ₂ OC ₂ H ₅ C ₂ H ₅ 6-C ₂ H ₅ 6-C ₂ H ₅ H H H H H H H H H H -CH ₂ OSO ₂ CH ₃ C ₂ H ₅ C ₂ H ₅ 6-C ₂ H ₅ H H H H H -CHCl ₂ . -COOCH ₃ C ₂ H ₅ 6-C ₂ H ₅ H H H H H -Ό C ₂ H ₅ 6-C ₂ H ₅ H H H H H -CH ₂ SCH ₃ C ₂ H ₅ -CH ₂ "-0 <\ 0 /

Le A 19 517

91 Q 7 K QR ² R ³ R ⁴

- 28 -

R ⁵ "R ⁶ .R ⁷

C ₂ H ₅ 6-C ₂ H ₅ HC ₂ H ₃ 6-C ₂ H ₅ H

CH ₃ CH ₃

6-C ₉ H, H CH,

H H

R ^e

H H

-CH ₂ pCHj

H -CH.

/ N =] -N I

\ HN

C ₂ H ₅ 6-C ₂ H ₅ H CH ₃ H H . H , N- CH ₂ -N C ₂ H ₅ 6-C ₂ H ₅ H CH ₃ H H H C ₂ H _s 6-C ₂ H ₅ H CH ₃ H H H -CH ₂ OC ₂ H ₅ C ₂ H ₃ 6-C ₂ H ₅ H CH ₃ •H H H -CH ₂ OSO ₂ CH ₃ C ₂ H ₃ 6-Ca H ₃ H. CH ₃ H H H -CHCl ₂ C ₂ H ₃ 6-C ₂ H ₅ H CH ₃ H H H -COOCH ₃ C ₂ H ₃ DC ₂ H5 H CH ₃ H H H -UJ C ₂ H ₅ 6-C ₂ H ₅ H CH ₃ H H H -CH ₂ SCH ₃ -CH ₂ -θ /

Le A 19 517

21 97

R ¹

R ² R ³

C ₂ H ₅ 6-C ₂ H ₅ HHC ₂ H ₅ 6-C ₂ H ₅ HH

C ₂ H ₅ 6-C ₂ H ₅ HH

CH ₃ H CH ₃ H

CH ₃ H

R ⁸

R ⁷

H -CH, OCH,

H -CE

/ Ν =] -Nl

C ₂ H ₅ 6-C ₂ H ₅ H H CH ₃ H  Η , N- CH ₂ -N C ₂ H ₅ 6-C ₂ H ₅ H H CH ₃ H H C ₂ H ₅ 6-C ₂ H ₅ H H CH ₃ H H -CH ₂ OC ₂ H ₅ C ₂ H ₅ 6-C ₂ H ₅ H H CH ₃ H H -CH ₂ OSO ₂ CH ₃ C ₂ H ₅ 6-C ₂ H ₅ H H QI ₃ H H -CHCl ₂ C ₂ H ₅ 6-C ₂ H ₅ H H CH ₃ H H -COOCH ₅ C ₂ H ₅ 6-C ₂ H ₅ H H CH ₃ H H ~ \ O ^ CH. 6-C ₅ H ₁₅ H H CH ₃ H H -CH ₂ SCH ₃ -CH ₂ -0 \

0- /

Le A 19 517

-ΒΟR2 R ³ R * R ⁵ . R ⁶ R ⁷

R ⁸

C ₂ H ₅ 6-C ₂ H ₅ HC ₂ H ₅ 6-C ₂ H ₅ H

C ₂ H ₅ 6-C ₂ H ₃ H

C ₂ H ₅ 6-C ₂ H ₅ HH

 Η Cl H -CH ₂ OCH ₃ H H Cl H / N =] -CH ₂ -N H H Cl H H

C ₂ H ₅ 6-C ₂ H ₅ H H C ₂ H ₅ 6-C ₂ H ₅ . H · H C ₂ H ₃ 6-C ₂ H ₅ K H C ₂ H ₅ 6-C ₂ H ₅ H H C ₂ H ₅ 6-C ₂ H ₅ H H C ₂ H ₅ 6-C ₂ H ₅ H H

C ₂ H ₅ 6-C _S H, HH

Cl H

-CH ₂ -N

H Cl H -CH ₂ OC ₂ H ₅ H Cl H -CH ₂ OSO ₂ CH ₃ H Cl H -CHCl ₂ H Cl H -COOCH ₃ H Cl H H Cl H -CH ₂ SCH ₃ H Cl H -CH ₂ -0 <

Le A 19 517

R ² 2197 5 « R * H R ⁵ 31 - R ⁷ R ⁸ R ¹ 6-CHj R ³ H H R ⁶ H 6-CHj H H H H H JP Cl 6-CHj H H H H H Cl 6-CHj H H H H H -CH ₂ OCHj egg 6-CHj H H H H H / N =] -CH ₂ -NI Cl 6-CHj H H H H H , N = -CH ₂ -N Cl 6-CHj H . H H H H Cl 6-CHj H H H H H -CH ₂ OC ₂ H ₅ Cl 6-CH ₅ H H H H H -CH ₂ OSO ₂ CH ₃ Cl 6-CHj H H H H -CHCl ₂ Cl H H -COOCHj Cl -M) / -CH, SCH,

Cl 6 -CH, H H

H-

H. -CH _;

0 /

Le A 19 517

R ¹

R ²

R ³

R5

R6

R ⁸

'6-CH ₃ H CH ₃ H H H - ¹ L Cl 6-CH ₃ H CH ₃ Ή H H Cl 6-CH ₃ H CH ₃ H H Ή Cl 6-CH ₃ H CH ₃ H H H Cl 6-CH ₃ H CH ₃ H H H -CH ₂ OCH ₃ Cl 6-CH ₃ H CH ₃ H H H / N = I -CH ₂ -NI Cl 6-C ¹ H ₃ H " CH ₃ H H H -CH ₂ -N Cl 6-CH ₃ H CH ₃ H H H Cl 6-CH ₃ H CH ₃ H H H -CH ₂ OC ₂ H ₅ Cl 6-CH ₃ H CH ₃ H H H -CH ₂ OSO ₂ CH ₃ Cl 6-CH ₃ H CH ₃ H H H -CHCl ₂ Cl -COOCH ₃ - -CH ₂ SCH ₃ -CH ₂ -C / "Λ

0-

Le A 19 517

219759

₃₃

If, for example, 2,6-dimethyl-N-allyl-anlline and furan-2-carboxylic acid chloride are used as starting materials, the reaction time can be represented by the following formula scheme (process a):

CH ₂ -CH = CH ₂

Cl-CO-

CHo - CH-

+ Base -HCl

If, for example, 2,6-dimethylmethoxyacetanilide and allyl bromide are used as starting materials, the course of the reaction can be represented by the following formula scheme (process b):

.H

Br-CH ₂ -CH = CH ₂

+ Base

_ru C-CH ₂ OCH ₃ 0

-HBr

CH ₂ -CH = CH ₂

CH ₃ ^X C-CH ₂ 0CHj 0

If, for example, 2,6-dimethyl-N- (2-furoyl) -N-acetylmethyl-aniline and triphenyl-phosphin-methylene are used as starting materials, the course of the reaction can be represented by the following formula scheme (process c):

CH ₂ -CO-CH

+ (C ₆ IL) ₃ P = CH ₂

- (C ₆ H.), P =

, CH ₂ -C-CH ₂

'W

If, for example, 2,6-dimethyl-N-propargylmethoxyacetanilide and hydrogen are used as starting materials, the course of the reaction can be represented by the following formula scheme (process d):

^CH

³ CH ₂ -C =

³ CH ₂ -CH = CH ₂ N

-CH, C-CH ₂ OCH ₃ 0

If, for example, 2,6-dimethyl-N-propargylmethoxyacetanilide and hydrogen bromide are used as starting materials, the course of the reaction can be represented by the following formula scheme (process e):

, br

γη ι • ³ CH ₂ -C = CH ₂

CH ₂ -C = CH

+ HBr

C-CH, OCH,

If, for example, 2,6-dimethyl-N-allyl-chloroacetanilide and pyrazole are used as starting materials, the course of the reaction can be represented by the following formula scheme (process f):

CH

³ CH ₂ -CH = CH ₂

+ HN

C-CH ₂ -Cl 0

³ CH, -CH = CH,

+ Base

-HCl

\ / -! _r " C-CH ₂ -N CH ₃ κ Vt-0 ^ ~

If, for example, 2,6-dimethyl-N-allyl-hydroxyacetanilide and ethoxymethyl chloride are used as starting materials, the course of the reaction can be represented by the following formula scheme (process g / a):

Le A 19 517

21 9759

CH.

CH,

CH ₂ -CH = CH ₂

N- + Cl-CH ₂ OC ₂ H ₅ ^ C-CH ₂ -OH 0

+ Base -HCl

^CH

^s CH ₂ -CH = CH ₂

_CH X-CH ₂ -O-CH ₂ OC ₂ H ₅

If, for example, 2,6-dimethyl-N-allyl-hydroxyacetanilide and 3,4-dihydro-2H-pyran are used as starting materials, the course of the reaction can be represented by the following equation 5 (process g / β):

CH ₃

CH ₅ -CH = CHo

'CH ₃

-OH

Cat.

CH ₂ -CH = CH ₂

CH,

If, for example, 1 mol of 2,6-dimethyl-hydroxyacetanilide and 2 mol of allyl bromide are used as starting materials, the course of the reaction can be represented by the following equation 10 (process h):

CH ₃

C-CH ₂ -OH

+ 2 Br-CH ₂ -CH = CH ₂ phase transfer _>

-2HBr

^CH

^s CH ₂ -CH = CH ₂

C-CH ₂ -O-CH ₂ -CH = CH ₂ O

Le A 19

5> -36- 11.8.1980

57 039/18

The in carrying out the process (a) as starting materials to be used li-allyl-anilines are represented by the formula

1 7 (II) generally defined. In this formula, R to R are preferably those radicals which have already been mentioned as preferred in connection with the description of the erfindungsgeniäßen .Stoffe of formula (I) for these substituents.

The N-allyl-anilines of the formula (II) are widely known (cf., inter alia, US Pat. No. 3,475,156 and DE-OS No. 2,218,097 and DE-OS No. 2,805,525), or they can be obtained by known processes, by z, B, corresponding anilines with allyl halides of the formula (V) or the corresponding allylsulfonates, such as mesylates or 'osylaten, in the presence of an acid binder such as ^ e B. potassium carbonate, optionally in the presence of an inert organic solvent, such as ethanol, , at temperatures between 20 and 120 C, wherein preferably also an excess of aniline can be used, -A-Is examples of the. Starting materials of the formula (II) may be mentioned?

(II)

R ² R ¹ -H ' CH - t C = r3 / ^ H = C ' _x R ⁶ ^ R ⁷

219 759 -. 37 _ R ⁵ ' R ⁶ R ⁷ R ¹ R ² , R ³ R * H H H CHj 6-CH ₃ H · H H H H C ₂ H ₅ 6-C ₂ H ₅ ' H H H H H C ₂ H ₅ 6-CHj H H H H H (CHj) j C H H H H H H CH ₃ 3-CH ₃ H H H H H CH ₃ 5-CH ₃ H , H H H H Cl 6-CH ₃ H H H H H Cl 6-C (CHj) ₃ H H H H H CH ₃ 3-CH ₃ . 6-CH ₃ H H H H CH ₃ 6-CH ₃ H CH ₃ H H H C ₂ H ₅ 6-C ₂ H ₅ H CH ₃ H H H C ₂ H ₅ 6-CH ₃ H CH ₃ H H H Cl 6-CH ₃ H CH ₃ CH ₃ H H CH ₃ • 6 -CH ₃ H H CH ₃ H H C ₂ H ₅ 6-C ₂ Hy H H CH ₃ H H C ₂ H ₅ 6-CH ₃ H H H CH ₃ H CH ₃ 6-CHj H H H CH ₃ H C ₂ H ₅ 6-C ₂ H ₅ H H H CH ₃ H C ₂ H ₅ 6-CH ₃ H H H Cl CH ₃ CH ₃ 6-CH ₃ H H H Cl CH ₃ C ₂ H ₅ 6-C ₂ H ₅ H H H Cl CH ₃ C ₂ H ₅ 6-CH ₃ H H H H Cl CH ₃ 6-CH ₃ H H H H Cl C ₂ H ₅ 6-C ₂ H ₅ H H H H Cl C ₂ H ₅ 6-CH ₃ H H H Cl Cl CH ₃ 6-CH ₃ H H H Cl Cl C ₂ H ₅ 6-C ₂ H ₅ H H H Cl Cl C ₂ H ₅ 6-CH ₃ H H Cl Cl H CH ₃ 6-CH ₃ H H Cl Cl H C ₂ H ₅ · 6-C ₂ H ₅ H H Cl Cl Ή C ₂ H ₅ 6-CH ₃ H H

Le A 19 517

I 57 5 a ^e -38-

R ¹ R ² CH ₃ 6-CH ₃ C ₂ H ₅ 6-C ₂ H ₅ CH ₃ 6-CH ₃ 6-CH ₃ C ₂ H ₅ 6-CH ₃ CH ₃ 6-CH ₃ C ₂ H ₅ 6-C ₂ H ₅

H H H H H H H H

The acid chlorides or bromides or anhydrides which are also to be used as starting materials for process (a) are generally defined by the formula (IIIa) and (IIIb). In this formula, R preferably represents those radicals which have already been used in connection with the description of the substances of the formula (I) according to the invention were preferably mentioned for this substituent.

r5 R ⁶ 08/11/1980 Cl H 57 039/18 R ⁴ Cl H R? H Cl H H H br H H H br H H H br H H H CH ₃ H H H CH ₃ H H CH ₃ CH ₃ H H CH ₃ H CH ₃ H

2 1 97 5 9. -39- 11.8.1980

57 039 /

Acid chlorides or bromides or anhydrides of the formulas (IIIa) and (IIIb) are generally known compounds of organic chemistry.

The anilides required as starting materials in carrying out the process (b) are represented by the formula (IV)

1 2 3

generally defined. In this formula, R, R, R and R preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The anilides of formula (IV) can be obtained in a well-known manner by reacting corresponding anilines with an acid chloride or bromide or hydride of the formulas (IIIa) and (IIIb) according to the conditions of process (a) in The presence of an inert organic solvent, such as toluene or methylene chloride, optionally in the presence of an acid binder, such as potassium carbonate or triethylamine, or in the presence of a catalyst, such as dimethylformamide, at temperatures between 0 and 100 C (see also the production examples).

As examples of the starting materials of the formula (IV) may be mentioned:

- R8

(IV)

R ³

6-CH ₃ H - U - -CH ₂ -O-CH ₃ CH ₃ 6-CH ₃ H ^J ^ J -CH ₂ -O-CH ₃ C ₂ H ₃ 6-C ₂ H ₅ H - -CH ₂ -0-CH ₅ C ₂ H ₅ 3-CH ₃ 6-CH ₃ -CH ₂ -O-CH ₃ CH ₃ 6-CH ₃ H Cl 6-CH ₃ H -COOCH ₃ CH ₅ 6-CH ₃ H -COOCH ₃ C ₂ H ₅ 6-C ₂ H ₃ H -COOCH ₃ CH ₃ 3-CH ₃ 6-CH ₃ -COOCH ₃ CH ₃ 6-CH ₃ H -COOCHs Cl 6-CH3 H CH ₃ 6-CH ₃ H C ₂ H ₅ 6-C ₂ H ₅ · H- • C ₂ H ₅ 3-CH ₃ 6-CH ₃ CH ₅ 6-CH ₃ H Cl Le A 19 517

R ¹

R ²

-41 -

re

C ₂ H ₅

C ₂ H ₉

6-CH ₅

6-CH ₃

3-CH ₃

6-CH ₃

6-C ₂ H ₅

3-CH ₃

Cl 6-CH ₃

Le A 19 517

H '

6-C ₂ H ₅ H

6-CH,

CH ₃ 6-CH ₃ H C ₂ H ₃ 6-CH ₃ H C ₂ H ₅ 6-C ₂ H ₅ .H CH ₃ 3-CH ₃ 6 Cl 6-CH ₃ H CH ₃ - 6-CH ₃ H C ₂ H ₅ 6-CH. H

6-CH,

-CH-

-Π

-CH ₂ -N ² M -CH,

-Π

^ N-J

-CH ₂ -n

-CH ₂

-N "I

-CH ₂ -NI -CH.

-a -CH ₂ -N

/ -CH ₂ -N

N =

-CH ₂ -NIX =. N

-CH ₂ -NΠ

-CH ₂ -

C ₂ H ₅ C ₂ H ₅

R ²

6-CH ₃

6-CH ₃

R ³

CH ₃ 6-CH ₃ H C ₂ H ₃ 6-CH ₃ H C ₂ H ₃ D-Cj Hg H . CH ₅ 3-CH ₃ 6-CH ₃ Cl 6-CH ₃ H CH ₃ 6-CH ₃ H C ₂ Hg 6-CH ₃ H C _£ H ₃ 6-C ₂ H ₃ , H CH ₃ 3-CH's H Cl 6-CHs H CH ₃ 6-CH ₃ , H Cg H ₃ 6-CH _s H C ₂ H ₃ 6-C ₂ H ₃ H CH ₃ 3-CH ₃ 6-CH ₃ Cl 6-CH ₃ H

6-CH ₃

6-CH,

CH ₂ -O-SO ₂ CH ₃ CH _£ -O-SO ₂ CH ₃ CH ₂ -O-SO ₂ CH ₅ CH ₂ -O-SO ₂ CH ₃ CH ₂ -O-SO ₂ CH ₃ CHCl ₂ CHCl ₂ CHCl ₂ CHCl ₂ CHCl ₂ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₃ OC ₂ H ₅

Le A 19

21 97 5 9 ~ ⁴³ ~ 11.8.1980

57 039 /

R ¹ R ² R ³ CH ₃ 6-CH ₃ H C ₂ H ₅ 6-CH ₃ H C ₂ H ₅ 6-C ₂ H ₅ H CH ₃ 3-CH ₃ 6-CH ₃ Cl 6-CH ₃ H CH ₃ 6-CH ₃ H C ₂ H ₅ 6-CH ₃ H

R ⁸

-CH ₂ -O-CH ₂ -OC ₂ H ₅ -CH ₂ -O-CH ₂ -OC ₂ H ₅ -CH _o -0-CH -0-C _{o o} H _K

-CH ₂ -OQ

C ₂ H ₅ 6-C ₂ H ₅ H

CH >> 3-CH., 6-CHo -νηη-υ- \ j *>~> * ^c \ 0 ^y

Cl 6 -CH- H -CH ₀ -O-,

* ^ά \ 0-

The Auyihalogenide also to be used as starting materials for the process (b) are generally defined by the formula (V). In this formula, R to R preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention »

The allyl halides of the formula (V) are generally known compounds of organic chemistry.

3 3? _e -44 ™ 11.8.1980

, 57 039/18

The aldehydes or ketones to be used as starting materials in the implementation of process (c) are generally defined by the formula (VI). In this formula

R 8 to R and R are preferably those radicals which have already been mentioned in connection with the description of the compounds of formula (I) according to the invention preferably for these substituents.

The aldehydes or "ketones of the formula (VI) are not yet known. However, they can be prepared in a simple manner according to several processes." Thus one obtains aldehydes or ketones of the formula (VI), if one

i) acetanilides of the formula ^X C Il 0 -R ⁸ 1 ? * ϊ r> 'η'- D- * K, K, K Q and R the above anite R ³ In which

(IV),

with known keto derivatives of ^ 'orrael

Y - CH - C = O (XVI),

in which

R, R and Y are as defined above,

in the presence of an acid binder and optionally in the presence of a diluent ₉ or

219759 _ ₄₅ _

j) aniline derivatives of the formula

(XVII)

in which

R ¹ to R ^{5 have} the abovementioned meaning, with acid chlorides or bromides of the formula

R ⁸ - C - Cl (Br) (HIa)

in the presence of a diluent and optionally in the presence of an acid binder.

The aniline derivatives of the formula (XVII) required as starting materials in the preparation of the aldehydes or ketones of the formula (VI) can be prepared by reacting corresponding amines according to process (i) with keto derivatives of the formula (XVI).

In the preparation of the aldehydes or ketones of the formula (VI) according to processes (i) and (j), all customary acid acceptors can be used as the acid binder. Preferably in Eetracht come alkali metal carbonates, such as potassium or sodium carbonate.

Suitable diluents for the processes (i) and (j) are all customary inert organic solvents. Preferably suitable are aromatic solvents, in particular toluene, and dimethylformamide.

Le A 19 517

Sf -46-. 08/11/1980

57 039/18

According to a preferred embodiment, the reaction according to process (j) is carried out in a two-phase system, such as, for example, aqueous sodium hydroxide or potassium hydroxide / toluene or methylene chloride, optionally with the addition of from 0.1 to 1 mol of a phase transfer catalyst, such as Ammonium «or phosphonium compound, performed.

The reaction temperatures can be varied within a wider range in processes (i) and (j). In general, one works between 0 ⁰ C and 180 ⁰ C, preferably between 20 ⁰ C and 150 ⁰ C,

In the reaction according to processes (i) and (j), it is preferable to use equimolar amounts. "The workup and isolation of the reaction products are carried out by customary methods."

The phosphinalkylenes additionally used for the process (c) as starting materials are generally defined by the formula (VII). In this formula, R and R preferably represent those radicals which have already toffe in connection with the Description of the erfindungegernäßen ^ü of the formula (I) as being preferred for these substituents.

The phosphinalkylenes of the formula (VII) are generally known compounds of organic chemistry.

The K-propargylacetanilides to be used as starting materials for carrying out the processes (d) and (e) according to the invention are generally defined by the formula (VIII). In this formula, R to R, R and R are preferably those radicals which have already been mentioned as preferred in connection with the description of the compounds of the formula (I) according to the invention for these substituents.

21 97 5 9 -47- 11.8.1980

57 039/18

The N-propargyl-acetanilides of the formula (VIII) are not yet known; However, they are the subject of a separate earlier application, which is not yet part of the state of the art (see German Patent Application P 28 47 dated 31. 10. 1978). They can be obtained according to processes (a), (b), (f) and (g) by substituting the corresponding propargyl derivatives as starting compounds for each of the allyl derivatives.

The haloacetanilides to be used as starting materials in carrying out the process (f) are generally defined by the formula (X). Stand in this ormel

17

R to R preferably for those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention preferably for these substituents.

The haloacetanilides of the formula (X) are known in some cases (see, inter alia, US Pat. Nos. 3,442,945 and 3,465,156 and DE-OS No. 2,218,079 and DE-OS No. 2,805,525). Not yet known can be obtained according to the methods described therein and according to the process variant (a), by reacting N-allylanilines of the formula (II) with haloacetic acid halides.

The compounds also to be used as starting materials for the process (f) are generally defined by the formula (XI). In this formula, Az and R are preferably those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention preferably for these substituents. B is preferably hydrogen, sodium and potassium.

The compounds of the formula (XI) are generally known compounds of organic chemistry.

11.8.1980 57 039/18

For carrying out the process (g) as ^A usgangsstoffe to be used substituted N-allyl-hydroxyacetanilides are represented by the formula (SLI) generally Defi-

17

ned _e In this formula, R to R preferably represents those radicals which have already been in connection with the description of the substances of the formula (I) mentioned as preferred for these substituents.

The substituted N-allyl-hydroxyacetanilides of the formula (XII) are not yet known; However, they can be obtained in a generally known & vt and manner by

Acyloxyacetanilide of the formula * ^{1 5}

CH ₂ - OCOR

¹²

(XVIII)

in v / elcher R ¹ to R ⁷

12

have the meaning given above

and

for alkyl of 1 to 4 carbon atoms

stands,

with sodium or Kaiiumhydroxid or with an alkali metal alcoholate of a lower alcohol, such as. B, Katriummethylat or sodium ethylate, saponified at temperatures between 20 and 40 C and after acidification in the usual way, the compounds of formula (XII) isolated

21 97 5 9 -49- 11.8.1980

57 039/18

The acyloxyacetanilides of the formula (XVIII) can be obtained by adding e.g. "Halogehacetaniliden the formula (X) exchanges the reactive substituent Hai ¹ by reaction with a lower alkanecarboxylic acid, wherein the acid is preferably used in the form of their alkali metal or alkaline earth metal salts, or by IT-allyl-anilines of the formula ( II) with appropriate Acyloxyacethalogeniden.

The halides which are also to be used as starting materials for the process (g / o) are defined by the general formula (XIII).

11

my defines. In this formula, R and Hal ¹ are preferably those specified in 4p Krfindungsdefinition residues.

The halides of the formula (XIII) are generally known compounds of organic chemistry.

The bihydropyran to be used as the starting material for the process (g / β) is also a known compound of organic chemistry.

The hydroxyacetanilides to be used as starting materials in the performance of process (h) are represented by the formula (XV)

12 3

generally defined. In this formula, R, R and R preferably represent those radicals which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for these substituents.

The hydroxyacetanilides of the formula (XV) are obtained analogously to the hydroxyacetanilides of the formula (XII).

i # V -50- 11.8.1980

57 039/18

Suitable diluents for the reaction according to process variant (a) are preferably inert organic solvents in embossing. These include, preferably, ketones, such as ethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene and esters, such as ethyl acetate *

The method (a) can be carried out in the presence of acid-binding agent (hydrogen halide acceptor) optionally "are all the customary ^ü äurebindemittel can be used" These preferably include organic bases such as tertiary amines, for example triethylamine, or such as pyridine, and also inorganic bases, such as alkali hydroxides and alkali carbonates. Optionally, a catalyst, such as dimethylformamide, may also be used.

The reaction temperatures can be varied within a relatively wide range when carrying out the process (a) according to the invention. In general, one works between 0 C and 120 ⁰ C, preferably between 20 ⁰ C and 100 ⁰ C.

In carrying out the process (a) is preferably carried out in molar amounts. The isolation of the compounds of the formula. (I) takes place in the usual way «

21 97 5 9 - ⁵¹ - 11.8,

57 039/18

Diluents are suitable for the reaction according to process (b) all inert organic solvents. These include, preferably, ethers, such as diethyl ether, dioxane or tetrahydrofuran; aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; Esters, such as ethyl acetate; Ketones, such as methyl isobutyl ketone; Nitriles, such as acetonitrile and dimethylformamide or dimethyl sulfoxide.

The reaction according to process (b) is carried out in the presence of an acid binder. As such, all common acid binders can be used. These include preferably inorganic bases, such as alkali metal hydroxides and alkali metal carbonates.

The reaction temperatures can be varied within a substantial range when carrying out process (b). In general, one works between -70 ⁰ C and + 100 ⁰ C, preferably between -20 ⁰ C and + 80 ⁰ C.

In carrying out the process (b), it is preferable to use 1 to 1.5 mol of allyl halide of the formula (V) for 1 mol of the acid ore (IV). The isolation of the compounds of formula (I) is carried out in the usual manner.

In a preferred embodiment, the reaction according to process (b) is in a two-phase system, such as aqueous Hatron- or potassium hydroxide / toluene or methylene chloride, optionally with the addition of 0.1 to 1 mol of a phase transfer catalyst, such as ammonium or phosphonium compounds, for example Benzyldodecyl-dimethyl-amnonium chloride and triethyl-benzyl-arnmoniumchlorid called performed.

S 9 -52- August 11, 1980

57 039/18

As diluents come for. the reaction according to process (c) preferably inert organic solvents, preferably ethers, such as diethyl ether, dioxane or tetrahydrofuran, aromatic hydrocarbons, such as benzene and toluene, halogenated hydrocarbons, such as methylene chloride and carbon tetrachloride, alcohols, such as ethanol and Methanol, and dimethylformamide or dimethyl sulfoxide.

The reaction temperatures can be varied within a relatively wide range when carrying out process (c). In general, one works between 0 ⁰ C and 100 ⁰ C, preferably between 20 ⁰ C and 80 C,

When carrying out the process (c), the reaction is preferably carried out in molar amounts. The isolation of the compounds of the formula (I) is carried out in the customary manner.

Suitable diluents for the reaction according to process (d) are preferably polar organic solvents. These include, preferably, alcohols, such as methanol and ethanol; and nitriles, such as acetonitrile »

The reaction according to process (d) is carried out in the presence of a catalyst. Preference is given to using noble metal noble metal oxide (or noble metal hydroxide catalysts or so-called "Raney catalysts", in particular platinum, platinum oxide and nickel.

The reaction temperatures can be varied within a wide range in the practice of Verfalirens (d). In general, one works between 20 ⁰ C and 60 ⁰ C, preferably at 20 ⁰ C to 40 ⁰ C,

21 97 5 9 " ⁵³ ~ 11.8.1980

57 039/18

The reaction according to process (d) can be carried out at normal pressure but also at elevated pressure, in particular 1 to 2 atm.

When carrying out the process (d), it is preferable to use about 1 mol of hydrogen and 0.1 mol of catalyst per mole of the compounds of the formula (VIII). To isolate the compounds of formula (I) is filtered off from the catalyst and worked up in the usual manner.

Suitable diluents for the reaction according to process (e) are preferably inert organic solvents. These preferably include chlorinated hydrocarbons, such as carbon tetrachloride, chloroform or dichloromethane; Alcohols, such as ethanol; aromatic hydrocarbons, such as chlorobenzene or nitrobenzene; as well as glacial acetic acid.

The reaction according to process (e) is carried out in the presence of a catalyst. These include preferably metal halides, such as. B, ferric halide, Aiuminiumhalogenid, ^ ismut- (III) halide, antimony (III) halide, mercury (II) halide and copper (I) - or (II) halide and Metallhalogenidgemische.

The reaction according to process (e) can also be carried out in the gas phase and at a slight overpressure.

Reaction temperatures may be varied over a wider range in the practice of process (e). In general, one works between -20 ⁰ C to + 250 ⁰ C, preferably at 0 ⁰ C to 200 ⁰ C.

In carrying out the process (e) is preferably carried out in molar amounts. The isolation of the compounds of formula (I) takes place in the usual way.

5 9 -54- "11.8.1980

57 039 /

Preferred diluents for the reaction according to process (f) are inert organic solvents ", which preferably include the solvents already mentioned in process (a),

Reaction according to process (f) can optionally be carried out in the presence of an acid binder. Any of the commonly used inorganic or organic acid binders can be added, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, dimethyibenzylamine; or pyridine and diazebicyclooctane. Preferably, an excess of azole is used.

The reaction temperatures can be varied in a wider range in process (f). In general, one works between about 20 ⁰ C to 150 ⁰ C, preferably at 60 C to 120 ⁰ C »In the presence of a solvent is advantageously carried out at the boiling point of the respective solvent.

When carrying out the process (f), 1 to 2 mol of the compounds of the formula (XI) and, if appropriate, 1 to 1 mol of acid binder are used per mole of the compounds of the formula (X). The isolation of the compounds of formula (I) is carried out in the usual manner.

Preferred diluents for the reaction according to process (g) are embossed inert organic solvents. These preferably include the solvent already mentioned in process (a).

21 97 5 9 -55-. 08/11/1980

57 039/18

If desired, the reaction according to process (g / o) can be carried out in the presence of an acid binder All the commonly used inorganic or organic acid binders can be added, which preferably include the compounds already mentioned in process (a).

The reaction temperatures can be varied in the process (g / oc) in a wider range. In general carried out between 20 ⁰ C and 150 ⁰ C, preferably between 20 ⁰ C and 100 ⁰ C.

In carrying out the process (g / CO), 1 mol of the halide of the formula (XIII) is added to 1 mol of the compounds of the formula (XII), if appropriate after addition of 1 to 2 mols of a strong base such as, for example, an alkali metal hydride. and optionally 1 to 2 moles äurebinder ^ a. For the isolation of the final products is the ^ eaktionsgemisch the solvent be freed ^v and the residue treated with water and an organic solvent added to the organic phase is separated off and worked up in the usual "else..

In a preferred embodiment of the process (g /%) it is expedient to proceed from a hydroxyacetanilide of the formula (XII), converting the latter into the alkali metal alkoxide by means of an alkali metal hydroxide or amide in a suitable inert solvent, and the latter without isolation immediately reacted with a halide of the formula (XIII), the compounds of the formula (I) according to the invention being obtained in one operation while leaving alkali metal halide.

In a further preferred ^A, the reaction according to process (g / cc) is carried out in an aqueous-organic two-phase system is en usführungsform (compare the information in process (b)).

g 9 ~ ⁵⁶ "11.8.1980

57 039/18

The reaction according to process (g / β) may optionally be carried out in the presence of a catalyst. To this end, preferably (J.. See. On ^ü hem. Soc. 6 £ 2246 (1947), ibid. 70, 4187 (1948)) used hydrogen chloride.

The reaction temperatures can be varied in a wider range during the process (g / β). In general, one works between 0 ⁰ C and 100 ⁰ C, preferably between 20 ⁰ C and 60 ⁰ C.

When carrying out the process (g / β), the reaction is preferably carried out in molar amounts. The isolation of the compounds of the formula (I) is carried out in the usual manner.

Is diluents for the reaction according to method (h) preferably inert organic solvents in • fc'rage. These preferably include the solvent already mentioned in process (a).

The reaction according to process (h) can optionally be carried out in the presence of an acid binder. All commonly used inorganic or organic acid binders can be added. These preferably include the compounds already mentioned in process (a).

The reaction temperatures can be varied in a broader range in process (h). In general, one works between 20 ⁰ C and 120 ⁰ C, preferably between 20 ⁰ C and 80 ⁰ C,

In carrying out the process (h) is used for 1 mole of the compounds of formula (XV), optionally after the addition of 1 to 2 moles of a strong base, such as ζ. Eines »an alkali hydride j 2 to 2.5 moles of halide of the formula (V) and optionally 2 to 4 moles of acid binder. The isolation of the end products as well as preferred embodiments correspond to those in the process (g / ou) »

219759

The erfir.dungsgernjißen agents have a strong

• have a microbicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are for use as. Plant protection agents suitable.

Fungicidal agents in crop protection are used to combat Plasaodiophoromycetes, Ooaiycetes, Chytridiornycetes, Zygomycetes, Ascomycetes, Basidionycetes, Deuteromycetes.

Pil "» "good plant tolerance of the active ingredients in the concentrations necessary for the control of plant diseases allows a treatment of aboveground plant parts, of planting and seed, and of the soil.

As plant protection agents, the active compounds according to the invention can be used with particular success to combat Oomycetes, e.g. against the causative agent of cabbage and brown rot tomato and potato (Phytophthora infestans) are used. Particularly noteworthy is that the active compounds according to the invention not only develop a protective, but also a curative-oradicative effect. They also have systemic properties. So it is possible to protect plants against fungal infestation, if the active ingredient on the soil and the root or on the seed feeds the aerial parts of the plant.

Le A 19 517

rf 9 - 58 -

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, furthermore in formulations with Fuel packs, such as smoke cartridges, cans, spirals and others, as well as ULV-KaIt and warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active ingredients with StrecXmitteln, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethyl or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their esters and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; By liquefied gaseous diluents or carriers is meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerasol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen

Le A 19 517

21 97 5 9 _ _S9 _

and carbon dioxide; as solid carriers there are suitable: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates; suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and arionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: for example, lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azole metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 9% by weight of active ingredient, preferably between 0.5 and 90%. ·

Le A 19 517

The active compounds according to the invention can be present in the formulations or in the various application forms in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nerubicides, herbicides, bird repellents, growth substances, plant nutrients and soil conditioners.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions. Emulsions, suspensions, powders, pastes and granules are applied. The application is done in the usual way, e.g. by pouring, dipping, spraying, spraying, misting, vaporizing, injecting, silting, spreading, dusting, spreading, dry pickling, moist pickling, wet pickling, whitish pickling or encrusting.

In the treatment of parts of plants, the concentrations of active ingredients in the preparation can be varied over a wider range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001 %.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably Ο, ΟΊ to 10 g, needed.

When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

Le A 19 517

21 97 5 9 -61- · · 11.8.1980

57 039/18

embodiment Example A

Phytophthora test (tomato) / Protective

Solvent: 4.7 parts by weight of acetone emulsifier: 0.3 part by weight of alkylaryl polyglycol

ether water: 95 »0 parts by weight

Mixing the necessary for the desired drug concentration in the spray liquid amount of active with the other, given amount of the solvent and the concentrate is diluted with the specified amount of water containing the additives mentioned.

With the spray liquid splashed young tomato plants with 2 to 4 leaves to drip. The plants remain 24 hours at 20 ⁰ C and a relative humidity of 70% in the greenhouse. Subsequently, the tomato plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with a 100% humidity and a temperature of 18 to 20 ⁰ C.

After 5 days, the infection of tomato plants is determined. The obtained rating values are converted to percent infestations. 0 % means no infestation, 100 % means that the plants are completely infested. In this test, z. For example, the following compounds a very good effect, which is clearly superior to those of au3 known in the prior art compounds.

Compounds according to Preparation Examples 3, 1, 4, 5, 6, 7, 8, 9, 10 and 11.

Example B - 62 -

Phytophthora test (tomato) / Systemic

Solvent: 4.7 parts by weight of acetone Dispersant: 0.3 parts by weight of alkylaryl polyglycol ether Water: 95.0 parts by weight

The active ingredients required for the desired active ingredient concentration in the casting liquid are mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water containing the additives mentioned.

Tomato plants grown on unit soil with 2 to 4 leaves are poured with 10 ml of the liquid in the stated active substance concentration, relative to 100 ml of soil,

The treated plants are inoculated after treatment with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with a humidity of 100% and a temperature of 18 to 2O ⁰ C. After 5 days the infestation of tomato plants is determined. The resulting rating values are converted to percent infestation. 0 % means no infestation, 100 % means that the plants are completely infested.

In this test, e.g. the following compounds have a very good action, which is clearly superior to that of the compounds known from the prior art:

Compounds according to Preparation Examples, 3, 1, 4, 5 »6, 7, 8, 9, 10 and 11. '

Le A 19 517

97 59 1 / - C CH ₂ CH = 63 21 Preparation Examples Q Beisüiel ^N c - ti CH ₂ . O OCH ₃ , CH ₃ 1 • CH ₃

(Method b)

19.3 g (0.1 mol) of 2,6-dimethyl-methoxyacetanilid are dissolved in 200 ml of toluene and after addition of 0.5 g of triethylbenzyl-ammonium chloride with 60 ml of 50% sodium hydroxide ver. Thereafter, 13.3 g (0.11 mol) of allyl bromide are added dropwise with rapid stirring. The mixture is stirred, "separates" the toluene, washed several times with water, dried over sodium sulfate and distilled under reduced pressure for 5 hours at 25 ⁰ C. This gives 15.2 g (65% of theory) of 2,6-dimethyl N-allyl methoxyacetanilide of boiling point 100-103 ° C / O, lmra or melting point 45 ° C.

Herstellung_des_Au ^ ^ it gangsprcduk

_CH ^X C - CH ₂ OCH ₃ 0

12Ig (1 mol) of 2,6-dimethylaniline and 101 g of triethylamine are dissolved in 300 ml of toluene and admixed dropwise at about 5.degree. C. while stirring with 108.5 g (1 mol) of methoxyacetic acid chloride. The mixture is stirred for 4 hours at 2O ⁰ C, filtered, washed the toluene phase twice with 50 ml of water, dried over sodium sulfate and concentrated. The oily residue is distilled in vacuo. Obtained (83% of theory) of 2,6-dimethyl-methoxyacetanilide boiling 134-139 ° C / 0, lmm or melting point 60-6l ° C.

Le A 19 517

Example 2 - 64 -

C-CH ₂ -O-CH ₂ -CH = CH ₂

υ ^z ί-

(Method h).

26.6 g (0.22 mol) of allyl bromide are added to a vigorously stirred mixture of 17.9 g (0.1 mol) of 2,6-dimethyl-hydroxy-acetanilide, Ig triethyl-benzyl-ammonium chloride, 300 ml of methylene chloride and 50 g of 50% strength Sodium hydroxide solution dripped. The two-phase system is allowed to stir for 12 hours, the organic phase is separated off, washed neutral with water, dried over sodium sulfate and concentrated by distilling off the solution. by means of in a vacuum. The residue is distilled under high vacuum. This gives 22.6 g (87 ^ of theory) of 2,6-dimethyl-N-allyl-allyloxyacetanilide of boiling point 115-12O ° C / 0.05 mm.

K5 According to processes (a) to (h), the following compounds of the general formula

R * f ^

R ¹ CH - C = C

N ^ R ⁷ (I) CR ⁸

to be obtained:

Le A 19 517

219759 - «ε-

Example no. R ¹ R ² R ³ R * R ⁵ R ⁶ R7 R ⁸ Fp ( ⁰ C) or Kp ( ⁰ C) / mmHg column 3 CH ₃ 6-CH ₃ H H H Ή H 68-70 4 CH ₃ 6-CH ₃ H H H H H -CH ₂ -N ^ l ⁿ D: 1.5637 5 CH ₃ 6-CH ₃ H H H Cl CH ₃ -CH ₂ OCH ₃ 124-26 / 0.2 6 CH ₃ 6-CH ₃ H H CH ₃ H H -CH ₂ OCH ₃ 110 / 0.2 7 CH ₃ 6-CH ₃ ' H H H CH ₃ H -CH ₂ OCH ₃ 111 / 0.2 8th CH ₃ 6-CH ₃ H H br H H -CH ₂ OCH ₃ 128-29 / 0.2 9 CH ₃ 6-CH ₃ H H Cl H Cl -CH ₂ OCH ₃ 128-29 / 0.2 10 CH ₃ 6-CH ₃ H H Η " Cl Cl -CH ₂ OCH ₃ 46-47 11 12 CH ₃ CH ₃ 6-CH ₃ '6-CH ₃ H H H H H H Cl H H CH ₃ -CH ₂ OCH ₃ 128-29 / 0.1 75-77

13 CH ₃ 6-CH ₃ HH CH ₃ H

14 CH, 6-CH, H

15 CH ₃ 6-CH ₃ H

HH Cl CH,

H CH ₃ H Cl

16 CH ₃ 6 -CH ₃ HHHH Cl

17 CH ₃ 6 -CH ₃ HHH Cl Cl 18 CH ₃ 6 -CH ₃ HH Br HH

19 C ₂ H ₅ 6-C ₂ H ₅ H HH H

20 CH ₃ 6 -CH ₃ HH CH ₃ H 'Cl -CH ₂ OCH ₃

21 C ₂ H ₅ 6-C ₂ H ₅ HHHH H-CHCl ₂

22 CH ₃ 6-C ₂ H ₅ H Le A 19 517

HHHH-CHCl,

75-77

1C6-C8

81-32

84-86

89-91

53-55

36-37

130-35 / 0.1

ng>: 1.5442 ng ¹ : 1.5464

Fp ( ⁰ C)

Eg no. 'R ¹ RZ R ³ R * H R = 'R ⁶ R ⁷ R ⁸ BZV /. Kp ( ⁰ C) / mniHg-S. 23 CHj 6-CH ₃ H H H H H -CHCl ₂ 66-67 2k CHj 6-CHj H -CH ₂ O CHj H H H -CH ₂ OCHj 132-35 / 0.2 25 CHj 6-CH ₃ H -CH ₂ O H H H 182 / 0.3 CH ₃ 26 CHj 6-C ₂ H ₃ H -CH ₂ O CHj H H H -CH ₂ OCH ₃ 150-54 / 0.1 27 CHj. 6-C ₂ H ₅ H -CH ₂ OI H. H H -u 67-72 CHj 28 CHj 6-C ₂ 'H ₅ H -CH ₂ 0 I H H H -CH ₂ OCHj n £ °: 1.5157 C ₂ H ₅ 29 CH ₃ 6-CH ₃ H H H H -CH ₂ SCH ₃ 150 / 0.2

Le A 19 517

219759

Example no. R ¹ 30 CH ₃ 31 CH ₃ 32 CH ₃ 33 CH ₃ 34 CH ₃ 35 CH ₃ 36 CH ₃ 37 CH ₃ 38 CH ₃ 39 CH ₃ AO CH ₃ 41 CH ₃ 42 CH.

R ²

R ⁶ R ⁷

Mp (O

or Kp ( ⁰ C) /

mmHg-S.

6-CH ₃ 6-CH ₃

6-CH ₃ 6-CH ₃ 6-CH ₃ 6-CH ₃ 6-CH ₃ 6-CH ₃ 6-CH ₃ 6-CH ₃ 6-CH, 6-CH ₃ 6-CH ₀

TJ / -1TT

H CH ₃

H CH ₃

H CH ₃

H CH ₃

H CH ₃

H CH ₃

H CH ₃

H CH ₃

H CH ₃

K CH ₃

H CH,

H H

CH.

CH-

H H H H H H H H

Ή H H H H H H H

H H H H H H H H

CH ₂ OCH ₃

η ²¹ : 1.5172 70 η ²⁶ : 1.5339 η ²⁶ : 1.5069 η ²³ : 1.5373 η ²³ : 1.5229

CH ₂ -O-CO-CH ₃ η ²² ' ⁵ : 1.5080

CO-OCH. CHCl.

Λ = "N

CH ₅ -M ^Χ Ν

k 1 ^ k * «

r. ²² ' ⁵ : 1,5053

90 -

57 rip 1.5290

H H

r. ²² : 1.5415-

Le A 19 517

Claims (4)

«68-8.11.1980 57 039 / * Fungicidal agent, characterized in that it contains at least one substituted H ^- alkylacetanilide of the formula (D, R ^{1 is} Yfesserstoff, alkyl, halogen, alkozyalkyl or alkylthioalkyl, R is hydrogen, alkyl, alkoxyalkyl or alkylthioalkyl, R 1 is Y / oxygen, alkyl, alkoxyalkyl or alkylthioalkyl, R 1 is hydrogen, alkyl or alkoxyalkyl, R is hydrogen, alkyl, halogen or optionally substituted phenyl, R is hydrogen, alkyl, halogen or optionally substituted phenyl, R ^{1 is} hydrogen, alkyl, halogen or optionally substituted phenyl, 21 97 S 9 -69- 11.8.1980 57 039/13 R ^{8 is} puryl, tetrahydrpfuryl, thiophenyl, tetrahydrothiophenyl; optionally substituted by alkyl isoxazolyl; if necessary. UyoxLo or ^r i'hiocyano substituted alkyl, alkenyl and alkynyl; dihaloalkyl; as well as the groupings -CII ₂ -Az, -CH ₂ -OR ⁹ , -CH ₂ -SR ⁹ , -OR ⁹ , -SR ⁹ , -CH ₂ -OSO ₂ R ⁹ , -COOR ⁹ and -CHg-O- ^} is j in which R "is optionally substituted alkyl, alkenyl, alkynyl or alkoxyalkyl and
Az for pyrazol-1-yl, 1,2,4-triazol-1-yl and imidazol-1-yl, in addition to extenders and / or surface-active agents. 2 »A method for combating fungi, characterized in that substituted U-allyl-acetanilides of the formula (I) are allowed to act on fungi or their habitat. 3 »Use of substituted N-allyl-acetanilides of the formula (I), characterized in that they are used for combating fungi. 4 »Process for the preparation of fungicidal agents, characterized in that substituted ii-allyl-acetanilides of the formula (I) are mixed with extuders and / or surface-active agents *