WO1993012094A1 - Pyrimidinyl- or triazinyl-oxy(or thio)aldehyde derivatives and their use as herbicides or plant-growth regulators - Google Patents

Abstract

It is already known in the art that pyrimidinyloxy(thio)- and triazinyloxy(or thio)carboxylic acid derivatives exhibit herbicidal and plant-growth-regulatory properties. Some of the prior art active substances with this type of structure have disadvantages in use, however, such as their insufficient selectivity in commercially important cultures. The invention concerns pyrimidinyloxy(thio)- and triazinyloxy(or thio)aldehyde derivatives, which have useful herbicidal properties, of formula (I), in which X, Y, Z, A, R?a and Rb¿ are as defined in claim 1.

Description

 PYRIMIDINYL OR TRIAZINYL OXY (OR THIO) ALDEHYDE DERIVATIVES, AND USE AS HEBRICIDES OR PLANT GROWTH REGULATORS

 description

Pyrimidinyl or triazinyl oxy (or thio) aldehyde derivatives, process for their preparation and use as herbicides or plant growth regulators

It is known that pyrimidinyloxy (thio) and triazinyloxy (thio) carboxylic acid derivatives have herbicidal and plant growth-regulating properties (see EP-A-0347811, EP-A-0409369, EP-A-0409368, EP-A-400741). However, some of the known active ingredients of this structure type have disadvantages when used, such as inadequate selectivity in important crops.

Pyrimidinyloxy (thio) - and triazinyloxy (thio) -aldehyde derivatives with advantageous herbicidal properties have now been found.

The invention relates to compounds of the general formula (I)

wherein

 X O or S,

 Y, Z N or CH, where not both Y and Z are CH at the same time,

R ^a , R ^b independently of one another hydrogen, alkyl, alkoxy, alkylthio,

 Halogen, haloalkoxy, haloalkyl, amino, alkylamino or

 Dialkylamino,

A is a radical of the formula - CH - CO - R ² - CH - CH = N - R ³ | | |

R ¹ R ¹ (O) _n

(A1) (A2) - C = CH NR ⁴ R ⁵ - CH CH - X ¹ - R ⁶ | | | R ¹ R ¹ X ² - R ⁷ -

(A3) (A4)

- CH - CH - NR ⁹ R ¹⁰ - CH - CH - NR ⁹ R 10

| | | | R ¹ X ³ - R ⁸ R ¹ NR ⁹ R ¹⁰

(A5) (A6) - CH - CH - SOo - O ^" M ⁺ - CH - CH P (= O) R ¹¹ R ¹² I | | |

R ¹ OH R ¹ OH

 (A7) (A8)

X ¹ , X ² , X ³ and X ⁴ independently of one another O or S, preferably O, an aliphatic or araliphatic radical of the formula or

Hydrogen or trialkylsilyl,

 Alkyl, alkenyl, alkynyl, aikoxy, alkenyloxy, alkynyloxy, alkylthio,

 where the latter seven radicals are independently unsubstituted or mono- or polysubstituted by radicals from the group aikoxy, alkylthio, amino, alkylamino, dialkylamino, nitro, cyano, halogen, phenyl and substituted phenyl, or

 Alkylcarbonyl, arylcarbonyl substituted arylcarbonyl, hydroxy

Radical of the formula NR'R ", in which R 'and R" are independently of one another Are hydrogen, alkyl, benzyl or phenyl, or aminocarbonyl,

Aminocarbonylamino, aminothiocarbonyl, aminothiocarbonylamino or

 Cycloalkyl, cycloalkenyl, cycloalkenyloxy or phenyl, where the last four radicals independently of one another are unsubstituted or substituted one or more times by radicals from the group alkyl, aikoxy, alkylthio, amino, alkylamino, dialkylamino, nitro, halogen, cyano, phenyl and substituted phenyl ,

R ⁴ , R ⁵ independently of one another are hydrogen, alkyl, alkenyl, alkynyl,

 Cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl, where both radicals are not simultaneously hydrogen, or

R ⁴ and R ⁵ together with the connected N atom form a 3- to 7-membered heterocyclic ring which, in addition to the N atom, can contain further heteroatoms from the group N, O and S and are substituted by one or more alkyl groups or an oxo group can be,

R ⁶ , R ⁷ independently of one another are hydrogen, alkyl, alkenyl, alkynyl,

 Cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl or

R ⁶ and R ⁷ together with the connected group -X ¹ -CH-X ² - a 4- to 8-membered heterocyclic ring which, in addition to the two heteroatoms, can contain further heteroatoms from the group N, O and S and by one or several alkyl groups can be substituted,

R ^{8 is} hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl

 Phenyl, benzyl, alkylcarbonyl or arylcarbonyl,

R ⁹ , R ¹⁰ independently of one another are hydrogen, alkyl, alkenyl, alkynyl,

 Cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl or

R ⁹ and R ¹⁰ together with the connected N atom form a 3- to 7-membered heterocyclic ring which, in addition to the N atom, can contain further heteroatoms from the group N, O and S and by one or several alkyl groups or one oxo group can be substituted, R ¹¹ , R ¹² independently of one another hydroxyl, alkyl, aikoxy, phenyl, substituted

 Phenyl, phenoxy or substituted phenoxy,

R ^{13 is} hydrogen or alkyl,

R ^{14 is} hydrogen, halogen, alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, aikoxy, alkylthio, phenyl or substituted phenyl, or hydroxy, cyano, cycloalkyl, aryl, preferably phenyl, thienyl, naphthyl or Dihydronaphthyl, where aryl or cycloalkyl are unsubstituted or substituted,

R ¹⁵ , R ¹⁶ independently of one another are hydrogen or alkyl or

R ¹⁵ and R ¹⁶ together with the connected carbon atom form a 3- to 8-membered group

 Ring which may contain an oxygen atom and which may be substituted by one or more alkyl groups,

R ^{17 is} hydrogen or alkyl,

R ^{18 is} independently of R ^{19 is} hydrogen or alkyl,

R ^{19 is} independently of R ¹⁸ alkyl, aryl or substituted aryl or

R ¹⁸ and R ¹⁹ together with the connected alkenylene group form a 3- to 8-membered ring which can contain an oxygen atom and can be substituted by one or more alkyl groups,

M ⁺ the equivalent of a cation, preferably an alkali metal cation, and

n is the number 0 or 1

mean.

In the formula (I) and below, the alkyl, aikoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals can each be straight-chain or branched. Unless specifically stated, the carbon atom chains for these radicals are or

Carbon skeletons with 1 to 4 carbon atoms or, in the case of unsaturated groups, with 2 to carbon atoms are preferred. Alkyl radicals, also in the composite meanings ie aikoxy, haloalkyl etc., mean methyl, ethyl, n- or i-propyl, n-, i-, t- or 2- Butyl; Alkenyl and alkynyl radicals have the meaning of the alkyl radicals

corresponding unsaturated radicals, such as 2-propenyl, 2- or 3-butenyl, 2-propynyl, 2- or 3-butynyl. Halogen means fluorine, chlorine, bromine or iodine, haloalkyl means alkyl which is substituted by one or more atoms from the group halogen; Haloalkyl is, for example, CF ₃ , CHF ₂ , CH ₂ CF ₃ .

 The same applies to haloalkenyl, haloalkoxy and other halogen-substituted radicals. Aryl means, for example, phenyl, naphthyl,

 Tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; Aryloxy means the corresponding aryl radicals which are bonded via an oxy group, preferably phenoxy. Heteroaryl or heteroaryl in heteroaryloxy means, for example, pyridyl, pyrimidyl, pyridazyl, thienyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, preferably pyridyl and thienyl, but also bicyclic or polycyclic aromatic or araliphatic compounds.

Substituted cycloalkyl means, for example, cycloalkyl which is substituted by radicals from the group alkyl and aikoxy. Optionally substituted aryl, aryloxy, heteroaryl, heteroaryloxy, phenyl, phenoxy, benzyl and benzyloxy as well as bicyclic radicals with aromatic components preferably each represent the corresponding unsubstituted radical or represent a substituted radical derived therefrom, the substituents being for example one or more, preferably 1, 2 or 3 radicals from the group halogen, alkyl, haloalkyl, aikoxy, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, alkanoyl, carbamoyl, mono- and dialkylaminocarbonyl, mono- and dialkylamino, alkylsulfinyl and

Mean alkylsulfonyl and in the case of radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Substituents from the group halogen, such as fluorine and chlorine, C ₁ -C ₄ -alkyl, preferably methyl or ethyl, C ₁ -C ₄ -haloalkyl, preferably trifluoromethyl, C _r C ₄ -alkoxy, preferably methoxy or, are generally preferred Ethoxy, C ₁ -C ₄ haloalkoxy, nitro and

Cyano. Methyl, methoxy and chlorine are particularly preferred.

The invention also relates to all stereoisomers and their mixtures which are encompassed by formula (I) but are not specifically mentioned. Of particular interest are compounds of the formula (I) according to the invention in which Y is a nitrogen atom and Z is a nitrogen atom or a methine group.

Compounds of the formula according to the invention are also of particular interest

(I) where

R ^a , R ^{b are} independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, halogen, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ hafoalkyl , C ₁ -C ₄ alkylamino or di- (C ₁ -C ₄ -alkyl) amino, preferably methyl, methoxy, chlorine or methylamine, in particular one of the two methoxy radicals and the other radical methyl, methoxy, chlorine or methylamino

mean.

Compounds of the formula according to the invention are also of particular interest

(I) where

R ^{2 is} hydrogen or tri- (C ₁ -C ₄ -alkyl) -silyI, preferably

 Hydrogen,

R ³ C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ -

Alkenyloxy, C ₂ -C ₄ alkynyloxy, C ₁ -C ₄ alkylthio,

 the latter seven residues being independent

 unsubstituted or one or more times

Radicals from the group C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio,

Amino, (C ₁ -C ₄ alkyl) amino, di (C ₁ -C ₄ alkyl) amino, nitro,

 Cyano, halogen, phenyl and substituted phenyl

 are substituted, or

(C ₁ -C ₄ alkyl) carbonyl, benzoyl, substituted benzoyl, hydroxy, a radical of the formula NR'R ", where R 'and R" independently of one another are hydrogen, C ₁ -C ₄ alkyl, benzyl or phenyl stand, or aminocarbonyl, aminocarbonylamino,

Aminothiocarbonyl, aminothiocarbonylamino or C ₃ -C ₈ cyctoalkyl, C ₅ -C ₈ cycloalkenyl, C ₅ -C ₈ cycloalkenyloxy or phenyl, the latter four residues being independent

unsubstituted or one or more times by radicals from the group C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, amino, (C ₁ -C ₄ alkyl) amino, Di- (C ₁ -C ₄ alkyl) amino, nitro, halogen, cyano, phenyl and substituted

 Phenyl are substituted,

R ⁴ , R ⁵ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ -

Alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₈ cycloalkyl, phenyl

Phenyl, benzyl, (C ₁ -C ₄ alkyl) -carbonyl or benzoyl, where not both radicals are simultaneously hydrogen, or

R ⁴ and R ⁵ together with the connected N atom form a 5- to 6-membered heterocyclic ring which, in addition to the N atom, has one or two more

Can contain heteroatoms from the group N, O and S and can be substituted by one or more C ₁ -C ₄ -alkyl groups and an oxo group,

R ⁶ , R ⁷ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -

C ₄ alkynyl, C ₃ -C ₈ cycloalkyl, phenyl, substituted phenyl, benzyl,

(C ₁ -C ₄ alkyl) carbonyl or benzoyl or

R ⁶ and R ⁷ together with the connected group -X ¹ -CH-X ² - a 5- to 6-membered heterocyclic ring, which in addition to the two

Heteroatoms can contain a further heteroatom from the group N, O and S and can be substituted by one or more C ₁ -C ₄ alkyl groups,

R ^{8 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₈ -

Cycloalkyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl,

R ⁹ , R ¹⁰ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl, C ₂ -

C ₄ alkynyl, C ₃ -C ₈ cycloalkyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl or

R ⁹ and R ¹⁰ together with the connected N atom form a 5- to 6-membered heterocyclic ring which, in addition to the N atom, has one or two more

Heteroatoms from the group N, O and S can contain and by one or more C ₁ -C ₄ alkyl groups and an oxo group can be substituted,

R ¹¹ , R ¹² independently of one another are hydroxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, phenyl, substituted phenyl, phenoxy or substituted phenoxy,

R ^{13 is} hydrogen or C ₁ -C ₄ -alkyl,

R ^{14 is} hydrogen, halogen, C ₁ -C ₄ alkyl which is unsubstituted or by

one or more radicals from the group halogen, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, phenyl or substituted phenyl is substituted, or C ₃ -C ₈ cycloalkyI, C ₅ -C ₈ cycloalkenyl , the latter two radicals being unsubstituted or substituted by one or more C ₁ -C ₄ -alkyl groups, or hydroxy, cyano, phenyl, thienyl, naphthyl or dihydronaphthyl, the

 the latter four radicals are unsubstituted or substituted,

R ¹⁵ , R ¹⁶ independently of one another are hydrogen or C ₁ -C ₈ -alkyl or

R ¹⁵ and R ¹⁶ together with the connected carbon atom form a 5- to 6-membered

Ring which may contain an oxygen atom and which may be substituted by one or more C ₁ -C ₄ alkyl groups,

R ^{17 is} hydrogen or C ₁ -C ₄ alkyl,

R ¹⁸ independently of R ^{19 is} hydrogen or C ₁ -C ₄ alkyl,

R ^{19 is} independently of R ¹⁸ C ₁ -C ₄ alkyl, phenyl or substituted phenyl or

R ¹⁸ and R ¹⁹ together with the connected alkenylene group form a 5- or 6-membered ring which may contain an oxygen atom and which may be substituted by one or more C ₁ -C ₄ -alkyl groups, M ⁺ sodium or potassium cation and

n is the number 0 or 1, preferably 0,

mean.

Preferred compounds of the formula (I) according to the invention are those in which

R ^{2 is} hydrogen or tri (C ₁ -C ₂ alkyl) silyl, preferably hydrogen,

Trimethylsilyl or triethylsilyl, in particular hydrogen, R ³ C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, the latter two radicals independently of one another unsubstituted or halogenated once or more or by C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, amino, (C ₁ -C ₄ -alkyl) -amino, di- (C ₁ -C ₄ alkyl) amino, nitro, cyano, phenyl and substituted phenyl are substituted, or

(C ₁ -C ₄ alkyl) carbonyl, benzoyl, substituted benzoyl, hydroxy, a radical of the formula NR'R ", where R 'and R" independently of one another are hydrogen, C ₁ -C ₄ alkyl, benzyl or phenyl stand, or

 Aminocarbonyl, aminocarbonylamino, aminothiocarbonyl,

 Aminothiocarbonylamino, cyclopentyl, cyclohexyl, phenyl or substituted phenyl,

R ⁴ , R ⁵ independently of one another are hydrogen, C ₁ -C ₄ alkyl, cyclopentyl,

Cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbony or benzoyl, where both radicals are not simultaneously hydrogen, or

R ⁴ and R ⁵ together with the connected N atom form a 5- or 6-membered heterocyclic ring which, in addition to the N atom, is another

 Can contain heteroatoms from the group N and O and can be substituted by one or more methyl groups,

R ⁶ , R ⁷ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -

C ₄ alkynyl, cyclopentyl, cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl or

R ⁶ and R ⁷ together with the connected group -X ¹ -CH-X ² - a 5- to 6-membered heterocyclic ring which can be substituted by one or more methyl groups,

R ^{8 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, cyclopentyl,

Cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl,

R ⁹ , R ¹⁰ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, cyclopentyl,

Cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl or

R ⁹ and R ¹⁰ together with the connected N atom have a 5- to 6-membered heterocyclic ring, which is another in addition to the N atom

 Can contain heteroatoms from the group N and O and can be substituted by one or more methyl groups,

R ¹¹ , R ¹² independently of one another are hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, substituted phenyl, phenoxy or substituted phenoxy and

R ^{13 is} hydrogen or C ₁ -C ₂ alkyl

 mean.

Compounds of the formula (I) according to the invention are also preferred in which

R ^{1 is} an aliphatic or araliphatic radical of the formula

-CR ¹⁴ R ¹⁵ R ¹⁶

 is what

R ^{14 is} hydrogen, halogen, C ₁ -C ₆ alkyl which is unsubstituted or by.

one or more radicals from the group halogen, hydroxy, C ₁ -C ₄ alkoxy, in particular methoxy or ethoxy, or C ₁ -C ₄ alkylthio, phenyl or substituted phenyl, or C ₃ -C ₆ cycloalkyl, C ₅ -C ₆ cycloalkenyl, the latter two radicals being unsubstituted or substituted by one or more C ₁ -C ₄ alkyl groups, or hydroxy, cyano, phenyl, thienyl, naphthyl or dihydronaphthyl, the latter four radicals being unsubstituted or by methyl , Ethyl, methoxy, ethoxy, trifluoromethyl or halogen are substituted,

R ¹⁵ , R ¹⁶ independently of one another are hydrogen or C ₁ -C ₄ -alkyl or

R ¹⁵ and R ¹⁶ together with the connected carbon atom have a 5- or 6-membered group

Ring which may contain an oxygen atom and which may be substituted by one or more C ₁ -C ₄ -alkyl groups,

mean.

R ¹ particularly preferably denotes C ₁ -C ₄ -alkyl which is unsubstituted or substituted by methoxy or phenyl, or C ₃ -C ₆ -cycloalkyl which is unsubstituted or substituted by one to three methyl groups, in particular isopropyl, tert-butyl or Cyclopentyl. Preference is also given to compounds of the formula (I) according to the invention, in which A denotes a radical of the formula (A1) or (A2) mentioned.

Preference is also given to compounds of the formula (I) according to the invention in which the individual radicals and groups contain two or more radicals or groups designated as preferred.

Another object of the present invention is the method for

Preparation of compounds of the formula (I) mentioned, characterized in that a) in the case where A has the meaning of formula (A1) and R ² = H, a

 Reacting compound of formula (II) with a compound of formula (III),

wherein in formulas (II) and (III) R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (I) and Nuf ¹ for a nucleofugic leaving group, e.g. B. from the group of halogen, mesylate, p- and m-tosylate, or b) in the case that A has the meaning of formula (A1) and R ² = H, one

 Reacting compound of formula (IV) with a compound of formula (V),

b

where in the formulas (IV) and (V) R ^a , R ^b , X, Y, Z and R ¹ as in formula (I) are defined and Nuf ² for a nucleofugic leaving group, e.g. B. from the group consisting of halogen, alkylsulfonyl and benzylsulfonyl, or c) a compound of formula (VI),

wherein R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (I),

c ₁ ) in the case of A = (A2) and R ² = H, with a compound of the formula

H- (O) _n NH-R ³ , where n is as defined in formula (A2),

c ₂ ) in the case A = (A3), with a compound of the formula HNR ⁴ R ⁵ ,

c ₃ ) in the case of A = (A4), with a compound of the formula HX ¹ -R ⁶ —R ⁷ -X ² H, c ₄ ) in the case of A = (A5), initially with a compound of the formula HNR ⁹ R ¹⁰ to a compound of formula (I) in which A = A6 and then with a compound of formula CICH ₂ X ³ R ⁸ ,

c ₅ ) in the case A = (A6), with a compound of the formula H-NR ⁹ R ¹⁰ ,

c ₆ ) in the case A = (A7), with a compound of the formula MSO ₃ H,

c ₇ ) in the case of A = (A8), with a compound of the formula HP (= O) R ¹¹ R ¹² and c ₈ ) in the case of A = (A9), with a compound of the formula HX ⁴ -CO-CH (SH ) R ¹³ or d) reacting a compound of the formula (VI) listed under c) in a multi-stage process which involves reaction with the compound of the formula HS- (CH ₂ ) ₃ -SH, subsequent reaction with lithium alkyl and trialkyl silicon halide and reaction with Mercury halide is converted into the compound of formula (I) wherein A = (A2) and R ² = trialkylsilyl.

Compounds of the formula (V) in variant b) also comprise dimers of the formula (V '),

 which are in equilibrium with the respective monomers or under the

 Reaction conditions can be easily converted into it.

The reactions of variants a) and b) are preferably carried out in the presence of an inorganic or organic base. As bases therefor are, for example, inorganic bases from the group of alkali metal carbonates, such as Na ₂ CO ₃ , K ₂ CO ₃ , NaHCO ₃ or KHCO ₃ , alkali and alkaline earth metal hydrides such as NaH and KH, alkali metals such as sodium and potassium, and alkali metal hydroxides, how

Sodium hydroxide and potassium hydroxide, or organic bases such as triethylamine or DBU (1,8-diazabicyclo [5.4.0] undec-7-en) are suitable.

As a rule, it is expedient to carry out these reactions in the presence of a solvent which is inert under the reaction conditions, for. B. with a solvent from the group of aliphatic or aromatic, optionally halogenated hydrocarbons, such as n-heptane, benzene, toluene, xylene,

Dichloromethane, trichloromethane and carbon tetrachloride, or alcohols, such as. B.

Methanol, ethanol and isopropanol, or ether, such as. As diethyl ether, diglyme, monoglyme, tetrahydrofuran and dioxane, or ketones, such as. B. acetone and methyl ethyl ketone, or esters such as ethyl acetate, or other aprotic polar

Solvents such as dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and acetonitrile, or else water and mixtures of two or more of the solvents mentioned.

The reactions of variants c ₁₎ to c ₈₎ can be prepared analogously to conventional methods for reaction of aldehydes with nucleophiles and acetal preparation, for example, without a catalyst or under basic or acidic catalysis, are preferably carried out usually under weakly ^'acidic conditions. The two-stage Reaction according to c ₄ ) can be carried out according to or analogously to the process for the preparation of mixed acetals, e.g. B. according to Chem. Ber. 103 (1970) 3918 ff.

The implementations of variant d) can be carried out analogously to conventional methods

 Exchange of the aldehyde hydrogen atom for silyl groups, for example as described in J. Am. Chem. Soc. 89 (1967) 434.

The compounds of the formulas (II) and (III) are known or commercially available or can be synthesized analogously to known processes (cf. published European patent application EP-A-347811 and J. Chem. Research 1986 (5), 428 and cited therein) References).

The compounds of the formulas (VI) are new and also a subject of the invention.

The compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Also difficult to fight perennials

 Weeds that sprout from rhizomes, rhizomes or other permanent organs are well captured by the active ingredients. It does not matter whether the substances are applied by pre-sowing, pre-emergence or post-emergence.

Some representatives of mono- and dicotyledons are examples

Weed flora mentioned, which can be controlled by the compounds according to the invention, without any restriction to certain species being made by the name.

On the side of the monocot weed species, e.g. Avena, Lolium,

Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria as well as Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum as well as perennial Cyperus species are well recorded. With dicotyledon weed species, the spectrum of activity extends to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea,

 Matricaria, Abutilon and Sida on the annual side as well as Convolvulus, Cirsium, Rumex and Artemisia on the perennial weeds.

Weeds occurring in rice under the specific crop conditions, e.g. Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are from the

 Active ingredients according to the invention also fought excellently.

Are the compounds of the invention prior to germination on the

 Applied to the earth's surface, either weed seedlings are completely prevented from growing or the weeds grow up to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.

When the active ingredients are applied to the green parts of the plant in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the growth stage at the time of application or die completely after a certain time, so that one for the crop plants harmful weed competition is eliminated very early and sustainably.

Although the compounds of the invention have excellent herbicidal activity against mono- and dicotyledon weeds, they will

Cultivated plants of economically important crops such as Wheat, barley,

Rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops.

In addition, the substances according to the invention have excellent growth-regulating properties in crop plants. You grab regulate the plant's own metabolism and can thus be used to specifically influence plant ingredients and to facilitate harvesting, such as by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent gas storage.

The compounds of the formula (I) according to the invention can be used in the customary formulations, for example in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. The invention therefore also relates to herbicides and

 plant growth regulating agents which contain compounds of the formula (I).

The choice of a particular wording is made by the desired

 Applϊkatϊonsverfahren and determined by the predetermined biological and / or chemical-physical parameters, the optimization of

 Formulation components usually require systematic test series. Examples of formulation types are wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions,

Suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusts (DP), pickling agents, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual types of formulation are known in principle and will

described for example in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986, Wade van Valkenburg,

Pestϊcide Formulations, Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London. The necessary formulation aids such as inert materials, surfactants,

 Solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluent and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, Εncyclopedia of Surface Active Agents ", Chem. Publ. Co. Inc., NY 1964; Schoenfeldt,

"Surface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976;

Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides,

Manufacture fungicides, safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.

Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,

Fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates,

sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalene sulfonic acid sodium or also oleoylmethyl tauric acid sodium. To produce the wettable powders, the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and simultaneously or subsequently with the

Formulation aids mixed.

Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons or mixtures the organic solvent with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). The following can be used as emulsifiers: alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as

 Fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as, for. B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B.

 Polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding surfactants, such as z. B. above with the others

 Formulation types already listed can be produced.

Emulsions e.g. B. oil-in-water emulsions (EW) can be, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as z. B. are already listed above for the other types of formulation.

Granules can either by spraying the active ingredient

adsorbable, granulated inert material or by

Application of active ingredient concentrates using adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of

Carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

Water-dispersible granules are generally produced using the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material. For the production of plate, fluidized bed, extruder and spray granules, see, for example, the process in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For more details on the formulation of crop protection products see e.g. G.C. Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pages 81-96, and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical preparations usually contain 0.1 to 99

% By weight, in particular 0.1 to 95% by weight, of active compound of the formula (I).

The active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight. Dust-like formulations contain 1 to 30, preferably mostly 5 to 20% by weight of active ingredient, sprayable

Solutions about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient. at

Water-dispersible granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which granulation aids, fillers, etc. are used. The active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight,

preferably between 10 and 80% by weight.

In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers,

Evaporation inhibitors and agents that affect pH and viscosity.

Based on these formulations, combinations with others can also be made Manufacture pesticidal substances, fertilizers and / or growth regulators, for example in the form of a ready-to-use formulation or as a tank mix. As

 Combination partners for the active substances according to the invention can be used, for example, known active substances, such as those found in e.g. from Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Bracknell, England, and the literature cited therein. As herbicides known from the literature, which can be combined with the compounds of formula (I), z. For example, to name the following active substances (Note: The

 Compounds are identified either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, possibly together with a common code number): acetochlor; acifluorfen; aclonifen; AKH 7088, d. H. [[[[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] -oxy] - acetic acid and methyl acetate; alachlor; alloxydim; ametryn;

 amidosulfuron; amitrole; AMS, i.e. H. Ammonium sulfamate; anilofos; asulam; atrazine; aziprotryn; barban; BAS 516 H, i.e. H. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensuiide; bentazone;

 benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox;

 bromacϊl; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos;

 busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butylates;

 carbetamide; CDAA, i.e. H. 2-chloro-N, N-di-2-propenylacetamide; CDEC, i.e. H.

 2-chloroallyl ester of diethyldithiocarbamic acid; CGA 184927, d. H. 2- [4 - [(5-chloro-3-fluoro-2-pyridinyl) oxy] phenoxy] propanoic acid and 2-propynyiester;

chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron;

chforbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl;

chbrnitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron;

chlororthal dimethyl; chlorothiamide; cinmethylin; cinosulfuron; clethodim; clomazone; clomeprop; cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim; cycluron;

cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmediphan; desmetryn;

di-allate; dicamba; dichlobenil; dichlorprop; diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethazone, clomazone; dimethipin; dimetrasulfuron, cinosulfuron; dinitramine; dinoseb; dinoterb; diphenamide; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, ie 5-cyano-1- (1,1-dimethylethyl) -N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin;

 ethofumesate; F5231, i.e. H. N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1 H-tetrazol-1-yl] phenyl] ethanesulfonamide; F6285, d. H. 1- [5- (N-methylsulfonyl) amino ^^ - dichlorophenyl] -3-methyW-difluoromethyl-1,24, -triazol-5-one; fenoprop; fenoxan, p. clomazone; fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasulfuron; fluazifop and its ester derivatives; fluchloralin; flumetsulam; N- [2,6-difluorophenyl] -5-methyl- (1,2,4) -triazolo [1,5a] pyrimidine-2-sulfonamide; flumeturon; flumipropyn;

fluorodifen; fluoroglycofen-ethyl; fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosates; haloxyfop and its ester derivatives; hexazinone; Hw 52, d. H. N- (2,3-dichlorophenyl) -4- (ethoxymethoxy) benzamide; imazamethabenz-methyl; imazapyr; imazaquin;

imazethamethapyr; imazethapyr; imazosulfuron; ioxynil; isocarbamide; isopropaline; isoproturon; isouron; isoxaben; isoxapyrifop; carbutilates; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitrol; metazachlor;

methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron;

metobromuron; metolachlor; metoxuron; metribuzin; metsulfuron-methyl; MH;

molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, i.e. H. 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. H. 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitraline; nitrofen;

nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenmedipham; phenisopham;

phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl;

prometon; prometryn; propachlor; propanil; propaquizafop and its

Ester derivatives; propazine; propham; propyzamide; prosulfalin; prosulfocarb;

prynachlor; pyrazolinates; pyrazone; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate;

quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and its Ester derivatives; quizalofop-ethyl; quizalofop-p-tefuryl; renriduron; dymron; S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole; S 482, ie 2- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -4,5,6,7- tetrahydro-1H-isoindole-1,3 (2H) dione; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulfometuron-methyl; sulfazuron; flazasulfuron; TCA; tebutam; tebuthiuron; terbacif; terbucarb; terbuchlor;

 terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. H. N, N-Diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1H-1,2,4-triazole-1-carboxamide; thiazafluron;

 thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triciopyr; tridiphane; trietazine; trifluralin;

 trimeturon; vernolate; WL 110547, i.e. H. 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1H-tetrazole.

For use, the formulations present in the commercial form are optionally diluted in the usual manner, e.g. for spray powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Preparations in the form of dust, ground granules or scattering granules and sprayable solutions are usually no longer diluted with other inert substances before use. The compounds of the formula (I) are applied, for. B. in the post-emergence process by overhead application to the plants,

 Parts of plants and / or the soil on or in which they grow, or pre-emergence on the soil and / or plant seeds. In the case of use as herbicides, the plants are harmful plants or theirs

Plant seeds, the application because of the selectivity of the

compounds according to the invention can be carried out in the presence of crop plants. In the case of use as a plant growth regulator, the lances mean the crop plants or the soil the area under cultivation. With the outside

Conditions such as temperature, humidity, the type of herbicide used, among other things, vary the required application rate of the compounds of formula (I). It can vary within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha. A. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and in a

 Crushed crushing mill.

 b) An easily dispersible in water. Wettable powder is obtained by mixing 25 parts by weight of a compound of formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyl taurine as a wetting and dispersing agent and grinding in a pin mill.

c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight

 Alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight

 Isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. approx. 255 to above 277 ° C) are mixed and ground in a grinder mill to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of one

 Compound of formula (I), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of oxyethylated nonylphenol as an emulsifier.

e) A water-dispersible granulate is obtained by:

 75 parts by weight of a compound of the formula (I),

 10 "calcium lignosulfonic acid,

 5 "sodium lauryl sulfate,

 3 "polyvinyl alcohol and

 7 "kaolin

 mixes, grinds on a pin mill and granulates the powder in a fluidized bed by spraying water as granulating liquid.

f) A water-dispersible granulate is also obtained by

 25 parts by weight of a compound of the formula (I),

 5 "2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium

2 "oleolymethyl tauric acid sodium,

1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and

 50 parts by weight of water

 homogenized and pre-shredded on a colloid mill, then on a

Pearl mill grinds and the suspension thus obtained is atomized and dried in a spray tower using a single-component nozzle.

B. Chemical examples

2- (4,6-Dimethoxypyrimidinyl-2-oxy) -3-methylbutanal (see Table 1, Ex. 1)

With stirring, 9.1 g (66 mmol) of potassium carbonate are added to a solution of 10 g (60 mmol) of 2-bromo-3-methyl-butanal, 9.4 g (60 mmol) of 4,6-dimethoxy at 25 ° C. -2-hydroxy-pyrimidine and a spatula tip PEG 2000 (PEG = polyethylene glycol). - After 6 hours of stirring at 90 ° C, the reaction solution is poured onto ice water, adjusted to pH 5-6 and extracted with dichloromethane. After drying over

Magnesium sulfate, the solution is concentrated under reduced pressure, taken up with n-heptane, decanted and the clear solution is concentrated again. 10.4 g (72% of theory) of 2- (4,6-dimethoxypyrimidinyI-2-oxy) -3-methylbutanal are obtained in the form of a yellow oil with a refractive index of n _D ²⁴ = 1.4977.

2- (4,6-Dimethoxypyrimidinyl-2-oxy) -3-methylbutanaldoxime (see Table 2, Ex. 25)

While stirring, 1 g (10 mmol) of sodium hydrogen carbonate is added to a solution of 2 g (8 mmol) of 2- (4,6-dimethoxypyrimidinyl-2-oxy) -3-methyl-butanal and 0.6 g ( 8 mmol) hydroxylamine hydrochloride in 40 ml methanol. After stirring for 2 hours at room temperature, the reaction solution is poured onto ice water, extracted with ethyl acetate and the organic phase is concentrated under reduced pressure. After column chromatography (ethyl acetate / n-heptane 3: 7), 1.7 g (85% of theory) of 2- (4,6-dimethoxypyrfmidiny! -2-oxy) -3-methyIbutanaIdoxime are obtained in the form of a colorless wax.

The other compounds in Table I below are analogous to Obtain the examples and process variants described above.

Table 1: Compounds of the formula (Ia)

1

1

1

1

1

Table 2: Compounds of formula (Ib)

Table 3: Compounds of formula (Ic)

 B

Biological examples

The damage to the harmful plants and the tolerance to crop plants was rated according to a key in which the effectiveness is expressed by value numbers from 0 to 5. Here means

0 = without effect

 1 = 0 to 20% effect or damage

 2 = 20 to 40% effect or damage

 3 = 40 to 60% effect or damage

 4 = 60 to 80% effect or damage

 5 = 80 to 100% effect or damage

1. Pre-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy loam in plastic pots and covered with soil. Formulated in the form of wettable powders or emulsion concentrates

 Compounds according to the invention were then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth.

After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds. The visual assessment of the damage to the plants and the emergence occurred after the emergence of the

Test plants after a test period of 3 to 4 weeks compared to untreated controls. As the test results show, the

Compounds according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds. For example, the compounds (Ia) of Examples 1 and 11 from Table 1, the compounds (Ib) of Examples 25, 29, 37, 41, 49, 53 and 61 from Table 2 and the compounds (Ic) of Examples 1 and 5 from Table 3 very good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum and Avena fatua in the pre-emergence process.

2. Post-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were found in

Plastic pots laid out in sandy clay soil, covered with soil and grown in the greenhouse under good growing conditions. The test plants were treated at the three-leaf stage three weeks after sowing.

The compounds according to the invention formulated as wettable powder or as emulsion concentrates were mixed in different doses with a

Water application rate of the equivalent of 600 to 800 l / ha on the green

Plant parts sprayed and after about 3 to 4 weeks of the test plants in the greenhouse under optimal growth conditions the effect of

Preparations rated optically in comparison to untreated controls. The

Agents according to the invention have good herbicidal properties even after emergence

Efficacy against a wide range of economically important grasses and weeds. For example, the compounds (Ia) of Examples 1 and 11 from Table 1, the compounds (Ib) of Examples 25, 29, 37, 41, 49, 53 and 61 from Table 2 and the compounds (Ic) of Examples 1 and 5 from Table 3 very good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media,

Echinochloa crus-galli, Lolium multiflorum and Avena fatua in the post-emergence process.

Claims

Claims

1. Compounds of formula (I)

wherein

X O or S,

 Y, Z N or CH, where not both Y and Z are CH at the same time,

R ^a , R ^b independently of one another hydrogen, alkyl, aikoxy, alkylthio, halogen,

 Haloalkoxy, haloalkyl, amino, alkylamino or dialkylamino, a radical of the formulas (A1) to (A9),

- CH - CO - R ² - CH - CH = N - R ³ | | | R ¹

R ¹ (O) _n

(A1) (A2) - C = CH-NR ⁴ R ⁵ - CH - CH - X

| | R ⁶ ,

R ^{1 |}

R ¹ X ² -R ⁷ - '

 (A3) (A4)

- CH - CH-NR ⁹ R ¹⁰ - CH

| CH-NR ⁹ R ¹⁰

 | |

R ¹ R ¹ NR ⁹ R ¹⁰

 (A5) (A6)

- CH - CH - SO ₂ - O- M ⁺ - CH CH-P (= O) R ¹¹ R ¹² | | | |

R ¹ OH R ¹ OH

(A7) (A8)

X ¹ , X ² , X ³ and X ⁴ independently of one another O or S,

R ^{1 is} an aliphatic or araliphatic radical of the formula or

R ^{2 is} hydrogen or trialkylsilyl,

R ³ alkyl, alkenyl, alkynyl, aikoxy, alkenyloxy, alkynyloxy, alkylthio,

 where the latter seven radicals are independently unsubstituted or mono- or polysubstituted by radicals from the group aikoxy, alkylthio, amino, alkylamino, dialkylamino, nitro, cyano, halogen, phenyl and substituted phenyl, or

 Alkylcarbonyl, arylcarbonyl-substituted arylcarbonyl, hydroxy, a radical of the formula NR'R "in which R 'and R" independently of one another are hydrogen, alkyl, benzyl or phenyl, or aminocarbonyl, aminocarbonylamino, aminothiocarbonyl, aminothiocarbonylamino or

 Cycloalkyl, cycloalkenyl, cycloalkenyloxy or phenyl, where the last four radicals independently of one another are unsubstituted or substituted one or more times by radicals from the group alkyl, aikoxy, alkylthio, amino, alkylamino, dialkylamino, nitro, halogen, cyano, phenyl and substituted phenyl ,

R ⁴ , R ⁵ independently of one another are hydrogen, alkyl, alkenyl, alkynyl,

Cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl, where both radicals are not simultaneously hydrogen, or R ⁴ and R ⁵ together with the connected N atom form a 3- to 7-membered heterocyclic ring which, in addition to the N atom, can contain further heteroatoms from the group N, 0 and S and are substituted by one or more alkyl groups or an oxo group can be R ⁶ , R ⁷ independently of one another hydrogen, alkyl, alkenyl, alkynyl,

 Cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl or

R ⁶ and R ⁷ together with the connected group -X ¹ -CH-X ² - a 4- to 8-membered heterocyclic ring which, in addition to the two heteroatoms, can contain further heteroatoms from the group N, O and S and by one or several alkyl groups can be substituted,

R ^{8 is} hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl

 Phenyl, benzyl, alkylcarbonyl or arylcarbonyl,

R ⁹ , R ¹⁰ independently of one another are hydrogen, alkyl, alkenyl, alkynyl,

 Cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl or

R ⁹ and R ¹⁰ together with the connected N atom form a 3- to 7-membered heterocyclic ring which, in addition to the N atom, can contain further heteroatoms from the group N, O and S and are substituted by one or more alkyl groups or an oxo group can be, R ¹¹ , R ¹² independently of one another hydroxy, alkyl, aikoxy, phenyl,

substituted phenyl, phenoxy or substituted phenoxy, R ^{13 is} hydrogen or alkyl,

R ^{14 is} hydrogen, halogen, alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, aikoxy, alkylthio, phenyl or substituted phenyl, or hydroxy, cyano, cycloalkyl, aryl, where aryl or cycloalkyl is unsubstituted or are substituted,

R ¹⁵ , R ¹⁶ independently of one another are hydrogen or alkyl or

R ¹⁵ and R ¹⁶ together with the connected carbon atom form a 3- to 8-membered group

Ring which may contain an oxygen atom and which may be substituted by one or more alkyl groups, R ^{17 is} hydrogen or alkyl,

R ^{18 is} independently of R ^{19 is} hydrogen or alkyl,

R ^{19 is} independently of R ¹⁸ alkyl, aryl or substituted aryl or

R ¹⁸ and R ¹⁹ together with the connected alkenylene group form a 3- to 8-membered ring which can contain an oxygen atom and can be substituted by one or more alkyl groups,

M ⁺ the equivalent of a cation and

n is the number 0 or 1

mean.

2. Compounds according to claim 1, characterized in that

R ^a , R ^b independently of one another hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -

C ₄ alkylthio, halogen, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ haloalkyl, C ₁ - C ₄ -, alkylamino or di- (C ₁ - C ₄ alkyl) amino

mean.

3. Compounds according to claim 1 or 2, characterized in that

R ^{2 is} hydrogen or tri (C ₁ -C ₄ alkyl) silyl,

R ³ C ₁ - C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ - C ₄ alkoxy, C ₂ -C ₄ -

Alkenyloxy, C ₂ -C ₄ alkynyloxy, C ₁ -C ₄ alkylthio,

the latter seven radicals independently of one another unsubstituted or one or more radicals from the group C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, amino, (C ₁ -C ₄ -alkyl) amino, di- (C ₁ -C ₄ alkyl) amino, nitro, cyano, halogen, phenyl and substituted phenyl are substituted, or

(C ₁ -C ₄ alkyl) carbonyl, benzoyl, substituted benzoyl, hydroxy, a radical of the formula NR'R ", where R 'and R" independently of one another are hydrogen, C ₁ -C ₄ alkyl, benzyl or phenyl stand, or aminocarbonyl, aminocarbonylamino, aminothiocarbonyl, aminothiocarbonylamino or

C ₃ -C ₈ cycloalkyl, C ₅ -C ₈ cycloalkenyl, C ₅ -C ₈ cycloalkenyloxy or phenyl, the latter four radicals independently of one another unsubstituted or one or more radicals from the group C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, amino, (C ₁ - C ₄ -Alkyl) -amino, di- (C ₁ -C ₄ -alkyl) -amino, nitro, halogen, cyano, phenyl and substituted phenyl,

R ⁴ , R ⁵ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -

C ₄ -alkynyl, C ₃ -C ₈ -cycloalkyl, phenyl, substituted phenyl, benzyl, (C ₁ - C ₄ -alkyl) -carbony or benzoyl, where both radicals are not simultaneously hydrogen, or

R ⁴ and R ⁵ together with the connected N atom form a 5- to 6-membered heterocyclic ring which, in addition to the N atom, can contain one or two further heteroatoms from the group N, O and S and by one or more C ₁ -C ₄ alkyl groups and an oxo group can be substituted,

R ⁶ , R ⁷ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -

C ₄ -alkynyl, C ₃ -C ₈ -cycloalkyl, phenyl, substituted phenyl, benzyl, (C ₁ - C ₄ -alkyI) carbonyl or benzoyl or

R ⁶ and R ⁷ together with the connected group -X ¹ - CH-X ² - form a 5- to 6-membered heterocyclic ring which, in addition to the two heteroatoms, can contain a further heteroatom from the group N, O and S and through a or more C ₁ -C ₄ -Alky [groups can be substituted,

R ^{8 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₈ -

Cycloalkyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl,

R ⁹ , R ¹⁰ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl, C ₂ -

C ₄ -alkynyl, C ₃ -C ₈ -cycloalkyl, phenyl, substituted phenyl, benzyl, (C ₁ - C ₄ -alkyl) -carbonyl or benzoyl or

R ⁹ and R ¹⁰ together with the connected N atom have a 5- to 6-membered

heterocyclic ring which, in addition to the N atom, can contain one or two further heteroatoms from the group N, O and S and by one or more C ₁ -C ₄ alkyl groups and an oxo group can be substituted

R ¹¹ , R ¹² independently of one another are hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl,

 Phenyl, substituted phenyl, phenoxy or substituted

 Phenoxy,

R ^{13 is} hydrogen or C ₁ -C ₄ alkyl,

R ¹⁴ is unsubstituted hydrogen, halogen, C ₁ -C ₈ alkyl or by one or more radicals from the group halogen, hydroxy, C ₁ - C ₄ alkoxy, C ₁ -C ₄ alkylthio, phenyl or substituted phenyl substituted or C ₃ -C ₈ cycloalkyl, C ₅ -C ₈ cycloalkenyl, the latter two radicals being unsubstituted or substituted by one or more C ₁ -C ₄ alkyl groups,

R ¹⁵ , R ¹⁶ independently of one another are hydrogen or C ₁ -C ₈ -alkyl or

R ¹⁵ and R ¹⁶ together with the connected carbon atom form a 5- to 6-membered

Ring which may contain an oxygen atom and which may be substituted by one or more C ₁ -C ₄ alkyl groups,

R ^{17 is} hydrogen or C ₁ -C ₄ alkyl,

R ¹⁸ independently of R ^{19 is} hydrogen or C ₁ -C ₄ alkyl,

R ^{19 is} independently of R ¹⁸ C ₁ -C ₄ alkyl, phenyl or substituted phenyl or

R ¹⁸ and R ¹⁹ together with the connected alkenylene group form a 5- or 6-membered ring which may contain an oxygen atom and which may be substituted by one or more C ₁ -C ₄ -alkyl groups, M ⁺ sodium or potassium cation ,

n is the number 0 or 1

mean.

4. Compounds according to one of claims 1 to 3, characterized in that

R ^{2 is} hydrogen or tri (C ₁ -C ₂ alkyl) silyl,

R ^{3 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy,

wherein the last-mentioned two radicals independently of one another unsubstituted or mono- or polyhalogenated, or by C ₁ - C ₄ alkoxy, C ₁ -C ₄ alkylthio, amino, (C ₁ -C ₄ alkyl) amino, di (C ₁ - C ₄ alkyl I amino, nitro, cyano, phenyl and substituted phenyl are substituted, or

(C ^ C ^ AlkyiJ-carbonyl, benzoyl, substituted benzoyl, hydroxy, a radical of the formula NR'R ", wherein R 'and R" independently of one another are hydrogen, C ₁ -C ₄ alkyl, benzyl or phenyl, or

 Aminocarbonyl, aminocarbonylamino, aminothiocarbonyl,

 Aminothiocarbonylamino, cyclopentyl, cyclohexyl, phenyl or substituted phenyl,

R ⁴ , R ⁵ independently of one another are hydrogen, C ₁ -C ₄ alkyl, cyclopentyl,

Cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbony or benzoyl, where both radicals are not simultaneously hydrogen, or

R ⁴ and R ⁵ together with the connected N atom form a 5- or 6-membered heterocyclic ring which, in addition to the N atom, is another

 Can contain heteroatoms from the group N and O and can be substituted by one or more methyl groups,

R ⁶ , R ⁷ independently of one another are hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -

C ₄ -alkynyl, cyclopentyl, cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl or

R ⁶ and R ⁷ together with the connected group -X ¹ -CH-X ² - a 5- to 6-membered heterocyclic ring which is replaced by one or more

 Methyl groups can be substituted,

R ^{8 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, cyclopentyl,

Cyclohexyl, phenyl, substituted phenyl, benzyl, (C _C -C ₄ alkyl) - carbonyl or benzoyl,

R ⁹ , R ¹⁰ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, cyclopentyl,

Cyclohexyl, phenyl, substituted phenyl, benzyl, (C ₁ -C ₄ alkyl) carbonyl or benzoyl or

R ⁹ and R ¹⁰ together with the connected N atom form a 5- to 6-membered heterocyclic ring which, in addition to the N atom, can contain a further heteroatom from the group N and O and can be substituted by one or more methyl groups, R ¹¹ , R ¹² independently of one another are hydroxy, C ₁ -C ₂ alkyl, C ₁ -C ₄ alkoxy,

Phenyl, substituted phenyl, phenoxy or substituted

 Phenoxy and

R ^{13 is} hydrogen or C ₁ -C ₄ alkyl.

5. Compounds according to any one of claims 1 to 4, characterized in that R ^{1 is} an aliphatic or araliphatic radical of the formula

-CR ¹⁴ R ¹⁵ R ¹⁶

is what

R ^{14 is} hydrogen, halogen, C ₁ -C ₆ -alkyl which is unsubstituted or by one or more radicals from the group halogen, hydroxy, C ₁ -C ₄ -alkoxy, in particular methoxy or ethoxy, or C ₁ -C ₄ -alkylthio , Phenyl or substituted phenyl, or C ₃ -C ₆ cycloalkyl, C ₅ -C ₆ cycloalkenyl, the latter two radicals being unsubstituted or substituted by one or more C ₁ -C ₄ alkyl groups, or hydroxy, cyano , Phenyl, thienyl, naphthyl or dihydronaphthyl, the latter four radicals being unsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, trifluoromethyl or halogen,

R ¹⁵ , R ¹⁶ independently of one another are hydrogen or C ₁ -C ₄ -alkyl or

R ¹⁵ and R ¹⁶ together with the connected carbon atom have a 5- or 6-membered group

Ring which may contain an oxygen atom and which may be substituted by one or more C ₁ -C ₄ alkyl groups,

mean.

6. A process for the preparation of compounds of formula (I) according to any one of claims 1 to 5, characterized in that

a) in the event that A has the meaning of formula (A1) and R ² = H, one

Reacting compound of formula (II) with a compound of formula (III),

wherein in formulas (II) and (III) R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (I) and Nuf ^{1 is} a nucleofugic leaving group, or b) in the case that A has the meaning of formula (A1) and R ² = H, reacts a compound of the formula (IV) with a compound of the formula (V),

where in the formulas (IV) and (V) R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (I) and Nuf ^{2 is} a nucleofugic leaving group, or c) a compound of the formula ( VI),

wherein R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (I),

c ₁ ) in the case of A = (A2) and R ² = H, with a compound of the formula

H- (O) _n NH-R ³ , where n is as defined in formula (A2),

c ₂ ) in the case of A = (A3), with a compound of the formula HNR ⁴ R ⁵ , c ₃ ) in the case of A = (A4), with a compound of the formula HX ¹ -R ⁶ -R ⁷ -X ² H, c ₄ ) in the case A = (A5), first with a compound of the formula HNR ⁹ R ¹⁰ to a compound of the formula (I) in which A = A6, and then with a compound of the formula CICH ₂ X ³ R ⁸ ,

c ₅ ) in the case A = (A6), with a compound of the formula H-NR ⁹ R ¹⁰ ,

c ₆ ) in the case A = (A7), with a compound of the formula MSO ₃ H,

c ₇ ) in the case of A = (A8), with a compound of the formula HP (= O) R ¹¹ R ¹² and c ₈ ) in the case of A = (A9), with a compound of the formula HX ⁴ -CO-CH (SH ) R ¹³ or d) reacting a compound of the formula (VI) listed under c) in a multi-stage process which involves reaction with the compound of the formula HS- (CH ₂ ) ₃ -SH, subsequent reaction with lithium alkyl and trialkyl silicon halide and reaction with Mercury halide is converted into the compound of formula (I) wherein A = (A2) and R ² = trialkylsilyl.

7. Compounds of the formula (VI),

wherein R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (I) according to any one of claims 1 to 5.

8. A process for the preparation of compounds of the formula (VI) according to claim 7, characterized in that reacting a compound of the formula (II) with a compound of the formula (III),

wherein in formulas (II) and (III) R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (VI) according to claim 7 and Nuf ^{1 is} a nucleofugic leaving group, or a compound of the formula (IV) reacted with a compound of formula (V),

wherein in formulas (IV) and (V) R ^a , R ^b , X, Y, Z and R ^{1 are} as defined in formula (VI) and Nuf ^{2 stands} for a nucleofugic leaving group.

9. Herbicides and plant growth regulators, thereby

 characterized in that they contain a compound of formula (I) according to one of Claims 1 to 5 and customary formulation auxiliaries.

10. Use of the compounds of formula (I) according to one of claims 1 to 5 as herbicides or plant growth regulators.

11. Processes for controlling harmful plants or

 Regulating the growth of plants, characterized in that one or more compounds of the formula (I) according to one of Claims 1 to 5 are applied to the plants, plant seeds or the soil on or in which the plants grow.