RU2171801C2 - N-sulfonyl and n-sulfinyl derivatives of amino acids as fungicides - Google Patents

Abstract

FIELD: organic chemistry, amino acids, fungicides. SUBSTANCE: invention describes amides of α-amino acids of the formula (I)

where n, R₂,R₃,R₄-R₇,R₈,R₉, p, g, R₁₃-R₁₆, X and

Description

 The invention relates to new α-amino acid amides of the following formula I, to a method for producing these compounds, and to agrochemical compositions comprising at least one of these compounds as an active substance. The invention also relates to a method for producing these compositions and to the use of active substances or compositions for controlling or preventing plant damage by phytopathogenic microorganisms, especially fungi.

где n = 0 или 1;
R₁ обозначает C₁-C₁₂алкил, который может быть незамещенным или может быть замещен C₁-C₄алкокси-, C₁-C₄алкилтиогруппой, C₁-C₄алкилсульфонилом,
C₃-C₈циклоалкилом, цианогруппой, C₁-C₆алкоксикарбонилом, C₃-C₆алкенилоксикарбонилом или C₃- C₆алкинилоксикарбонилом; C₃-C₈циклоалкил;
C₂-C₁₂алкенил; C₂-C₁₂алкинил; C₁-C₁₂галоидалкил или группу формулы NR₁₁R₁₂, где R₁₁ и R₁₂ каждый независимо друг от друга обозначает водород или C₁-C₆алкил или вместе обозначают тетраметилен или пентаметилен;
R₂ и R₃ каждый независимо друг от друга обозначает водород; C₁-C₈алкил; C₁-C₈алкил, замещенный гидрокси-, C₁-C₄алкокси-, меркапто- или C₁-C₄алкилтиогруппой; C₃-C₈алкенил; C₃-C₈алкинил или C₃-C₈циклоалкил-C1-C₄алкил; или две группы R₂ и R₃ вместе с атомом углерода, к которому они присоединены, образуют трех-восьмичленное карбоциклическое кольцо;
R₄-R₇ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил;
R₈ обозначает C₁-C₆алкил, C₃-C₆алкенил или C₃-C₆алкинил;
R₉ обозначает C₃-C₈циклоалкил; C₁-C₆алкил-, C₃-C₆алкенил- или C₃-C₆алкинильную группу, замещенную одним или несколькими атомами галогена, или группу

где p и q имеют одинаковые или различные значения и каждый независимо друг от друга равен нулю или единице,
R₁₃-R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил и
X обозначает водород при условии, что p и q = 0; фенил, незамещенный или моно- или полизамещенный галогеном, нитро-, циано-, карбоксигруппой, С₂-С₆алкенилом, С₂-С₆алкинилом, С₁-С₆галоидалкилом, С₃-С₆алкенилокси-,
С₃-С₆алкинилоксигруппой, С₃-С₇циклоалкилом, C₁-С₆галоидалкокси-, С₁-С₆алкилтиогруппой, C₁-С₆алкоксикарбонилом, С₃-С₆алкенилоксикарбонилом,
С₃-С₆алкинилоксикарбонилом, C₁-С₆алкилом или С₁-С₆алкоксигруппой; цианогруппу; -COOR₁₇; -COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-С₆алкил, С₃-С₆алкенил или С₃-С₆алкинил;
R₁₈ обозначает водород; С₁-С₆алкил, С₂-С₆алкенил, С₂-С₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-С₄алкилом или С₁-С₄алкоксигруппой; и
R₁₉ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-С₄алкил.The compounds of the invention correspond to general formula I

where n = 0 or 1;
R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl,
C ₃ -C ₈ cycloalkyl, cyano, C ₁ -C ₆ alkoxycarbonyl, C ₃ -C ₆ alkenyloxycarbonyl or C ₃ -C ₆ alkynyloxycarbonyl; C ₃ -C ₈ cycloalkyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently hydrogen and C ₁ -C ₆ alkyl, or together are tetramethylene or pentamethylene;
R ₂ and R ₃ each independently of one another is hydrogen; C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C1-C ₄ alkyl; or two groups R ₂ and R ₃ together with the carbon atom to which they are attached form a three to eight membered carbocyclic ring;
R ₄ -R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₉ is C ₃ -C ₈ cycloalkyl; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted by one or more halogen atoms, or a group

where p and q have the same or different values and each independently from each other is zero or one,
R ₁₃ -R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl and
X is hydrogen, provided that p and q = 0; phenyl unsubstituted or mono- or polysubstituted with halogen, nitro, cyano, carboxy, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ alkenyloxy,
C ₃ -C ₆ alkynyloxy group, C ₃ -C ₇ cycloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkoxycarbonyl, C ₃ -C ₆ alkenyloxycarbonyl,
C ₃ -C ₆ alkynyloxycarbonyl, C ₁ -C ₆ alkyl or a C ₁ -C ₆ alkoxy group; cyano group; -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently of one another is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl.

где n = 0 или 1.A preferred group includes compounds of formula I

where n = 0 or 1.

где p и q имеют одинаковые или различные значения и каждый независимо друг от друга равен 0 или 1;
R₁₃-R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил; и
X обозначает водород при условии, что p и q = 0; фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; -COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-C₆алкил, C₃-C₆алкенил или C₃-C₆алкинил;
R₁₈ обозначает водород; C₁-C₆алкил, C₃-C₆алкенил, C₃-C₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₉ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил (подгруппа 1А).R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl,
C ₃ -C ₈ cycloalkyl, cyano, C ₁ -C ₆ alkoxycarbonyl, C ₃ -C ₆ alkenyloxycarbonyl or C ₃ -C ₆ alkynyloxycarbonyl; C ₃ -C ₈ cycloalkyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently hydrogen and C ₁ -C ₆ alkyl, or together are tetramethylene or pentamethylene;
R ₂ and R ₃ each independently of one another is hydrogen; C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl; or two groups R ₂ and R ₃ together with the carbon atom to which they are attached form a three to eight membered carbocyclic ring;
R ₄ -R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p and q have the same or different values and each independently of one another is 0 or 1;
R ₁₃ -R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p and q = 0; phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently of one another is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl (subgroup 1A).

где p и q имеют одинаковые или различные значения и каждый независимо друг от друга равен 0 или 1;
R₁₃-R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил; и
X обозначает водород при условии, что p и q = 0; фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; -COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-C₆алкил, C₃-C₆алкенил или C₃-C₆алкинил;
R₁₈ обозначает водород; C₁-C₆алкил, C₃-C₆алкенил, C₃-C₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₉ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил (подгруппа А).Essential groups form compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkylsulfonyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently hydrogen and C ₁ -C ₆ alkyl, or together are tetramethylene or pentamethylene;
R ₂ is hydrogen;
R ₃ is C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl;
R ₄ -R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p and q have the same or different values and each independently of one another is 0 or 1;
R ₁₃ -R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p and q = 0; phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently of one another is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl (subgroup A).

где p и q имеют одинаковые или различные значения и каждый независимо друг от друга равен 0 или 1; и
R₁₃-R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил; и
X обозначает водород при условии, что p и q = 0; фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; -COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-C₆алкил, C₃-C₆алкенил или C₃-C₆алкинил;
R₁₈ обозначает водород; C₁-C₆алкил, C₃-C₆алкенил, C₃-C₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₉ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил (подгруппа В).An important group consists of compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkylsulfonyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently C ₁ -C ₆ alkyl or together are tetramethylene or pentamethylene;
R ₂ is hydrogen;
R ₃ is C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl;
R ₄ -R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p and q have the same or different values and each independently of one another is 0 or 1; and
R ₁₃ -R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p and q = 0; phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently of one another is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl (subgroup B).

где p и q имеют одинаковые или различные значения и каждый независимо друг друга равен 0 или 1;
R₁₃-R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил; и
X обозначает водород при условии, что p и q = 0, фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; - COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-C₆алкил, C₃-C₆алкенил или Cg-Cалкинил;
R₁₈ обозначает водород; C₁-C₆алкил, C₃-C₆алкенил, C₃-C₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₉ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил (подгруппа Ва).Particularly important are the compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₁₂ alkyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R ₁₂ are C ₁ -C ₆ alkyl;
R ₂ is hydrogen;
R ₃ is C ₁ -C ₈ alkyl;
R ₄ is hydrogen or C ₁ -C ₄ alkyl;
R ₅ -R ₇ are hydrogen;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p and q have the same or different values and each independently of one another is 0 or 1;
R ₁₃ -R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p and q = 0, phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; - COR ₁₈ or a group of the formula

where R ₁₇ and R _{21 are} each independently hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or Cg-C alkynyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl (subgroup Ba).

где p и q имеют одинаковые или различные значения и каждый независимо друг от друга равен 0 или 1;
R₁₃-R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил; и
X обозначает водород при условии, что p и q = 0; фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; -COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-C₆алкил, C₃-C₆алкенил или C₃-C₆алкинил; и
R₁₈ обозначает водород; C₁-C₆алкил, C₃-C₆алкенил, C₃-C₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₀ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил (подгруппа Вb).Another important group consists of compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₄ alkyl or dimethylamino;
R ₂ is hydrogen;
R ₃ is C ₃ -C ₄ alkyl;
R ₄ is hydrogen or methyl;
R ₅ -R ₇ are hydrogen;
R ₈ is C ₁ -C ₂ alkyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p and q have the same or different values and each independently of one another is 0 or 1;
R ₁₃ -R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p and q = 0; phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently of one another is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl; and
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₀ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl (subgroup Bb).

где p и q имеют одинаковые или различные значения и каждый независимо друг от друга равен 0 или 1;
R₁₃ - R₁₆ имеют одинаковые или различные значения и каждый независимо от других обозначает водород или C₁-C₄алкил; и
X обозначает водород при условии, что p и g = 0; фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; - COR₁₈ или группу формулы

где R₁₇ и R₂₁ каждый независимо друг от друга обозначает водород, C₁-C₆алкил, C₃-C₆алкенил или C₃-C₆алкинил;
R₁₈ обозначает водород; C₁-C₆алкил, C₃-C₆алкенил, C₃-C₆алкинил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₉ и R₂₀ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил (подгруппа Вc).Among these groups, preferred are compounds where
n is 1;
R ₁ is C ₂ -C ₄ alkyl or dimethylamino;
R ₂ is hydrogen; and
R ₃ is 2-propyl;
R ₄ is hydrogen;
R ₅ , R ₆ and R ₇ are hydrogen;
R ₈ is methyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p and q have the same or different values and each independently of one another is 0 or 1;
R ₁₃ - R ₁₆ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p and g = 0; phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; - COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently of one another is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl (subgroup Bc).

где p = 0 или 1
q = 0, и
R₁₃ и R₁₄ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил; и
X обозначает водород, при условии, что p = 0; фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; -COOR₁₇; -COR₁₈ или группу формулы

где R₁₇ и R₂₁ обозначают C₁-C₆алкил;
R₁₈ обозначает водород; C₁-C₆алкил или фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; и
R₁₉ и R₂₀ обозначают водород (подгруппа C).Another preferred group consists of compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkylsulfonyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently C ₁ -C ₆ alkyl or together are tetramethylene or pentamethylene;
R ₂ is hydrogen;
R ₃ is C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl;
R ₄ - R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is C ₃ -C ₈ cycloalkyl; A C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p = 0 or 1
q = 0, and
R ₁₃ and R ₁₄ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl; and
X is hydrogen, provided that p = 0; phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ are C ₁ -C ₆ alkyl;
R ₁₈ is hydrogen; C ₁ -C ₆ alkyl or phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and
R ₁₉ and R ₂₀ are hydrogen (subgroup C).

где p = 0 или 1;
q = 0;
R₁₃ и R₁₄ имеют одинаковые или различные значения и каждый независимо друг от друга обозначает водород или C₁-C₄алкил; и
X обозначает фенил, незамещенный или замещенный галогеном, нитро-, цианогруппой, C₁-C₄алкилом или C₁-C₄алкоксигруппой; цианогруппу; или -COR₁₈ и где
R₁₈ обозначает водород или C₁-C₄алкил (подгруппа Ca).Important compounds of subgroup C within the scope of formula I are compounds wherein n = 1;
R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkylsulfonyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently C ₁ -C ₆ alkyl or together are tetramethylene or pentamethylene;
R ₂ is hydrogen;
R ₃ is C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl;
R ₄ - R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is a C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group substituted with one or more halogen atoms; or group

where p = 0 or 1;
q is 0;
R ₁₃ and R ₁₄ have the same or different meanings and each independently of one another is hydrogen or C ₁ -C ₄ alkyl; and
X is phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; cyano group; or -COR ₁₈ and where
R ₁₈ is hydrogen or C ₁ -C ₄ alkyl (a subgroup of Ca).

где p = 1 и
q = 0; и
R₁₃ и R₁₄ - водород; и
X обозначает фенил; циано или -COR₁₈ и
где R₁₈ обозначает водород или C₁-C₄алкил (подгруппа Cb).An important subgroup consists of compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₁₂ alkyl, which may be unsubstituted or may be substituted with C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ alkylsulfonyl;
C ₂ -C ₁₂ alkenyl; C ₂ -C ₁₂ alkynyl; C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently C ₁ -C ₆ alkyl or together are tetramethylene or pentamethylene;
R ₂ is hydrogen;
R ₃ is C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy, mercapto or C ₁ -C ₄ alkylthio; C ₃ -C ₈ alkenyl; C ₃ -C ₈ alkynyl or C ₃ -C ₈ cycloalkyl-C ₁ -C ₄ alkyl;
R ₄ - R ₇ have the same or different meanings and each independently of the others is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is a C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl group substituted with one or more halogen atoms; or group

where p = 1 and
q is 0; and
R ₁₃ and R ₁₄ are hydrogen; and
X is phenyl; cyano or -COR ₁₈ and
where R ₁₈ denotes hydrogen or C ₁ -C ₄ alkyl (subgroup Cb).

где p = 1; q = 0;
R₁₃ и R₁₄ обозначают водород;
X обозначает фенил; циано или -COR₁₈,
где R₁₈ обозначает водород или C₁-C₄алкил (подгруппа Cd).A preferred subgroup is the compounds of formula I, where n = 1;
R ₁ is C ₁ -C ₆ alkyl; C ₂ -C ₄ alkenyl; C ₁ -C ₆ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently C ₁ -C ₂ alkyl;
R ₂ is hydrogen;
R ₃ is C ₂ -C ₅ alkyl;
R ₄ is hydrogen or C ₁ -C ₄ alkyl;
R ₅ - R ₇ are hydrogen;
R ₈ is C ₁ -C ₂ alkyl;
R ₉ is a C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl group substituted with one or more halogen atoms; or group

where p = 1; q is 0;
R ₁₃ and R ₁₄ are hydrogen;
X is phenyl; cyano or -COR ₁₈ ,
where R ₁₈ denotes hydrogen or C ₁ -C ₄ alkyl (subgroup Cd).

где p = 1; q = 0;
R₁₃ и R₁₄ обозначают водород; и
X обозначает фенил; циано или -COR₁₈,
где R₁₈ обозначает водород или C₁-C₄алкил (подгруппа Cе).It should be noted that preferred compounds of the Cd subgroup are those wherein
n is 1;
R ₁ is C ₂ -C ₄ alkyl or dimethylamino;
R ₂ is hydrogen; and
R ₃ is C ₃ -C ₄ alkyl;
R ₄ - R ₇ is hydrogen;
R ₈ is methyl;
R ₉ is a C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl group substituted with one or more halogen atoms; or group

where p = 1; q is 0;
R ₁₃ and R ₁₄ are hydrogen; and
X is phenyl; cyano or -COR ₁₈ ,
where R ₁₈ denotes hydrogen or C ₁ -C ₄ alkyl (subgroup Ce).

 In the above formula I, the term “halogen” includes fluoro, chloro, bromo and iodo.

 Alkyl, alkenyl and alkynyl radicals may be straight or branched chain, which also applies to the alkyl, alkenyl and alkynyl moieties of other groups containing alkyl, alkenyl or alkynyl.

 It should be noted that depending on the number of these carbon atoms, alkyl, individually or as part of another substituent, is, for example, methyl, ethyl, propyl, butyl, pentyl and their isomers such as isopropyl, isobutyl, tert-butyl or sec-butyl. Cycloalkyl, depending on the number of carbon atoms indicated, is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

A haloalkyl group may have one or more (same or different) halogen atoms, for example, CHCl ₂ , CH ₂ F, CCl ₃ , CH ₂ Cl, CHF ₂ , CF ₃ , CH ₂ CH ₂ Br, C ₂ Cl ₅ , CH ₂ Br, CHBrCl, etc.

 Due to the presence of at least one asymmetric carbon atom and / or at least one asymmetric sulfur atom in the compounds of formula I, the compounds can be in the form of optical isomers. Due to the presence of the aliphatic -C = C- double bond, geometric isomerism may also occur. It is understood that Formula I covers all of these possible isomeric forms and mixtures thereof.

 Certain derivatives of α-amino acids having different types of structure have already been proposed for combating plants harmful to plants (see, for example, EP-398072, EP-425925, DE-4026966, EP-477639, EP-493683, DE-4035851 , EP-487154, EP-496239, EP-550788 and EP-554729). However, these compositions are not satisfactory in their action. It was unexpectedly found that the compound having the structure represented by formula I is a new type of bactericides with high activity.

где радикалы R₁ - R₃ и n имеют значения, указанные выше, или ее производных с активированной карбоксильной функцией в присутствии катализатора или без него, в присутствии агента, связывающего кислоту, или без него и в присутствии растворителя или без него, с амином формулы III

где R₄ - R₉ имеют значения, указанные выше.Description of the method for producing compounds of the invention
The compounds of formula I can be obtained
a) the interaction of a substituted amino acid of the formula II

where the radicals R ₁ - R ₃ and n have the meanings indicated above, or its derivatives with activated carboxy function in the presence or absence of a catalyst, in the presence or without an acid binding agent and in the presence or absence of a solvent, with an amine of the formula III

where R ₄ - R ₉ have the meanings indicated above.

 The amino acid derivatives of formula II necessary for the implementation of step a) of the method according to the invention are well known or can be obtained in accordance with step aa) described below.

 Amines of formula III are usually compounds known in organic chemistry.

 As derivatives of an amino acid of formula II with an activated carboxy function, any of its derivatives with an activated carboxy function, such as acid halides, for example acid chlorides, are suitable; symmetric or mixed anhydrides, for example, mixed anhydrides of O-alkylcarboxylic acid; activated esters, for example, para-nitrophenyl esters or N-hydroxysuccinimide esters, and activated forms of amino acids obtained in situ using condensation reaction agents (for example, dicyclohexylcarbodiimide, carbonyldiimidazole, O- (benzotriaz-1-yl) -N, N, N ', N'-bis (pentamethylene) uronium, O- (benzotriaz-1-yl) hexafluorophosphate-N, N, N', N'-bis (tetramethylene) uronium, hexafluorophosphate (benzotriazole-1-yloxy) tripyrrolidine phosphonium , hexafluorophosphate (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium or hex aftorfosfata O- (benzotriazol-1-yl) -N, N, N ', N'- tetramethyluronium hexafluorophosphate).

 Halides corresponding to an amino acid of formula II can be prepared by reacting an amino acid of formula II in a well known manner with a halogenating agent, for example, phosphorus pentachloride, thionyl chloride or oxalyl chloride.

 Mixed anhydrides corresponding to an amino acid of formula II can be prepared by reacting an amino acid of formula II with chloroformic acid esters, for example, chloroformic acid alkyl esters, preferably with chloroformic acid isobutyl ether, in the presence of an acid binding agent such as an inorganic or organic base, for example, a tertiary amine, for example triethylamine, pyridine, N-methylpiperidine or N-methylmorpholine, or without it.

The reaction between an amino acid of formula II or its derivatives with an activated carboxy function and an amine of formula III is carried out in an inert solvent. Among them, aromatic, non-aromatic or halogenated hydrocarbons, for example, chlorinated hydrocarbons, for example methylene chloride or toluene; ketones, for example acetone; esters, for example ethyl acetate; amides, for example dimethylformamide; nitriles, for example acetonitrile; or ethers, for example tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; water or mixtures of these inert solvents. Examples of acid binding agents that may be involved in the reaction are inorganic or organic bases, for example, alkali metal or alkaline earth metal hydroxides or carbonates, for example sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or, for example, a tertiary amine, for example triethylamine , pyridine, N-methylpiperidine or N-methylmorpholine. Temperatures range from -80 ^° C to +150 ^° C, preferably from -40 to +40 ^° C.

где R₁ - R₉ имеют значения, указанные выше, при условии, что ни один из заместителей R₁-R₃ не содержит тиольной или алкилтиогруппы.The compounds of formula I can also be obtained
b) the oxidation of the compounds of formula I '

where R ₁ - R ₉ have the meanings indicated above, provided that none of the substituents R ₁ -R ₃ contains a thiol or alkylthio group.

 Suitable oxidizing agents are organic oxidizing agents, such as alkyl hydroperoxides, for example cumyl hydroperoxide, and inorganic oxidizing agents, such as peroxides, for example hydrogen peroxide, or transition metal oxides, for example chromium trioxide, and transition metal oxide salts, for example, permanganate potassium, potassium or sodium dichromate.

The interaction of the compounds of formula I 'with oxidizing agents is carried out in an inert solvent, such as water or a ketone, for example acetone, or in a mixture thereof, with or without acid, with or without a base, at temperatures in the range from -80 ^° C up to +150 ^o C.

где R₁ - R₈ имеют значения, указанные выше, с соединением формулы VI
Y-R₉, (VI)
где R₉ имеет значения, указанные выше, a Y обозначает уходящую группу. Приемлемыми уходящими группами являются галогениды, например, хлориды или бромиды, или сульфонаты, например, тозилаты, мезилаты или трифлаты.The compounds of formula I can also be obtained further
C) the interaction of the compounds of formula I "

where R ₁ - R ₈ have the meanings indicated above, with a compound of formula VI
YR ₉ , (VI)
where R ₉ has the meanings indicated above, a Y denotes a leaving group. Suitable leaving groups are halides, for example, chlorides or bromides, or sulfonates, for example, tosylates, mesylates or triflates.

 The reaction of compounds of formula I ″ with a compound of formula VI is carried out in an inert solvent. Among them, aromatic, non-aromatic or halogenated hydrocarbons, for example methylene chloride or toluene; ketones, for example acetone; esters, for example ethyl acetate; amides, for example dimethylformamide; nitriles, for example acetonitrile; or ethers, for example tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; alcohols, for example, methanol, ethanol, n-butanol, isopropanol or tert-butanol; or water; or mixtures of these inert solvents.

The reaction of compounds of formula I ″ with a compound of formula VI is carried out in the presence or absence of an acid binding agent. Suitable acid binding agents are inorganic or organic bases, for example, alkali metal or alkaline earth metal hydroxides, alkoxides or carbonates, for example sodium hydroxide, potassium hydroxide, sodium methanolate, potassium methanolate, sodium ethanolate, potassium ethanolate, sodium tert-butanolate, tert. potassium butanolate, sodium carbonate or potassium carbonate. Temperatures range from -80 ^° C to +200 ^° C, preferably from 0 to +120 ^° C.

где R₂ и R₃ имеют значения, указанные выше, с сульфоновой кислотой либо с сульфиновой кислотой или с производным сульфоновой кислоты либо сульфиновой кислоты формулы IV

где R₁ и n имеют значения, указанные выше, a Z обозначает OH-группу или уходящую группу соответственно.The necessary amino acid derivatives of formula II can be obtained by the interaction of amino acids of formula VII

where R ₂ and R ₃ have the meanings given above, with a sulfonic acid or with sulfinic acid or with a derivative of sulfonic acid or sulfinic acid of the formula IV

where R ₁ and n are as defined above, and Z is an OH group or a leaving group, respectively.

 Sulfonic or sulfinic acid or a sulfonic or sulfinic acid derivative of the formula IV and amino acids of the formula V necessary for step aa) of the process are well known.

 Acceptable sulfonic or sulfinic acid derivatives of formula IV are any compounds in which Z represents a leaving group, such as sulfonic acid halides or sulfinic acid halides, for example sulfonic chlorides or sulfinic acid chlorides; symmetric or mixed anhydrides; and activated forms of sulfonic acid or sulfinic acid obtained in situ using condensation reaction agents such as dicyclohexylcarbodiimide or carbonyldiimidazole.

The reaction between a sulfonic or sulfinic acid or a sulfonic or sulfinic acid derivative of the formula IV with an amine of the formula V is carried out in an inert solvent. Aromatic, non-aromatic or halogenated hydrocarbons, for example, chlorinated hydrocarbons, for example, methylene chloride or toluene; ketones, for example acetone; esters, for example ethyl acetate; amides, for example dimethylformamide; nitriles, for example acetonitrile; or ethers, for example tetrahydrofuran, dioxane, diethyl ether or tert-butyl methyl ether; or water; or mixtures of these inert solvents. Examples of acid binding agents that may be involved in the reaction are inorganic or organic bases, for example, alkali metal or alkaline earth metal hydroxides or carbonates, for example sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate or, for example, a tertiary amine, for example triethylamine, pyridine, N-methylpiperidine or N-methylmorpholine. Temperatures range from -80 ^° C to +150 ^° C, preferably from -20 ^° to +60 ^° C.

 The compounds of formula I are oils or solids which are stable at room temperature and are characterized by a wide spectrum of bactericidal activity. They can be used in agriculture or in areas close to it for preventive and therapeutic measures aimed at combating microorganisms harmful to plants. The compounds of formula I according to the invention are characterized not only by the fact that they have a pronounced bactericidal, especially fungicidal activity in low concentrations, but also that they are especially well tolerated by plants.

 It was unexpectedly found that the compounds of formula I possess such a spectrum of bactericidal activity, which is especially preferred for practical requirements in the fight against phytopathogenic microorganisms, in particular with fungi. They have very useful therapeutic, prophylactic properties and can be used to protect a wide range of plants. When using compounds of formula I, the number of pests that can be found on plants or on parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various crops can be limited, or these pests can be destroyed, while protecting against phytopathogenic organisms also applies to those parts of plants that form in a later period, for example, they remain protected from phytopathogenic fungi.

 It was found that the new compounds of formula I are particularly preferred for a particular genus of fungi belonging to the class of imperfect fungi (e.g., Cercospora), basidiomycetes (e.g., Puccinia) and ascomycetes (e.g., Erysiphe and Venturia), but especially in against oomycetes (e.g., Plasmopara, Peronospora, Bremia, Pythium, Phytophthora). In addition, in the plant protection system, they can be successfully added to compositions intended for combating phytopathogenic fungi. The compounds of formula I can also be used as agents for seed dressing, in the processing of seed material (fruits, tubers, grains) and plant nurseries in order to protect them from fungal infections and soil-borne phytopathogenic fungi.

 The invention also relates to compositions containing compounds of the formula I as active substances, in particular to compositions intended for the protection of plants, and to their use in agriculture or in related fields.

 In addition, the present invention includes a method for producing such compositions, in which the active substance is mixed to a homogeneous state with one or more compounds or groups of compounds described in this description. The invention also includes a method of treating plants, which consists in applying new compounds of formula I or new compositions.

 Cultivated plants to be protected according to the present invention include, for example, the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum, spelled, triticale and related crops); beetroot (sugar beets and fodder beets); stone fruits, seeds, berries (apple trees, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), legumes (beans, lentils, peas and soybeans), oilseeds (rapeseed, mustard, poppy seeds, olives, sunflower , coconut, castor oil, cocoa beans and peanuts), cucumber plants (cucumber, pumpkin and melon), fiber plants (cotton, flax, hemp and jute), citrus fruits (oranges, lemons, grapefruits and tangerines), vegetables (spinach , salad, asparagus, cabbage, carrots, onions, tomatoes, potatoes and bell peppers), laurel (avocado, cinnamon tree and camphor tree) and plants such as tobacco, nuts, coffee, sugarcane, tea, pepper, grapes, hops, bananas and natural rubber noses, as well as ornamental plants.

 The compounds of formula I are usually used in the form of compositions, and they can be used to treat the cultivated crop area or plant simultaneously or sequentially with other active substances. These other active ingredients may be fertilizers, micronutrient donors or other drugs that affect plant growth. It is also possible to use certain herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures consisting of several of these preparations and, if necessary, including other suitable carriers, surfactants or other adjuvants that are suitable for the application of formulations, which are usually used for the manufacture of preparative forms.

 Suitable carriers and adjuvants can be solid or liquid and are compounds that are useful in the manufacture of formulations, for example, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

 A preferred method of using a compound of formula I or an agrochemical composition that contains at least one of these compounds is to treat the leaves of a plant (leaf treatment), the frequency of treatment and the rate of application depending on the severity of the pathogen being treated against. The compounds of formula I can also be used to process material for propagating a plant (grains, fruits, tubers, sprouts, cuttings, roots, etc.) (pan-coating), for example, either by impregnating cereal grains (seeds) or potato tubers, or freshly cut sprouts with a liquid preparation of the active substance, or by applying a layer of a solid preparation.

 The compounds of formula I are used in the form of pure active ingredients or preferably together with adjuvants, which are usually used in preparative forms, and for this purpose the formulations are prepared in the usual way, for example, emulsion concentrates, coating pastes, ready to use sprayed or diluted solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, as well as encapsulated forms, for example, in polymers. Processing methods, such as spraying, misting, dusting, scattering, spreading or watering, as well as the type of composition, are selected in accordance with the objectives and prevailing circumstances. Preferred application rates are usually from 1 g to 2 kg of active ingredient (a.i.) per hectare, preferably from 10 g to 1 kg a.i. / ha, most preferably from 25 g to 750 g a.i. / ha . When used for seed treatment, the consumption rates of the active substance are preferably from 0.001 g to 1.0 g per kg of seeds.

 Formulations, i.e. compositions, preparations or their mixtures containing a compound of formula I (active ingredient) and, if necessary, with a solid or liquid adjuvant, are obtained in a known manner, for example, by thoroughly mixing and / or grinding the active substance with excipients, for example, solvents, with a solid carrier and, if necessary, with surfactants (detergents).

 Acceptable solvents are aromatic hydrocarbons, preferably fractions with 8-12 carbon atoms, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their simple and complex esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ethers, ketones such as cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylphospho mamid, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; and water.

 Solid carriers commonly used, for example, for dusts and dispersible powders, are typically natural mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add finely divided silicic acid or finely dispersed absorbing polymers. Suitable granular adsorption supports are those of a porous type, such as pumice, broken brick, sepiolite or bentonite, and suitable non-absorbent supports are calcite or sand. In addition, a large number of pre-granulated materials of inorganic or organic origin, such as dolomite or powdered plant residues, can be used.

 Depending on the type of compound of formula I on the basis of which the formulation is prepared, suitable surfactants are nonionic, cationogenic and / or anionic surfactants providing good emulsifying, dispersing and wetting properties. Surfactants should also be understood as mixtures of surfactants.

 Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surfactants.

 Examples of nonionic surfactants that should be mentioned are nonylphenolpolyethoxyethanol, polyglycol esters of castor oil, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

 Other suitable nonionic surfactants are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

Cationic surfactants are preferably quaternary ammonium salts, which have at least one C ₈ -C ₂₂ alkyl radical as an N substituent and unsubstituted or halogenated lower alkyl, benzyl or hydroxy lower substituents. alkyl.

 Other surfactants commonly used in the manufacture of formulations are known to those skilled in the art or can be found in the literature known to those skilled in the art.

 As a rule, agrochemical compositions contain from 0.1 to 99 wt.%, Preferably from 0.1 to 95 wt.% Of the compounds of formula I, from 99.9 to 1 wt.%, Preferably from 99.8 to 5 wt.% solid or liquid adjuvant and from 0 to 25 wt. %, preferably from 0.1 to 25 wt.% surfactant.

 While concentrated compositions are more preferred as commercially available products, the immediate consumer typically uses diluted compositions.

 The compositions may also contain other adjuvants, such as stabilizers, antifoam agents, viscosity regulators, binders and adhesives, as well as fertilizers, micronutrient donors or other drugs that affect plant growth, contributing to the achievement of specific effects.

 Below the invention is illustrated by examples, not limiting its scope. Temperature is in degrees Celsius.

21,1 г (S)-2-(этилсульфониламино)-3-метилмасляной кислоты и 12 мл N-метилморфолина охлаждают до -20^oC при перемешивании в 450 мл тетрагидрофуранана. К смеси по каплям в течение 10 мин добавляют 13,2 мл изобутилового эфира хлормуравьиной кислоты и полученную реакционную смесь перемешивают в течение 1 ч при -10^oC. Затем ее охлаждают до -20^oC и по каплям в течение 20 мин добавляют 26,1 г 2-(4-бензилокси-3-метоксифенил)этиламина в 100 мл тетрагидрофурана. После этого реакционную смесь перемешивают без охлаждения в течение 4 ч, а затем внутреннюю температуру постепенно повышают до комнатной температуры. Реакционную смесь вносят в 400 мл 2 н. соляной кислоты и экстрагируют дважды, используя каждый раз по 500 мл этилацетата. Органические фазы однократно промывают 250 мл 2 н. соляной кислоты, однократно 250 мл насыщенного раствора хлорида натрия, дважды 2 н. раствором бикарбоната калия порциями по 250 мл и однократно 250 мл насыщенного раствора хлорида натрия, сушат над сульфатом магния и концентрируют, получая N-[2-(4-бензилокси-3-метоксифе-нил)этил] амид (S)-2-(этилсульфониламино)-3-метилмасляной кислоты, который может быть очищен перекристаллизацией из трет-бутилметилового эфира, t_пл 140-142^oC.Examples of the preparation of compounds of formula I
P-1.1 .: N- [2- (4-benzyloxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3-methylbutyric acid [compound 1.1]

21.1 g of (S) -2- (ethylsulfonylamino) -3-methylbutyric acid and 12 ml of N-methylmorpholine are cooled to -20 ^° C. with stirring in 450 ml of tetrahydrofuranan. To the mixture was added dropwise 13.2 ml of isobutyl ether of chloroformic acid over 10 minutes, and the resulting reaction mixture was stirred for 1 h at -10 ^° C. Then it was cooled to -20 ^° C and 26 were added dropwise over 20 minutes. 1 g of 2- (4-benzyloxy-3-methoxyphenyl) ethylamine in 100 ml of tetrahydrofuran. After this, the reaction mixture was stirred without cooling for 4 hours, and then the internal temperature was gradually raised to room temperature. The reaction mixture was added to 400 ml of 2 N. hydrochloric acid and extracted twice, using 500 ml of ethyl acetate each time. The organic phases are washed once with 250 ml of 2 N. hydrochloric acid, once 250 ml of a saturated solution of sodium chloride, twice 2 N. a solution of potassium bicarbonate in portions of 250 ml and once 250 ml of a saturated solution of sodium chloride, dried over magnesium sulfate and concentrated, obtaining N- [2- (4-benzyloxy-3-methoxyphenyl) ethyl] amide (S) -2- ( ethylsulfonylamino) -3-methylbutyric acid, which can be purified by recrystallization from tert-butyl methyl ether, _mp 140-142 ^° C.

 Table 1 shows the compounds that can be obtained analogously to this example.

a) 5,1 г (S)-2-(этилсульфониламино)-3-метилмасляной кислоты и 5,7 мл N-метилморфолина охлаждают до -20^oC при перемешивании в 200 мл тетрагидрофуранана. К смеси по каплям добавляют 3,15 мл изобутилового эфира хлормуравьиной кислоты. Затем реакционную смесь перемешивают в течение 30 мин, при этом температура реакционной смеси повышается до -10^oC. Затем ее вновь охлаждают до -20^oC и добавляют 5,0 г гидрохлорида 2-(4-гидрокси-3-метоксифенил)этиламина. Реакционной смеси дают нагреться до комнатной температуры и перемешивают в течение еще 24 ч. Реакционную смесь вносят в 300 мл 2 н. соляной кислоты. Затем смесь дважды экстрагируют, используя каждый раз по 500 мл этилацетата. Органические фазы дважды промывают, используя каждый раз по 100 мл насыщенного раствора хлорида натрия, объединяют, сушат над сульфатом магния и концентрируют. Остаток очищают с помощью хроматографии быстрого разрешения на силикагеле с использованием смеси этилацетат/н-гексан 3:1, получая N-[2-(4-гидрокси-3-метоксифенил)этил]амид (S)-2-(этилсульфониламино)-3-метилмасляной кислоты в виде бесцветного масла.P-2: N- [2- (4-hydroxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3-methylbutyric acid

a) 5.1 g of (S) -2- (ethylsulfonylamino) -3-methylbutyric acid and 5.7 ml of N-methylmorpholine are cooled to -20 ^° C. with stirring in 200 ml of tetrahydrofuranan. 3.15 ml of isobutyl chloroformate is added to the mixture dropwise. Then the reaction mixture is stirred for 30 minutes, while the temperature of the reaction mixture rises to -10 ^° C. Then it is again cooled to -20 ^° C. and 5.0 g of 2- (4-hydroxy-3-methoxyphenyl) ethylamine hydrochloride are added. The reaction mixture was allowed to warm to room temperature and stirred for another 24 hours. The reaction mixture was added to 300 ml of 2 N. of hydrochloric acid. The mixture is then extracted twice using 500 ml of ethyl acetate each time. The organic phases are washed twice, each time using 100 ml of a saturated solution of sodium chloride, combined, dried over magnesium sulfate and concentrated. The residue was purified by flash chromatography on silica gel using 3: 1 ethyl acetate / n-hexane to give N- [2- (4-hydroxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3 -methylbutyric acid in the form of a colorless oil.

 b) 14.5 g of N- [2- (4-benzyloxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3-methylbutyric acid (Example P-1.1) are dissolved in 420 ml of tetrahydrofuran and shake together with 3 g of palladium on carbon (5%) in a hydrogenation reactor (weft) for 5 hours in a hydrogen atmosphere at normal pressure. Then the catalyst is removed by filtration. The filtrate was concentrated. The residue was purified by flash chromatography on silica gel using 3: 1 ethyl acetate / n-hexane to give N- [2- (4-hydroxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3 -methylbutyric acid in the form of a colorless oil.

 c) A mixture containing 2.1 g of (S) -2- (ethylsulfonylamino) -3-methylbutyric acid, 1.7 g of 2- (4-hydroxy-3-methoxyphenyl) ethylamine, 4.6 g of hexafluorophosphate (benzotriazol-1-yloxy) ) Tris (dimethylamino) phosphonium (BOP) and 4.5 ml of N, N-diisopropylethylamine, stirred in 40 ml of N, N-dimethylformamide at room temperature for 2 hours. The reaction mixture was added to 500 ml of water and extracted twice using each 400 ml each time ethyl acetate. The organic phases are washed once with 300 ml of water and once with 200 ml of a saturated solution of sodium chloride, dried over magnesium sulfate and concentrated. In this way, N- [2- (4-hydroxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3-methylbutyric acid is obtained as an oil, which can be purified by flash chromatography on silica gel with using a mixture of ethyl acetate / n-hexane 3.1.

Смесь, содержащую 2,4 г N-[2-(4-гидрокси-3- метоксифенил)этил]амида (S)-2-(этилсульфониламино)-3-метилмасляной кислоты, 1,2 мл 4-бромбут-2-еновой кислоты и 9,1 мл 1,1 М раствора метанолята натрия в метаноле (предварительно полученного растворением 44 г натрия в 1 л метанола) и 30 мл метанола, кипятят с обратным холодильником в течение 4 ч. После охлаждения реакционной смеси ее вносят в 300 мл воды и экстрагируют дважды, используя каждый раз по 300 мл этилацетата. Органические фазы дважды промывают, используя каждый раз по 100 мл насыщенного раствора хлорида натрия, сушат над сульфатом магния и концентрируют, получая N-{2- [4-(3-метоксикарбонилпроп-2-ен-1-ил)окси-3-метоксифенил] этил} амид (S)-2-(этилсульфониламино)-3-метилмасляной кислоты в виде масла, который может быть дополнительно очищен с помощью хроматографии быстрого разрешения на силикагеле с использованием этилацетата.P-3.12. : N- {2- [4- (3-methoxycarbonylprop-2-en-1-yl) oxy-3-methoxyphenyl] ethyl} amide (S) -2- (ethylsulfonylamino) -3-methylbutyric acid

A mixture containing 2.4 g of N- [2- (4-hydroxy-3-methoxyphenyl) ethyl] amide (S) -2- (ethylsulfonylamino) -3-methylbutyric acid, 1.2 ml of 4-bromobut-2-enoic acid and 9.1 ml of a 1.1 M solution of sodium methanolate in methanol (previously obtained by dissolving 44 g of sodium in 1 l of methanol) and 30 ml of methanol are refluxed for 4 hours. After cooling the reaction mixture, it is added to 300 ml water and extracted twice, using 300 ml of ethyl acetate each time. The organic phases are washed twice, each time using 100 ml of a saturated solution of sodium chloride, dried over magnesium sulfate and concentrated, obtaining N- {2- [4- (3-methoxycarbonylprop-2-en-1-yl) oxy-3-methoxyphenyl ] ethyl} amide of (S) -2- (ethylsulfonylamino) -3-methylbutyric acid as an oil, which can be further purified by flash chromatography on silica gel using ethyl acetate.

 The compounds shown in table 3 can be obtained in a similar manner.

30 г D, L-валина и 10,2 г гидроксида натрия растворяют в 250 мл воды и охлаждают при перемешивании до 0^oC. К этому раствору одновременно добавляют по каплям в течение 1 ч раствор, содержащий 10,2 г гидроксида натрия в 250 мл воды, и раствор, содержащий 20 мл хлорида метансульфоновой кислоты в 250 мл толуола. Реакционную смесь выдерживают при 0^oC в течение 2 ч и затем дополнительно перемешивают в течение 16 ч при комнатной температуре. Толуоловую фазу удаляют с помощью делительной воронки и отбрасывают. С помощью концентрированной соляной кислоты значение pH водной фазы доводят до менее 3. Экстракцию проводят дважды, используя каждый раз по 100 мл простого эфира. Органические фазы дважды промывают, используя каждый раз по 200 мл насыщенного раствора хлорида натрия, объединяют, сушат над сульфатом магния и концентрируют, получая N-(2-метил-1-карбокси)пропиламид (R,S)-метансульфоновой кислоты, который может быть очищен перекристаллизацией из этилацетата/гексана; t_пл 90-91^oC.An example of obtaining intermediate products
I-1.1: N- (2-methyl-1-carboxy) propylamide (R, S-methanesulfonic acid

30 g of D, L-valine and 10.2 g of sodium hydroxide are dissolved in 250 ml of water and cooled with stirring to 0 ^° C. A solution containing 10.2 g of sodium hydroxide in 250 is added dropwise to this solution over 1 hour. ml of water, and a solution containing 20 ml of methanesulfonic acid chloride in 250 ml of toluene. The reaction mixture was kept at 0 ^° C. for 2 hours and then further stirred for 16 hours at room temperature. The toluene phase is removed using a separatory funnel and discarded. Using concentrated hydrochloric acid, the pH of the aqueous phase is adjusted to less than 3. Extraction is carried out twice, using 100 ml of ether each time. The organic phases are washed twice, each time with 200 ml of a saturated solution of sodium chloride, combined, dried over magnesium sulfate and concentrated to obtain N- (2-methyl-1-carboxy) propylamide (R, S) methanesulfonic acid, which can be purified by recrystallization from ethyl acetate / hexane; t _pl 90-91 ^o C.

 Intermediates shown in Table 4 were prepared analogously to this example.

2. Examples of formulations of compounds of formula I (percentages in all cases represent wt.%)
F-2.1. Wettable powder
Components,% - a)
The connection from tables 1 and 3 - 25
Sodium lignosulfonate - 5
Sodium Lauryl Sulfate - 3
Sodium diisobutylnaphthalenesulfonate - -
Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide units) - -
Fine Silica - 5
Kaolin - 62
Components,% - b)
The connection from tables 1 and 3 - 50
Sodium lignosulfonate - 5
Sodium Lauryl Sulfate - -
Sodium diisobutylnaphthalenesulfonate - 6
Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide units) - 2
Fine Silica - 10
Kaolin - 27
Components,% - c)
The connection from tables 1 and 3 - 75
Sodium lignosulfonate - -
Sodium Lauryl Sulfate - 5
Sodium diisobutylnaphthalenesulfonate - 10
Octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide units) - -
Fine Silica - 10
Kaolin - -
The active substance is thoroughly mixed with adjuvants and the mixture is finely ground in an appropriate mill to obtain wettable powders that can be diluted with water to obtain suspensions of any desired concentration.

F-2.2. Emulsion concentrate,%
The connection from tables 1 and 3 - 10
Octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide units) - 3
Calcium Dodecylbenzenesulfonate - 3
Castor oil polyethylene glycol ether (35 mol of ethylene oxide units) - 4
Cyclohexanone - 34
Xylene mixture - 50
Emulsions of any desired concentration can be prepared by diluting such a concentrate with water.

 F-2.3. Dusty.

Components,% - a)
The connection from tables 1 and 3 - 5
Talc - 95
Kaolin - -
Components,% - b)
The connection from tables 1 and 3 - 8
Talc - -
Kaolin - 92
Ready-to-use dusts are obtained by mixing the active substance with a carrier and grinding in an appropriate mill.

F-2.4. Extruded granules,%:
The connection from tables 1 and 3 - 10
Sodium lignosulfonate - 2
Carboxymethyl cellulose - 1
Kaolin - 87
The active substance is mixed and ground with adjuvants and moisten the mixture with water. The mixture is extruded and then dried in a stream of air.

F-2.5. Granules coated%:
The connection from tables 1 and 3 - 3
Polyethylene glycol (mol.m. 200) - 3
Kaolin - 94
The finely divided active substance is uniformly fed into the mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

F-2.6. Suspension concentrates,%:
The connection from tables 1 and 3 - 40
Ethylene Glycol - 10
Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide units) - 6
Sodium Lignosulfonate - 10
Carboxymethyl cellulose - 1
37% aqueous formaldehyde solution - 0.2
Silicone oil in the form of a 75% aqueous emulsion - 0.8
Water - 32
The finely divided active substance is thoroughly mixed with adjuvants to obtain a suspension concentrate, from which suspensions of any desired concentration can be prepared by dilution with water.

Biological Examples
B-1: Activity against Plasmopara viticola on cultivated grapes
a) residual preventive effect
Chubuki cultivated grapes at the stage of 4-5 leaves are sprayed with a mixture (0.02% of the active substance) obtained from the formulation of the test compound in the form of a wettable powder. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. The defeat of the fungus is evaluated after incubation for 6 days at 95-100% relative humidity and at 20 ^o C.

b) The residual therapeutic effect
Chubuki cultivated grapes at the stage of 4-5 leaves are infected with a suspension of fungal sporangia. After incubation for 24 hours in a humidification chamber at 95-100% relative humidity and at 20 ^o C, the infected plants are dried and sprayed with a mixture (0.02% of the active substance) obtained from the formulation of the test compound in the form of a wettable powder.

 After drying the spray coating, the treated plants are again placed in the chamber. The fungus infection is evaluated 6 days after infection.

 The compounds shown in tables 1 and 3 show a very good fungicidal effect against Plasmopara viticola on cultivated grapes. The active substances, numbered 1.1, 1.11 and others, cause complete suppression of the lesion by the fungus (residual lesion of 0-5%). On the other hand, the Plasmopara viticola lesion of untreated and infected control plants is 100%.

B-2: Activity against Phytophthora on tomatoes
a) residual preventive effect
After a 3-week cultivation period, tomato plants are sprayed with a mixture (0.02% of the active ingredient) obtained from the formulation of the test compound in the form of a wettable powder. After 48 hours, the treated plants are infected with a suspension of fungal sporangia. The fungus infection is evaluated after incubation of infected plants for 4 days at 90-100% relative humidity and at 20 ^o C.

b) Systemic action
After a 3-week cultivation period, tomato plants are watered with a mixture (0.02% of the active substance relative to the volume of soil) obtained from the formulation of the test compound in the form of a wettable powder. Appropriate precautions are taken to ensure that the spray mixture does not come into contact with the aboveground parts of the plants. After 4 days, the treated plants are infected with a suspension of fungal sporangia. The fungus infection is evaluated after incubation of infected plants for 4 days at 90-100% relative humidity and at 20 ^o C.

 The compounds shown in tables 1 and 3 exhibit a long-term effect (the defeat of the fungus is less than 20%). The active substances, numbered 1.1, 1.11, and others, cause almost complete suppression of the lesion by the fungus (residual lesion of 0-5%). On the other hand, the defeat of Phytophthora untreated and infected control plants is 100%.

B-3: Activity against Phytophthora on potato plants
a) residual preventive effect
2-3-week-old potato plants (cultivar Bintje) are sprayed with a mixture (0.02% of the active ingredient) obtained from the formulation of the test compound as a wettable powder. After 48 hours, the treated plants are infected with a suspension of fungal sporangia. The fungus infection is evaluated after incubation of infected plants for 4 days at 90-100% relative humidity and at 20 ^o C.

b) Systemic action
2-3-week-old potato plants (cultivar Bintje) are watered with a mixture (0.02% of active ingredient relative to the volume of soil) obtained from the formulation of the test compound in the form of a wettable powder. Appropriate precautions are taken to ensure that the spray mixture does not come into contact with the aboveground parts of the plants. After 48 hours, the treated plants are infected with a suspension of fungal sporangia. The fungus infection is evaluated after incubation of infected plants for 4 days at 90-100% relative humidity and at 20 ^o C.

 The compounds shown in tables 1 and 3 exhibit a long-term effect (the defeat of the fungus is less than 20%). The active substances, numbered 1.1, 1.11, and others, cause almost complete suppression of the lesion by the fungus (residual lesion of 0-5%). On the other hand, the defeat of Phytophthora untreated and infected control plants is 100%.

Claims (11)

1. N-sulfonyl and N-sulfinyl derivatives of amino acids of the formula I

where n = 0 or 1;
R ₁ is C ₁ -C ₁₂ alkyl which may be unsubstituted or may be substituted with C ₁ -C ₄ alkylsulfonyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently hydrogen or C ₁ -C ₆ alkyl or together are tetramethylene;
R ₂ and R _{3 are} each independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio, C ₃ -C ₈ alkenyl C ₃ -C ₈ alkynyl;
R ₄ - R ₇ , identical or different — hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl substituted with one or more halogen atoms, or a group

where p and q, the same or different, are 0 or 1;
R ₁₃ - R ₁₆ , identical or different, each independently hydrogen or C ₁ -C ₄ alkyl;
X is hydrogen, provided that p and q = 0, phenyl unsubstituted or mono- or polysubstituted with halogen, nitro, cyano, C ₂ -C ₆ alkenyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkoxycarbonyl,
C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy group, cyano group; —COOR ₁₇ , —COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ each independently is hydrogen or C ₁ -C ₆ alkyl;
R ₁₈ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or phenyl unsubstituted or substituted by a nitro group;
R ₁₉ and R ₂₀ each is hydrogen. 2. The compound of formula I

where n = 0 or 1;
R ₁ is C ₁ -C ₁₂ alkyl which may be unsubstituted or may be substituted with C ₁ -C ₄ alkylsulfonyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ , where R ₁₁ and R _{12 are} each independently hydrogen or C ₁ -C ₆ alkyl or together are tetramethylene;
R ₂ and R _{3 are} each independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio, C ₃ -C ₈ alkenyl C ₃ -C ₈ alkynyl;
R ₄ is R ₇ , identical or different, is hydrogen or C ₁ -C ₄ alkyl;
R ₈ is C ₁ -C ₆ alkyl;
R ₉ is C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl substituted with one or more halogen atoms, or a group

where p and q, the same or different, are 0 or 1;
R ₁₃ - R ₁₆ , the same or different, and each independently hydrogen or C ₁ -C ₄ alkyl;
X is hydrogen, provided that p and q = 0, phenyl unsubstituted or substituted by halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, cyano, -COOR ₁₇ , -COR ₁₈ or a group formulas

where R ₁₇ and R ₂₁ each independently is hydrogen or C ₁ -C ₆ alkyl;
R ₁₈ is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or phenyl unsubstituted or substituted by a nitro group;
R ₁₉ and R ₂₀ each is hydrogen. 3. The compound of formula I according to claim 2, in which n = 1; R ₁ is C ₁ -C ₁₂ alkyl which may be unsubstituted or may be substituted with C ₁ -C ₄ alkylsulfonyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ haloalkyl or a group of the formula NR ₁₁ R ₁₂ where R ₁₁ and R _{12 is} each independently hydrogen or C ₁ -C ₆ alkyl or together is tetramethylene; R ₂ is hydrogen; R ₃ is C ₁ -C ₈ alkyl; C ₁ -C ₈ alkyl substituted with hydroxy, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio, C ₃ -C ₈ alkenyl or C ₃ -C ₈ alkynyl. 4. The compound of formula I according to claim 3, in which R ₈ is C ₁ -C ₆ alkyl. 5. The compound of formula I according to claim 4, in which R ₁ is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ haloalkyl or a group of formula NR ₁₁ R ₁₂ , where R ₁₁ and R ₁₂ are C ₁ -C ₆ alkyl; R ₃ is C ₁ -C ₈ alkyl; R ₄ is hydrogen or C ₁ -C ₄ alkyl; and R ₅ is R ₇ is hydrogen. 6. The compound of formula I according to claim 5, in which R ₁ is C ₁ -C ₄ alkyl or dimethylamino; R ₃ is C ₃ -C ₄ alkyl; R ₄ is hydrogen or methyl; and R ₈ is C ₁ -C ₂ alkyl. 7. The compound of formula I according to claim 6, in which R ₁ is C ₂ -C ₄ alkyl or dimethylamino; R ₃ is 2-propyl; R ₄ is hydrogen and R ₈ is methyl. 8. The compound of formula I according to claim 4, in which R ₉ is C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl substituted with one or more halogen atoms, or a group

where p = 0 or 1;
q is 0;
R ₁₃ and R ₁₄ , the same or different, each independently hydrogen or C ₁ -C ₄ alkyl; X is hydrogen, provided that p = 0, phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, cyano, -COOR ₁₇ ; -COR ₁₈ or a group of the formula

where R ₁₇ and R ₂₁ is C ₁ -C ₆ alkyl;
R ₁₈ is hydrogen, C ₁ -C ₆ alkyl or phenyl unsubstituted or substituted by a nitro group;
R ₁₉ and R ₂₀ are hydrogen. 9. The compound of formula I according to claim 8, in which R ₉ is C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl substituted with one or more halogen atoms, or a group

where p = 1;
q is 0;
X is phenyl unsubstituted or substituted with halogen, nitro, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, cyano or -COR ₁₈ , where R ₁₈ is hydrogen or C ₁ -C ₄ alkyl. 10. The compound of formula I according to claim 9, in which R ₉ is a C ₁ -C ₆ alkyl or C ₃ -C ₆ alkenyl group substituted by one or more halogen atoms, or a group

where p = 1;
q is 0;
R ₁₃ and R ₁₄ are hydrogen;
X is phenyl, cyano or -COR ₁₈ . 11. The compound of formula I according to claim 10, in which R ₁ is C ₁ -C ₆ alkyl, C ₂ -C ₄ alkenyl, C ₁ -C ₆ haloalkyl or a group of formula NR ₁₁ R ₁₂ , where R ₁₁ and R ₁₂ each independently C ₁ -C ₂ alkyl; R ₃ is C ₂ -C ₅ alkyl; R ₄ is hydrogen or C ₁ -C ₄ alkyl; R ₅ - R ₇ is hydrogen and R ₈ is C ₁ -C ₂ alkyl. 12. The compound of formula I according to claim 11, in which R ₁ is C ₂ -C ₄ alkyl or dimethylamino; R ₃ is C ₃ -C ₄ alkyl; R ₄ is R ₇ is hydrogen and R ₈ is methyl. Priority on points:
10/18/1995 - according to claims 2-12;
07/09/1996 - according to claim 1.

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