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United States Patent (19) 11 Patent Number: 4,571,432 Telschow 45) Date of Patent: Feb

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United States Patent (19) 11 Patent Number: 4,571,432 Telschow 45) Date of Patent: Feb United States Patent (19) 11 Patent Number: 4,571,432 Telschow 45) Date of Patent: Feb. 18, 1986 54) PREPARATION OF CINNAMIC ACID FOREIGN PATENT DOCUMENTS 75) Inventor: Jeffrey E. Telschow, Tarrytown, N.Y. 17467 8/1895 Fed. Rep. of Germany ...... 562/495 81830 1 1/1973 Japan ................................... 562/495 73) Assignee: Stauffer Chemical Company, Westport, Conn. OTHER PUBLICATIONS Kirk. Othmer, Encyclopedia of Chem. Technology, 3rd 21 Appl. No.: 685,353 Ed., vol. 6, pp. 142-149, 1981. 22 Filed: Dec. 24, 1984 Primary Examiner-Paul J. Killos 51) ... CO7C 63/64 52 U.S. Cl. .................................................... 562/495 157) ABSTRACT 58 Field of Search ......................................... 562/495 A process for the production of cinnamic acid is dis closed. The process uses an inert diluent to increase the (56) References Cited stirrability of the reaction mixture and uses an amine U.S. PATENT DOCUMENTS derivative as a catalyst. The present process also uses 2,370,067 5/1945 Long ................................... 562/495 combinations of acetic acid derivatives to produce the 2.98.494 12/1959 Closson .................. 562/495 cinnamic acid. 3,870,751 3/1975 Houlihan et al. ...... 562/495 4,433,160 2/1984 Amano et al. ...................... 562/495 15 Claims, No Drawings 4,571,432 1. 2 In another embodiment of the present invention, it PREPARATION OF CINNAMIC ACID has also been found that other amine catalysts may be used in the above reaction. FIELD OF THE INVENTION In yet another embodiment of the present invention, The present invention relates to an improved process a process for the production of cinnamic acid is dis closed wherein combinations of acetic acid derivatives for the production of cinnamic acid. may be used. BACKGROUND OF THE INVENTION DETAILED DESCRIPTION OF THE Cinnamic acid, or 3-phenyl-2-propenoic acid, is an 10 INVENTION important industrial chemical. Cinnamic acid and its The present invention relates to a process for manu derivatives are used as sun screening agents, flame re facturing cinnamic acid and/or salts thereof from a tardants, cosmetics, fungicides, insecticides, food pre halogenated benzal derivative and an acetic acid deriva servatives, pharmaceuticals and photographic agents. tive. The above reaction can be expressed as follows: Cinnamic acid has also received considerable attention 15 recently since it is a precursor of phenylalanine, one of the ingredients in the artificial sweetener aspartame. The most widely used commercial process for the production of cinnamic acid has used benzaldehyde, wherein X is halogen, i.e. Cl, Br or I, M and M1 are the acetic anhydride and anhydrous sodium or potassium 20 same or different and are alkali metals and m and n are acetate in a Perkin condensation reaction. In another integers from 0-3. commercial process for the production of cinnamic In one embodiment of the invention, the halogenated acid, benzal chloride and anhydrous sodium acetate are benzal derivative and the acetic acid derivative are heated to 180 to 200 C. Since benzal chloride is reacted together in the presence of an amine catalyst. 25 To improve the stirrability of the reaction, an inert cheaper than benzaldehyde, this method is especially diluent is added to the reaction mixture. favored by manufacturers who obtain by-product ben The halogenated benzal derivative is chosen from the zal chloride from their benzyl chloride plants. This group consisting of benzal chloride, benzal iodide and basic reaction, disclosed in German Pat. Nos. 17467 and benzal bromide. The preferred compound is benzal 18251, required severe reaction conditions, namely 20 30 chloride. atmospheres pressure and temperatures above 200 C. The halogenated benzal derivative can in addition be for 10-20 hours. These severe reaction conditions are ring substituted with additional sterically compatible undesirable due to the attendant dangers associated groups which are non-reactive under the conditions of with high pressure as well as for economic reasons. the reaction such as chloro, fluoro, nitro, cyano, alkyl, Furthermore, large quantities of a tarry component are 35 alkoxy, alkylthio, aryl, alkyl substituted aryl, alkoxy produced under the above reaction conditions. substituted aryl, or aryloxy. Thus, when the above ring An improvement in the above described process is substituted halogenated benzal derivative is used in the reported in Japanese Pat. No. 48-81830 (1973) wherein reaction of the present invention, a ring substituted the inventors in this Japanese application disclose that cinnamic acid would be produced. potassium acetate can be reacted with benzal chloride The term "acetic acid derivative' includes acetic acid under normal pressure to produce high yields of cin as well as salts of acetic acid, sodium acetate, potassium namic acid if an amine such as pyridine, quinoline or acetate or other acetic acid derivatives. The molar ratio aniline is used as a catalyst. The process reported in the of the reactants used can range from about 2 to about 5 above Japanese patent is not easily reproducible. Pres moles of the acetic acid derivative per mole of the halo ent attempts to reproduce the results reported in this 45 genated benzal derivative. In an especially preferred patent have resulted in yields of cinnamic acid signifi embodiment of the invention, the sodium and potassium cantly lower than those reported by the Japanese inven salts of acetic acid are used in a 2 moles sodium aceta tors. Moreover, under the conditions reported in the te/1 mole potassium acetate ratio. Thus, the reaction is above patent, a difficultly stirrable reaction mixture is run at a 3 mole salt of acetic acid derivative/l mole produced. In the process disclosed in the above Japa 50 halogenated benzal derivative ratio. Hereinafter, by the nese patent, the preferred amount of potassium acetate term "acetic acid derivative' is meant either a single salt is 4-5 moles per mole of benzal chloride. The Japanese or combinations of salts of acetic acid. inventors disclose that 3 moles can be used but regard The catalyst used in the reaction can be any conven less of the molar amount of potassium acetate used, the tional catalyst reported in the literature to which this 55 invention pertains. Preferred catalysts are amines such above process still requires the use of large amounts of as pyridine, quinoline and aniline. Especially preferred the expensive potassium salt for the desired yields. amine catalysts are tetramethylethylenediamine, herein The use of condensing agents in Friedel-Crafts syn after called TMEDA, and 4-dimethylaminopyridine. thesis is also well documented. A complete discussion The amount of catalyst can range from about 2 to about of this subject can be found in the article entitled "The 60 10 percent by weight of the halogenated benzal deriva Friedel-Crafts Synthesis', Chem. Rev. 17, p. 376, 1936. tive. SUMMARY OF THE INVENTION Inert diluents used in the present invention include any liquid which has a boiling point high enough to In accordance with the present invention, it has now permit the desired reaction to occur and is non-reactive surprisingly been found that the yield of cinnamic acid 65 under the reaction conditions used. Examples of inert produced when an acetic acid derivative is allowed to diluents include mineral oil, Tetralin (R) diluent, 2 react with a halogenated benzal derivative is increased ethoxyethyl ether, and high boiling hydrocarbons. The when an inert diluent is added to the reaction mixture. amount of inert diluent used is not critical and amounts 4,571,432 3 4. ranging from about 0.5 to about 5 milliliters of diluent The filtered solid did partially dissolve in hot NaOH. per milliliter of reaction mixture can be used. The basic washes were then acidified with 6NHC and The temperature at which the reaction is carried out another 4.5 grams of faint yellow crystals were pro can range from about 145° to about 210° C. An espe duced. Melting point of the crystals was 130-131 C. cially preferred temperature at which the process of the The total yield was 36.5 percent. present invention is carried out is about 180° C. The reaction time can range from about 5 to about 40 COMPARISON EXAMPLE 2 hours. A preferred reaction time for the process of the The procedure was essentially that of Comparison present invention is about 17 hours. Example 1, i.e. that of Japanese Pat. No. 48-81830 The order in which the reactants are added is not 10 (1973), except sodium acetate, in the same molar pro critical. The halogenated benzal derivative, acetic acid portions, was substituted for potassium acetate. derivative and catalyst can be added to the inert diluent The reaction was carried out under nitrogen for 18 or the inert diluent can be added to mixture of the halo hours and at the end of the reaction, a total of 100 milli genated benzal derivative, catalyst, and acetic acid de liters of water was added to the cool solid to aid in rivative. 5 distillation. The reaction mixture contained a nearly The process of the present invention is carried out in colorless solution with small amounts of brownish and an inert atmosphere such as nitrogen. whitish suspended solids. A total of 20.9 grams of The stirring of the reaction mixture can be accom NaOH was added to bring the solution to pH 11 but the plished by using a mechanical stirrer. suspended solids did not go into solution. An additional At the conclusion of the reaction, usually after about 20 50 milliliters of water was added but the solids still did 15-20 hours, the cinnamic acid, ring-substituted cin not go into solution. After repeated filterings, a yellow namic acid, and/or salt form thereof, remains in the curdy solid was obtained. This solid was then acidified thick mixture.
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