DE4039940A1 - New pyrimidinyl-substd. salicylaldehyde and salicylic acid derivs. - Google Patents

Abstract

Pyrimidinyl-substd. (thio)salicylaldehyde and (thio)salicylic acid derivs. (I) and their salts are new. In (I), R1 = H; succinylimidooxy; 5-membered heteroaryl contg. 1-3 N atoms and opt. 1-4 halo and/or 1-2 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy and/or 1-4C alkylthio substits.; OR5; -N=CR6R7; -(O)mNR14R15, -(CH2)l-CO-NR16NR17, -(CH2)l-S(O)kR18; -O-(CH2)l-P(O)(OR18)2 or -NHSO2R19, R2 = 1-4C alkyl, 1-4C alkoxy, 1-4C haloalkoxy or halogen; R3 = H; and R4 = H; halogen; 1-4C alkoxy; 1-4C haloalkoxy; aryloxy; 1-4C haloalkyl; formyl; 1-8C alkoxycarbonyl; R3+R4 = -Z=CH-CH=CH- where Z = CH or N; R5 = H; alkali metal, alkaline earth metal or organic ammonium cation; 3-12C cycloalkyl opt. contg. 1-3 1-4C alkyl substits; 1-10C alkyl opt. contg. 1-5 halo and/or 1 1-4C alkoxy, 1-4C alkylthio, cyano, 1-8C alkylcarbonyl, 1-8C alkoxycarbonyl, 3-12C cycloalkyl or phenyl, phenoxy or phenylcarbonyl substits. R6, R7 = 1-20C alkyl opt. substd. by phenyl, 1-4C alkoxy and/or 1-4C alkylthio; phenyl; or R6+R7 = 3-12C alkylene opt. contg. 1-3 1-3C alkyl substits.; R14, R15 = H; 1-6C alkyl, 3-6C alkenyl or 3-6C alkynyl opt. contg. 1-5 halo and/or 1-2 1-6C alkoxy, 3-6C alkenyloxy, 3-6C alkynyloxy, 1-6C alkylthio, 3-6C alkenylthio, 3-6C alkynylthio, 1-6C haloalkoxy, cyano, 1-6C alkylcarbonyl, 3-6C alkenylcarbonyl, 3-6C alkynylcarbonyl, 1-6C alkoxycarbonyl, 3-6C alkenyloxycarbonyl; R16, R17 = H; 1-6C alkyl; 3-6C alkenyl or 3-6C alkynyl; R18 = 1-6C alkyl; 3-6C alkenyl or 3-6C alkynyl; R19 = 1-6C alkyl or phenyl opt. contg. 1-4 halo, nitro, cyano or 1-6C alkyl substits; X = O or S; Y = N when R3 = H and n = 0 or when R4 = O and n = 1; or C when R3+R4 form a ring or when R3 = H and k = 0-2; n = 1; l = 1-4; m = 0 or 1; and n = 1 when Y = C or when Y = N and R4 = O or 0 when Y = N and R4 is other than O.

Description

The present invention relates to salicylaldehyde and salicylic acid derivatives and their sulfur analogues of the formula I,

in which the substituents have the following meanings:
R¹ is hydrogen
a succinyliminooxy group;
a 5-membered heteroaromatic containing one to three nitrogen atoms, which may carry one to four halogen atoms and / or one to two of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄alkoxy, C₁-C₄ Haloalkoxy and / or C₁-C₄-alkylthio;
a radical -OR⁵ or a radical ON = CR⁶R⁷, in which
R⁵
Hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium ion;
a C₃-C₁₂-cycloalkyl group which can carry one to three C₁-C₄-alkyl radicals;
a C₁-C₁₀-alkyl group which may carry one to five halogen atoms and / or one of the following radicals: C₁-C₄-alkoxy, C₁-C₄-alkylthio, cyano, C₁-C₈-alkylcarbonyl, C₁-C₈-alkoxycarbonyl, C₃-C₁₂ -Cycloalkyl, phenyl, phenoxy or phenylcarbonyl, wherein the aromatic radicals in turn may carry one to five halogen atoms and / or one to three of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁- C₄-haloalkoxy and / or C₁-C₄-alkylthio;
a C₁-C₁₀-alkyl group which may carry one to five halogen atoms and carries one of the following radicals: a 5-membered heteroaromatic containing one to three nitrogen atoms which may carry one to four halogen atoms and / or one to two of the following radicals:
C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and / or C₁-C₄-alkylthio;
a C₂-C₆ alkyl group which carries in the 2-position one of the following radicals: C₁-C₆ alkoxyimino, C₃-C₆ alkenyloxyimino, C₃-C₆ haloalkenyloxyimino or benzyloxyimino;
a C₃-C₆ alkenyl or a C₃-C₆ alkynyl group, which groups may in turn carry one to five halogen atoms;
unsubstituted or mono- to trisubstituted by C₁-C₄-alkyl or C₁-C₄-alkoxy or mono- to fivefold by halogen-substituted phenyl;
means and
R⁶ and R⁷
C₁-C₂₀-alkyl which may carry a phenyl radical, a C₁-C₄-alkoxy and / or a C₁-C₄-alkylthio group, phenyl or together a C₃-C₁₂-alkylene chain which may carry one to three C₁-C₃-alkyl groups , mean;
R² is C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy or halogen;
R³ is hydrogen or together with R⁴ is a group CH₂ = CH-CH = CH₂ or N = CH-CH = CH₂;
R⁴ is hydrogen, halogen, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, aryloxy, C₁-C₄-haloalkyl, formyl, C₁-C₈-alkoxycarbonyl;
an optionally monosubstituted to trisubstituted, in the case of halogen as a substituent one to five times substituted phenyl radical

R³-R¹²
Hydrogen, halogen, cyano, nitro;
a C₃-C₆ alkenyl, C₃-C₆ alkenyloxy, C₃-C₆ alkynyloxy or a C₃-C₆ alkynyl group, which groups may in turn carry one to five halogen atoms;
Di-C₁-C₄-alkylamino, C₃-C₈-cycloalkyl, which may carry one to three C₁-C₄-alkyl radicals;
C₁-C₁₀ alkoxycarbonyl, C₁-C₄ alkylthio;
a phenoxy group, wherein the aromatic radical may carry one to five halogen atoms and / or one to three of the following radicals; C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, C₁-C₄ alkoxy, C₁-C₄ alkylthio;
a C₁-C₁₀ alkyl or alkoxy group which may carry one to five halogen atoms and / or one of the following radicals: C₁-C₄-alkoxy, C₁-C₄-alkylthio, phenyl or phenoxy, wherein the aromatic radicals in turn have one to five halogen atoms and / or one to three of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio;
mean;
a 5-membered heteroaromatic, having two to four nitrogen atoms or one to two nitrogen atoms and additionally a sulfur or oxygen atom in the ring, which can carry one to three halogen atoms and / or one to three of the following radicals: nitro, cyano, C₁-C₄ -Alkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkyl or phenyl which is unsubstituted or substituted by one to three halogen atoms and / or one to three methyl groups;
a thienyl radical which may carry one to three halogen atoms and / or one to three of the following radicals: C₁-C₄-alkyl, C₁-C₂-haloalkyl or nitro;
or oxygen when Y is nitrogen and n is 1;
n 1, when Y is carbon or when Y is nitrogen and R⁴ is oxygen and 0, when Y is nitrogen and R⁴ is not oxygen;
X oxygen or sulfur;
Y is nitrogen when R³ is hydrogen and n is 0 or when R⁴ is oxygen and n is 1; Carbon, when R³ and R⁴ together represent a group CH₂ = CH-CH = CH₂ or N = CH-CH = CH₂ or carbon, when R³ is hydrogen and n is 1;
and environmentally acceptable salts of compounds I.

Furthermore, the invention relates to processes for the preparation of the compound I and their use as herbicides and growth regulators, as well new sulfones of formula III

as intermediates for the preparation of the compounds of the formula I. In the formula III, the radicals R² and R¹³ have the following meanings:
R² is C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄-haloalkoxy or halogen
R¹³ C₁-C₁₂-alkyl, optionally substituted by alkyl, halogen or alkoxy-substituted phenyl.

In the literature (EP-A 223 406, EP-A 249 708, EP-A 287 072 and EP-A 287 079) are herbicidally active substituted salicylic acids and their Sulfur analogues described. Their effect, however, is unsatisfactory.

The object of the present invention was therefore new salicylic acid derivatives or their sulfur analogues with improved herbicidal properties and with plant growth regulating properties.

According to this task, the compounds defined above of the formula I found. In addition, methods for preparing the compounds I and methods of controlling undesired plant growth the compounds I found. It has also been found that salicylic acid derivatives the above-defined general formula I excellent have plant growth regulating properties. As intermediates for the preparation of the compounds I, the new sulfones III were found.

Compounds of the formula I are obtained, for example, by adding an appropriate substituted salicylic acid derivative of the formula II with a corresponding compound of formula III in the presence of a base.  

R¹³ SO₂ in formula III means a common nucleofugic leaving group, for example Arylsulfonyl such as phenyl or substituted phenylsulfonyl, where as substituents one or more, for. B. 1 to 3 low molecular weight Alkyl or alkoxy radicals such as C₁-C₄-alkyl or alkoxy or halogen, for. B. Chlorine, fluorine or bromine come into consideration; or alkylsulfonyl such as C₁-C₄- Alkylsulfonyl, e.g. As methylsulfonyl. As the base, alkali or alkaline earth metal hydrides such as NaH and CaH₂, alkali metal hydroxides such as NaOH and KOH, alkali metal alcohols such as potassium tert-butoxide, alkali metal carbonates such as Na₂CO₃ and K₂CO₃, alkali metal amides such as NaNH₂ and lithium diisopropylamide or tertiary amines find use. When using an inorganic Base can be added to a phase transfer catalyst, if this promotes sales.

The sulfones of general formula III are obtained by a corresponding 2-alkylthio-5,6-dihydrofuran [2,3-d] pyrimidine (see Collect. Czech. Chem. Commun. 32, 1582 (1967))

by oxidizing agents such as. As chlorine in water or hydrogen peroxide in Glacial acetic acid oxidizes under mild conditions.

The intermediates of the formula II are known in individual cases or can be prepared by conventional methods, starting from known precursors (see, for example, EP-A-249 707, EP-A-315 889 or JP-A 20 56 469). Note No. 310 741v. 08. 12. 87). The following intermediates of formula II are Subject of the earlier German application P 39 19 435.3 of 14. 06. 89 and can be when X is an oxygen atom and A is one over a carbon atom bonded aromatics or heteroaromatics, according to the Scheme below of a 1,3-dicarbonyl compound IV (with R⁵ = optionally phenyl-substituted C₁-C₁₀-alkyl, in particular C₁-C₄-alkyl) and an α, β-unsaturated ketone V build up:  

Alternatively, the intermediates of formula II can be after below diagram of a Methylenphosphoran IV '(Ph = phenyl) and an α, β-unsaturated ketone V:

In this case, the compounds IV, IV 'and V are generally known or after the usual method easily produced. As base come the above Connections in question. Suitable acids are strong acids, for example Hydrogen chloride, hydrogen bromide, tetrafluoroboric acid, Toluenesulfonic acid or trifluoroacetic acid. The Bromwasserstoffabspaltung may be thermally or in the presence of a base, for example one organic amine.

If R⁴ in formula II is a heteroaromatic compound bound via a nitrogen atom and X is an oxygen atom, so you can this intermediate build up according to the following scheme:

Here is M⁺R⁴ ^- for each Alkalimetallazolid. Suitable alcohols in the cleavage of the nitrile VII according to variant a), in particular C₁-C₄-alkyl alcohols in question.

The intermediates of formula II prepared as described above usually occur as alkyl esters. These can be after the known Hydrolyze process to the carboxylic acids. You can do the latter now convert according to literature methods in various esters, the for the preparation of active compounds of the formula I according to claim 1 needed.

Alternatively, you can also the intermediates of formula VII according to general known methods with alkali metal or tetraalkylammonium hydroxides to the corresponding amides and then with mineral acids, eg. B. conc. Hydrochloric acid, too the carboxylic acids and then with conc. Hydrobromic acid to the React salicylic acids IIb. These steps can be done without need Isolation of the intermediates are carried out.

As far as in the compounds prepared in the manner described of formula I is carboxylic acids (when R¹ is hydroxyl), may be other compounds described z. B. also produced thereby be that the carboxylic acid in a conventional manner in a first converted activated form such as a halide or imidazolide and this then reacted with the corresponding hydroxyl compound. These two Steps can also be simplified, for example, by using the Carboxylic acid in the presence of a dehydrating agent such as a carbodiimide allowed to act on the hydroxyl compound.

With regard to the herbicidal activity, preference is given to compounds I in which the substituents have the following meanings:
R¹ is hydrogen, succinyliminooxy,
5-membered heteroaryl such as pyrrolyl, pyrazolyl, imidazolyl and triazolyl, in particular imidazolyl and pyrzolyl, wherein the aromatic radical is bonded via nitrogen and in turn carry one to four halogen atoms as mentioned above, in particular fluorine and chlorine and / or one or two of the following radicals can:
Alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, preferably methyl, ethyl and 1-methylethyl,
Haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- Dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, especially difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and pentafluoroethyl;
Alkoxy as mentioned above having one to four carbon atoms, haloalkoxy such as difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,2 Trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy and pentafluoroethoxy, especially trifluoromethoxy and / or
Alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio, especially methylthio and ethylthio;
a residue OR⁵, in which
R⁵ is hydrogen, the cation of an alkali metal or the cation of an alkaline earth metal such as lithium, sodium, potassium, calcium, magnesium and barium, or an environmentally acceptable organic ammonium ion;
Alkyl such as in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpenyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl 2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl and octyl, which are one to five of the above Halogen atoms, in particular fluorine and chlorine and / or one of the following radicals can carry;
Cyano, alkoxy or alkylthio having one to four carbon atoms as mentioned above, in particular methoxy, ethoxy, 1-methylethoxy and methylthio;
Alkylcarbonyl such as in particular methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1,1-dimethylpropylcarbonyl, 1 , 2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl , 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1,2-trimethylpropylcarbonyl, 1,2,2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl and 1-ethyl-2-methylpropylcarbonyl;
Alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, 1-methylethoxycarbonyl, butyloxycarbonyl, 1-methylpropyloxycarbonyl, 2-methylpropyloxycarbonyl, 1,1-dimethylethoxycarbonyl, n-pentyloxycarbonyl, 1-methylbutyloxycarbonyl, 2-methylbutyloxycarbonyl, 3-methylbutyloxycarbonyl, 1,2-dimethylpropyloxycarbonyl, 1,1-dimethylpropyloxycarbonyl, 2,2-dimethylpropyloxycarbonyl, 1-ethylpropyloxycarbonyl, n-hexyloxycarbonyl, 1-methylpentyloxycarbonyl, 2-methylpentyloxycarbonyl, 3-methylpentyloxycarbonyl, 4-methylpentyloxycarbonyl, 1,2-dimethylbutyloxycarbonyl, 1,3-dimethylbutyloxycarbonyl, 2, 3-dimethylbutyloxycarbonyl, 1,1-dimethylbutyloxycarbonyl, 2,2-dimethylbutyloxycarbonyl, 3,3-dimethylbutyloxycarbonyl, 1,1,2-trimethylpropyloxycarbonyl, 1,2,2-trimethylpropyloxycarbonyl, 1-ethylbutyloxycarbonyl, 2-ethylbutyloxycarbonyl, 1-ethyl- 2-methylpropyloxycarbonyl, n-heptyloxycarbonyl, 1-methylhexyloxycarbonyl, 2-methylhexyloxycarbonyl, 3-methylhexyloxycarbonyl, 4-methylhexyloxycarbonyl, 5 Methylhexyloxycarbonyl, 1-ethylpentyloxycarbonyl, 2-ethylpentyloxycarbonyl, 1-propylbutyloxycarbonyl and octyloxycarbonyl, especially methoxycarbonyl, ethoxycarbonyl, 1-methylethoxycarbonyl and 1-methylpropyloxycarbonyl.

Phenyl, phenoxy or phenylcarbonyl, these aromatic radicals in turn being able to carry one to five halogen atoms as mentioned above, in particular fluorine, chlorine and bromine and / or one to three of the following radicals:
Alkyl, haloalkyl, alkoxy, haloalkoxy and / or alkylthio each having one to four carbon atoms as generally and in particular mentioned above, or
C₁-C₁₀-alkyl as mentioned above, which may carry one to five halogen atoms such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine and additionally carries one of the following radicals:
5-membered heteroaryl having one to three nitrogen atoms as mentioned above for R¹.

C₂-C₆-alkyl, in particular C₂-C₄-alkyl, substituted in the 2-position is C₁-C₆-alkoxyimino, z. For example, methoxy, ethoxy or propoxyimino; C₃-C₆ alkenyloxyimino such as 2-propenyloxyimino, 2-butenyloxyimino, 3-butenyloxyimino; C₃-Halogenalkenyloxyimino such as 3,3-dichloro-2-propenyloxyimino, 2,3,3-trichloro-2-one propenoxyimino or benzyloxyimino.

Alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 Methyl 4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3- butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, especially 2-propenyl, 2-butenyl, 3-methyl-2-butenyl and 3-methyl-2-pentenyl;
Alkynyl, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-alkynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl 3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, preferably 2-propynyl, 2-butynyl, 1-methyl-2-propynyl and 1-methyl-2-butynyl, especially 2-propynyl, wherein these alkenyl and alkynyl groups may carry one to five of the above generally and in particular the halogen atoms;
C₃-C₁₂-cycloalkyl, in particular C₃-C₆-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, which is optionally substituted by one to three C₁-C₄-alkyl radicals;
Phenyl, phenyl substituted one to three times by C₁-C₄ alkyl or alkoxy such as methyl, ethyl, propyl, butyl, methoxy, ethoxy or phenyl substituted by one to five halogen atoms, e.g. For example, chlorine or fluorine;
a radical ON = CR⁶R⁷, in which
R⁶ R⁷ is unbranched or branched C₁-C₂₀-alkyl, preferably C₁-C₁₅-alkyl, in particular C₁-C₉-alkyl, which may carry a phenyl, a C₁-C₄-alkoxy or a C₁-C₄-alkylthio, phenyl or jointly C₃- C₁₂-alkylene, preferably C₄-C₇-alkylene, which may carry one to three C₁-C₃-alkyl groups, preferably methyl or ethyl groups, means;
R² in general and in particular the alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and / or each having one to four carbon atoms and halogens such as fluorine, chlorine, bromine or iodine, in particular methyl, chlorine, methoxy mentioned in R¹;
R³ is hydrogen or together with R⁴ is a group CH₂ = CH-CH = CH₂ or N = CH-CH = CH₂;
R⁴ hydrogen; Halogen as mentioned for R¹, in particular fluorine, chlorine and bromine;
C₁-C₄ alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, tert-butoxy;
C₁-C₃-haloalkoxy, z. B. C₁-C₃-alkoxy substituted by 1 to 5 halogen atoms such as fluorine, chlorine or bromine, for. Trifluoromethoxy, difluoromethoxy;
Aryloxy such as phenoxy optionally substituted by methyl, fluoro, chloro or methoxy;
C₁-C₄-haloalkyl as mentioned for R¹, in particular C₁-C₂-haloalkyl such as trifluoromethyl;
formyl;
C₂-C₈ alkoxycarbonyl as detailed above for R¹ in particular methoxycarbonyl, ethoxycarbonyl;
unsubstituted or substituted phenyl in which substituents R⁸ to R¹² are suitable: halogen, such as fluorine, chlorine, bromine or iodine; cyano; Nitro, optionally halogen-substituted alkenyl, alkenyloxy, alkynyloxy or alkynyl having in each case 3 to 6 carbon atoms; Di-C₁-C₄-alkylamino such as di-methylamino, di-ethylamino, di-propylamino, di-1-methylethylamino, di-butylamino, di-1-methylpropylamino, di-2-methylpropylamino, di-1,1-dimethylethylamino, Ethylmethylamino, propylmethylamino, 1-methylethylmethylamino or butylmethylamino; optionally alkyl-substituted cycloalkyl as listed above for R⁵, alkoxycarbonyl or alkylthio as listed above for R⁵, optionally substituted phenoxy as listed under R⁵, C₁-C₁₀-alkyl or alkoxy, in particular C₁-C₆, preferably C₁-C₄alkyl or alkoxy which unsubstituted or substituted by said radicals; for example, the following substituted phenyl radicals may be mentioned for A:
2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,6-difluorophenyl, 2,4-difluorophenyl, 2-fluoro-4-trifluoromethylphenyl, 2,3-difluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 2-iodophenyl, 2-bromophenyl, 2-chloro-6-fluorophenyl, pentafluorophenyl, pentachlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-4-fluorophenyl, 3,5-dichlorophenyl, 2-chloro-6-methylphenyl, 2,3,5-trichlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-chloro 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-chloro-2-methoxyphenyl, 2-trifluoromethylphenyl, 2,3-dimethyl-4-methoxyphenyl, 4-dimethylamino-2-methylphenyl, 3-cyanophenyl, 3-nitrophenyl, 3-phenoxyphenyl, 3- (3-trifluoromethylphenoxy) phenyl, 3-trifluoromethylphenyl,
optionally substituted 5-membered hetaryl having 2 to 4 nitrogen atoms as mentioned for R¹ or one to 2 nitrogen atoms and additionally a sulfur or oxygen atom such as optionally substituted 5-membered hetaryl having 2 to 4 nitrogen atoms as mentioned for R¹ or one to 2 nitrogen atoms and additionally a sulfur or oxygen atom such as isoxazolyl, oxazolyl, thiazolyl, thiadiazolyl.

For example, the following hetaryl radicals may be mentioned:
Pyrazol-1-yl, 4-methylpyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 3,4,5-trimethylpyrazol-1-yl, 4-chloropyrazol-1-yl, 4-phenylpyrazole-1 yl, 4-isopropylpyrazol-1-yl, 4-nitropyrazol-1-yl, imidazol-1-yl, 4,5-dimethylimidazolyl, 2-methyl-4,5-dichloro-imidazolyl, 4 (5) -nitroimidazol-1-yl , [1,2,4] triazol-1-yl, 3 (5) -methyl- [1,2,4] triazol-1-yl, [1,2,3] triazol-1-yl, 4,5-Dimethyl- [1,2,3] triazol-1-yl, [1,2,3,4] tetrazol-1-yl, 1-methylpyrazol-4-yl, 1-phenylpyrazole-4 yl, 1,3,5-trimethylpyrazol-4-yl, 1-methylpyrazol-5-yl, 1-phenylpyrazol-5-yl, 1-methylpyrazol-3-yl, 1-phenylpyrazol-3-yl, 1-methylimidazole 2-yl, 1-methylimidazol-5-yl, 1-phenylimidazol-5-yl, 1-phenyl- [1,2,3] -triazol-4-yl, isoxazol-5-yl, isoxazol-4-yl, 3-methyl-isoxazol-5-yl, 3-isopropyl-isoxazol-5-yl, 3-phenyl-isoxazol-5-yl, oxazol-2-yl, 2-methyloxazol-4-yl, thiazol-4-yl, 2-Benzothiazol-4-yl, 4-methylthiazol-2-yl, 4-methylthioazol-5-yl, 4-phenylthiazol-2-yl, 2-phenylthiazol-5-yl.

Optionally substituted thienyl radicals are, for. 2-thienyl, 3-thienyl, 2,3-dichloro-4-thienyl, 2-methyl-5-thienyl, 2-nitro-5-thienyl.

Particular preference is given to compounds of the formula I in which the radical R² is methoxy, X is oxygen and Y and the radicals R¹, R³ and R⁴ have the meaning mentioned above.

Salts of the compounds of the formula I are environmentally compatible salts, for example, alkali metal salts, in particular the potassium or sodium salt, Alkaline earth metal salts, especially the calcium, magnesium or Barium salt, manganese, copper, zinc or iron salts and ammonium, Phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, Tetraalkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts or Trialkylsulfoxoniumsalze into consideration.

The herbicidal and growth-regulating compounds I according to the invention or the agents containing them, for example, in the form of direct sprayable solutions, powders, suspensions, even high percentage aqueous, oily or other suspensions or dispersions, emulsions, Oil dispersions, pastes, dusts, litter or granules applied by spraying, atomizing, dusting, scattering or pouring become. The forms of application depend on the intended use; you should in each case as possible the finest distribution of the invention Ensure active ingredients.  

The compounds I are generally suitable for the preparation of direct sprayable solutions, emulsions, pastes or oil dispersions. As inert Additives come from mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and vegetable oils or of animal origin, aliphatic, cyclic and aromatic Hydrocarbons, eg. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, Butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strong polar solvents, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Aqueous application forms can be prepared from emulsion concentrates, dispersions, Pastes, wettable powders or water-dispersible granules by addition to be prepared from water. For the preparation of emulsions, pastes or oil dispersions may be the substrates as such or in an oil or Solvent dissolved by means of wetting, adhesion, dispersing or emulsifying agent be homogenized in water. It can also be more effective Substance, wetting, adhesion, dispersing or emulsifying agent and possibly Solvent or oil existing concentrates are produced, the Dilution with water are suitable.

As surface-active substances are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, Alkyl, lauryl ether and fatty alcohol sulfates, as well as salts sulfated Hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, Condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated iso-octyl, octyl or nonylphenol, alkylphenol, Tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, Sorbitol esters, lignin-sulphite liquors or methylcellulose in Consideration.

Powders, litter and dusts can be mixed or mixed Grinding the active substances with a solid carrier become.

Granules, for. B. coated, impregnated and homogeneous granules be prepared by binding the active compounds to solid carriers. Solid carriers are mineral earths such as silica gel, silicas, silica gels,  Silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, Dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground Plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products, such as cereal flour, Bark, wood and nutshell flour, cellulose powder or other solid Carriers.

The formulations contain between 0.1 and 95% by weight, preferably between 0.5 and 90 wt .-%, active ingredient. The active ingredients are in one Purity from 90% to 100%, preferably 95 to 100% (according to NMR spectrum) used.

The compounds I according to the invention can be, for example, as follows be formulated:

• I. Mix 90 parts by weight of compound no. 3008 with 10 parts by weight of N-methyl-α-pyrrolidone and receives a solution, which is suitable for use in the form of very small drops.
• II. 20 parts by weight of compound no. 3008 are in a mixture dissolved, consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole Oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight Water is obtained an aqueous dispersion containing 0.2 wt .-% of the Contains active substance.
• III. 20 parts by weight of compound no. 3008 are mixed dissolved, consisting of 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide 1 mole of castor oil exists. By pouring and finely distributing the Solution in 100 000 parts by weight of water gives an aqueous Dispersion containing 0.02 wt .-% of the active ingredient.
• IV. 20 parts by weight of the active ingredient No. 3008 are in a mixture dissolved, which consists of 25 parts by weight of cyclohexanone, 25 parts by weight a mineral oil fraction of boiling point 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and fine Distributing the solution in 100 000 parts by weight of water is obtained an aqueous dispersion containing 0.02% by weight of the active ingredient.  
• V. 20 parts by weight of the active ingredient No. 3008 are with 3 parts by weight the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water To obtain a spray mixture containing 0.1 wt .-% of the active ingredient contains.
• VI. 3 parts by weight of drug # 3008 are 97 parts by weight finely divided kaolin mixed. You get that way a dust containing 3% by weight of the active ingredient.
• VII. 30 parts by weight of the active ingredient No. 3008 are mixed with a mixture from 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which is on the surface of this silica gel was sprayed, intimately mixed. You get on this Make a preparation of the drug with good adhesion.
• VIII. 20 parts by weight of the active ingredient No. 3008 are with 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight Fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a Phenol-urea-formaldehyde condensates and 68 parts by weight a paraffinic mineral oil intimately mixed. You get one stable oily dispersion.

The application of the herbicidal and growth-regulating agents or the Active ingredients can be pre-emergence or postemergence. are the active ingredients for certain crops less compatible, so can Application techniques are applied, in which the herbicidal agents be sprayed with the help of sprayers so that the leaves of the sensitive Cultivated plants are not taken if possible while the active ingredients on the leaves underneath growing unwanted Plants or the uncovered ground surface arrive (post-directed, lay-by).

The amounts of herbicidal active ingredient depending on the target, Season, target plants and growth stage 0.001 to 1, preferably 0.01 to 0.5 kg / ha of active substance (see above).

The growth-regulating salicylic acid derivatives of the formula I Virtually all stages of development of a plant can be varied influence and are therefore used as growth regulators. The The variety of effects of plant growth regulators depends above all

• a) the plant species and variety,
• b) from the time of application, based on the development stage the plant and the season,
• c) from the application site and method z. B. (seed pickling, soil treatment, Foliar application or strain injection in trees)
• d) of climatic factors, eg. As temperature, rainfall, as well also day length and light intensity
• e) the soil condition (including fertilization),
• f) the formulation of the active substance and finally
• g) the concentrations of the active substance used.

From the series of various applications of the invention Plant growth regulators of the formula Ia in plant cultivation, in agriculture and horticulture, some are mentioned below.  

A. With the compounds which can be used according to the invention, the vegetative Strong inhibition of plant growth, which is particularly in a reduction of the length growth expresses. The treated plants accordingly have a stocky growth; also is a darker one Leaf staining observed.

As advantageous for the practice proves a reduced intensity of Growth of grasses on roadsides, hedges, channel embankments and on lawns such as park, sport and fruit plants, ornamental lawns and Airfields, so that the labor and costly lawn cuts reduced can be.

Of economic interest is also increasing the stability of susceptible crops such as cereals, corn, sunflowers and Soy. Reduce the stem shortening and stalk reinforcement caused thereby or eliminate the risk of "storing" (kinking) of Plants under unfavorable weather conditions before harvest.

Also important is the use of growth regulators for inhibition the length growth and the temporal change of maturity course in cotton. This will be a fully mechanized harvesting this important crop.

In fruit and other trees can be with the growth regulators Save on cutting costs. In addition, the alternation of fruit trees be broken by growth regulators.

By applying growth regulators, lateral branching can also be achieved the plants are increased or inhibited. There is interest if z. B. in tobacco plants, the formation of lateral shoots  Stocks by treatment with compounds of the invention in the fall Although well-stocked, but not too lush to go into the winter. This can increase the sensitivity to frost and - because of the relatively low leaf or plant mass - the infestation with different Diseases (eg fungal disease) can be prevented. The inhibition Vegetative growth also allows for many crops a denser planting of the soil, so that an extra yield can be achieved based on the floor area.

B. With the growth regulators can be increased yield both on plant parts as well as plant ingredients. That's the way it is, for example possible, growing larger amounts of buds, flowers, Leaves, fruits, seeds, roots and tubers to induce the sugar content in sugar beets, sugarcane and citrus fruits increase the protein content in grains or soy or increase Rubber trees to stimulate increased latex flow.

The salicylic acid derivatives of the formula I can increase yields by interventions in the plant metabolism or by promotion or inhibition of vegetative and / or generative growth.

C. Finally, plant growth regulators can be used to treat both Shortening or lengthening the stages of development as well as an acceleration or delaying the maturity of harvested plant parts reach before or after the harvest.

Of economic interest, for example, the harvest relief, by the time-concentrated decrease or decrease the adhesion to the tree with citrus fruits, olives or others Species and varieties of core, stone and peel fruit is made possible. The same mechanism, ie the promotion of training of Separating tissue between fruit or leaf and shoot part of the plant is also for a good controllable defoliation of crops such as For example, cotton is essential.

D. Growth regulators can further reduce the water consumption of plants. This is particularly important for agricultural land, which must be artificially irrigated at a high cost, eg. B. in arid or semi-arid areas. By using the substances according to the invention, the intensity of the irrigation can be reduced and thus carry out a more cost-effective management. Under the influence of growth regulators, there is a better utilization of the existing water, because, inter alia
- the opening width of the stomata is reduced
- A thicker epidermis and cuticle are formed
- the rooting of the soil is improved and
- The microclimate in the plant population is favorably influenced by a more compact growth.

The active compounds of the formula I to be used according to the invention can be Crops both from the seed (as seed dressing) and over the ground, d. H. through the root and - most preferably - by Be injected over the sheet.

Due to the high plant compatibility, the application rate can be strong be varied.

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g, preferably 0.01 to 10 g, per kilogram of seed needed.

For foliar and soil treatment are generally gifts from 0.001 to 10 kg / ha, preferably 0.01 to 3 kg / ha, in particular 0.01 to 0.5 kg / ha as enough to look at.

The application of the herbicidal compositions or of the active ingredients can be carried out in the pre-emergence phase. or post-emergence. Are the active ingredients for certain Crop plants less compatible, so may application techniques be applied, in which the herbicidal agents using the sprayers be sprayed so that the leaves of sensitive crops if possible, are not taken while the active ingredients on the leaves underneath growing unwanted plants or the uncovered Floor area (post-directed, lay-by).  

The application rates of active ingredient are depending on the target, season, Target plants and growth stage 0.001 to 3.0, preferably 0.01 up to 1.0 kg / ha of active substance (see above).

In view of the versatility of the application methods, the Compounds according to the invention or agents containing them in one further number of crops for the removal of unwanted plants be used. For example, the following cultures may be considered:

Botanical name German name Allium cepa onion Pineapple comosus pineapple Arachis hypogaea Peanut Asparagus officinalis asparagus Beta vulgaris spp. altissima sugar beet Beta vulagis spp. rapa mangel Brassica napus var. Napus rape Brassica napus var. Napobrassica Turnip Brassica rapa var. Silvestris rape Camellia sinensis Teestrauch Carthamus tinctorius Safflower - safflower Carya illinoinensis Pecan Citrus limon lemon Citrus sinensis Orange, orange Coffea arabica (Coffea canephora, Coffea liberica) coffee Cucumis sativus cucumber Cynodon dactylon Bermuda grass Daucus carota carrot Elaeis guineensis oil palm Fragaria vesca strawberry Glycine max Soybean Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflower Hevea brasiliensis Para rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potato Juglans regia walnut tree Lens culinaris lens Linum usitatissimum flax Lycopersicon lycopersicum tomato Malus spp. Apple Manihot esculenta manioc Medicago sativa alfalfa Musa spp. Fruit and flour banana Nicotiana tabacum (N. rustica) tobacco Olea europaea olive tree Oryza sativa rice Phaseolus lunatus butterbean Phaseolus vulgaris bush bean Picea abies Rotfichte Pinus spp. pine Pisum sativum garden pea Prunus avium sweet cherry Prunus persica peach Pyrus communis pear Ribes sylvestre Red currant Ricinus communis castor-oil plant Saccharum officinarum sugarcane Secale cereal rye Solanum tuberosum potato Sorghum bicolor (see vulgare) sorghum Theobroma cacao cacao Trifolium pratense Red clover Triticum aestivum wheat Triticum durum durum wheat Vicia faba Broad bean Vitis vinifera grapevine Zea mays Corn

To broaden the spectrum of action and to achieve synergistic Effects, the compounds I according to the invention with numerous Representatives of other herbicidal or growth-regulating active ingredient groups mixed and applied together. For example, come as Mixing partners diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, Triazines, amides, ureas, diphenyl ethers, triazinones, uracils, Benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acid derivatives, Aryloxy, heteroaryloxyphenoxypropionic acids and their salts, Esters and amides and others.  

In addition, it may be useful to use the compounds I alone or in Combination with other herbicides also with other pesticides together with, for example, funds for Control of pests or phytopathogenic fungi or bacteria. From Interest is also the miscibility with mineral salt solutions, which for Eliminate nutritional and trace element deficiencies. It It is also possible to add non-phytotoxic oils and oil concentrates.

synthesis Examples

The instructions given in the Synthesis Examples below were obtained with appropriate modification of the starting compounds for recovery further compounds I and II used. The compounds thus obtained are listed in the tables below with physical information. Compounds without this information can be taken from the corresponding Synthesize educts analogously. The reproduced in Table 3 Structures describe particularly preferred active compounds of the formula I.

Example 1 6-Phenylsalicylsäuremethylester Version 1

58 g (0.5 mol) of methyl acetoacetate are added to a solution of 0.5 g of sodium hydride in 100 ml of dried ethanol, 66 g (0.5 mol) are added dropwise Cinnamaldehyde quickly and stirred for about 10 h at room temperature. The mixture is then saturated at 0 ° C with dry HCl glass and then about 1 d at room temperature (20 ° C) stirred. Remove the solvent and distilling the remaining residue in vacuo, initially HCl Glass is released. The fractions passing from 115 to 165 ° C / 0.2 mbar are combined and purified on silica gel (elution with toluene / cyclohexane) Chromatograph. This gives 33.7 g of a yellow oil as an intermediate. This is dissolved in 150 ml of methylene chloride and treated at 0 ° C with a Solution of 22.9 g (0.14 mol) of bromine in 150 ml of glacial acetic acid, warms slowly and boil for an hour under reflux. The reaction solution becomes too Poured 200 ml of methylene chloride and 500 ml of water. The organic phase is separated and worked up in the usual way. You get one yellow solid as an intermediate for further processing in 400 ml Methyl t.-butyl ether is dissolved. 55 g (0.56 mol) are added Triethylamine and refluxed for 5 h. Then add 300 ml Water, separates the organic phase and works in the usual way on. The residue is distilled at 100 to 114 ° C / 0.2 mbar. Yield: 11.9 g.  

Variant 2

To dissolve 57 g (0.15 mol) of 4- (Triphenylphosphoranyliden) -acetessigsäuremethylester in 700 ml of THF are added in portions under a nitrogen atmosphere 8.55 g (0.3 mol) of sodium hydride (85%) and then heated to about 35 ° C. At this temperature, 20 g are added in portions (0.15 mol) of cinnamaldehyde and then added 5-10 drops of water, wherein the reaction is initially exothermic and must be cooled. It will be now continue at 35 ° C until the ylide is fully reacted (DC control, approx. 12-14 h). The reaction mixture is now 10% Hydrochloric sour and after adding 1 l of water with four times extracted 150 ml of ether. The combined ether phases are mixed with 200 ml Shaken out water and 200 ml of saturated saline solution and after Drying concentrated over sodium sulfate. The remaining black-brown Residue is taken up with 400 ml of methyl tert-butyl ether and several Cooked for hours. After cooling, the insoluble residue is filtered (Triphenylphosphine oxide) and concentrated the filtrate. The remaining one Oil is purified by chromatography on silica gel (eluent: Toluene / ethyl acetate with gradually increasing ethyl acetate content). All Fractions before the triphenylphosphine oxide are combined and analogously above Procedure brominated, flavored and worked up. This gives 14.5 g of Product.

Analogously, for example, the following compounds can be prepared become:

Methyl 6- (3,5-dichlorophenyl) salicylate, 1 H-NMR (CDCl₃: δ = 3.58 (s; 3H); 6.70 (d; 1H); 7.05 (d; 1H); 7,10 (d; 2H); 7.25-7.40 (m, 2H); 10.85 (s; 1H).

Methyl 6- (2,4-dichlorophenyl) salicylate, 1 H-NMR (CDCl₃: δ = 3.58 (s; 3H); 6.65 (d; 1H); 7.0-7.5 (m; 5H); 11.1 (s, 1H).

example 2 General procedure for the preparation of the salicylic acid derivatives of Formula I

0.073 moles of the respective aromatic 2-hydroxycarboxylic acid are dissolved in Dissolved 320 ml of dried dimethyl sulfoxide and portionwise with 16.4 g (0.146 mol) of potassium tert-butoxide, the temperature of the Reaction mixture rises to about 30 ° C. Cool to room temperature, give  16.8 g (0.073 mol) of 4-methoxy-2-methylsulfonyl-5,6-dihydrofuran [2,3-d] - pyrimidine and stirred for about 1 h at room temperature. The reaction mixture is poured into about 2 liters of cold water, acidified with hydrochloric acid and extracted with methyl tert-butyl ether. After usual work-up The remaining crude product, if necessary, by stirring with a suitable solvent or by chromatography Silica gel to be cleaned.

example 3 General procedure for the preparation of the salicylic acid derivatives of Formula I

5.1 g of potassium hydroxide and 0.08 mol of the respective 2-hydroxycarboxylic acid are dissolved in 80 ml of methanol, stirred for 10 min at room temperature and in Vacuum concentrated. It is then repeated with toluene to dry and this evaporated at 50 ° C in vacuo. The bright red Powder is taken up in 300 ml of dimethyl sulfoxide and at room temperature added in portions with 2.9 g of 80% sodium hydride, wherein a gas evolution occurs. If no gas is released, you drip a solution of 0.08 mol of 4-methoxy-2-methylsulfonyl-5,6-dihydrofuran [2,3-d] pyrimidine in 80 ml of dimethyl sulfoxide and stirred for 0.5 h after. you poured into 2 liters of water, neutralized with acetic acid and washed with methylene chloride. Then it is strongly acidified with hydrochloric acid and repeatedly with Extracted methyl tert-butyl ether. The organic phase is dried over Sodium sulfate and the solvent is evaporated in vacuo. The remaining Substance can be purified by chromatography on silica gel become.

example 4 General procedure for the preparation of aromatic carboxylic acid oxime esters or similar compounds of the formula I.

3.2 mmol of the respective aromatic 2- (4-methoxy-5,6-dihydrofuran [2,3-d] - pyrimidin-2-yl) oxycarboxylic acid are introduced into 20 ml of dimethoxyethane and with 3.2 mmol of sodium hydride, with immediate gas evolution occurs. It is stirred for 1 h at room temperature, cooled to 0 ° C and with 3.5 mmol of oxalyl chloride. The mixture is stirred at 0 ° C for 1 h and then evaporates to remove the excess oxalyl chloride about 30% of the solvent in vacuo. There are now 4.2 mmol of the respective oxime or a comparable hydroxy compound dissolved in 10 ml of dimethoxyethane  and then 3.2 mmol of pyridine at 0 ° C and heated within from 1 h to room temperature. The mixture is poured into 120 ml of cold water poured and extracted with methylene chloride. The organic phase becomes dried over sodium sulfate and concentrated in vacuo. The remaining Substance can be further purified by chromatography on silica gel.

example 5 a) 2-Methoxy-6- (pyrazol-1-yl) -benzonitrile

To a solution of 41.2 g (0.273 mol) of 2-methoxy-6-fluorobenzonitrile (Preparation: J. Heterocycl Chem 25, 1173 (1988) in 50 ml of N, N-dimethylethyleneurea become a solution under nitrogen at 50 ° C of 0.273 mol of sodium pyrazolide (prepared from equimolar amounts Pyrazole and sodium hydride) in 140 ml of N, N-dimethylethyleneurea added dropwise and stirred at 60 ° C for 2 h. After cooling and stirring of the mixture in 4 l of ice water, suction and drying the precipitated Crystals are obtained 37.1 g of the product from the melting point 93-94 ° C.

b) 2-Methoxy-6- (pyrazol-1-yl) benzoic acid O-ethyliminoester

In 68.0 g of a 30% solution of dry HCl glass in ethanol 37.1 g (0.168 mol) of 2-methoxy-6- (pyrazol-1-yl) are added with stirring. Benzonitrile registered at 0 ° C with exclusion of moisture. To Diluting with 20 ml of ethanol, the mixture is 48 h at room temperature stirred, added to 500 ml of ice-water and by adding 2-normal Sodium hydroxide solution and then saturated sodium bicarbonate solution set a pH of 7. After vacuuming and drying the Precipitated crystals are obtained 30.3 g of the product of the melting point 72-73 ° C.

c) 2-Methoxy-6- (pyrazol-1-yl) benzoic acid ethyl ester

29.0 g (0.118 mol) of 2-methoxy-6- (pyrazol-1-yl) benzoic acid O-ethyliminoester and 300 ml of hydrochloric acid are stirred at 50 ° C for 16 h. After this The reaction mixture is cooled 3 times with 100 ml of methylene chloride extracted. After concentration of the extract gives 16.7 g of residue, on silica gel with toluene / ethyl acetate (9: 1) is chromatographed. 13.4 g of the product are obtained from the melting point 159-163 ° C.  

d) 6- (pyrazol-1-yl) -salicylic acid ethyl ester

To a solution of 15.3 g (0.062 mol) of 2-methoxy-6- (pyrazol-1-yl) - Ethyl benzoate in 140 ml of methylene chloride are at 20 to 25 ° C. 200 ml (0.2 mol) of 1 molar Bortribromid solution was added dropwise. Man stirred 10 h at room temperature and then added dropwise at 0 ° C 160 ml of ethanol. you Stirred for 15 min, then removed the solvent at 30 ° C on in vacuo and the residue is stirred with 200 ml of water. you Extract the residue 3 times with 70 ml of diethyl ether, concentrated and the crude product is chromatographed on silica gel with toluene / ethyl acetate. Yield: 8.7 g of the product as an oil. 1 H-NMR (selected Signals): δ = 0.98 (t); 4,10 (q); 6.38; 6.90; 7.10; 7.45 (t); 7.60; 7.70; 10.70 (s).

From this compound, 6- (pyrazol-1-yl) -salicylic acid by Hydrolysis with dilute sodium hydroxide solution (melting point: 175-179 ° C).  

Table 1: Salicylic acid derivatives of the formula II

example 6 Preparation of 2-methylsulfonyl-4-methoxy-5,6-dihydrofuran [2,3-d] - pyrimidine 2-methylthio-4-chloro-5,6-dihydrofuran [2,3-d] pyrimidine

To a suspension of 65.8 g (0.357 mol) of 2-methylthio-4-hydroxy-5,6-dihydrofuran [2,3-d] pyrimidine (Collect. Czech Chem. Commun., 32, 1582 (1967)) in 900 ml of chlorobenzene is added dropwise at 125-130 ° C (1.07 mol) trichloromethyl chloroformate in 3 hrs, wherein three times each added 0.5 ml of DMF becomes. After stirring for 1 hour at 130 ° C, the reaction mixture in Concentrated vacuum and the residue (74 g of oil) chromatographed on silica gel (Toluene-cyclohexane mixture 9: 1). Yield: 17.0 g of the o. G. product of the Mp. 68-71 ° C.

2-methylthio-4-methoxy-5,6-dihydrofuran [2,3-d] pyrimidine

17.0 g (84 mmol) of 2-methylthio-4-chloro-5,6-dihydrofuran [2,3-d] pyrimidine are added in 90 ml of methanol, at 45 ° C 21.1 g (0.171 mol) 30% Sodium methylate solution was added dropwise and stirred for 2 hrs. At 50 ° C. To Neutralizing to pH 6 with a little glacial acetic acid, the reaction mixture is in Stirred in 350 ml of ice-water. After aspirating, washing with water and Drying gives 15.1 g of o. G. Product of the mp. 90-92 ° C.

2-methylsulfonyl-4-methoxy-5,6-dihydrofuran [2,3-d] pyrimidine

In a mixture of 15.1 g (76 mmol) of 2-methylthio-4-methoxy-5,6-dihydrofuran Pass [2,3-d] pyrimidine in 120 ml of methylene chloride and 76 ml of water Chlorine is added at 0 ° to 5 ° C. with stirring until the reaction mixture turns pale is colored yellow. After 30 minutes of stirring, the organic phase separated and the water phase extracted with 100 ml of methylene chloride. The The combined organic phases are dried and concentrated. From the The residue (16.7 g) is isolated after chromatography on silica (toluene). Ethyl acetate mixture 4: 1) 5.5 g of the o. Products of the melting point 122-24 ° C.

example 7 Preparation of 2-methylsulfonyl-4-methyl-5,6-dihydrofuran [2,3-d] pyrimidine

Analogously to Example 6 is obtained from 2-methylthio-4-methyl-5,6-dihydrofuran [2,3-d] pyrimidine (Collect. Czech Chem. Commun. 32, 1582 (1967)) the above product of mp. 85-90 ° C in 80% yield.  

Similarly, the sulfones listed in Table 2 are III available.

Table 2

example 8 3- (4-Methoxy-5,6-dihydrofuran [2,3-d] pyrimidin-2-yl) oxy-biphenyl-2-ca-rbonsäure (Compound No. 5,001)

To 1.50 g (7 mmol) of 6-phenylsalicylic acid in 15 ml of dry dimethyl sulfoxide 1.57 g (14 mmol) of potassium tert-butoxide are added and Stirred for 1 hour at room temperature. After addition of 1.61 g (7 mmol) 2-methylsulfonyl-4,6-dimethoxy-5,6-dihydrofuran [2,3-d] pyrimidine becomes Reaction mixture stirred for 48 hours at room temperature and then to 300 ml Water to which 2.5 ml of phosphoric acid are added, added. The rainfall is isolated, pasted with toluene and filtered with suction. From the crude product is obtained by stirring for one hour in a mixture of 0.5 ml Phosphoric acid and 10 ml of water after suction and drying 1.3 g of the above Product of the Mp .: 176-178 ° C.  

Table 3: Compounds I in which Y is carbon

Table 4: Compounds I in which Y is nitrogen

Table 5: Compounds I in which Y is carbon and R⁴ represents an optionally substituted phenyl radical

Table 6: Compounds I in which R⁴ represents a heterocyclic radical and Y represents carbon

Table 6 (continued)

Examples of use for herbicidal activity

The herbicidal action of the carboxylic acid derivatives of the formula I was by Greenhouse experiments show:

To cultivate the test plants were plastic flower pots with 300 cc Content and loamy sand with about 3% humus as substrate. The seeds of Test plants were sown flat by species separately.

In pre-emergence treatment, the processed active ingredients became immediate then applied to the earth's surface. They were here in water as Dispersing agent suspended or emulsified and by means of finely distributing Nozzles sprayed. After applying the agents, the vessels became light irrigated to start germination and growth. After that, the Vessels covered with transparent plastic hoods until the plants had grown. This cover promotes a uniform germination of Test plants, if not affected by the active substances.

For the post-emergence treatment, the test plants were changed according to Growth form first grown to a stature height of 3 to 15 cm and only then with the active ingredients suspended in water or emulsified treated. The test plants were either sown directly and in the the same vessels were raised or they were separated as seedlings bred and placed in the test vessels a few days before treatment transplanted. The application rate for postemergence treatment was 0.06 kg Active ingredient / ha a. S. A cover was omitted during the post-emergence treatment.

The test vessels were placed in the greenhouse, with heat-loving Species warmer areas (20 to 35 ° C) and more temperate for those Climates 10 to 25 ° C were preferred. The trial period extended over 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.

The rating was based on a scale from 0 to 100. 100 means no Rising of the plants or complete destruction of at least the above ground Parts and 0 no damage or normal growth.  

The plants used in the greenhouse experiments were composed of the following species:

Claims (7)

1. salicylaldehyde and salicylic acid derivatives and their sulfur analogues of the formula I, in which the substituents have the following meanings:
R¹ is hydrogen
a succinyliminooxy group;
a 5-membered heteroaromatic containing one to three nitrogen atoms, which may carry one to four halogen atoms and / or one to two of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ Haloalkoxy and / or C₁-C₄-alkylthio;
a radical -OR⁵ or a radical ON = CR⁶R⁷, in which
R⁵ is hydrogen, an alkali metal cation, the equivalent of an alkaline earth metal cation or an organic ammonium;
a C₃-C₁₂-cycloalkyl group which can carry one to three C₁-C₄-alkyl radicals;
a C₁-C₁₀-alkyl group which may carry one to five halogen atoms and / or one of the following radicals: C₁-C₄-alkoxy, C₁-C₄-alkylthio, cyano, C₁-C₈-alkylcarbonyl, C₁-C₈-alkoxycarbonyl, C₃-C₁₂ - Cycloalkyl, phenyl, phenoxy or phenylcarbonyl, wherein the aromatic radicals in turn may carry one to five halogen atoms and / or one to three of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁- C₄-haloalkoxy and / or C₁-C₄alkylthio;
a C₁-C₁₀-alkyl group which can carry one to five halogen atoms and carries one of the following radicals: a 5-membered heteroaromatic containing one to three nitrogen atoms which can carry one to four halogen atoms and / or one to two of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and / or C₁-C₄-alkylthio;
a C₂-C₆ alkyl group which carries in the 2-position one of the following radicals: C₁-C₆ alkoxyimino, C₃-C₆ alkenyloxyimino, C₃-C₆ haloalkenyloxyimino or benzyloxyimino;
a C₃-C₆ alkenyl or a C₃-C₆ alkynyl group, which groups may in turn carry one to five halogen atoms;
unsubstituted or mono- to trisubstituted by C₁-C₄-alkyl or C₁-C₄-alkoxy or mono- to fivefold by halogen-substituted phenyl;
means, and
R⁶ and R⁷
C₁-C₂₀-alkyl which may carry a phenyl radical, a C₁-C₄-alkoxy and / or a C₁-C₄-alkylthio group, phenyl or together a C₃-C₁₂-alkylene chain which may carry one to three C₁-C₃-alkyl groups , mean;
R² is C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, or halogen;
R³ is hydrogen or together with R⁴ is a group CH₂ = CH-CH = CH₂ or N = CH-CH = CH₂;
R⁴ is hydrogen, halogen, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, aryloxy, C₁-C₄-haloalkyl, formyl, C₁-C₈-alkoxycarbonyl;
an optionally monosubstituted to trisubstituted, in the case of halogen as a substituent one to five times substituted phenyl radical wherein R⁸-R¹²
Hydrogen, halogen, cyano, nitro;
a C₃-C₆ alkenyl, C₃-C₆ alkenyloxy, C₃-C₆ alkynyloxy or a C₃-C₆ alkynyl groups, which groups may in turn carry one to five halogen atoms;
Di-C₁-C₄-alkylamino, C₃-C₈-cycloalkyl, which may carry one to three C₁-C₄-alkyl radicals;
C₁-C₁₀ alkoxycarbonyl, C₁-C₄ alkylthio;
a phenoxy group, wherein the aromatic radical may carry one to five halogen atoms and / or one to three of the following radicals, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄ alkylthio;
a C₁-C₁₀ alkyl or alkoxy group which may carry one to five halogen atoms and / or one of the following radicals: C₁-C₄-alkoxy, C₁-C₄-alkylthio, phenyl or phenoxy, wherein the aromatic radicals in turn have one to five halogen atoms and / or one to three of the following radicals: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio;
mean;
a 5-membered heteroaromatic, having two to four nitrogen atoms or one to two nitrogen atoms and additionally a sulfur or oxygen atom in the ring, which can carry one to three halogen atoms and / or one to three of the following radicals: nitro, cyano, C₁-C₄ -Alkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkyl or phenyl which is unsubstituted or substituted by one to three halogen atoms and / or one to three methyl groups;
a thienyl radical which may carry one to three halogen atoms and / or one to three of the following radicals: C₁-C₄-alkyl, C₁-C₂-haloalkyl or nitro;
or oxygen when Y is nitrogen and n is 1;
n 1 when Y is carbon or when Y is nitrogen and R⁴ is oxygen and 0 when Y is nitrogen and R⁴ is not oxygen;
X oxygen or sulfur;
Y is nitrogen when R³ is hydrogen and n is 0 or when R⁴ is oxygen and n is 1; Carbon, when R³ and R⁴ together represent a group CH₂ = CH-CH = CH₂ or N = CH-CH = CH₂ or carbon, when R³ is hydrogen and n is 1;
and environmentally acceptable salts of compounds I. 2. A herbicidal composition containing a compound of the formula I according to claim 1. 3. A method for controlling undesired plant growth, characterized that the unwanted plants and / or their Habitat with a herbicidally effective amount of a derivative I according to Claim 1 treated. 4. means for influencing plant growth, containing Salicylaldehyde or salicylic acid derivative of the formula I according to Claim 1. 5. A method for regulating plant growth, characterized that a bioregulatory effective amount of a salicylaldehyde or Salicylsäurederivats of the general formula I according to Claim 1 to the seeds, the plants and / or their habitat allow to act. 6. New sulfones of the general formula III in which the substituents have the following meanings:
R² is C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄-haloalkoxy or halogen
R¹³ C₁-C₁₂-alkyl, unsubstituted or substituted by alkyl, halogen or alkoxy phenyl. 7. salicylaldehyde and salicylic acid derivatives of the formula I according to Claim 1, wherein R² is methoxy and X is oxygen and Y and the radicals R¹, R³ and R⁴ have the meaning given in claim 1.