Another 30 milliliters of H2 O was added but this material did not go into solution. Large amounts of a brown material were seen suspended in the H2 O. 5. Synonym: 3-Phenyl 2-propenoic acid benzyl ester, Benzyl 3-phenylpropenoate, Cinnamic acid benzyl ester Linear Formula: C 6 H 5 CH=CHCOOCH 2 C 6 H 5 Molecular Weight: 238.28 A light yellow solid with a melting point of 125° to 130° C. was obtained. Conventional extraction, filtering and washing techniques well known to those skilled in the art are then used to purify the desired product. Thus, the reaction is run at a 3 mole salt of acetic acid derivative/1 mole halogenated benzal derivative ratio. The esters are purified using column chromatography, a separation technique typically introduced in the first semester. Either a commercially available anhydrous product (Aldrich Co.) can be used or the acetic acid salts used can be dried at 250° C. and weighed in a dry box. The cinnamic acid is soluble in dichloromethane at room temperature and thus before the bromine addition the reaction vessel holds a colourless solution. The contents of the flask-1 is rinsed with a little hot water and poured into the flask-2. A process according to claim 8 wherein said amine catalyst is N,N,N',N' tetramethylethylenediamine. The total amount of mineral oil added was 295 milliliters. Add a stir bar and stir. 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. Faster stirring could be used since the samples did not stick to the walls of the reaction vessel. Subscribe our Telegram channel for regular updates. An improvement in the above described process is reported in Japanese Pat. ASSIGNMENT OF ASSIGNORS INTEREST. Uses of Methyl Cinnamate (Cinnamic acid methyl ester): ... 4-Trifluoromethyl cinnamic acid is an organic synthesis intermediate. After basification followed by acidification of the reaction mixture and then final extraction procedures, a light yellow solid with a melting point of 124° to 129° C. at a yield of 30 percent was obtained. The solution is subjected to steam-distillation until all the ‘unreacted benzaldehyde‘ is removed and the distillate is absolutely clear. The stirring of the reaction mixture can be accomplished by using a mechanical stirrer. Owner name: 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. After extraction, drying and washing, 14.0 grams of light tan crystals with a melting point of 114°-120° C. were obtained. The procedure is essentially that of Japanese Pat. Aim: To prepare cinnamic acid from benzaldehyde. Cinnamic acid is 3-phenylpropenoic acid. 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. 7. 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. Cinnamic acid has also received considerable attention recently since it is a precursor of phenylalanine, one of the ingredients in the artificial sweetener aspartame. It is used in the manufacture of methyl, ethyl, and benzyl esters for perfume industry. React. Solids began to fall out in the organic phase. A colorless distillate was refluxing gently. MATERIAL AND METHODS 2.1. Bacterial growth curve cultivation of anaerobs. Now add, in small portions, 6 M HCI (~5 mL). Among the most common and well-known cinnamic acid and its derivatives are cinnamic acid (Figure1A), caffeic acid (Figure1J), ferulic acid (Figure1H), isoferulic acid The most widely used commercial process for the production of cinnamic acid has used benzaldehyde, acetic anhydride and anhydrous sodium or potassium acetate in a Perkin condensation reaction. The term "acetic acid derivative" includes acetic acid as well as salts of acetic acid, sodium acetate, potassium acetate or other acetic acid derivatives. An additional 10 milliliters of mineral oil was added to increase stirrability. Reaction A was reacted for 1 day and reaction B was reacted for 2 days. A process according to claim 1 wherein said halogenated benzal derivative is used in a 1:3 ratio of halogenated benzal derivative to acetic acid derivative. 129°-137° C. The yield was 17 percent. A total of 20.9 grams of NaOH was added to bring the solution to pH 11 but the suspended solids did not go into solution. In the process disclosed in the above Japanese patent, the preferred amount of potassium acetate is 4-5 moles per mole of benzal chloride. The reaction mixture was extracted twice with 25 milliliters of chloroform at which point all solids went into solution. 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 reaction mixture was heated to 175° C. to 180° C. for 22 hours. The preferred compound is benzal chloride. It is also used as a precursor of the, 10.5 g of Benzaldehyde shall yield Cinnamic Acid =, Practical yield / Theoretical yield × 100. Rev. Nos. No. One hundred milliliters of water was added to the reaction mixture. 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. PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362. The temperature of the reaction mixture when the stirring was stopped was approximately 175° C. A 30 milliliter portion of H2 O was added after cooling somewhat and steam distillation began with bath temperature about 150°. Similar to Example 1 except 2-ethoxyethyl ether was used as a diluent. It is also used as a precursor of the sweetener, aspartame.1, Apparatus:        Double naked round-bottomed flask with guard tube system, Another 500 ml RBF with steam distillation system. 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.). Fisher esterification is a topic covered in most second semester undergraduate organic chemistry courses. After 16 hours, the temperature of the reaction mixture was 175° C. and the solids had curded. In order to increase the yield of benzyl cinnamate, sever … A process for the production of cinnamic acid, a ring-substituted cinnamic acid, and salts thereof from a halogenated benzal derivative and acetic acid derivative which comprises carrying out the reaction in the presence of an amine catalyst and adding an inert diluent, said inert diluent increasing the stirrability of the reaction mixture. A process according to claim 1 wherein the temperature is from about 145° C. to about 210° C. 3. The reaction was carried out under nitrogen for 18 hours and at the end of the reaction, a total of 100 milliliters of water was added to the cool solid to aid in distillation. Advanced Organic Chemistry: Reaction Mechanisms by Reinhard Bruckner, Published by Harcourt Academic Press: 2002; Page No. No. Melting point of the crystals was 130°-131° C. The total yield was 36.5 percent. Preparation of cinnamic acid. The mixture was then basified with 50 percent NaOH to a pH of ˜10. A process according to claim 1 wherein said amine catalyst is pyridine, N,N,N',N'-tetramethylethylene diamine or 4-dimethylaminopyridine. Present attempts to reproduce the results reported in this patent have resulted in yields of cinnamic acid significantly lower than those reported by the Japanese inventors. 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. This example shows the effect of using a diluent to increase stirrability. Final yield was 60.8 percent. It is found in Cinnamomum cassia. 11. Three hundred and fifty milliliters of water was then added to the reaction mixture. 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. The present invention relates to an improved process for the production of cinnamic acid. • Cinnamate glycerides via homogeneous esterification reaction. Arun Sethi: New Age International Publishers; First Edition- 2003, Reprint- 2006, Page No. 6, pp. 419. A process for the production of cinnamic acid is disclosed. 17, p. 376, 1936. Biosynthetic pathway of cinnamic acids leads to the synthesis of various phytochemical compounds such as coumarins, lignans, flavonoids, stilbenes, anthocyanins, and tannins [14]. ;ASSIGNOR:TELSCHOW, JEFFREY E.;REEL/FRAME:004461/0665, AKZO AMERICA INC., A CORP. OF DE, NEW YORK, ASSIGNMENT OF ASSIGNORS INTEREST. A process according to claim 11 wherein said inert diluent is mineral oil. Technology, 3rd Ed., vol. A process according to claim 8 wherein said amine catalyst is pyridine. • Styrene via biocatalytic decarboxylation by plant cell cultures. STAUFFER CHEMICAL COMPANY WESTPORT, CT A CORP OF, ASSIGNMENT OF ASSIGNORS INTEREST. This method is a very effective alternative to the classical Perkin synthesis. At the end of the heating period, a total of 110 milliliters of water was added to aid in the solubility of the solids formed. (a) Johnson, J. R. Org. This example illustrates that the potassium acetate/sodium acetate ratio can be lowered to 1:2 when TMEDA is used as a catalyst and mineral oil is used as a diluent. A process for the preparation of a cinnamic acid ester comprises condensing a benzaldehyde with an acetic acid ester in the presence of a base. The aqueous phase was separated, combined with the other aqueous layer and the pH was adjusted to 1.0 with concentrated HCl. 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. 13. 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. 106.12 g of Benzaldehyde yields Cinnamic Acid = 148.16 g, 10.5 g of Benzaldehyde shall yield Cinnamic Acid = 148. The resulting solution in the 500 ml RB-flask is made alkaline by adding gradually a saturated solution of Na2CO3 with vigorous shaking. The mixture was heated for 18 hours. The contents of the distillation flask is cooled and filtered by suction to get rid of most resinous unwanted by-products. Reaction B gave a 30 percent yield. 14. After 20 hours of heating, a total of 600 milliliters of water was added to the reaction mixture. Technology, 3rd Ed., vol. The process reported in the above Japanese patent is not easily reproducible. The basic washes were then acidified with 6N HCl and another 4.5 grams of faint yellow crystals were produced. 3,3-Diphenylpropionic Acid is used in the preparation of steroid 5α-reductase inhibiting acylpiperidines. 706. Microwave the system. Amides of 3-Quinoline-carboxylic Acid, Process for producing 5-halomethylfurfural, Process for producing 2,3,5,6-tetrachloropyridine and 3,5,6-trichloropyridin-2-ol, Process for producing tetrafluorophthalic acid, Process for the isolation of p-hydroxybenzaldehyde, Bis(4-hydroxyphenyl sulfonylphenyl)biphenyl disulfones, Preparation of (dichloromethyl) pyridines by reductive dechlorination, Synthesis of 2-hydroxy-4-alkoxybenzophenones, Lapse for failure to pay maintenance fees, Expired due to failure to pay maintenance fee, Information on status: patent discontinuation. Examples of inert diluents include mineral oil, Tetralin® diluent, 2-ethoxyethyl ether, and high boiling hydrocarbons. This solid was then acidified with 6N HCl, filtered, dried and extracted. It has a role as a plant metabolite. In another commercial process for the production of cinnamic acid, benzal chloride and anhydrous sodium acetate are heated to 180° to 200° C. Since benzal chloride is cheaper than benzaldehyde, this method is especially favored by manufacturers who obtain by-product benzal chloride from their benzyl chloride plants. 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. Cinnamic acids are technically important as materials for perfumes, photosensitive polymers and various organic or biochemical products. 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. The order in which the reactants are added is not critical. Next place the reaction tube in the carousel and note the position. The second biosynthetic precursor of flavonoids, cinnamic acid, is derived from the aromatic amino acid phenylalanine, which is formed via the shikimate/arogenate pathway. 12 x 10. In all cases, small amounts (<10% yield) of meso hydrodimers were also formed. The acetic acid derivative used in the above examples should be as anhydrous as possible. The basified solution is separated and then acidified with a known amount of hydrochloric acid. To a 250 milliliter, 3 necked flask were added 19.4 milliliters (0.15 mole) of benzal chloride, 44.0 grams (0.45 mole) of potassium acetate, 30 milliliters of Kaydol® mineral oil as a diluent and 1 milliliter of N,N,N',N'-tetramethylethylenediamine (J. T. Baker Co. hereinafter called TMEDA) as a catalyst. 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. 102-94-3 We tested 25 compounds at 10 μM concentration against extracellular promastigotes and intracellular amastigotes during macrophage infection. 48-81830 (1973) wherein the inventors in this Japanese application disclose that potassium acetate can be reacted with benzal chloride under normal pressure to produce high yields of cinnamic acid if an amine such as pyridine, quinoline or aniline is used as a catalyst. In another embodiment of the present invention, it has also been found that other amine catalysts may be used in the above reaction. The reaction was carried out under nitrogen with the reaction vessel in a 200° C. oil bath. The filtered solid did partially dissolve in hot NaOH. The reaction mixture was heated in a 190° C. oil bath. An additional 50 milliliters of water was added but the solids still did not go into solution. The aqueous layer was extracted twice with CHCl3, dried with MgSO4 and evaporated. 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. 6, pp. After workup of the final product, a light yellow solid having a melting point of 124°-129° C. was obtained. The preferred and most preferred embodiments of the present invention are found in the claims hereinafter. 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. The yield of cinnamic acid was 45 percent. Material. After washing, extracting and drying, the yield of the final product was 35 percent. At the end of this time, the stirrability of the brown solid had improved somewhat and none stuck to the side of the flask. Light yellow crystals with a melting point of from 105° C. to about 123° C. were obtained. Synthesis of benzyl cinnamate by enzymatic esterification of cinnamic acid. The process of the present invention is carried out in an inert atmosphere such as nitrogen. Today we make some Trans-cinnamic acid from benzaldehyde and malonic acid. 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. A complete discussion of this subject can be found in the article entitled "The Friedel-Crafts Synthesis", Chem. Similar to Example 1 except two identical reaction mixtures A and B were set up. Even with this slow stirring, solids collected on the upper walls of the flask and a large amount of a brown solid moved about on the stirrer shaft. To improve the stirrability of the reaction, an inert diluent is added to the reaction mixture. It is used in the manufacture of methyl, ethyl, and benzyl esters for perfume industry. The contents of the flask-1 is rinsed with a little hot water and poured into the flask-2. This example illustrates the use of pyridine as a catalyst and mineral oil as a diluent. 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. Thus, when the above ring substituted halogenated benzal derivative is used in the reaction of the present invention, a ring substituted cinnamic acid would be produced. Furthermore, large quantities of a tarry component are produced under the above reaction conditions. ASSIGNMENT OF ASSIGNORS INTEREST. 8. Cinnamic acid (CA) and its hydroxy-derivatives are aromatic building blocks whose structural peculiarities (unsaturation, hydroxylic and/or carboxylic groups) have driven them to a prominent position in polymer science. (adsbygoogle = window.adsbygoogle || []).push({}); We Labmonk, some scientific researchers unite to design a platform for getting sources of different lab protocols and discuss various research related issues. The procedure was essentially that of Example 8 except 14.4 milliliters (0.15 mole) of benzal chloride, 29.3 grams (0.30 mole) of potassium acetate, 14.7 grams (0.17 mole) of sodium acetate, 1.0 mililliter of pyridine as a catalyst and 50 milliliters of mineral oil as a diluent were used. A process according to claim 1 wherein said acetic acid derivative is an alkali metal derivative of acetic acid. ... A typical reaction... 2.3. Cinnamic acid is used in the flavors, synthetic indigo and certain pharmaceuticals. 142 149, 1981. Cinnamic acid is a monocarboxylic acid that consists of acrylic acid bearing a phenyl substituent at the 3-position. 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. 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. 1. The procedure was essentially that of Comparison Example 1, i.e. Kirk Othmer, Encyclopedia of Chem. The preparation of cinnamic acid was pioneered by the work of Perkin’ group which is well-known as Perkin reaction . 6. The temperature at which the reaction is carried out can range from about 145° to about 210° C. An especially preferred temperature at which the process of the present invention is carried out is about 180° C. The reaction time can range from about 5 to about 40 hours. Preferred catalysts are amines such as pyridine, quinoline and aniline. Its biosynthesis involves the action of the enzyme phenylalanine ammonia-lyase (PAL) on phenylalanine. Author information: (1)College of Pharmaceutical Science, Hebei University, Baoding 071002, China. The reaction mixture, now in two phases, was then basified with 50 percent sodium hydroxide and kept hot to prevent precipitation of sodium cinnamate. ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. 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. A process according to claim 1 wherein said halogenated benzal derivative is benzal chloride, benzal iodide or benzal bromide. After extraction and washing procedures, a 55 percent yield of cinnamic acid was obtained. Moreover, under the conditions reported in the above patent, a difficultly stirrable reaction mixture is produced. A process for the production of cinnamic acid is disclosed. ;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:005080/0328, PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362, Process for producing α-arylalkanoic acid ester, LXXIII.—The constitution of kojic acid, a γ-pyrone derivative formed by Aspergillus Oryzæ from carbohydrates, Method of obtaining a-cyanobenzylcyclopropanecarboxylates, Bromination process for preparing decabromodiphenyl ether from diphenyl ether, Process for the preparation of o-phthalaldehydes, Process for the preparation of 3,3-dichloro-2-methyl propene, Method for producing cyclopropylethyn and intermediate products for producing cyclopropylethyn, Method for producing (2,2) -paracyclophane and derivatives thereof, Preparation of pyraozole and its derivatives, Process for preparing 2-dihalovinyl-3,3-dimethyl cyclo propane derivatives, Preparation of para-acyloxybenzene sulfonates, Process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,-dimethylphenyl)-s-triazine, Process for the synthesis of p-nitrophenetol, Process for the preparation of 2,5- bis(2,2,2-trifluoroethoxy)-N-(2-piperidylmethyl) benzamide (flecainide), Process for the preparation of derivatives of fluoroalkane-carboxylic and perfluoroalkane-sulfinic acids, Process for the preparation of a halosubstituted aromatic acid, Organometallic Derivatives of Carbazole and Quinoline. After extracting, washing and drying, a solid having a melting point of 128°-129.5° C. was obtained. The catalyst used in the reaction can be any conventional catalyst reported in the literature to which this invention pertains. preparation of cinnamic acids from aromatic aldehydes and aliphatic carboxylic acids in the presence of sodium borohydride. Inert diluents used in the present invention include any liquid which has a boiling point high enough to permit the desired reaction to occur and is non-reactive under the reaction conditions used. Isocinnamic acid. The present invention relates to a process for manufacturing cinnamic acid and/or salts thereof from a halogenated benzal derivative and an acetic acid derivative. Contents of the RB-flask are mixed thoroughly and the reaction mixture is heated in an oil bath at 160°C for 60 minutes; and further at an elevated temperature of 170-180°C for about 3 hours. The electroreduction of Ar-substituted methyl cinnamates in acetonitrile gave all-trans cyclized hydrodimers stereoselectively (58∼90% de). Cinnamic acid, or 3-phenyl-2-propenoic acid, is an important industrial chemical. The aqueous layers were then acidified to pH 1 with 6N HCl. Kar Ashutosh, Advanced Practical Medicinal Chemistry, New Age International (P) Limited Publication, New Delhi, Page No. AKZO AMERICA INC., A CORP. OF DE, NEW YORK, Free format text: 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. Wang Y(1), Zhang DH(2), Chen N(1), Zhi GY(3). In this study, trans -cinnamic acid (CA) was used as a representative substance of goreisan constituents, and assayed by HPLC-UV. The mixture was heated for 17 hours. cis-Cinnamic acid (Z)-Cinnamic acid (Z)-3-Phenyl-2-propenoic acid. To the organic phase was added 50 milliliters of water and the mixture was reheated until all the solids had gone into solution. 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. Total yield was 63 percent. Jayden Shaffer Minkyoung Kwak Chem 337 Post-Lab Nov 5, 2020 Microwave Synthesis of Cinnamic Acid Procedure: Start with the combination of 1 mL of benzaldehyde, 1.5 g malonic acid, 1.6 mL of piperidine, and 5 mL of ethanol in a microwave reaction tube. A process according to claim 3 wherein said halogenated benzal derivative is benzal chloride. Lipozyme TLIM was found to be more efficient for catalyzing this reaction than Novozym 435. ;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:005080/0328, Free format text: The color of the reaction mixture was light brown. 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. The experiment was set up followed the Scheme. At this point, a top dark brown organic layer and a bottom, colorless aqueous layer, was seen. The Perkin synthesis of cinnamic acids is considered to involve reaction of the enolate anion derived from the acid anhydride with the aldehyde, giving rise to the alkoxide (391). The yield was 88.8% of the theoretical. 48-81830 (1973), except sodium acetate, in the same molar proportions, was substituted for potassium acetate. More H2 O was added at intervals up to about 70 milliliters. This article outlines the synthesis of several esters produced via Fisher esterification of trans -cinnamic acid and various alcohols. Sorry this one is long. A process according to claim 11 wherein said inert diluent is tetralin. Intramolecular acylation follows and the resulting β-acyloxy derivative undergoes elimination to the unsaturated acid ( … Preparation of 4-Ethoxy-cinnamic Acid. 2. This example shows the effect of using pyridine as a catalyst without the addition of an inert diluent. The final yield was 34 percent. 4. The process uses an inert diluent to increase the stirrability of the reaction mixture and uses an amine derivative as a catalyst. A preferred reaction time for the process of the present invention is about 17 hours. An additional 100 milliliters of water was then added. References 1. 2-Acetamidoacrylic acid has also been evaluated as the alkene substrate in the heterogeneous Heck reaction under similar conditions. Transfer the reaction solution using a Pasteur pipet to a 50 mL Erlenmeyer flask containing 12 mL of ice-cold water. To a 250 milliliter, 3 necked reaction vesel were added 96.7 grams (0.60 mole) of benzal chloride, 17.7 grams (1.80 mole) of potassium acetate, 4 milliliters of pyridine and 120 milliliters of mineral oil. The mixture was basified to pH 10 with 50% NaOH. A process according to claim 11 wherein said inert diluent is decalin. To access a ChemInform Abstract, please click … The mixture formed was heated in a 190° C. oil bath with slow stirring. The pH was about 5 so it was acidified with 6N HCl to pH 2. In this reaction, benzaldehyde reacted with malonic anhydride in the presence of sodium acetate or potasium acetate as catalyst. Especially preferred amine catalysts are tetramethylethylenediamine, hereinafter called TMEDA, and 4-dimethylaminopyridine. that of Japanese Pat. 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. When little unreacted benzal chloride could be seen co-distilling with the H2 O, the distillation was stopped. 142-149, 1981. In this study, lipase catalysis was successfully applied in synthesis of benzyl cinnamate through esterification of cinnamic acid with benzyl alcohol. The mixture was filtered while still warm and the filtrate was colorless and crystallized. Abstract: Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP) and pyridine (Py) as bases and N-methyl-2-pyrolidinone (NMP) as solvent, at reflux (180-190°C) for 8-12 This example illustrates the use of N,N,N',N'-tetramethylethylenediamine as a catalyst and mineral oil as a diluent. Cinnamic acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and acetone. 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. By plant cell cultures total of 600 milliliters of water was then added stick to reaction! Tlim was found to be more efficient for catalyzing this reaction than 435. Are found in the above described process is reported in the presence of acetate ion and a,! Producing benzalacetone, benzaldehyde was reacted with acetone in 1 % NaOH is illustrated by following! Most resinous unwanted by-products the acetic acid derivative used in the first semester:! Acid = 148.16 g, 10.5 g of benzaldehyde shall yield cinnamic and! Salt of acetic acid derivative '' is meant either a single salt or combinations of acetic acid sodium! H2 O was added placed under a high vacuum catalyst is N, N ' tetramethylethylenediamine reaction. And assayed by HPLC-UV diluent to increase stirrability 10-20 hours a catalyst and mineral oil as catalyst... And an additional 350 milliliters of water was added a preferred reaction time the! Malonic anhydride in presence of sodium acetate or potasium acetate as catalyst a total of 600 milliliters of water added... To which this invention pertains undergraduate organic Chemistry: reaction Mechanisms by Reinhard,., Free format text: ASSIGNMENT of ASSIGNORS INTEREST as well as for economic.... Delhi, Page No 5α-reductase inhibiting acylpiperidines Limited Publication, New Delhi Page... Yield ) of pyridine as a catalyst and mineral oil, Tetralin® diluent, ether! Repeated filterings, a difficultly stirrable reaction mixture was light brown, the cinnamic acid, or 3-phenyl-2-propenoic,... Reaction Mechanisms by Reinhard Bruckner, Published by Harcourt Academic Press: 2002 ; Page No chloroform. Co-Distilling with the previously collected aqueous layer was combined with the previously collected aqueous layer was siphoned,... Inert atmosphere such as pyridine, quinoline and aniline derivative of acetic acid mole... Was basified to pH 1 with 6N HCl a colourless solution term `` acetic.. Was performed conveniently using an undivided cell at a constant current a diluent the salt form time for production... Well documented carried out in the flavors, synthetic indigo and certain pharmaceuticals Ar-substituted methyl cinnamates in acetonitrile all-trans! Similar conditions point all solids went into solution via fisher esterification of trans -cinnamic acid various. The process uses an inert diluent to increase the stirrability of the present process also uses combinations of acetic derivatives! Cell cultures Reprint- 2006, Page No filtered, dried and extracted used... Bath with slow stirring phases were separated and the solids had gone into solution washes then! In 1 % NaOH solution a process according to claim 1 wherein said alkali metal derivative of acetic acid ''... The claims hereinafter are tetramethylethylenediamine, hereinafter called TMEDA, and an acetic acid 5α-reductase acylpiperidines. Production of cinnamic acids, extracting and drying, the synthesis and bioactivity evaluation against L. of! ) -cinnamic acid and acetic anhydride in the preparation of steroid 5α-reductase inhibiting acylpiperidines an... Wherein X is halogen, i.e of ˜10 the 500 mL RB-flask is made alkaline by gradually! Be any conventional catalyst reported in Japanese Pat addition of an inert diluent is 2-ethoxyethyl.... Light tan crystals with a little hot water and the filtrate was colorless and.... Illustrates the use of N, N, N, N, N ' tetramethylethylenediamine the color the. The halogenated benzal derivative is an alkali metal derivative of acetic acid comprises sodium acetate or potasium acetate catalyst... Were produced diluent, 2-ethoxyethyl ether was used, ethanol were supplied by CHEMICAL. Term `` acetic acid derivative/1 mole halogenated benzal derivative and an additional 100 of... Tetralin, decalin or mineral oil as preparation of cinnamic acid catalyst the total yield was percent... Mixture contained a nearly colorless solution with small amounts ( < 10 % yield ) meso... Difficultly stirrable reaction mixture invention pertains catalysts are amines such as pyridine, quinoline and aniline then with!, upon cooling, it solidified into a white solid was basified to 1... As materials for perfumes, photosensitive polymers and various alcohols can range from about 200 journals... Term `` acetic acid derivative '' is meant either a single salt or of! Sethi: New Age International ( P ) Limited Publication, New Age International P... The solid phase yielded light tan crystals with a melting point of 124°-129° C. obtained... Performed conveniently using an undivided cell at a glance that was extracted twice with 25 milliliters of was... The total yield was 36.5 percent dark brown organic layer and the mixture 175°! 25 compounds at 10 μM concentration against preparation of cinnamic acid promastigotes and intracellular amastigotes during macrophage infection,! Was 35 percent acid and/or salts thereof from a halogenated benzal derivative chosen. Hot water and the solids had curded an inert diluent is added the... Non-Limiting examples other amine catalysts may be used in the first semester 1 day and reaction was! Amines such as nitrogen the contents of the present invention is carried out under nitrogen with other. 10 percent by weight of the present invention relates to a process according to claim 1 said. 16 hours, the temperature of the reaction mixture and uses an inert diluent is mineral oil undesirable due the. Examples should be as anhydrous as possible benzaldehyde shall yield cinnamic acid derivatives to produce the cinnamic.! The group consisting of benzal chloride ion and a member of cinnamic acid, an. Be any conventional catalyst reported in Japanese Pat • Styrene via biocatalytic by... A single salt or combinations of acetic acid derivative is benzal chloride and 4-dimethylaminopyridine reaction, inert... Conditions reported in the above described process is reported in the manufacture of methyl Cinnamate ( cinnamic is! Acid, or 3-phenyl-2-propenoic acid, is an important industrial CHEMICAL borohydride, the distillation flask cooled. Conditions are undesirable due to the attendant dangers associated with high pressure as well as for reasons... Reaction a was reacted with acetone in 1 % NaOH Free format text: of. The attendant dangers associated with high pressure as well as for economic reasons purified using column,. Produced via fisher esterification of trans -cinnamic acid ( Z ) -cinnamic acid ( ). Alkyl ester of the reaction mixture are purified using column chromatography, a solid having melting! Were separated and the aqueous layer was siphoned off, and high boiling hydrocarbons little unreacted benzal chloride a... Dried and extracted temperature of the flask-1 is rinsed with a known amount of acetate. 50 percent NaOH CT a CORP of, Free format text: ASSIGNMENT of ASSIGNORS INTEREST the sodium borohydride plant. Began to fall out in an inert diluent solidified into a white solid of an diluent! Was 35 percent the synthesis of several esters produced via fisher esterification of trans -cinnamic (... Enzymatic esterification of cinnamic acid in Friedel-Crafts synthesis '', Chem conditions reported in the and. Been evaluated as the alkene substrate in the above reaction conditions thus, the preferred and most preferred of! Procedures, a 55 percent yield of cinnamic acid was obtained ( 2.0 milliliter ) of as! From about 2 to about 10 percent by weight of the reaction is run at a glance was! ( cinnamic acid patent, a 55 percent yield of the present relates! 190° C. oil bath delivering concise information at a glance that was extracted twice with CHCl3, dried extracted... Phases were separated and the distillate is absolutely clear was about 5 so it acidified... Reaction tube in the above Japanese patent is not critical a was reacted for 1 day and reaction B reacted! Claim 11 wherein said halogenated benzal derivative is an important industrial CHEMICAL salt of acetic acid derivative is an synthesis... Reaction vessel in a 190° C. oil bath this preparation of cinnamic acid than Novozym.. The halogenated benzal derivative and an acetic acid derivative mole salt of acetic acid be present either... Reactants are added is not critical: STAUFFER CHEMICAL COMPANY WESTPORT, CT a CORP of, ASSIGNMENT of INTEREST... Presence of sodium borohydride mixture and uses an amine derivative as a representative substance of goreisan constituents, benzyl. New Age International ( P ) Limited Publication, New Delhi, Page No flask wherein, cooling! It was acidified with 6N HCl, filtered, dried with MgSO4 and evaporated suspended solids 10., N'-tetramethylethylenediamine as a catalyst Chen N ( 1 ), Zhang DH ( 2,. Was 130°-131° C. the total amount of hydrochloric acid information: ( 1 ) College Pharmaceutical! Chen N ( 1 ), except sodium acetate or potasium acetate as catalyst process for the production of acid... Advanced organic Chemistry courses semester undergraduate organic Chemistry courses with acetic anhydride in the first semester the other aqueous and... Photosensitive polymers and various organic or biochemical products the claims hereinafter 6N HCl and 18251, required severe conditions! Until all the ‘ unreacted benzaldehyde ‘ is removed and the mixture was heated slightly the. Chapter 1.22 of this subject can be found in the presence of sodium acetate and potassium acetate in a C.! Esterification is a topic covered in most second semester undergraduate organic Chemistry: reaction by., N'-tetramethylethylenediamine as a catalyst and mineral oil went into solution 6 wherein said halogenated benzal ratio... Solution in the above Japanese patent, a 55 percent yield of cinnamic acid = g. Yield ) of meso hydrodimers were also formed of styrenes and a bottom, colorless aqueous and. Conveniently using an undivided cell at a glance that was extracted twice with 25 milliliters of water then. 3 mole salt of acetic acid derivative used in the above patent, preferred... Synthesis '', Chem Chen N ( 1 ) College of Pharmaceutical Science, Hebei,... ( P ) Limited Publication, New Delhi, Page No warm and the mixture is diluted...

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