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United States Patent Office Patented Jan United States Patent Office Patented Jan. 23, 1968 1. 2 3,365,500 Therefore, from what information appears in the litera HYDROXYBENZALDEHYDE PROCESS ture, there would seem to be little advantage to be gained Donald F. Pontz, Midland, Mich., assignor to The Dow by using aqueous ethyl alcohol as a solvent in the prepara Chemical Company, Midland, Mich., a corporation of tion of Salicylaldehyde by this method. There is nothing Delaware to incline a chemist to investigate other alcoholic solvents No Drawing. Filed Jan. 21, 1964, Ser. No. 339,104 as the means by which improved results might be obtained. 5 Claims. (C. 260-600) Consequently, it is surprising and unexpected to find that aqueous methanol used as the solvent medium for the preparation of Salicylaldehyde by the Reimer-Tiemann ABSTRACT OF THE DISCLosURE 10 reaction provides both better combined yields of hy In the Reimer-Tiemann reaction wherein phenol is droxyaldehydes and sharply reduced tar formation as com reacted with chloroform and an alkali metal base to make pared to the results obtained by using either water or salicylaldehyde and p-hydroxybenzaldehyde, improved aqueous ethyl alcohol as the reaction solvent. By using yields of total aldehydes and decreased tar formation are as the Solvent aqueous methanol containing from about obtained when the reaction medium is aqueous methanol 5 10% to about 75% by weight of methanol, the yield of of 10-75 percent by weight concentration as compared Salicylaldehyde is at least as good as that obtained with to reactions run in water alone or in aqueous ethanol. The Water or aqueous ethyl alcohol and the yield of the improvement in total aldehyde yield is due principally to valuable p-hydroxybenzaldehyde is considerably better. increased production of the para isomer. Preferably, 2-4 The reduced quantity of tar produced by this improved moles of phenol and 3-8 moles of sodium hydroxide are 20 method not only reflects more efficient use of the reactants, reacted with a mole of chloroform. but also is of great commercial value in simplifying the Separation of reaction products of good quality and in reducing the quantity of waste materials for disposal. The present invention relates to an improved process More evident advantages for this new method include for making salicylaldehyde and p-hydroxybenzaldehyde the lower boiling point of methanol and its inability to whereby there are obtained increased yields of products, form an azeotrope with water as compared to ethanol. decreased production of waste material, and easier separa Methanol is thereby rendered more easily recovered for tion of the desired products from the reaction mixture. reuse in the process as well as being a more attractive The usual method employed for making salicylaldehyde solvent commercially. and p-hydroxybenzaldehyde on a commercial scale is 30 The other conditions of this improved process are es the Reimer-Tiemann reaction where phenol and chloro sentially those under which the Reimer-Tiemann is con form are reacted with aqueous alkali at about 25-70° C. ventionally run. For example, the reaction temperature Although this reaction has been intensively investigated can be from about 25° C. up to about 70° C. and it is over the many years since its discovery, it has never been preferably about 50-60° C. The only commercially found possible to increase the yield of hydroxyaldehydes 35 practical alkali is sodium hydroxide although other such above about 50-60% of the theoretical. The hydroxyalde bases are operable. The quantity of solvent used in rela hydes produced consist of about 5 parts of salicylaldehyde tion to the amount of reactants is not critical to oper to one part of p-hydroxybenzaldehyde, and the remainder ability, but there are obvious practical limitations, partic of the reaction product is tar. ularly in commercial operation, to provide a reaction mix Various expedients have been tried in efforts to im 40 ture which is not excessively viscous and hard to handle prove these results, for example, other solvents or mix and yet which offers a maximum of product per volume tures of solvents to serve as reaction media. Aqueous ethyl of equipment. Additionally, many different mole ratios alcohol has been used successfully to facilitate the use as of reactants have been employed successfully in running starting materials in the Reimer-Tiemann reaction of such the Reimer-Tiemann reaction. The use of excess phenol insoluble phenols as nitrophenol and naphthol. Statements 45 and alkali over the chloroform has been found to give applying to the use of ethyl alcohol or aqueous ethyl good results, particularly a mole ratio of 2-4 moles of alcohol as a solvent for the reaction of phenol itself are phenol and 3-8 moles of sodium hydroxide per mole of vague and somewhat contradictory. Traub, German Patent chloroform. However, ratios outside these ranges can be 80,195 discloses the use of 95% ethyl alcohol as reaction used. solvent for the production of hydroxyaldehydes, partic 50 The proportion of methanol in the aqueous solvent em ularly vanillin, by the Reimer-Tiemann reaction and ployed in this improved process is about 10-75% by claims improved yields, lessened tar formation, and in weight. The use of aqueous solvent containing less than creased production of the para-hydroxy isomer at the about 10% of methanol gives little or no advantage over expense of the ortho-hydroxy compound as results of this 55 the old process as carried out in water alone. When a sol mode of operation. No actual experimental results are vent containing more than about 75% of methanol is em given. However, at the end of the text of this patent as ployed in the reaction, conversions drop to an undesirably reproduced in Friedlander's Fortschritte der Teerfarben low level and the proportion of p-hydroxybenzaldehyde fabrikation, vol. 4, p. 1289 (1894-7), there appears the disparaging comment that the yield of hydroxyaldehydes to salicylaldehyde in the product is reduced to about that from Traub's process is very unsatisfactory and is scarcely 60 obtained by the old process where water is the sole sol better than that from the original process. vent. Such higher proportions of methanol in the reac Sen et al., J. Indian Chem. Soc., 9, 173 (1932) state tion solvent also add to process problems, for example, that the use of chloroform as an ethyl alcohol solution in larger reaction volumes are required per unit of product the Reimer-Tiemann reaction increases the yield of aide and methanol recovery becomes an increasingly disad hyde. However, the only example describing the reaction vantageous factor. Preferably, the aqueous methanol sol of phenol with chloroform and sodium hydroxide in vent contains about 15-40 by weight of methanol, par aqueous ethyl alcohol shows a combined yield for salicyl ticularly for larger scale operation where it is desirable aldehyde and p-hydroxybenzaldehyde of only 33% based to use a liquid alkali such as aqueous sodium hydroxide on the phenol reacted. The proportion of salicylaldehyde 70 of about 50-55% by weight concentration and to main to p-hydroxybenzaldehyde in the product is about five to tain the concentration of all the reactants in the reaction one, the same as for the conventional aqueous reaction. mixture as high as possible without encountering unduly 3,365,500 3. 4. high viscosity or precipitation of solids which would make Example 4 for process difficulties. Similarly, the order and manner in which the compo By the procedure of Example 1, a solution of 240 g. nents of the reaction mixture are combined and the way of NaOH and 282.3 g of phenol in a solvent consisting in which the products are separated have been varied of 196 g. of water and 43 g. of methanol was reacted with widely. The batchwise procedure outlined in the exam 119.5 g. of chloroform. From a series of eight such runs, ples below has been found to give good results. Accord there was obtained a combined yield of 79.3% of hydroxy ing to this preferred batch procedure, chloroform is added benzaldehydes based on the phenol converted. The ratio portionwise, either as such or as its solution in methanol, of saicylaldehyde to p-hydroxybenzaldehyde was similar to a stirred mixture of the other reaction components to that shown in Example 1. An average of 16.0 g. of tar at the desired reaction temperature. After the reaction is O per run was obtained. substantially complete, the alkali is neutralized and the Example 5 reaction mixture is preferably made slightly acidic by By the procedure of Example 1, a solution of 240 g. addition of a suitable acid such as sulfuric acid or hydro of NaOH and 282.3 g. of phenol in a solvent consisting of chloric acid. The hydroxyaldehyde products can then be 240 g. of water and 43 g. of methanol was reacted with separated from the resulting organic layer by conventional 119.5 g. of chloroform. From a series of seven such runs, means, for example by distillation and extraction steps as there was obtained a combined yield of 80.4% of hy shown below. Unreacted phenol can be recycled to the droxybenzaldehydes based on the phenol converted. The process along with recovered methanol. This process can ratio of salicylaldehyde to p-hydroxybenzaldehyde was be varied and modified in obvious ways to adapt it to 20 various requirements, for example, to permit semi-con similar to that shown in Example 1. An average of 15.5 g. tinuous or continuous operation. of tar per run was obtained. Example 1 Example 6 By the procedure of Example 1, a solution of 240 g.
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