DE1210853B - Process for the production of carbonic acid esters or carboxylic acid esters or their anhydrides - Google Patents

Description

Process for the production of carbonic acid or carboxylic acid esters or Their anhydrides It is known to combine carbonic acid or carboxylic acid halides with organic Hydroxyl compounds or their alkali or alkaline earth salts in organic, with Water immiscible solvents for the acid halides and in the presence of water and at least equivalent amounts of alkali or alkaline earth metal hydroxides odei carbonates and using catalytic amounts of tertiary amines or to implement their quaternization products.

For this purpose, phosgene and in particular come as carbonic acid halides consider the chlorides of half-esters of carbonic acid with mono- or polyalcohols, z. B. the chlorocarbonic acid methyl ester, the bis-chlorocarbonic acid ester of butanediol or of 2,2- (4,4'-dihydroxydiphenyl) propane, the trischlorocarbonic acid ester of trimethylolpropane and the reaction products of 2,2- (4,4'-dihydroxydiphenyl) propane with phosgene, while among carboxylic acid halides, the chlorides in particular are more aliphatic and aromatic carboxylic acids, such as acetic acid, propionic acid, acrylic acid, sebacic acid, Benzoic acid and isophthalic acid, are to be understood. The hydroxyl compounds include besides the aliphatic and aromatic mono- and polyalcohols, such as methyl alcohol, Allyl alcohol, stearyl alcohol, butanediol, benzyl alcohol, cresol, resorcinol, 2.2 - (44 '- Dihydroxydiphenyl) propane and polyvinyl alcohol, also aliphatic and aromatic Mono- and polycarboxylic acids, such as acetic acid, stearic acid, acrylic acid, adipic acid, Benzoic acid and terephthalic acid, also monoesters of carbonic acid or monoesters of dicarboxylic acids, such as carbonic acid or isophthalic acid methyl ester, and oxycarboxylic acids, such as lactic acid and hydroxybenzoic acid. As catalytically active tertiary amines or their quaternization products are compounds which have the most diverse Containing hydrocarbon residues have been used, e.g. B. triethylamine, tributylamine, N, N-dimethylcyclohexylamine, N, N-dimethylaniline, pyridine and picoline or trimethylbenzylammonium chloride.

Depending on the type of components that are connected to each other - for example in Carbon tetrachloride or benzene - if they react, you get monomers Carbonic acid, pyrocarbonic acid or carboxylic acid esters, also polycarbonates, polypyrocarbonic acid esters, Polyesters of polyalcohols or polyphenols with monocarboxylic acids, polyesters of polycarboxylic acids with mono- or polyalcohols and mono- or polyphenols, carboxylic acid anhydrides, carbonic acid - carboxylic anhydrides, polycarboxylic anhydrides and polycarboxylic anhydrides.

As publications in which this state of the art is even more detailed is explained, may be mentioned, for example, the German patents 959497, 1046311 and 1101386, British patent 808 490 and French patent 1 169 802.

The present invention now relates to an improvement on these known ones Procedure; it consists in being used as tertiary amines or their quaternization products those compounds are used which contain at least one nitrogen-bonded oo-hydroxyalkyl, o-Hydroxyalkyläther- or ct) -Hydroxyalkylpolyäthergruppe contain.

Tertiary ones suitable for carrying out the process according to the invention Amines are e.g. B. N, N-dimethyl-ethanolamine, N-methyl-diethanolamine, triethanolamine and in particular the products of action of ethylene oxide and / or propylene oxide on N, N-dimethyl-ethanolamine, triethanolamine, diisopropylamine, diisobutylamine, N-methyl] stearylamil1, Piperidine, N-methylcyclohexylamine, N-methylaniline or N-ethylaniline, also the Products of the action of styrene oxide and ethylene oxide or propylene oxide on, for example Diisobutylamine. The molar ratio between alkylene oxide and amine can be in one wide range - approximately between 1 and 20: - lie; preferably it is 4 to 10: 1. As suitable.

Quaternization products are dimethyl octyl ethanol ammonium chloride and dimethylbenzylethanolammonium chloride are mentioned as examples.

The appropriate amounts of the tertiary amines or their quaternization products can easily be determined by preliminary tests; in general, 0.1 turns out to be up to 1 mole per 100 moles of halide is sufficient.

There is a particular embodiment of the present method in that the organic hydroxyl compounds used are those which only exist in the Reaction mixture have been formed by saponifying part of the acid halides used.

The use of the tertiary amines according to the invention and their quaternization products brings a number of compared to the use of the catalysts customary up to now Advantages: The conversions are faster, the yields are higher, and in those cases in which the reaction products are purified by distillation the catalysts of the invention remain, since they are not volatile, back in the sump so that they do not contaminate the process products. This is of particular importance for the production of diethyl pyrocarbonate.

Example 1 A mixture of 23.5 g (0.25 mole) phenol, 23.1 g (0.275 Mol) sodium bicarbonate, 150 ml water, 50 ml methylene chloride and 0.13 g (0.00025 Mole) of the product of the action of 4 moles of propylene oxide per mole of N-methylstearylamine is added dropwise within 5 minutes with stirring with 39.0 g (0.25 mol) of phenyl chlorocarbonate added, the temperature being kept at 20.degree. That free in the implementation carbon dioxide is collected over saturated saline, and the Implementation is considered complete when the gas volume is within 10 minutes no longer increased. This is the case after 60 minutes. Then will separating the organic layer from the aqueous layer, the solvent becomes largely distilled off under normal pressure, and the residue is then on the water pump distilled. The diphenyl carbonate formed has a boiling point ls = 163 to 168 "C. above; the yield is 50.3 g.

In the present case, instead of 0.00025 mol of the action product of 4 moles of propylene oxide to 1 mole of N-methylstearylamine 0.00025 moles (0.16 g) of the product of the action of 8 moles of ethylene oxide to 1 mole of N-methylstearylamine and proceeds otherwise As stated, the reaction is complete after 55 minutes and the yield is on Diphenyl carbonate is 52.5 g, while with a use of 0.00025 mol (0.046 g) tributylamine, the reaction is complete only after 170 minutes and the yield is only 45.2 g.

Example 2 A mixture of 23.5 g (0.25 mole) phenol, 8.8 g (0.22 Mol) sodium hydroxide, 5.8 g (0.055 mol) anhydrous soda, 100 ml water, 100 ml methylene chloride and 0.13 g (0.00025 moles) of the product of action of 4 moles of propylene oxide per 1 mole N-methylstearylamine is added dropwise with 39.0 g (0.25 mol) of phenyl chlorocarbonate are added, the temperature being reduced to 25 "C. is held. Then the stirring is interrupted, the forming aqueous layer a 1 ml sample is taken, diluted to 100 ml with distilled water and titrated with n / 10 silver nitrate solution.

Stirring is continued and every 10 minutes interrupted again for sampling. The implementation is finished when the No longer increased consumption of silver nitrate solution.

This is the case after 35 minutes. Then the reaction mixture worked up in the manner indicated in Example 1. The yield of diphenyl carbonate is 51.2 g.

In the present case, instead of 0.00025 mol of the action product from 4 moles of propylene oxide to 1 mole of N-methylstearylamine 0.00025 mole of the product of the action of 8 moles of ethylene oxide to 1 mole of N-methylstearylamine and proceeds otherwise as indicated, the reaction is complete after 20 minutes, and so is the yield of diphenyl carbonate is 51.2 g, while with a use of 0.00025 mol of tributylamine the reaction is only complete after 55 minutes and the yield is 50.3 g. When using tributylamine, the nitrogen content in the distillate is 2.8 mg and in the distillation residue 0.3 mg; in contrast, when using the Product of the action of ethylene oxide or

Propylene oxide on N-methylstearylamine in the distillate no nitrogen and the nitrogen content in the distillation residue is 3.2 in each case mg.

Example 3 A mixture of 18.5 grams (0.25 moles) of n-butyl alcohol, 100 g 120 /, the sodium hydroxide solution, 65 g methylene chloride and 0.16 g (0.00025 mol) of the action product of 8 moles of ethylene oxide to 1 mole of N-methylstearylamine is within 10 minutes with stirring dropwise with a solution of 40.8 g (0.27 mol) 920 /, the chlorocarbonic acid n-butyl ester in 30 g of methylene chloride are added, the temperature being kept at 5 to 10 ° C. The implementation, its course by determining the chlorine ion content of the aqueous Shift can be tracked is finished after 50 minutes. Then the The reaction mixture was worked up in the manner indicated in Example 1.

The yield of dibutyl carbonate is 37.2 g, that is 85.5% of theory, based on butyl alcohol.

Instead of 0.00025 moles of the product of action of 8 moles of ethylene oxide to 1 mole of N-methylstearylamine a 0.00025 mole of tributylamine, the reaction is only ended after 190 minutes, and the yield of dibutyl carbonate is only 30.2 g, that is 69.4% of theory, based on butyl alcohol.

Instead of the product of action of 8 moles of ethylene oxide on 1 mole of N-methylstearylamine, the action product of 2 moles of ethylene oxide on 1 Mole of N-methylstearylamine or the action product of 1 mole of ethylene oxide on N-methyldodecylamine a, a very good yield of dibutyl carbonate is also obtained.

Example 4 A solution of 67.8 g (0.6 mol) 960/0 of the ethyl chlorocarbonate in 140 g of methylene chloride is first 1.07 g (0.002 mol) of the action product of 4.3 moles of propylene oxide to 1 mole of N-methylstearylamine and then with stirring in Over the course of one minute, a solution is added which consists of 41.6 g (0.25 mol) of isophthalic acid, 20.0 g (0.5 mol) of sodium hydroxide and 250 ml of water is prepared. The reaction mixture, whose temperature is kept at 18 to 20 "C by cooling with ice, becomes 20 Stirred for minutes; the chlorine ion content of the aqueous layer is then about 18.5 G. The two layers are then separated in a separating funnel, and the aqueous one Layer is extracted with 100 ml of methylene chloride. The two methylene chloride solutions are combined, washed six times with 100 ml of water each time and finally over Dried sodium sulfate.

Under a water jet vacuum at 20 "C, methylene chloride and excess Ethyl chlorocarbonate distilled off. From the remaining Residue of a colorless solid substance can be obtained by washing with low boiling point Petroleum ether removed the residues of ethyl chlorocarbonate. The yield of isophthalic acid-bis-carbonic acid ethyl ester anhydride is 64.3 g, that is 82.9% of theory, based on isophthalic acid.

Freezing point: 23 to 24 ° C.

C14H14O8. (Molecular weight: 310.27.) Calculated: .......... C 54.20010, o 41.260 / o; found: ............ C 54.32 to 54.40%, O 41.20 to 41.30% CO2 Calculated after saponification; ........... 28.37%, found: ............ 28.60%.

Substituting 0.002 mol of the product of action of 4.3 Moles of propylene oxide to 1 mole of N-methylstearylamine 0.005 moles (0.64 g) of N, N-dimethylcyclohexylamine on, the chlorine ion content of the aqueous layer is even after 120 minutes only 9.4 g; the usual work-up of the reaction mixture only gives 13.5 g of anhydride formed, that is 17.40 /, of theory, based on isophthalic acid.

Example 5 A mixture of 94 g (1.0 mol) of phenol, 150 g of methylene chloride, 1.3 g (0.002 mol) of the product of action of 8 mol of ethylene oxide on 1 mol of N-methylstearylamine and 600 g of an aqueous solution containing 32 g (0.8 mol) of sodium hydroxide and 24.4 g (0.23 Mol) contains sodium carbonate, is added dropwise within 5 minutes with stirring with a solution of 119 g (1.1 mol) of ethyl chlorocarbonate in 75 g of methylene chloride added, the temperature being kept at 20 ° C. by cooling with ice water.

The implementation, the course of which in the manner indicated in Example 2 is followed is ended after 12 minutes. Then the reaction mixture worked up as described in Example 1. The yield of ethyl phenyl carbonate (Bp 14 = 1070 C) is 162 g.

If 0.002 mol (1.35 g) the product of action of 10 moles of propylene oxide to 1 mole of N, N-dimethylethanolamine or 0.002 mol (1.66 g) of the action product of 1 mole of styrene oxide and 10 moles Propylene oxide to 1 mole of diisobutylamine, the reaction is in each case after 25 Minutes completed and the yields are 161.5 and 159 g, respectively. When using 0.002 Mole (0.37 g) of tributylamine, the reaction is only complete after 50 minutes; the yield is then 149 g.

Example 6 Solutions of 118.7 g (1.05 mol) each of 96% ethyl chlorocarbonate in 110 g of methylene chloride are first with one of the in the table below tertiary amines listed under a) to f) are added in the amount specified there. Each solution is then added with stirring and cooling to 18 to 22 ° C. in the course one hour a solution of 40 g (1 mol) of sodium hydroxide in 560 ml of water is added dropwise. The chlorine ion content of the aqueous layer is then determined; subsequently becomes the methylene chloride layer separated from the aqueous layer, and the aqueous layer is extracted with 100 ml of methylene chloride. The two methylene chloride solutions are combined and dried over sodium sulfate. Then the methylene chloride distilled off at normal pressure and a bath temperature of 60 ° C, and the residue is distilled in a water jet vacuum, with a with dry ice - methanol provided cold trap is switched. First distill at a bath temperature of 600 C residues of methylene chloride, unconverted ethyl chlorocarbonate and diethyl carbonate, then the bath temperature is increased to 100 to 105 ° C, and now the pyrocarbonic acid diethyl ester formed distills at boiling point 11 = 83 bis 84 ° C with practically no residue; it is collected in the distillation receiver.

The content of ethyl chlorocarbonate and diethyl carbonate in the first runnings collected in the cold trap is determined by gas chromatography. The diethyl carbonate content of the pyrocarbonate is determined by means of an IR spectrum; in all cases it is below 0.50 / 0. The results are compiled in the following table. Under g) to i), the values obtained if the tertiary amines N, N-dimethylaniline or N, N, belonging to the type previously used, are used as catalysts in place of the tertiary amines a) to f) used according to the invention are also listed under g) to i) -Dimethylcyclohexylamine or the quaternary compound triethylbenzylammonium chloride is used. % Pyro Chlorine ion Back- yield carbonic acid- content of the yield Catalyst obtained from distilled diethyl ester aqueous to carbon Catalyst layer according to carbonic acid diethyl- tem pyro- (distilled), Addition of the acid ethyl ester based on carbonic acid g mol sodium hydroxide ester diethyl ester used Caustic soda a) Product of action of 8 moles of ethylene oxide 1 mole of N-methylstearyl- amine ................. 1.27 0.002 35.8 g 3.0 g 0.9 g 78.9 g 97.3 b) Product of action of 4 moles of ethylene oxide 1 mole of N-methylstearyl- amine. ...... ... 0.92 0.002 35.1 g 2.5 g 1.2 g 75.4 g 93.0 % Pyro Chlorine ion Back- yield carbonic acid- content of the yield Catalyst obtained from distilled diethyl ester aqueous to carbon Catalyst chlorinated pyro (distilled) Layer after acid diethyl acid ethyl carbonic acid based on Adding the ester ester diethyl ester used Caustic soda g moles of caustic soda c) Product of action of 4.3 moles of propylene oxide 1 mole of N-methylstearyl- amine ................ 1.07 0.002 34.9 g 2.4 g 1.4 g 77.3 g 95.3 d) Product of action of 9.7 moles of propylene oxide 1 mole of N-methylstearyl- amine ............... 1.69 0.002 35.6 g 3.0 g 1.3 g 78.7 g 97.1 e) impact product of 9.9 moles of propylene oxide 1 mole of N, N-dimethyl ethanolamine ......... 1.99 0.003 35.3 g 3, ig 2.0 g 72.8 g 89.9 f) Product of action of 19.9 moles of propylene oxide to 1 mole of N, N-dimethyl- ethanolamine .......... 3.73 0.003 35.7 g 3.2 g 1.9 g 73.4 g 90.5 g g) N, N-dimethylaniline .... 1.21 0.01 16.0 g 52.6 g 2.2 g 11.8 g 14.6 h) N, N-dimethylcyclohexyl- amine ................ 1.28 0.01 21.2 g 42.9 g 2.4 g 14.7 g 18.1 i) triethylbenzyl ammonium chloride. 2.05 0.01-17.7 g 52.0 g 2.5 g 12.3 g 15.2 EXAMPLE 7 Solutions of 118.7 g (1.05 mol) each of 96% ethyl chlorocarbonate in 110 g of methylene chloride are initially admixed with 1.27 g (0.002 mol) of the product of 8 mol of ethylene oxide per mol of N-methylstearylamine. A solution of 40 g (1 mol) of potassium hydroxide in 560 ml of water, a solution of 53 g (0.5 mol ) Add dropwise sodium carbonate in 547 ml of water or a solution of 84 g (1 mol) of sodium bicarbonate in 816 ml of water. The reaction mixtures are then worked up in the manner described in Example 6. The results are compiled in the following table. Chlorine ion content of the yield of 0 / o pyrocarbonic acid aqueous layer of distilled pyro diethyl ester (distilled) Acid binding agent after adding the carbonic acid diethyl - based on equivalents - acid binding agent ester acid binding agent Potassium hydroxide ........................ 36.0 g 76.3 g 94.1 Sodium Carbonate - 35.2g 71.8g 88.6 Sodium bicarbonate .................. .. 35.4 g 69.5 g 85.7 Example 8 124.4 g (1.1 mol) of 960/0 ethyl chlorocarbonate are mixed with 1.27 g (0.002 mol) of the product of action of 8 mol of ethylene oxide per 1 mol of N-methylstearylamine, and the mixture is then mixed within 20 minutes A solution of 40 g (1 mol) of sodium hydroxide in 540 nil of water is added to the stirring, the temperature of the mixture being kept at 18 to 20 ° C. by cooling with an ice-sodium chloride mixture. After all of the sodium hydroxide solution has been added, the chlorine ion content of the aqueous layer is determined; the result is an amount of 36.1 g. The organic layer is then separated off, dried over sodium sulfate and distilled under a water jet vacuum. After a forerun of 4.6 g, which consists essentially of ethyl chloroformate, the diethyl pyrocarbonate formed distills over at a boiling point of 83 to 84 ° C. with practically no residue. 76.6 g are obtained; this corresponds to a yield of 94.6%, based on the sodium hydroxide solution used.

C6H1005. (Molecular weight: 162.15.) Calculated: ........... C 44.44%, O 49.340 / o; found: ........... C 44.50 to 44.630 / o, O 49.25 to 49.31%.

CO2 after saponification Calculated: ........... 54.27%, found: ........... 54.2 to 54.40 / 0.

Diethyl carbonate content according to the IR spectrum: 0.5%.

Example 9 124.4 g (1.1 mol) of 96% strength ethyl chlorocarbonate and 0.64 g (0.001 mol) of the product of action of 8 mol of ethylene oxide on 1 mol of N-methylstearylamine will dissolved in 150 g of toluene, and the solution is stirred and cooled to 20 ° C in the course of one hour with a solution of 40 g (1 mol) sodium hydroxide in 540 ml of water are added. The organic phase is then separated off and dried over sodium sulfate dried. The toluene is distilled off in a water jet vacuum until the bath temperature is reached 500 C. Then the bath temperature is increased to 105 ° C. After a course of 3.6 g of the pyrocarbonic acid diethyl ester formed distills at boiling point 11 = 83 to 84 ° C with practically no residue. 77 g are obtained; this corresponds to a Yield of 95%, based on the sodium hydroxide solution used. Diethyl carbonate content according to the IR spectrum: 0.5 0! o.

Example 10 A solution of 64.5 g (0.6 mol) of 88% methyl chlorocarbonate in 100 g of methylene chloride is first 0.16 g (0.00025 mol) of the action product of 8 moles of ethylene oxide added to 1 mole of N-methylstearylamine. Then you let them Solution with stirring within 10 minutes a solution of 20 g (0.5 mol) of sodium hydroxide in 280 ml of water added dropwise, the temperature of the mixture by cooling with an ice-common salt cold mixture is kept at 18 to 220 C. After finished The chlorine ion content of the aqueous layer is determined by adding the sodium hydroxide solution; the result is an amount of 17.9 g. Then the methylene chloride layer separated from the aqueous layer, and the aqueous layer is mixed with 100 ml of methylene chloride shaken out. The two methylene chloride solutions are combined over sodium sulfate dried and, after filtering off the sodium sulfate, filtered through bleaching earth. The methylene chloride is at normal pressure and a bath temperature of about 50 ° C distilled off. The bath temperature is then increased to 90 "C. In a water-jet vacuum Then, after a forerun of 3 g, the dimethyl pyrocarbonate formed is distilled at b.p.II = 71 to 72 ° C, practically residue-free. 29 g are obtained; this corresponds to a yield of 86.5%, based on the sodium hydroxide solution used.

C4HFO5. (Molecular weight: 134.09.) Calculated: ........... C 35.83%, O 59.660 / o; found: ........... C 35.91 to 36.02%, O 59.31 to 59.40%.

CO2 after saponification Calculated: ........... 65.63%, found: ........... 65.5 to 65.6 ° / o.

Example 11 A solution of 75.2 grams (0.55 moles) of butyl chlorocarbonate in 130 g of methylene chloride is first with 0.64 g (0.001 mol) of the action product of 8 moles of ethylene oxide added to 1 mole of N-methylstearylamine. Then you let the Solution within one hour at 18 to 20 ° C with stirring 300g of a solution of Add dropwise 20 g (0.5 mol) of sodium hydroxide in 280 ml of water. After that, the Chlorine ion content of the aqueous layer determined; the result is an amount of 17.7 G. The reaction mixture is then prepared in the manner described in Example 6 worked up. To- the remainder of methylene chloride and chlorocarbonic acid ester in a water jet vacuum are distilled off at a bath temperature of up to 70 ° C, the distillation is at continued at a pressure of 0.1 torr. After a forerun of 4 g, the distilled dibutyl pyrocarbonate formed at boiling point 0.1 = 66 "C practically residue-free above. 50.9 g are obtained; this corresponds to a yield of 93.2%, based on on the caustic soda used.

Example 12 In a mixture of 137.6 g (0.6 mol) of 2,2- (4,4'-dihydroxydiphenyl) propane, 680 g of water, 84 g of sodium hydroxide and 250 g of methylene chloride are in the course of 71.6 g of phosgene were passed in for 115 minutes with stirring, the reaction temperature is kept at 20 to 25 "C. The mixture is then treated with a solution of 0.38 g (0.0006 mol) of the oxethylated N-methylstearylamine used in Example 11 mixed in 8 g of methylene chloride and stirred for a further 10 minutes. The accumulating viscous The solution of the polycarbonate formed is washed out electrolyte-free, and the solvent is then evaporated. A polycarbonate is obtained with the relative viscosity of 1.356 (measured in 0.5 0/0 methylene chloride solution), from solution or via the melt flow can be processed into high-quality moldings.

Example 13 147.7 g (1.05 mole) benzoyl chloride, 74.1 g (1 mole) n-butanol and 1.5 g (0.002 moles) of the product of action of 8 moles of propylene oxide per 1 mole N-methyl stearylamine is dissolved in 400 g of methylene chloride and the solution is within 30 minutes with stirring with a solution of 40 g (1 mol) of sodium hydroxide added in 460 ml of water, the temperature of the reaction mixture by cooling is kept at 20 ° C with ice. After adding all of the sodium hydroxide solution, the is Chlorine ion content of the aqueous layer 35.4 g. Then the methylene chloride layer separated from the aqueous layer, washed three times with water and then washed over sodium sulfate dried. After evaporation of the methylene chloride, 169.5 g of crude butyl benzoate are obtained obtained, and 146.8 g of pure butyl benzoate can be obtained therefrom by distillation in vacuo from bp = 115 ° C; this corresponds to a yield of 82.4% based on butanol used.

Is used as a catalyst in place of that used according to the invention tertiary amine 0.37 g (0.002 mol) of tributylamine, the chlorine ion content is the aqueous layer after adding all of the sodium hydroxide solution only 26.8 g, and in the The reaction mixture is then worked up in the manner indicated above 101.3 g of pure butyl benzoate with a boiling point of 8 = 118 to 119 ° C .; this corresponds to a Yield of 56.9% based on the butanol used.

Example 14 A solution of 72.1 g (0.5 mol) of sodium benzoate in 250 ml of water is added to a solution of 77.3 g within 5 minutes while stirring (0.55 moles) of benzoyl chloride and 0.75 g (0.001 moles) of the action product of 8 Moles of propylene oxide are added to N-methylstearylamine in 200g of methylene chloride, with the reaction mixture with ice water to 20 ° C is cooled. The chlorine ion content the aqueous layer is immediately after the two solutions have been mixed 10.4 g; after a further 5 minutes only traces of sodium benzoate can be detected, the theoretical chlorine ion content of 17.8 g is then reached. Afterward the methylene chloride is separated, washed three times with water and over Dried sodium sulfate. After evaporation of the methylene chloride, 106.8 g are obtained Obtain crude benzoic anhydride, and from this are obtained by distillation in vacuo 104 g of pure benzoic anhydride of Kpoo, os = 121 "C and melting point 42" C won; this corresponds to a yield of 91.8%, based on the amount used Sodium benzoate.

Is used as a catalyst in place of that used according to the invention tertiary amine 0.51 g (0.004 mol) of N, N-dimethylcyclohexylamine, then the Chlorine ion content of the aqueous layer immediately after the solutions are mixed only 6.4 g; the theoretical value is only reached after one hour.

When working up the reaction mixture in the above In this way, 95.6 g of pure benzoic anhydride with a boiling point of 0.1 = 1270 ° C. are obtained from melting point 41 to 420 C; this corresponds to a yield of 84.6%, based on on sodium benzoate used.

Example 15 A solution of 154.6 g (1.1 mol) of benzoyl chloride and 0.64 g (0.001 mol) of the product of action of 8 mol of ethylene oxide on 1 mol of N-methylstearylamine in 200 g of methylene chloride is added dropwise with stirring over the course of 30 minutes mixed with a solution of 40 g (1.Mol) sodium hydroxide in 560 ml of water, whereby the reaction mixture is cooled with ice to 20 "C. After adding all of the Sodium hydroxide solution, the chlorine ion content of the aqueous layer is 35.8 g. Afterward the methylene chloride layer is separated, washed three times with water and over Dried sodium sulfate. After evaporation of the methylene chloride, 110 g of crude become Benzoic anhydride is obtained, from which 107 g are obtained by vacuum distillation pure benzoic anhydride with a curve of 0.08 = 125 "C and a melting point of 42" C obtained; this corresponds to a yield of 94.50%, based on the sodium hydroxide solution used.

If the IR catalyst is used instead of that used according to the invention tertiary amine 0.4 g (0.004 mol) of triethylamine, the chlorine ion content is 21.7 g of the aqueous layer immediately after the addition of all of the sodium hydroxide solution; self if the reaction mixture is stirred for a further 30 minutes at 20 ° C., it increases the chlorine ion content only to 24.3 g. The pH of the aqueous layer is 6 what suggests that considerable saponification of the benzoyl chloride used or the resulting benzoic anhydride has taken place. By precipitation with Hydrochloric acid can be separated from the aqueous layer 34.7 g of benzoic acid. at the work-up of the methylene chloride layer is obtained in the manner indicated above one 34.9 g of benzoic anhydride and 51.1 g of unreacted benzoyl chloride.

Claims (2)

Claims: 1. Process for the production of carbonic acid or Carboxylic acid esters or their anhydrides by reaction of carbonic acid or carboxylic acid halides with organic hydroxyl compounds or their alkali or alkaline earth salts in organic, water-immiscible solvents for the acid halides and in the presence of water and at least equivalent amounts of alkali or alkaline earth metal hydroxides or carbonates and using catalytic amounts of tertiary amines or their quaternization products, d a d-u r c h g e k e n n nz e i c h n e t that such compounds are used as tertiary amines or their quaternization products, the at least one w-hydroxyalkyl, u-hydroxyalkyl ether or contain cv-hydroxyalkyl polyether group. 2. The method according to claim 1, characterized in that as organic hydroxyl compounds used that only occur in the reaction mixture Saponification of some of the acid halides used have been formed. Considered publications: German Patent Specifications No. 959 497, 1,046,311, 1101,386; British Patent No. 808,490; french Patent No. 1,169,802.