PROCESS FOR PRODUCTION OF AROMATIC HYDROXYCARBOXYLIC ACID

Abstract: The present invention provides a method of production of aromatic hydroxycarboxylic acids by the reaction of alkaline metal salts of phenols or naphthols with carbon dioxide, in which free phenols or free naphthols produced as by-products in the reaction system are removed from the system so as to control the content of free phenols or free naphthols at a suitable level, by which a purer objective compound can be obtained at high yield under the condition of lower temperature and shorter time.

Description: The present invention relates to a process for the production of aromatic hydroxycarboxylic acids. Aromatic hydroxycarboxylic acids are important as raw materials or intermediates for antiseptics, antifungals, pigments, dyes, liquid crystals, pharmaceuticals, agricultural chemicals and the like, and are generally produced by the reaction of alkaline metal salts of phenolic or naphtholic compounds with carbon dioxide. As such a method, a solid-vapour phase reaction (known as Kolbe-Schmitt reaction) has been used, but it has many problems attributed to the solid-vaper phase reaction, for instance, a long reaction time, a great loss of raw materials by side-reaction which is caused by a thermal unevenness, a variable yield due to difficulty in reaction control and so on. Various improvements proposed to solve the above problems have not satified industrial requirements. Japanese Patent Publication No. 9529/1970 (corresponding to U.S.P.3,816,521) discloses a method for the continuous production of p-hydroxybenzoic acid by the reaction of phenol and carbon dioxide. In this method, the potassium salt of phenol and free phenol (used in a given ratio) are dispersed in a specific reaction medium such as aliphatic hydrocarbons, aromatic hydrocarbons and the like, but there is no reference to the removal of by-products from the reaction system as a vapor. Japanese Patent Publication No. 53296/1981 (corresponding to U.S.P. 4,239,913) discloses the production of 2-hydroxynaphthalene-3-carboxylic acid by the reaction of the sodium salt of β-naphthol with carbon dioxide, in which the reaction is effected using a dispersion of a mixture of the sodium salt and β-naphthol in a specific reaction medium such as a light oil in a given ratio. This method does not refer to the removal of by-products produced during the reaction as a vapor from the reaction system. Both methods are based on the fact that the mixture of a free phenolic or naphtholic compound and its alkaline metal salt in a specific ratio can be maintained liquid at a reaction temperature, and the contact of the salts with the carbon dioxide is advantageously achieved in the dispersion of the alkaline metal salts in a specific reaction medium. According to these methods productivity, purity of aromatic hydroxycarboxylic acid produced, and yield are improved. Also the reaction can be continuously operated and completed within a short time. As apparent from the above, the mixture of the phenol (or naphthol) and its alkaline metal salts in the reaction medium (such a mixture is referred to as a reaction mixture through the present specification, and the alkaline metal salts alone in the reaction medium is also referred to a reaction mixture) should be maintained in a specified component ratio during the reaction process, but the amount of free phenols or free naphthols discharged from the reaction system is practically dependent on the amount of the reaction medium. Therefore, both processes still have following difficulties: (1) If the reaction mixture is maintained for a long time in the reaction system, free phenols or free naphthols produced during the reaction accumulate beyond a suitable ratio, and then by-products such as tars from phenols, naphthols and the like are still liable to increase; and (2) If excess amount of phenols or naphthols is discharged to decrease by-product formations, the amount of the reaction medium relatively increases, and the residence time of the reaction mixture becomes shorter, so that the conversion ratio from alkaline metal salts of phenols (naphthols) to the corresponding hydroxycarboxylic acids decreases. Additionally, when a batch reaction is used, there may be no means to discharge the phenols or naphthols produced during the reaction so that the specified ratio of the reaction mixture cannot be suitably maintained. Therefore, a higher yield cannot be expected. GB-A-1 205 447 discloses a process for the production of aromatic hydroxy carboxylic acids in which an excess of carbon dioxide is reacted, at elevated temperature, with alkali metal phenate particles having an average size of less than 70 microns. The carbon dioxide is passed continuously through the reaction zone and serves to remove by-product phenolic compound (so as to prevent the formation of "doughy" reaction mass). US-A-1725 395 discloses a process for manufacturing 2-naphthol-3-carboxylic acid by reacting a dry alkali metal salt of beta-naphthol with carbon dioxide at a temperature of 120° to 285° C. The reaction is effected using carbon dioxide at atmospheric pressure whilst the solids are thoroughly agitated (e.g. in a ball mill). During the process some beta-naphthol distils from the reaction mixture and is carried out of the apparatus along with a small amount of carbon dioxide which escapes. The object of the present invention is to provide a process for producing an aromatic hydroxycarboxylic acid with higher purity and in a higher yield at a lower temperature for a shorter reaction time. According to the present invention there is provided a process for producing an aromatic hydroxycarboxylic acid which comprises reacting an alkali metal salt of a phenol or of a naphthol, the salt being from sodium phenolates, potassium phenolates, sodium alpha-naphtholates, potassium alpha-naphtholates, and sodium beta-naphtholates, with carbon dioxide, and removing by-products by discharging, during the reaction, carbon dioxide containing a vapour of the by-products out of the reaction vessel characterised in that said reaction is effected in a reaction medium in which said alkali metal salt is melted. This process can be applied to a batch reaction and a continuous reaction, and excellent results can be obtained in each reaction. The process of the present invention is carried out in the presence of a reaction medium substantially stable at a reaction temperature of the alkaline metal salts of the phenols or naphthols with carbon dioxide. The alkaline metal salts of phenols and naphthols which may be used in the present invention include sodium phenolate, potassium phenolate, sodium β-naphtholate, sodium α-naphtholate, potassium α-naphtholate and the like. These may include salts of phenols or naphthols having at least one substituent on the aromatic ring. Examples of such substituents include halogen atoms such as a fluorine atom, a bromine atom, and a chlorine atom; an alkyl group such as methyl, ethyl, propyl and the like; an alkoxy group such as methoxy, ethoxy and the like; and others such as nitro, sulfonyl, amino, phenyl, benzyl and the like. In order to melt the alkaline metal salts of phenols or naphthols in the presence of the reaction medium, the temperature of reaction medium (i.e. reaction temperature) may be raised above the melting point of the salts. In the case where the melting point of the alkaline metal salts of the phenols or naphthols is higher than a desirable reaction temperature or a lower reaction temperature is desirably employed, the corresponding free phenols or free naphthols may be added to the salts so as to lower the melting point of the mixture to a desirable temperature. Such a mixture is extremely preferable because the salts, the liquid phase of the free phenols or free naphthols and the reaction medium form an excellent dispersion. The alkaline metal salts of the phenols or naphthols or the mixture of these salts and free phenols or free naphthols should be sufficiently dehydrated. Such dehydrated salts can be easily prepared from phenols or naphthols and their alkaline alkali metal salts according to known methods. The reaction mixture may be dehydrated by, for example, suspending the alkaline metal salts containing water into the reaction medium and heating the suspension whilst blowing an inert gas such as nitrogen gas into the suspension. The dehydration may be made at any stage of the preparation of the reaction mixture containing alkaline metal salts of phenols or naphthols and, if necessary, free phenols or free naphthols. In order to practise the present invention the alkaline metal salts of the phenols or naphthols are melted in the reaction medium. In a preferable embodiment, the corresponding free phenols or free naphthols are allowed to exist constantly in the reaction mixture. A preferable ratio of the alkaline metal salts of the phenols or naphthols to free phenols or free naphthols is one mole to 0.05 - 3 mole, more preferably one mole to 0.1 - 3 mole, most preferably one mole to 0.2 - 2 mole. The reaction of the alkaline metal salts of phenols or naphthols with carbon dioxide may be carried out at or more than 150 °C, preferably 160 - 300 °C, under a carbon dioxide pressure of not more than 1.47 MPa(G) (15 kg/cm²(G)), preferably 0-9.81x10⁵Pa(G) (0 - 10 kg/cm²(G)). When a substantially stable reaction medium which is not vaporized at the reaction temperature is used, it is unnecessary to apply an additional pressure higher than the pressure of carbon dioxide to the reaction system. This is because a substantial amount of the reaction medium does not vaporise and the increase of pressure caused by the vaporized reaction medium is negligible. Therefore, in such case even when carbon dioxide gas is introduced into the reaction vessel from the bottom at a conventionally applied pressure, i.e. ambient pressure such as about 0 Pa(G) (0 kg/cm² (G)) to be dispersed into the reaction mixture, an objective compound can be obtained at a high yield and a high selective ratio. The reaction medium is preferably used in an amount of more than 0.5 times by weight the alkaline metal salts of the phenols or naphtols, more preferably 1 - 10 times the weight of the salts to be used. The reaction medium usable in the present invention is preferably substantially stable at the reaction temperature. That is, a reaction medium having a boiling point higher than the reaction temperature is preferably used. Such a reaction medium does not vaporise to a substantial extents, so that the content of the alkaline metal salts of phenols or naphthols in the reaction mixture can be maintained constant. However, when the reaction medium having a boiling point close to the reaction temperature is used, the reaction medium may be fed in an amount equal to the amount of the reaction medium vaporised. As a reaction medium there are exemplified aliphatic, alicyclic or aromatic hydrocarbons or ethers having such hydrocarbon residues, for example, light oil, kerosene, gasoline, lubricant oil, white oil, alkylbenzenes, alkylnaphthalenes, diphenyls, diphenylalkanes, alkyldiphenyls, triphenyls, hydrogenated triphenyls, diphenyl ethers, alkylphenyl ethers, alkyl diphenyl ethers, higher alcohols having a high boiling point such as isooctyl alcohol and the like. Mixtures thereof may, of course, be used. A reaction medium having a comparatively high boiling point, e.g. more than 240 °C, has advantages such as reduction of the energy necessary for the production of hydroxycarboxylic acid and so on, because the evaporation of the reaction medium is minimized without substantial change of removing amount of the phenols or naphthols because of the comparatively low steam pressure of the medium. The following processes are exemplified as methods of removing a part of the phenols or naphthols with carbon dioxide to the vapor phase: (1) A gas in the reaction system is intermittently discharged during the reaction, and carbon dioxide is freshly pressurized into the system; (2) A gas in the reaction system is continuously discharged during the reaction as carbon dioxide gas is pressurized into the system so that the pressure in the reaction system is constantly maintained at the same level. The discharged gas may be wholly or partially used again by circulation. A part of the discharged gas may be exhausted; (3) A gas in the reaction system is cooled with a condenser connected to the reaction vessel, so that a part of the phenols or naphthols is condensed and continuously or intermittently removed from the reaction system. Carbon dioxide gas and the rest of the phenols or naphthols may be collected and returned to the reaction system, if necessary. In any case, carbon dioxide gas is dispersed into a reaction mixture to progress the reaction as well as the removal of phenols or naphthols out of the reaction system. The above process may be carried out by any of batch or continuous manners. During the reaction of alkaline metals salts of phenols or naphthols with carbon dioxide, there may be added alkaline metal souces such as alkaline metal carbonate, bicarbonate, alkyl carbonate, alcoholate, alkylate, sulfonate and the like to the reaction mixture. The finishing of the reaction product may be carried out by standard procedures. For instance, water may be added to the cooled reaction medium to form separate aqueous and reaction medium phases. Unreacted alkaline metal salts of phenols or naphthols as well as free phenols or free naphthols may be collected from the each phase by standard methods such as control of pH value, separation with acid, extraction with an organic solvent, evaporation under reduced pressure, and the like. The separated unreacted compounds may be used again by recirculation. The present invention will be illustrated by the following Examples. Example 1 Into an autoclave of 1 liter an aqueous sodium β-naphtholate (50 wt %) 332 g, and hydrogenated triphenyl 388 g were charged and dehydrated at 260 °C for 3 hours with stirring. To the dehydrated mixture hydrogenated triphenyl was additionally added so that the total amount of the hydrogenated triphenyl was 2.32 times by weight the sodium β-naphtholate. The obtained mixture was further dehydrated at 260 °C for 2 hours, and cooled to 100 °C. To the cooled mixture were added β-naphthol 144 g and additional hydrogenated triphenyl in a supplemental amount corresponding to the loss during the second dehydration. The resultant mixture was heated to 285 °C, and carbon dioxide gas was then blown into the mixture such that the pressure in the reaction system was maintained at 5.9 x 10⁵Pa (6 kg/cm²) whilst gas (including carbon dioxide) in the reaction system was discharged from another nozzle at a rate of 2.4 liter/h. The reaction was continued for 3 hours as vaporized β-naphthol and a part of hydrogenated triphenyl were removed out of the reaction system with the discharged carbon dioxide gas, and collected by a condenser. After the reaction, the pressure of the reaction system was reduced to ambient pressure and the temperature lowered to 100 °C under a current of nitrogen. Water was then added to the reaction mixture, which was then heated to 120 °C in a closed system and then stirred for 30 minutes to decompose by-products. The resultant mixture was cooled, removed from the autoclave, and separated. The obtained aqueous phase was acidified to give 2-hydroxy-3-naphthoic acid (103.2 g; yield 60 %). Example 2 An aqueous solution of potassium phenolate (50 % by weight) was prepared in a flask (2 liter) under a nitrogen current. The solution was dehydrated by an evaporator to give a dry potassium phenolate powder. The potassium phenolate powder obtained 132 g was charged with phenol 35 g and hydrogenated triphenyl 400 g (ratio by weight of reaction medium: 3) into an autoclave (1 liter). After the air in the autoclave was substituted with a nitrogen gas, the reaction mixture was heated at 260 °C, and then the nitrogen gas was substituted with a carbon dioxide gas. The inner pressure was increased to 5.9 x 10⁵ Pa (6 kg/cm²) and retained at this level as carbon dioxide gas was blown into the reaction mixture with stirring and simultaneously a gas containing a carbon dioxide gas, vaporized phenol and hydrogenated triphenol was discharged another nozzle at a rate of 1.2 liter/h. The discharged gas was condensed by a condenser, and the separated carbon dioxide gas was returned to a compressor and recycled into the reaction system. The reaction was continued under the above condition for 3 hours. The reaction the reaction mixture was then cooled to 100 °C and water was added. The mixture was removed from the reaction vessel, and separated to a water phase and an organic phase. The separated water phase was extracted with xylene to collect phenol, and then the residual water phase was acidified to separate p-hydroxy benzoic acid (124.2 g, yield 90 %). Example 3 Into an autoclave (50 liter) sodium β-naphtholate 8.3 kg, halogenated triphenyl 19 kg (ratio by weight of reaction medium: 2.3) and β-naphthol 7.2 kg were charged. The obtained reaction mixture was heated at 285 °C, and then carbon dioxide gas was blown into the mixture such that the pressure in the reaction system was maintained at 5.9 x 10⁵ Pa (6 kg/cm²) whilst gas from the reaction system was discharged from another nozzle at a rate of 200 l/min. A mixture of sodium β-naphtholate and hydrogenated triphenyl which was dehydrated in a similar manner as in Example 1 was continuously charged into the reaction system at a rate of 3.32 kg/h of the former and 6.3 kg/h of the latter, and the surface of the reaction mixture was maintained at the same level by removing the reaction mixture out of the reaction system at a rate of 8 - 9 kg/h. The above condition was controlled such that the theoretical residence time of sodium β-naphtholate in the reaction system was 3 hours. The reaction product was separated by batch according to the manner in Example 1. Yield 61 % Example 4 Into an autoclave (50 liter) potassium phenolate 6 kg, phenol 1.8 kg and hydrogenated triphenyl 20 kg were charged (ratio by weight of reaction medium: 3.3). Finaly dispersed carbon dioxide gas was blown into the reaction mixture at 260 °C, and the inner pressure was retained at 39x10⁴Pa (4 kg/cm²) by discharging a gas from the reaction system through another nozzle at a rate of 160 liter/min. A mixed vapor of phenol and hydrogenated triphenyl in the gas was condensed by a condenser. The reaction was continued as the separated carbon dioxide gas was recycled into the reaction system through a compressor, and fresh potassium phenolate and hydrogenated triphenyl were fed into the reaction mixture at a rate of 2 kg/h and 7 kg/h respectively. The reaction product was separated by batch as described in the Example 2. Yield 91 % Examples 5 - 17 (batch method) The reaction was carried out according to the same manner as described in the Example 1 or 2 except that the conditions specifically shown in Table 1 were used. The raw material, conditions, objective compounds and yield are shown in Table 1, in which the molar ratio (A/B) indicates mole of phenols per one mole of alkaline metal salts of phenols or mole of naphthols per one mole of alkaline metal salts of naphthols. Examples 18 - 23 (continuous method) The reaction was carried out according to the same manner as described in the Example 3 or 4 except that the conditions specifically shown in Table 2 were used. The results are shown in Table 2. Examples 24, 25, Comparative Examples 1 and 2 The reaction was carried out according to the same manner as described in the Example 1 or 2 except that the conditions specifically shown in Table 3 were used. In order to provide a comparison with a conventional method, Comparative Example 1 (C.1) and Comparative Example 2 (C.2) were carried out in the same manner as described for Examples 24 and 25 respectively except that the phenols or naphthols were not removed as a vapor together with the carbon dioxide gas out of the reaction system. The results are shown in Table 3. Examples 26, 27, Comparative Examples 3 and 4 The reaction was carried out according to the same manner as described in the Example 3 except using the conditions indicated in Table 4 The Comparative Example 3 (C.3) was carried out according to the manner described in Japanese Patent Publication No. 9529/1970 (corresponding to U.S.P. 3,816,521). The Comparative Example 4 (C.4) was carried out according to the manner described in Japanese Patent Publication No.53296/1981 (corresponding to U.S.P. 4,239,913). The results are shown in Table 4. Example 28 (continuous method) 2-Hydroxy-3-naphthoic acid was prepared using a 50 liter autoclave using a procedure similar to that of Example 3 but under the conditions shown in Table 5. The yield of 2-hydroxy-3-naphthoic acid was determined after 0.25 h and 0.5 h. The results are shown in Table 5. Comparative Example 5 The process of Example 28 was repeated except that β-naphthol was not removed with carbon dioxide from the reaction system as a vapor. The results are shown in Table 5. In Tables 1 - 5 the abbreviations used have the following meanings: 2,6-diMePh: 2,6-dimethylphenol, 2-ClPh: 2-chlorophenol, 2-MeOPh: 2-methoxyphenol 2-AmPh: 2-aminophenol, 1-Br β-naph: 1-bromo-β-naphthol, Ph: phenol, β-Naph: β-naphthol, H-TPh: hydrogenated triphenyl POB: p-hydroxy benzoic acid, SA: salicylic acid, 3,5MePOB: 3,5-dimethyl-4-hydroxy benzoic acid, 3ClPOB: 3-chloro-4-hydroxy benzoic acid, 3MeOSA: 3-methoxy-2-hydroxy benzoic acid, 3NH₂SA: 3-amino-2-hydroxy benzoic acid, BON-3: 2-hydroxy-3-naphthoic acid, lBrBON-3: 2-hydroxy-1-bromo-3-naphthoenic acid ratio by weight of reaction medium: ratio by weight of reaction medium to alkaline metal salts of phenols or naphthols, molar ratio: A/B A: mole of added phenols or naphthols, B: mole of alkaline metal salts of phenols or naphthols to be charged, yield: calculated based on alkaline metal salts of phenols or naphthols.

Claims: A process for producing an aromatic hydroxycarboxylic acid which comprises reacting an alkali metal salt of a phenol or of a naphthol, the salt being from sodium phenolates, potassium phenolates, sodium alpha-naphtholates, potassium alpha-naphtholates, and sodium beta-naphtholates, with carbon dioxide, and removing by-products by discharging, during the reaction, carbon dioxide containing a vapour of the by-products out of the reaction vessel characterised in that said reaction is effected in a reaction medium in which said alkali metal salt is melted. A process as claimed in claim 1 for the production of an aromatic hydroxycarboxylic acid, in which the reaction medium is selected form hydrocarbons or ethers having a boiling point of more than 150°C. A process as claimed in claim 1 for the production of an aromatic hydroxycarboxylic acid, in which the reaction is carried out in a reaction mixture containing phenols or naphthols, the alkaline metal salts as described in the claim 1, and the reaction medium. A process as claimed in claim 3 for the production of an aromatic hydroxycarboxylic acid, in which a molar ratio of the phenols or naphthols to the alkaline metal salts of the phenols or naphthols in a reaction mixture is from 0.1 to 3. A process as claimed in claim 1 for the production of an aromatic hydroxycarboxylic acid, in which the reaction is carried out under a pressure of 0-9.81 x 10⁵ Pa (0-10 kg/cm²) of carbon dioxide gas. A process as claimed in claim 1 for the production of an aromatic hydroxycarboxylic acid, in which the discharged gas is condensed to separate carbon dioxide which is re-circulated to the reaction vessel. A process as claimed in claim 1 for the production of an aromatic hydroxycarboxylic acid, wherein the by-products include phenols or naphthols.

Inventors: KAWATA, KEIJI, KUWAE, YOSHIHIKO, MASADA, YOSHIYASU, UENO, RYUZO
Applicants: KABUSHIKI KAISHA UENO SEIYAKU OYO KENKYUJO
Application year: 1989
Main classification: C07C51
IPC codes: C07C51, C07C65