DE2410723A1 - PROCESS FOR THE PREPARATION OF AROMATIC HYDROXYCARBONIC ACID CHLORIDES - Google Patents

Description

QBAr-GEIGY

CLBA-GEiQYAG, CH-4002 Base!

or. F. Zumstein Sr. - Dr. E. Arsmann Or.R.Koenig3bsrcor - C \ 'A.''L·; xR. üo.'rbauer

Dr. P. Ζ; ': - .. ϊ- · υϊ. "J-.n.

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8 Munich 2, EiuuhcassJrnße 4 / III

Case 3-8676 +
GERMANY

Process for the production of aromatic hydroxycarboxylic acid chloride

It is known that the conversion of aromatic hydroxycarboxylic acids, especially the o-hydroxycarboxylic acids in their chlorides by means of thionyl chloride with unsatisfactory Yields and leads to impure products. Various attempts have therefore been made to carry out the process Use of Catalysts to Improve. For example according to the method of US patent specification 2,899 ^ 58 tertiary bases and according to the method of German

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see patent 1,026,750 dialkylforinamides used. By using these catalysts it is possible to improve the yields and the purity of the carboxylic acid chlorides obtained however, especially in the case of 2, ^ - hydroxynaphthoic acid after x- / ie before unsatisfactory, so that Purification of the carboxylic acid chlorides before their further implementation is in very few cases dispensed with can. Isolation of the acid chlorides obtained is also indicated because the tertiary bases and dialkylformamides reduce the thermal stability of the acid chlorides. The tertiary bases and the dialkyl formamides provide also ecological problems.

It has now been found that aromatic Hydroxyearboxylic acid chlorides, in particular o-hydroxycarboxylic acid chlorides are obtained in high yield and purity if the reaction is carried out aromatic hydroxycarboxylic acids with thionyl chloride in the presence of quaternary ammonium salts.

Examples of aromatic hydroxycarboxylic acids that may be mentioned are hydroxybenzenecarboxylic acids, such as salicylic acid, halogenated salicylic acids, such as 5-chlorosalicylic acid, 5-5 ¹ IuOr = salicylic acid, 5-chromosalicylic acid, 3j5-dichlorosalicylic acid, alkylated salicylic acids such as I-, 4- or 5- methyl salicyl = acid, J>, 5-dimethylsalicylic acid, also 5-Methoxysalicyl =

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acid, 2,4-dihydroxybenzoic acid., 5- or 5-nitrocalioyl acid, J- or 5-phenylsalicylic acid, ^ -phenylazo-calicyl = acid, hydroxynaphthoic acids, such as 1,2-kydrox; / naphthoe.? ivaren, but in particular 2,3> -hydroxynaphthoic acids before ^ ug. ^ v / eise those of the formula

wherein X is a hydrogen, a halogen atom, an alkoxy, Means nitro or cyano group.

Also l-arylazo-2, ^ -hydroxynaphthalene-carboxylic acids, for example 1- (2 ', 5'-dichlorophenylazo) -2,3-hydroxynaphthoic acid, as well as 2,3-hydroxyphenanthrene carboxylic acid can be used with advantage can be used.

All known tetraalkylammonium salts can be used as quaternary ammonium salts in embossing, i.e. halides, pluoborates, perchlorates, methanesulfonates, p-toluene sulfonates, acetates, Benzoates. Tetraalkylammonium halides of the formula are particularly preferred

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_ Yy _

where X is a halogen atom, H and R are alkyl groups containing 1-6 carbon atoms, R and R ^, alkyl or cycloalkyl groups containing 1-6 carbon atoms or two of the radicals B. R and R ^ together with the N- Atom form a heterocyclic ring. "Alkyl" is also to be understood as meaning alkonyl radicals with a double bond in a position other than the vicinal position to the quaternary nitrogen atom. The alkyl groups can also be branched and contain substituents, for example phenyl radicals.

Examples are:

Tetramethylammonium chloride
Tetramethylammonium bromide
Trimethyl-ethyl-ammonium-chloride
Trimethyl-n-propyl-ammonium-chloride Trimethyl-n-butyl-ammonium-chloride Trimethyl-n-amyl-ammonium-chloride
Trimethyl-isoamyl-ammonium-chloride Trimethyl-cyclopentyl-ammonium-chloride Trimethyl-cyclohexyl-ammonium-chloride Trimethyl-benzyl-ammonium-chloride
-Dimethyl diethyl ammonium chloride
Dimethyl di (η-propyl) ammonium chloride Dimethyl di (n-butyl JajTimoniiim chloride

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Methyl-triethyl-ammonium-chloride, methyl-diethyl-n-propyl-ammonium-chloride, methyl-n-propyl-di- (η-butyl) -ammonium-chlorine! D methyl-tri- (n-butyl) -ammonium-chloride • Tetraethyl-ammonium-chloride Tetra- (n-propyl) -ammonium-chloride triethyl-n-propyl-ammonium-chloride triethyl-n-butyl-ammonium-chloride diethyl-di-isobutyl-ammonium-chloride ethyl-tri- (n -propyl) -ammonium-chloride Aethyl-tri- (n-butyl) -ammonium-chloride Tetra- (n-butyl) -ammonium-chloride Tetra- (n-penty1) -ammonium-chloride Tetra- (n-hexyl) -ammonium-chloride N, N, N ', N'-tetramethylpiperazinium-chloride NjN-dimethyl-morpholinium -chlorid NjNjN ₅ N', N ¹ jN'-hexamethyldiethylenammoniumchlorid Ν, Ν '-Dime thy l-tr: i äthylenendi ammonium- chloride

It is preferred to use 0.1-10 mol%, in particular Oj5-5 mole # of the quaternary ammonium salt per mole of starting acid.

Instead of the quaternary ammonium salts, the corresponding Hydroxides are used, which in turn

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by thionyl chloride into the quaternary ammonium chlorides be transferred.

The reaction is carried out in an inert organic solvent which has sufficient dissolving power for the acid chloride formed.

One uses, for example, aliphatic or aromatic, optionally substituted hydrocarbons such as cyclohexane, eenzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, benzonitrile and nitrobenzene; particularly halogenated aliphatic hydrocarbons are preferred, which have a lower boiling point than thionyl chloride, such as methylene chloride, chloroform, carbon tetrachloride or 1,1,1-trichloroethane. Mixtures can also be used with advantage Use aliphatic and aromatic solvents, e.g. chlorobenzene-chloroform or nitrobenzene-methylene = chloride.

The ratio of carboxylic acid to solvent is expediently chosen such that in the case of soluble acid chlorides the latter goes into solution, or in the case of sparingly soluble acid chlorides, that a well-miscible suspension is present.

To carry out the reaction, the carboxylic acid is expedient

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suspended in bulk in the solvent, possibly dissolved by heating and the catalyst dissolved; thereby vnrd the /. Thionyl chloride was gradually added to the reaction mixture. An excess of thionyl chlorides of 5 to 30 % is used, preferential prices of 5 to 10 ^l p.

The reaction temperature is expediently between 0, preferably between 30 -

The acid chlorides obtained generally have such a high degree of purity that they require no further cleaning., Ie that obtained in the reaction solution or suspension of the acid chlorides directly for further reactions ^ such as ester or amide formation reused v / can ground. Of particular interest are the acid chlorides obtained, which in turn are used for the preparation of 2, 3-Hydroxynaphtolsäurearyliden as coupling components for mono- and disazo pigments.

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example 1

2-hydroxy-3-naphthoc acid chlori d

376.4 g of dry 2-hydroxy-5-naphthoic acid are suspended in 1 liter of dry methylene chloride, and after the addition of 1.66 g of anhydrous tetraethylammonium chloride, the suspension is refluxed for 50 minutes. With vigorous stirring, 273 * 7 S thionyl chloride is then added dropwise within 1.5 to 2 hours. After running in, the mixture is stirred vigorously for about 2 hours under reflux until a clear, dark solution has formed and the evolution of hydrochloric acid has completely ceased. The reaction solution is then cooled to 25 ° C. and nitrogen is passed in until the acid gases that are still present have been completely removed. The acid chloride solution obtained can be processed further without further purification. Since the shelf life of the acid chloride is limited to a few days, it is advisable to carry out this further conversion as quickly as possible. To determine the yield, the product can be isolated as follows: The acid chloride solution is very carefully at 10 - 20 ⁰ C and evaporated to dryness and the solid residue at room temperature under high vacuum dried. About 420 g of crude 2-hydroxy -> - naphthoic acid chloride with a content of about yhfo pure substance (morpholine condensate) are obtained,

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which gives a yield of 95.4% of theory.

Example 2

' Conversion to 2-hydroxy-3-naphthoic acid-4' -benzoylamine oani lid. .- .. ■■.

3 * 7 kg of dry methylene chloride are initially charged, 3 ^ -0 g of N, N-diethylaniline and 403 g of 4-benzoylaminoaniline are added. The suspension obtained is warmed to 30 ^° C. and stirred vigorously for at least 1 hour. Then allowed while keeping the inner temperature at 30 - 35 ⁰ C, the obtained according to Example 1 Säurechlorld cold solution within run in 2-3 hours. Thereafter, the reaction mixture is heated to reflux and refluxed for k hours. Then the mixture is cooled to 3O ⁰ C and slowly passes approximately 55 g Aramoniakgas in the solution until they clearly alkaline (pH 8-9 on moistened pH paper) responding. The mixture is cooled to 25 ⁰ C and filtered there and washed portionwise with a total of 4 kg of methylene chloride. The moist filter cake is then poured into 2 liters of water and the suspension is gradually heated to 80.degree. The methylene chloride still present distills off azeotropically. At 80 ° C, the pH of the suspension becomes little

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Set sodium hydroxide solution to about 8.5, and after a stirring time of about jX) minutes, the whole mixture is filtered. Finally, the finished product is carefully washed with approx. 2.5 liters of hot water, unloaded and dried in a vacuum at Sun - 90 ° C. 690 g of anilide of about 97% purity are obtained, determined by potassium methylate titration, which corresponds to a yield of theory. of 92.5 % (based on 4-benzoylaminoaniline used).

Example 5

Conversion to the N, N ^r -Bis (2,3-hydroxynaphthoyI) -I, 4-phenylene diamide.

102.7 g of 1,4-phenylenediamine are suspended in 995 g of Ν, Ν-di ^ methylacetamide, and the mixture is heated to 7 ° C. As soon as a solution has been obtained, it is cooled to 25 ^° C. and the cold acid chloride solution obtained according to Example 1 is then allowed to run in regularly within 1.5-2 hours. The temperature is kept at 25-3O ⁰ C by slight external cooling. After running in, the mixture is heated to reflux and refluxed for 4 hours. Then you cool it down

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30 ° C and slowly introduces approx. 50 g of ammonia gas into the solution until it is clearly alkaline (pH 8-9 on moistened pH paper). The mixture is cooled further to 15 ° C., filtered and washed in portions with a total of
1.9 kg of methylene chloride. The moist filter cake will
then added to 1 liter of water and the suspension
gradually heated up to 80 ° C. This distills
any methylene chloride still present azeotropically. At 80 ° C., the pH of the suspension is increased to approx. 8.3 with a little sodium hydroxide solution
and, after stirring for about 30 minutes, the whole mixture is filtered. The finished product is finally hot carefully with about 1 liter V / ater washed unloaded and dried in vacuo at 90 - 100 ⁰ C dried. 383.5 g of practically pure goods are obtained, which corresponds to a yield of approx. 90 % of theory. (calculated on the 1,4-phenylenediamine used).

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Example 4

1 (2 ', 5'-dichlorophenylazo) -2,3-hydroxynaphthoic acid chloride.

72.2 g of technically pure 1- (2 ', 5' -dichlorophenylazo) -2,3-hydroxynaphthoic acid are suspended in 400 ml of dry methylene chloride and, after addition of 662 mg of anhydrous tetraethylammonium chloride, the suspension is refluxed. After 1 stundigem cooking the strong reflux (bath temp. Ca. 50 ⁰ C, internal temp. 40-41 ⁰ C) is initiated within 4 hours 31.0 g of technical thionyl chloride gradually shrink. Vigorous stirring and boiling are required throughout the duration of the reaction. After the addition of the thionyl chloride, the mixture is stirred at reflux for at least 6 hours until the elimination of gas has completely ceased. It is then cooled, the thin suspension at 0 ⁰ C., leaves them for about 2 hours. Stirring at this temperature, it was filtered on a suction filter and wash the product first with 20 ml of ice-cold methylene chloride and then with 200 ml Petrolaether. Drying takes place in vacuo at 50 ^° C. 70.5 g of very uniform acid chloride of 97.5% purity are obtained, which is a theoretical yield. of approx. 91%. The content was determined after condensation of the acid chloride with morpholine. The melting point of 208 to 210 ⁰ C and the IR spectrum indicate a practical

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pure product.

If you want to do without the isolation of the acid chloride (which is easily possible with this gentle process), proceed roughly as in example 1, ie the boiling acid chloride suspension is cooled to 25 ^° C., nitrogen is passed in until the acidic gases are completely removed and thus immediately carries out further reactions, e.g. formation of amides or esters.

If you wanted to work in o-dichlorobenzene, the chlorination process must be modified as follows: 72.2 g of technically pure l- (2 ', 5'-dichlorophenylazo-2,5-hydroxynaphthoic acid are suspended in 360 ml of anhydrous o-dichlorobenzene and the suspension at 120 ⁰ C for 30 minutes, stirred vigorously. After cooling to 85 ° C and adding 1.0 g of dry TetrabutylammoniuiBchlorid allowed within 2 hours. 31.0 g of technical thionyl chloride gradually shrink under level. Then, the thin suspension (stopped until the evolution of gas) maintained for 1 hr. at 85 ° C, cooled to 0 ⁰ C, and at least 2 hours. stirred at this temperature. the sparingly soluble acid chloride is filtered on a suction filter, washed with 30 ml of ice-cold dichlorobenzene, then suspended in 300 ml petroleum ether, stirred for 30 minutes, filtered again and washed with 100 ml petroleum ether

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in vacuo at 60-7O ⁰ C. One obtained 68.0 g approx uniform acid chloride of 97.5% purity, which corresponds to a yield of about 87.5% of theory.

Example 5

Acid chloride of 2-hydroxy-3-carboxy-1- [2'-methoxy-5 ^! carbonyl (3 "-trifluoromethylanilido) phenylazo] naphthalene.

25.5 g of practically pure 2-hydroxy-3-carboxy-1- [2'-methoxy-5 ^L carbony1- (3 "-trifluoromethylanilido) phenylazo] -naphthalene are suspended in 200 ml of dry nitrobenzene and the mixture heated to 140 ⁰ C. After half an hour, the suspension is cooled to 75 ° C., 556 mg of anhydrous tetrabutylammonium chloride are added and, with vigorous stirring, 9.7 g of technical thionyl chloride are run in over the course of 4 hours The suspension is ^{cooled to 0 °} C., stirred at this temperature for at least 2 hours and filtered. The moist filter cake is washed with 50 ml of ice-cold carbon tetrachloride, discharged and suspended in 200 ml of petroleum ether. As soon as a homogeneous suspension is obtained, the product is filtered again and wash it with about 100 ml Petrolaether The drying is carried out in vacuo at 70-8O ⁰ C. approximately, giving 23.2 g of dry acid chloride ä about 93% purity, corresponding to a yield of theory of about 82% corresponds.

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The melting point is 251-252 ° C,

As a result of the extremely poor solubility of the azocarboxylic acid neither aliphatic, chlorinated hydrocarbons nor aromatic, chlorinated hydrocarbons (e.g. chlorine and dichlorobenzene) can be used as solvents. This remark applies especially to the pure azocarboxylic acid. When the raw material is heavily contaminated is, the impurities have a catalytic effect on the chlorination and the reaction can under certain circumstances can also be completed in dichlorobenzene; the yield and quality of the acid chloride are but accordingly deeper.

Examples 6-10

The procedure is as in Example 1, but the hydroxycarboxylic acid used is salicylic acid, 3,5-dichlorosalicylic acid, 5-nitrosalicic acid, 6-bromo- or 6-methoxy-2,3 hydroxy-naphthoic acid e.

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Claims (1)

Claims 1. Process for the preparation of aromatic hydroxy = carboxylic acid chlorides by reacting aromatic hydroxycarboxylic acids with thionyl chloride in an inert organic solvents., characterized in that the reaction is carried out in the presence of quaternary ammonium salts. 2. The method according to claim 1, characterized in that that the quaternary ammonium salts are tetraalkylammonium halides used. 3. The method according to claim 2, characterized in that that one tetraalkylammonium chlorides of the formula used, where X is a halogen atom, R and B. alkyl = groups containing 1-6 carbon atoms, R ~ and Rjf, alkyl or cycloalkyl groups containing 1-6 carbon atoms, or two of the radicals R2 * R3 and Ru together with the N atom form a heterocyclic ring. 409838/1076 4. The method according to claim J5 *, characterized in that that you have a Tetraalkylarnmoniumchlorid of the specified formula | 5 R_ - N ⁵ I.
R_ Cl " used, wherein the R ^. Containing alkyl groups Mean 2-4 carbon atoms. 5. Process according to claims J>, characterized in that aromatic ο-hydroxycarboxylic acids are used as the starting point. 6. The method according to claim 5 *, characterized in that that one starts from 2,3-hydroxynaphthoic acids. 7- The method according to claims 1-6, characterized in that the inert organic solvent is a halogenated aliphatic hydrocarbon used. 8. The method according to claims 1-7 * characterized in that that one 0.1 - 10 MoI-Jo of the quaternary ammonium = salt used per mole of starting acid. 409838/1076 9- Process according to claims 1-8 ^ characterized in that the reaction between 0-150 ⁰ C is carried out. 10. The acid chlorides obtained according to claims 1-9. . 7th 409838/1076