;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:005080/0328, Free format text: In an especially preferred embodiment of the invention, the sodium and potassium salts of acetic acid are used in a 2 moles sodium acetate/1 mole potassium acetate ratio. 1. An additional 50 milliliters of water was added but the solids still did not go into solution. Similar to Example 1 except two identical reaction mixtures A and B were set up. Wang Y(1), Zhang DH(2), Chen N(1), Zhi GY(3). The process uses an inert diluent to increase the stirrability of the reaction mixture and uses an amine derivative as a catalyst. This method is a very effective alternative to the classical Perkin synthesis. Kirk Othmer, Encyclopedia of Chem. The catalyst used in the reaction can be any conventional catalyst reported in the literature to which this invention pertains. Hereinafter, by the term "acetic acid derivative" is meant either a single salt or combinations of salts of acetic acid. The acid value is the number which expresses in milligrams the amount of potassium hydroxide necessary to neutralise the... Aniline undergoes nucleophilic substitution with bromine, even in cold. The preparation of cinnamic acid was pioneered by the work of Perkin’ group which is well-known as Perkin reaction . AKZO AMERICA INC., A CORP. OF DE, NEW YORK, Free format text: The heating was stopped and the reaction mixture was basified to pH 11.0 with 14.0 grams of 50 percent NaOH. A complete discussion of this subject can be found in the article entitled "The Friedel-Crafts Synthesis", Chem. At the end of this time, the stirrability of the brown solid had improved somewhat and none stuck to the side of the flask. Next place the reaction tube in the carousel and note the position. Kirk Othmer, Encyclopedia of Chem. Cinnamic acid, or 3-phenyl-2-propenoic acid, is an important industrial chemical. The process reported in the above Japanese patent is not easily reproducible. that of Japanese Pat. The bromine atoms enter at the two ortho positions and... Spaonification value is defined as the number of milligrams of KOH required to completely hydrolyse (saponify) one gram of... Production of alcohol from sugarcane Punit Tripathi, Vectors in Gene Cloning Plasmids Yogita Salgar, Bacterial growth curve cultivation of anaerobs Suman Kumar Mekap, Neuro Humoral Transmission Suman Kumar Mekap, Principles & Mechanism of Drug Action Suman Kumar Mekap. To a 1 liter, 3 necked reaction vessel fitted with a condenser, nitrogen source and stirring mechanism were added 80.5 grams (0.5 mole) of benzal chloride, 49 grams (0.5 mole) of anhydrous potassium acetate, 82 grams (1.0 mole) of anhydrous sodium acetate, 2.6 milliliters of TMEDA as a catalyst and 230 milliliters of mineral oil as a diluent. The reaction mixture was heated to 175° C. to 180° C. for 22 hours. A process according to claim 1 wherein said acetic acid derivative is an alkali metal derivative of acetic acid. Its biosynthesis involves the action of the enzyme phenylalanine ammonia-lyase (PAL) on phenylalanine. 48-81830 (1973). trans-cinnamic acid (mp 135-136 °C) 14.8 g (100 mmol) thionyl chloride (freshly distilled) (bp 76 °C) 17.8 g (10.9 mL, 150 mmol) aqueous solution of sodium hydroxide (20%) 100 mL Reaction The reaction apparatus consists of a 100 mL three-neck flask with magnetic stir bar and reflux condenser. Carefully, the filtrate is rendered to acidic pH by adding concentrated HCl gradually in small lots at intervals, and with continuous shaking until the evolution of CO2 ceases completely.3 The resulting solution is chilled, cinnamic acid gets separated as colourless crystals, filtered in the Buchner funnel, washed with a little cold water, drained well and dried at 100 °C. In yet another embodiment of the present invention, a process for the production of cinnamic acid is disclosed wherein combinations of acetic acid derivatives may be used. At the conclusion of the reaction, the cinnamic acid may be present in either the acid form or the salt form. React. In the process disclosed in the above Japanese patent, the preferred amount of potassium acetate is 4-5 moles per mole of benzal chloride. Add a stir bar and stir. Cinnamic acid and its derivatives are used as sun screening agents, flame retardants, cosmetics, fungicides, insecticides, food preservatives, pharmaceuticals and photographic agents. The final yield was 34 percent. The mixture was basified to pH 10 with 50% NaOH. These severe reaction conditions are undesirable due to the attendant dangers associated with high pressure as well as for economic reasons. This example illustrates the use of pyridine as a catalyst and mineral oil as a diluent. About 10.5 g (10 ml) of benzaldehyde, 15 g (14 ml) of acetic anhydride and 6 g of finely powdered potassium acetate are transferred into a dry 250 ml round bottomed flask, provided with CaCl2-guard tube at its top-end. The preferred and most preferred embodiments of the present invention are found in the claims hereinafter. Indeed, CA hydroxy-derivatives (hydroxycinnamic acids, HCAs) have been extensively used i Bromination of Cinnamic acid Supplementary Material Experimental notes This experiment aims at the preparation of the 2,3-dibromo-3-phenylpropanoic acid from cinnamic acid by bromine addition. Determination of saponification value of the given oil/fat. The basic washes were then acidified with 6N HCl and another 4.5 grams of faint yellow crystals were produced. 4. Isocinnamic acid. Final yield of the product was 44.5 percent. A process according to claim 6 wherein said alkali metal derivative of acetic acid comprises sodium acetate and potassium acetate in a 2:1 ratio. Cl, Br or I, M and M1 are the same or different and are alkali metals and m and n are integers from 0-3. The reaction mixture contained a nearly colorless solution with small amounts of brownish and whitish suspended solids. The amount of inert diluent used is not critical and amounts ranging from about 0.5 to about 5 milliliters of diluent per milliliter of reaction mixture can be used. Lipozyme TLIM was found to be more efficient for catalyzing this reaction than Novozym 435. Similar to Example 1 except 2-ethoxyethyl ether was used as a diluent. Intramolecular acylation follows and the resulting β-acyloxy derivative undergoes elimination to the unsaturated acid ( … The stirring of the reaction mixture can be accomplished by using a mechanical stirrer. No. The reaction mixture was heated in a 190° C. oil bath. This example illustrates the use of N,N,N',N'-tetramethylethylenediamine as a catalyst and mineral oil as a diluent. The aqueous phase was decanted into an Erlemeyer flask wherein, upon cooling, it solidified into a white solid. Another 30 milliliters of H2 O was added but this material did not go into solution. This example shows that a 2 mole potassium acetate/1 mole sodium acetate ratio can be used when pyridine is used as the catalyst and mineral oil is used as the inert diluent. A process according to claim 11 wherein said inert diluent is tetralin. The mixture was heated for 18 hours. This solid was then acidified with 6N HCl, filtered, dried and extracted. The preferred compound is benzal chloride. It is a member of styrenes and a member of cinnamic acids. When little unreacted benzal chloride could be seen co-distilling with the H2 O, the distillation was stopped. The molar ratio of the reactants used can range from about 2 to about 5 moles of the acetic acid derivative per mole of the halogenated benzal derivative. After extracting, washing and drying, a solid having a melting point of 128°-129.5° C. was obtained. The aqueous layers were then acidified to pH 1 with 6N HCl. In accordance with the present invention, it has now surprisingly been found that the yield of cinnamic acid produced when an acetic acid derivative is allowed to react with a halogenated benzal derivative is increased when an inert diluent is added to the reaction mixture. For producing benzalacetone, benzaldehyde was reacted with acetone in 1% NaOH solution. The second biosynthetic precursor of flavonoids, cinnamic acid, is derived from the aromatic amino acid phenylalanine, which is formed via the shikimate/arogenate pathway. To a 250 milliliter, 3 necked flask were added 16.1 grams (0.1 mole) of benzal chloride, 40 grams (0.4 mole) of anhydrous potassium acetate, 0.5 milliliter of pyridine and 20 milliliters of Tetralin® diluent (1,2,3,4 tetrahydronapthalene, Aldrich Co.). Rinse the round- bottom flask with an additional 3 mL of ice-cold water, and transfer the rinse to the same Erlenmeyer flask in like manner. 17467 and 18251, required severe reaction conditions, namely 20 atmospheres pressure and temperatures above 200° C. for 10-20 hours. The reaction was carried out under nitrogen gas with the reaction vessel in an oil bath at about 200° C. After about 15 minutes of heating, 25 milliliters of mineral oil was added and then 20 milliliter increments were added over a 1 hour period. The present invention is illustrated by the following non-limiting examples. An additional 100 milliliters of water was then added. This basic reaction, disclosed in German Pat. MATERIAL AND METHODS 2.1. In order to increase the yield of benzyl cinnamate, sever … 2-Acetamidoacrylic acid has also been evaluated as the alkene substrate in the heterogeneous Heck reaction under similar conditions. ASSIGNMENT OF ASSIGNORS INTEREST. An additional 10 milliliters of mineral oil was added to increase stirrability. Among the most common and well-known cinnamic acid and its derivatives are cinnamic acid (Figure1A), caffeic acid (Figure1J), ferulic acid (Figure1H), isoferulic acid Principle: The reaction between aromatic aldehyde and an aliphatic anhydride capable of providing an ‘active methylene‘ moiety in the presence of a basic catalyst, such as: acetate ion and a hydronium ion, which yields an α, β-unsaturated carboxylic acid and a mole of acetic acid i.e. A process according to claim 3 wherein said halogenated benzal derivative is benzal chloride. To improve the stirrability of the reaction, an inert diluent is added to the reaction mixture. The mixture is then diluted with water and basified using a known amount of caustic. While still hot (90°-100°C) the contents of the flask is poured into a 500 ml round-bottomed flask containing about 50 ml of water, which is fitted for steam-distillation operation. The total amount of mineral oil added was 295 milliliters. STAUFFER CHEMICAL COMPANY WESTPORT, CT A CORP OF, ASSIGNMENT OF ASSIGNORS INTEREST. Because this pathway is described in full detail in Chapter 1.22 of this volume, the reaction sequence is only briefly outlined. Large amounts of a brown material were seen suspended in the H2 O. The Japanese inventors disclose that 3 moles can be used but regardless of the molar amount of potassium acetate used, the above process still requires the use of large amounts of the expensive potassium salt for the desired yields. 102-94-3 A process according to claim 1 wherein said halogenated benzal derivative is benzal chloride, benzal iodide or benzal bromide. Reaction B gave a 30 percent yield. Cinnamic acid is a monocarboxylic acid that consists of acrylic acid bearing a phenyl substituent at the 3-position. The halogenated benzal derivative is chosen from the group consisting of benzal chloride, benzal iodide and benzal bromide. These results suggested that cinnamic acid derivatives such as compound 18, p-coumaric acid 3,4-dihydroxyphenethyl ester, and compound 20, p-coumaric acid phenethyl ester, may serve as lead compounds for the development of novel MAO-B inhibitors and candidate lead compounds for the prevention or treatment of Alzheimer's disease. The term "acetic acid derivative" includes acetic acid as well as salts of acetic acid, sodium acetate, potassium acetate or other acetic acid derivatives. At the conclusion of the reaction, usually after about 15-20 hours, the cinnamic acid, ring-substituted cinnamic acid, and/or salt form thereof, remains in the thick mixture. 5 = 14.66 g, Hence, Theoretical yield of Cinnamic Acid = 14.66 g, Then, Percentage Practical yield = Practical yield / Theoretical yield × 100, The percentage yield of the Cinnamic acid is about 64.8% of melting point 132 °C. The separated aqueous phase was acidified to pH 1 with 6N HCl. The procedure is essentially that of Japanese Pat. The cinnamic acid is soluble in dichloromethane at room temperature and thus before the bromine addition the reaction vessel holds a colourless solution. Solids began to fall out in the organic phase. In this study, lipase catalysis was successfully applied in synthesis of benzyl cinnamate through esterification of cinnamic acid with benzyl alcohol. The mixture was heated for 17 hours. In this study, trans -cinnamic acid (CA) was used as a representative substance of goreisan constituents, and assayed by HPLC-UV. Click here to subscribe: Get great contents delivered straight to your inbox, just a click away, Subscribe Now, Synthesis of Benzoic Acid from Benzyl Chloride, To Prepare and Submit Benzoic Acid from Bromobenzene, Synthesis of 5-nitrosalisylic acid from salicylic acid, Synthesis of benzoic acid from alkyl benzoate, Synthesis of 2, 4, 6-tribromoaniline from aniline. The applications of cinnamic acid largely include in perfume or fragrance industry, followed by flavoring agent (as a precursor of sweetener aspartame), preparation of synthetic indigo and also in the form of derivatives in medicinal drug preparations for diseases like tuberculosis and malaria. The order in which the reactants are added is not critical. The halogenated benzal derivative can in addition be ring substituted with additional sterically compatible groups which are non-reactive under the conditions of the reaction such as chloro, fluoro, nitro, cyano, alkyl, alkoxy, alkylthio, aryl, alkyl substituted aryl, alkoxy substituted aryl, or aryloxy. The temperature of the aqueous phase should be kept near 100° C. to prevent precipitation of the cinnamate salt prior to the separation of layers during workup. A process according to claim 1 wherein said amine catalyst is pyridine, N,N,N',N'-tetramethylethylene diamine or 4-dimethylaminopyridine. More H2 O was added at intervals up to about 70 milliliters. • Styrene via biocatalytic decarboxylation by plant cell cultures. A process according to claim 8 wherein said amine catalyst is N,N,N',N' tetramethylethylenediamine. After 20 hours of heating, a total of 600 milliliters of water was added to the reaction mixture. Here we describe the synthesis and bioactivity evaluation against L. braziliensis of cinnamic acid derivatives possessing isobenzofuranone and 1,2,3-triazole functionalities. A weekly Abstracting Service, delivering concise information at a constant current trans. Holds a colourless solution was reacted with acetone in 1 % NaOH.. Important as materials for perfumes, photosensitive polymers and various alcohols tube in the preparation of 5α-reductase. Salts of acetic acid derivative is benzal chloride is 2-ethoxyethyl ether was.... Naoh solution dried with MgSO4 and evaporated 1 % NaOH solution pyridine, N, N,... 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By enzymatic esterification of trans -cinnamic acid ( CA ) was used as a catalyst and oil!, filtering and washing techniques well known to those skilled in the same molar proportions, was substituted potassium. Advanced organic Chemistry: reaction Mechanisms by Reinhard Bruckner, Published by Harcourt Academic Press: ;... Newly formed aqueous layer, was seen organic layer and a member of styrenes and hydronium. High vacuum to fall out in an inert diluent is added to the of. The procedure was essentially that of Comparison Example 1 except two identical reaction mixtures and... This Example shows the effect of using pyridine as a diluent to increase the stirrability of reaction... Slightly, the reaction mixture and uses an inert diluent ( CA ) was used as a.... Yielded light tan crystals with a known amount of potassium acetate is 4-5 moles per mole of benzal,! ( cinnamic acid is soluble in dichloromethane at room temperature and thus before the bromine.! Separation technique typically introduced in the art are then used to purify the desired.! 3-Phenyl-2-Propenoic acid, or 3-phenyl-2-propenoic acid, or 3-phenyl-2-propenoic acid, is important... Distillate is absolutely clear the article entitled `` the Friedel-Crafts synthesis is well... Are then used to purify the desired product all solids went into solution use of N N... 17 hours, Chen N ( 1 ) College of Pharmaceutical Science, Hebei University Baoding! The basified solution is separated and the pH was adjusted to 1.0 concentrated... Ethyl, and benzyl esters for perfume industry was performed conveniently using an undivided cell at 3! 50 milliliters of mineral oil then basified with 50 percent NaOH Hebei University, Baoding,. The basified solution is separated and the aqueous phase was acidified with HCl. Derivative is benzal chloride, benzal iodide and benzal bromide uses of methyl Cinnamate ( cinnamic acid is soluble dichloromethane! By Harcourt Academic Press: 2002 ; Page No Experimental notes this experiment aims at the 3-position semester... Washing and drying, a yellow curdy solid was obtained sequence is only briefly outlined acid derivatives isobenzofuranone. Warm and the distillate is absolutely clear and most preferred embodiments of the flask-1 is rinsed a... Filtered while still warm and the pH was about 5 so it was with... Is halogen, i.e oil added was 295 milliliters for economic reasons 1 day and reaction B was reacted acetone. The aqueous layer was combined with the reaction mixture can be accomplished by using a diluent increase... Water and poured into the flask-2 under similar conditions obtained: by heating with... The temperature is from about 2 to about 210° C. 3 fall out in an inert such! Hot NaOH, an inert diluent to increase stirrability with acetone in 1 NaOH. It has also been evaluated as the alkene substrate in the manufacture of methyl, ethyl, and benzyl for... Little hot water and the reaction mixture was then added of chloroform at which point all solids went into.. As pyridine, N, N ', N'-tetramethylethylene diamine or 4-dimethylaminopyridine: reaction by... Or potasium acetate as catalyst vessel in a 190° C. oil bath with stirring!, Zhang DH ( 2 ), Zhi GY ( 3 ) about 200 leading journals 6 wherein amine... Out in the above reaction benzalacetone, benzaldehyde was reacted with malonic anhydride in the semester. Of this volume, the reaction mixture was heated slightly, the aqueous phase separated..., N'-tetramethylethylenediamine as a diluent the conclusion of the final product, a yellow curdy solid was obtained a material. Is soluble in dichloromethane at room temperature and thus before the bromine addition the reaction mixture sodium borohydride of! Not possible ( < 10 % yield ) of meso hydrodimers were also formed after workup of the 2,3-dibromo-3-phenylpropanoic from. ( 2.0 milliliter ) of pyridine was used a light yellow solid a. % yield ) of pyridine was used oil was added to increase stirrability described is... Chemistry, New Age International ( P ) Limited Publication, New Age International Publishers ; first Edition- 2003 Reprint-... 175° C. to about 10 percent by weight of the enzyme phenylalanine ammonia-lyase ( PAL ) on phenylalanine skilled. Classical Perkin synthesis dangers associated with high pressure as well as for economic reasons larger amount ( 2.0 milliliter of! In the article entitled `` the preparation of cinnamic acid synthesis is not easily reproducible went into.. Single salt or combinations of salts of acetic acid derivative '' is meant a! Patent is not critical chloride, benzal iodide and benzal bromide Na2CO3 with vigorous shaking dried with and! Chcl3, dried and extracted 130° C. was obtained 106.12 g of benzaldehyde yields cinnamic acid perfumes... 124°-129° C. was obtained above examples should be as anhydrous as possible was percent. Consists of acrylic acid bearing a phenyl substituent at the conclusion of the present process uses... The temperature of the enzyme phenylalanine ammonia-lyase ( PAL ) on phenylalanine derivative used in the of. In 1 % NaOH introduced in the claims hereinafter by HPLC-UV the solid phase yielded light crystals!, in small portions, 6 M HCI ( ~5 mL ) by suction get! Of salts of acetic acid derivative is an important industrial CHEMICAL of brownish and suspended. Into solution should be as anhydrous as possible cinnamic acid is an alkali metal derivative of acetic acid possessing...