DE102006014722A1 - Preparation of 2-ethynylphenylacetamide derivative, useful as intermediates for plant protection agent such as fungicide, comprises reacting alkynyl-anilide compound in the presence of barium hydroxide in non-polar acetone diluent - Google Patents

Abstract

Preparation of 2-ethynylphenylacetamide derivative (I) comprises reacting an alkynyl-anilide compound (II) in the presence of barium hydroxide in a non-polar acetone diluent. Preparation of 2-ethynylphenylacetamide derivative of formula (I) comprises reacting an alkynyl-anilide compound of formula (II) in the presence of barium hydroxide in a non-polar diluent. R 1>H, F, Cl, 1-4C-(halo)alkyl, 1-4C-alkoxy or 1-4C-alkylthio; and R 2>H, 1-4C-alkyl or 1-4C-alkoxy. An independent claim is included for the preparation of a carboxamide compound of formula (III) comprising: preparing (I); reacting (I) with a thiophene dioxide compound of formula (IV) to obtain biphenyl amide compound of formula (V); separating the nitrogen protection group of formula (-C(O)R 2>) in (V) to obtain a biphenyl amine compound of formula (VI); and reacting (VI) with a carboxylic acid derivative (VII) of formula A-C(O)-Y 1>, optionally in the presence of a catalyst, condensation agent, acid binder and a diluent, to obtain (III). X 1>, X 2>F, Cl or Br; A : pyrazole-, thiazole-, phenyl-, thiophene-, oxathiine-, pyrrole- or furan derivatives of formula (A1-A7), respectively; R 3>1-3C-alkyl; R 4>, R 7>, R 10>H or Z; Z : halo, 1-3C-alkyl or 1-3C-haloalkyl containing 1-7 F, Cl and/or Br; R 5>H, halo or 1-3C-alkyl; R 6>H, halo, 1-3C-alkyl, amino, mono- or di(1-3C-alkyl)amino; R 8>, R 9>Z; and Y 1>halo or OH. [Image] [Image] [Image] [Image] [Image].

Description

The The present invention relates to a new method of manufacturing of substituted 2-ethynylphenylacetamides and a process for producing fungicidally active carboxamides.

It It is already known that 2-Ethinylphenylacetamide as intermediates for crop protection agents and fungicides are suitable (see WO 2006/024388). It is known whose production from the methylbutynol derivatives by retro-Favorskii reaction and Base-catalyzed acetone cleavage (see WO 2006/024388). This is preferably done by alkali metal hydroxides or carbonates (see. also J. Org. Chem. 1994, 59, 5818; ibid. 1992, 57, 6998; ibid. 1998, 63, 1109; Synthesis 1996, 589; Chem. Soc. Jpn. 1990, 63, 640).

adversely however, this process is for industrial production poor yield, which results in a number of simultaneous By-products is due. For example, intramolecular cyclization leads to the formation of indoles come. It is e.g. known to be sodium, potassium and cesium bases to a smooth ring closure of 2-alkynylanilines and -anilides lead to indoles (Angew Chem 2000, 112, 2607; Heterocycles 1996, 43, 2741; ibid. 1986, 24, 31). Further side reactions are the deacylation of the Aniline and the elimination of water from the Methylbutinolgruppierung. This requires elaborate Cleaning procedure to the desired Product for the next Be able to use stage.

Farther It is known that 2-Ethinylphenylacetamide by reaction of 2-iodoaniline and ethynyltrimethylsilane (Tetrahedron Lett. 1989, 30, 2581), wherein after Sonogashira coupling the trimethylsilyl protecting group is split off with potassium fluoride. However, ethynyltrimethylsilane is very expensive and therefore comes for the technical production big Tonnages out of the question.

The Object of the present invention was therefore in the provision a new process that the ethinylanilides in good purity and yields.

in welcher
R¹ für Wasserstoff, Fluor, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio oder C₁-C₄-Halogenalkyl steht, und
R² für Wasserstoff, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy steht,
dadurch gekennzeichnet, dass man (Verfahren A)
aus Alkinyl-Aniliden der Formel (II)

in welcher R¹ und R² die oben angegebenen Bedeutungen haben,
in Gegenwart von Bariumhydroxid in unpolaren Verdünnungsmitteln Aceton abspaltet.The present invention thus provides a process for the preparation of 2-ethynylphenylacetamides of the general formula (I)

in which
R ^{1 is} hydrogen, fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -haloalkyl, and
R ^{2 is} hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,
characterized in that (method A)
from alkynyl anilides of the formula (II)

in which R ¹ and R ^{2 have} the meanings given above,
in the presence of barium hydroxide in non-polar diluents acetone splits off.

Surprisingly was found from a variety of bases and solvents that the use of barium hydroxide as the base to a particularly selective Reaction progressed. Contrary to expectation, indole formation was practically not observed. By stopping the reaction after consumption of the starting material can be also largely prevent the deacylation. You get so pure product in much better yields than before of the technique.

used N- [4-fluoro-2- (3-hydroxy-3-methylbut-1-ynyl) phenyl] acetamide as the starting material and barium hydroxide as the base, so the process of the invention A can be illustrated by the following equation scheme.

Prefers is the implementation the method according to the invention A using starting materials in which the radicals indicated each have the following meanings. The preferred, most preferred and especially preferred meanings apply to all compounds, in which the respective residues occur.

R ¹ is preferably hydrogen.

R ¹ furthermore preferably represents fluorine, where fluorine is particularly preferably in the 3-, 4- or 5-position, very particularly preferably in the 3- or 5-position, in particular in the 5-position of the respective compound [cf. eg formula (I)].

R ¹ furthermore preferably represents chlorine, chlorine being particularly preferably in the 3- or 5-position of the respective compound.

R ¹ also preferably represents methyl or iso-propyl, with methyl or iso-propyl particularly preferably being in the 6-position of the respective compound.

R ¹ furthermore preferably represents trifluoromethyl, trifluoromethyl being particularly preferably in the 4- or 5-position of the respective compound.

R ¹ furthermore preferably represents methoxy or methylthio, with methoxy or methylthio being particularly preferably in the 4-, 5- or 6-position of the respective compound.

R ² is preferably hydrogen, methyl, ethyl, iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy or tert-butoxy.

R ² particularly preferably represents methyl, tert-butyl, methoxy or tert-butoxy.

R ² is very particularly preferably methyl.

Prefers is achieved by the method according to the invention A N- (2-ethynyl-4-fluoro-phenyl) -acetamide. This is called as Starting materials N- [4-fluoro-2- (3-hydroxy-3-methylbut-1-ynyl) phenyl] acetamide used.

The during execution the method according to the invention A as starting materials to be used alkynyl anilides of the formula (II) are known (see WO 2006/024388).

The inventive method A is preferred in a diluent carried out, the higher boils as acetone to keep it from the reaction mixture can be removed, optionally under reduced pressure.

questioning all come inert to bases, such as aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, Ethers, such as 1,2-dimethoxyethane and dioxane, or amides, such as dimethylformamide, Dimethylacetamide, N-methylpyrrolidinone. Preferably usable are nonpolar solvents like Methylcyclohexane, cyclohexane, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene. Particularly preferred are toluene and xylene.

In carrying out the process A according to the invention is generally carried out at temperatures between 40 ° C and 150 ° C. The temperature is chosen as low as possible to prevent side reactions but high enough so that the reaction is still fast enough and the liberated acetone can optionally be distilled off. Preference is given to working between 80 ° C and 130 ° C, most preferably between 95 ° and 125 ° C.

at the implementation the method according to the invention A is used to 1 mole of alkynyl anilide of the formula (II) in general between 0.001 mol and 2.0 mol of base, preferably between 0.01 Mole and 1 mole. For economic reasons and ecological establish is the catalytic variant particularly preferred. Here you go, for example of 1 mol% barium hydroxide out and gives while the reaction at regular intervals respectively Add small portions again to keep the reaction going to obtain. For example, you can after 1/3 and 2/3 of the total reaction time add in each case 0.5 to 1 mol% of barium hydroxide. Point of time the further addition, so if the reaction rate slows down, can be resolved by analytical reaction tracking, e.g. by thin layer chromatography, determine. The individual reaction rate may depend on Batch size, stirring speed as well as water content and grain size of the used Barium hydroxide.

The barium hydroxide used can be either in anhydrous form or be used as octahydrate. Also intermediate forms of hydration, such as. the monohydrate ("form C200 ") can be used become. It is also possible, the hydrates used are azeotropic before or during the reaction to drain. This can be useful, for example be used if instead of the catalytic variant equimolar amounts of base become.

The 2-Ethinylphenylacetamide are valuable intermediates for the preparation of crop protection agents and fungicides (see WO 2006/024388).

in welcher
R¹ für Wasserstoff, Fluor, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio oder C₁-C₄-Halogenalkyl steht,
X¹ für Fluor, Chlor oder Brom steht,
X² für Fluor, Chlor oder Brom steht,
A für einen der folgenden Reste A1 bis A7 steht:

R³ für C₁-C₃-Alkyl steht,
R⁴ für Wasserstoff, Halogen, C₁-C₃-Alkyl oder C₁-C₃-Halogenalkyl mit 1 bis 7 Fluor-, Chlor- und/oder Bromatomen steht,
R⁵ für Wasserstoff, Halogen oder C₁-C₃-Alkyl steht,
R⁶ für Wasserstoff, Halogen, C₁-C₃-Alkyl, Amino, Mono- oder Di(C₁-C₃-alkyl)amino steht,
R⁷ für Wasserstoff, Halogen, C₁-C₃-Alkyl oder C₁-C₃-Halogenalkyl mit 1 bis 7 Fluor-, Chlor- und/oder Bromatomen steht,
R⁸ für Halogen, C₁-C₃-Alkyl oder C₁-C₃-Halogenalkyl mit 1 bis 7 Fluor-, Chlor- und/oder Bromatomen steht,
R⁹ für Halogen, C₁-C₃-Alkyl oder C₁-C₃-Halogenalkyl mit 1 bis 7 Fluor-, Chlor- und/oder Bromatomen steht,
R¹⁰ für Wasserstoff, Halogen, C₁-C₃-Alkyl oder C₁-C₃-Halogenalkyl mit 1 bis 7 Fluor-, Chlor- und/oder Bromatomen steht,
herstellen, indem man (Verfahren B)

• (1) in einer ersten Stufe aus Alkinyl-Aniliden der Formel (II)
  
  in welcher R¹ und R² die oben angegebenen Bedeutungen haben, in Gegenwart von Bariumhydroxid in unpolaren Verdünnungsmitteln Aceton abspaltet,
• (2) in einer zweiten Stufe die so erhaltenen 2-Ethinylphenylacetamide der Formel (I)
  
  in welcher R¹ und R² die oben angegebenen Bedeutungen haben, mit Thiophendioxiden der Formel (IV)
  
  in welcher X¹ und X² die oben angegebenen Bedeutungen haben, umsetzt,
• (3) in einer dritten Stufe aus den so erhaltenen Biphenylamiden der Formel (V)
  
  in welcher R¹, R², X¹ und X² die oben angegebenen Bedeutungen haben, die Schutzgruppe [-C(=O)R²] am Stickstoff unter sauren oder basischen Bedingungen abspaltet, und
• (4) in einer vierten Stufe die so erhaltenen Biphenylamine der Formel (VI)
  
  in welcher R¹, X¹ und X² die oben angegebenen Bedeutungen haben, mit Carbonsäure-Derivaten der Formel (VII)
  
  in welcher A die oben angegebenen Bedeutungen hat und Y für Halogen oder Hydroxy steht, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.

Thus, fungicidally active carboxamides (cf., WO 03/070705) of the formula (III)

in which
R ^{1 is} hydrogen, fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -haloalkyl,
X ^{1 is} fluorine, chlorine or bromine,
X ^{2 is} fluorine, chlorine or bromine,
A is one of the following radicals A1 to A7:

R ^{3 is} C ₁ -C ₃ -alkyl,
R ^{4 is} hydrogen, halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
R ^{5 is} hydrogen, halogen or C ₁ -C ₃ -alkyl,
R ^{6 represents} hydrogen, halogen, C ₁ -C ₃ -alkyl, amino, mono- or di (C ₁ -C ₃ -alkyl) -amino,
R ^{7 is} hydrogen, halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
R ^{8 is} halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
R ^{9 is} halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
R ^{10 is} hydrogen, halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms,
by making (method B)

• (1) in a first stage of alkynyl anilides of the formula (II)
  
  in which R ¹ and R ^{2 have} the abovementioned meanings, acetone is split off in the presence of barium hydroxide in non-polar diluents,
• (2) in a second step, the thus obtained 2-ethynylphenylacetamides of the formula (I)
  
  in which R ¹ and R ^{2 have} the meanings given above, with thiophene dioxides of the formula (IV)
  
  in which X ¹ and X ^{2 have} the meanings given above,
• (3) in a third step from the resulting biphenylamides of the formula (V)
  
  in which R ¹ , R ² , X ¹ and X ^{2 have} the meanings given above, the protective group [-C (= O) R ² ] on the nitrogen cleaves under acidic or basic conditions, and
• (4) in a fourth step, the biphenylamines of the formula (VI) thus obtained
  
  in which R ¹ , X ¹ and X ^{2 have} the meanings given above, with carboxylic acid derivatives of the formula (VII)
  
  in which A has the abovementioned meanings and Y is halogen or hydroxyl, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a Ver converts fertilizer.

Prefers is the implementation the method according to the invention B using starting materials in which the radicals indicated each have the following meanings. The preferred, most preferred and especially preferred meanings apply to all compounds, in which the respective residues occur.

R ¹ and R ² have the preferred, particularly preferred and most preferred meanings given above
X ¹ is preferably fluorine.
X ¹ is also preferably chlorine.
X ¹ is also preferably bromine.
X ² is preferably fluorine.
X ² is also preferably chlorine.
X ² is also preferably bromine.
A is preferably A1, A2, A3, A4 or A5.
A particularly preferably represents A1 or A2.
R ³ is preferably methyl.
R ⁴ is preferably iodine, methyl, difluoromethyl or trifluoromethyl.
R ⁴ particularly preferably represents methyl, difluoromethyl or trifluoromethyl.
R ⁵ is preferably hydrogen, fluorine, chlorine or methyl.
R ⁵ particularly preferably represents hydrogen or fluorine.
R ⁶ is preferably hydrogen, chlorine, methyl, amino or dimethylamino.
R ⁶ particularly preferably represents methyl.
R ⁷ is preferably methyl, difluoromethyl or trifluoromethyl.
R ⁸ is preferably chlorine, bromine, iodine, methyl, difluoromethyl or trifluoromethyl.
R ⁸ particularly preferably represents iodine, difluoromethyl or trifluoromethyl.
R ⁹ is preferably bromine or methyl.
R ⁹ particularly preferably represents methyl.
R ¹⁰ is preferably methyl or trifluoromethyl.
R ¹⁰ particularly preferably represents methyl or trifluoromethyl.
Y is preferably chlorine or hydroxy.

The first stage of method B corresponds to the method according to the invention A and is performed according to the above description.

The remaining reaction steps and their implementation are known (vg. WO 2006/024388).

The inventive method for producing biphenylamines and for producing fungicidal effective carboxamides are described in the examples below, which further illustrate the above description. The examples however, are not in a limiting sense Way to interpret.

Preparation Examples

example 1

100 g (0.425 mol, 99.9%) of N- [4-fluoro-2- (3-hydroxy-3-methylbut-1-yn-1-yl) phenyl] acetamide are placed under argon in 500 ml of toluene and for 30 minutes cooked on a water, with 60 ml of toluene were removed.

26.7 g of "barium hydroxide, anhydrous C200" (0.148 mol, 95% pure, contains 0.8 equivalents of water) are introduced into 500 ml of toluene and boiled for 30 minutes on a water, with 70 ml of toluene abgezo be gene.

The 95 ° C warm solution of the N- [4-fluoro-2- (3-hydroxy-3-methylbut-1-yn-1-yl) phenyl] acetamide will be over within a minute a funnel to the 102 ° C be called Barium hydroxide suspension and heated with the preheated bath. At 104 ° C starts a slight frothing with reflux and a quick one Distillation of the released acetone in the water separator. Three times 70 ml were taken within 20 minutes, the Internal temperature 108 ° C has reached. The thin-layer chromatogram (DC) shows 30% sales. There are then distilled off a further 140 ml and replaced with fresh toluene. After a total of 40 minutes shows the DC 70% sales. There are then distilled off a further 140 ml and replaced with fresh toluene. After a total of 60 minutes shows the DC 90% conversion (internal temperature 110 ° C).

To a total of 80 minutes we use the reaction mixture with an ice bath cooled to room temperature, over a Fritted with suction, washed with 300 ml of toluene and 400 ml Shaken out water. The aqueous Phase and the Mulmphase are still twice with 100 ml of toluene and 50 ml of ethyl acetate extracted. The combined organic phases are dried and evaporated in vacuo.

you receives 72.2 g slightly light brownish Crystals in 91.9% purity vs. standard and 88.2% yield of Theory.

Example 2

69.8 g (0.3 mol, 99.9%) of N- [4-fluoro-2- (3-hydroxy-3-methylbut-1-yn-1-yl) phenyl] acetamide and 0.55 g of "barium hydroxide, anhydrous C200 "(1 mol%; 90% pure; C200; contains 1 equivalent Water) are placed in 420 ml of xylene and heated to 120 ° C. After 40 minutes, it is at 105 ° C add another 0.55 g (1 mol%) of barium hydroxide, heated again to 120 ° C and after 80 minutes again at 105 ° C 133 mg barium hydroxide (0.24 mol%). It is stirred for a further 30 minutes at 120 ° C. During this time were total 7 g of liquid distilled off.

you cools down 68 ° C, Add 150 ml of water and stir at 52 ° C out. Add 12 g of Celite, stir for 10 minutes and soak in 52 ° C from. The residue is twice at 60 ° C washed warm xylene. The filtrate is separated at 40 ° C from the water phase.

The organic phase is dried and evaporated in vacuo. you receives as a residue 51.3 g (93% yield) of the target compound in 95.1% purity (against Standard) with 2.7% indole compounds.

Example 3

71 g (0.3 mol, 98.5%) of N- [4-fluoro-2- (3-hydroxy-3-methylbut-1-yn-1-yl) phenyl] acetamide and 958 mg of "barium hydroxide Octahydrate "(1 mol%) are submitted under argon in 425 ml of xylene and heated to 120 ° C. After 60 minutes (46% target product, 53% starting material) and 120 minutes (85% Target product, 13% starting material) are again added at 120 ° C each time 951 mg (~ 1 mol%) Barium hydroxide added.

To 4 h can be found in the solution 94% target product and 1.3% starting material. During this time were total 5.7 g of liquid (mainly Acetone) distilled off.

you cools down 72 ° C, Add 8 g of Celite followed by 120 ml of water and stir 52 ° C for 8 minutes out. It sucks at 52 ° C over a -From steps. The residue is twice with 50 ml 50 ° C washed warm xylene. The filtrate is separated at 40 ° C from the water phase. The organic phase is evaporated in vacuo.

you receives as a residue 52.05 g (95% yield) of the title compound in 96.3% purity (vs. standard) with 2.2% indole compounds and 0.5% desacetylated Reactant.

Claims (4)

Process for the preparation of 2-ethynylphenylacetamides of general formula (I)

in which R ^{1 is} hydrogen, fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -haloalkyl, and R ^{2 is} hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, characterized in that (method A) is prepared from alkynyl-anilides of the formula (II)

in which R ¹ and R ^{2 have} the meanings given above, cleaves acetone in the presence of barium hydroxide in non-polar diluents. A method according to claim 1, characterized in that R ^{1 is} hydrogen, fluorine, chlorine, methyl, iso-propyl, trifluoromethyl, methoxy or methylthio, and R ^{2 is} hydrogen, methyl, ethyl, iso-propyl, tert-butyl, methoxy , Ethoxy, iso-propoxy or tert-butoxy. Method according to claim 1 or 2, characterized in that as starting material N- [4-fluoro-2- (3-hydroxy-3-methyl-1-butyryl) -phenyl] -acetamide starts. Process for the preparation of carboxamides of the formula (III)

in which R ^{1 is} hydrogen, fluorine, chlorine, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -haloalkyl, X ^{1 is} fluorine, chlorine or bromine, X ^{2 is} fluorine, chlorine or bromine, A is one of the following radicals A1 to A7:

R ^{3 is} C ₁ -C ₃ -alkyl, R ^{4 is} hydrogen, halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, R ^{5 is} hydrogen, halogen or C ₁ -C ₃ -alkyl, R ^{6 is} hydrogen, halogen, C ₁ -C ₃ -alkyl, amino, mono- or di (C ₁ -C ₃ -alkyl) -amino, R ⁷ is hydrogen, halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, R ^{8 is} halogen, C ₁ -C ₃ -alkyl or C ₁ -C ₃ -haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, R ^{9 is} halogen, C ₁ -C ₃ -alkyl or C ₁ C ₃ haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, R ^{10 is} hydrogen, halogen, C ₁ -C ₃ alkyl or C ₁ -C ₃ haloalkyl having 1 to 7 fluorine, chlorine and / or bromine atoms, characterized in that (method B) (1) in a first stage from alkinyl anilides of the formula (II)

in which R ¹ and R ^{2 have} the abovementioned meanings, acetone is split off in the presence of barium hydroxide in nonpolar diluents, (2) in a second stage the 2-ethynylphenylacetamides of the formula (I)

in which R ¹ and R ^{2 have} the meanings given above, with thiophene dioxides of the formula (IV)

in which X ¹ and X ^{2 have} the meanings given above, (3) in a third stage from the resulting biphenylamides of the formula (V)

in which R ¹ , R ² , X ¹ and X ^{2 have} the meanings given above, the protective group [-C (= O) R ² ] on nitrogen under acidic or basic conditions splits off, and (4) in a fourth stage the so obtained biphenylamines of the formula (VI)

in which R ¹ , X ¹ and X ^{2 have} the meanings given above, with carboxylic acid derivatives of the formula (VII)

in which A has the abovementioned meanings and Y is halogen or hydroxyl, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.