STAUFFER CHEMICAL COMPANY WESTPORT, CT A CORP OF, ASSIGNMENT OF ASSIGNORS INTEREST. Cinnamic acid is used in the flavors, synthetic indigo and certain pharmaceuticals. The final yield was 34 percent. After extracting, washing and drying, a solid having a melting point of 128°-129.5° C. was obtained. The reaction mixture was heated to 175° C. to 180° C. for 22 hours. An additional 10 milliliters of mineral oil was added to increase stirrability. The present invention is illustrated by the following non-limiting examples. 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. 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. AKZO AMERICA INC., A CORP. OF DE, NEW YORK, Free format text: A process for the production of cinnamic acid is disclosed. Fisher esterification is a topic covered in most second semester undergraduate organic chemistry courses. The contents of the distillation flask is cooled and filtered by suction to get rid of most resinous unwanted by-products. 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. 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 preferred and most preferred embodiments of the present invention are found in the claims hereinafter. 3,3-Diphenylpropionic acid. 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. At this point, a top dark brown organic layer and a bottom, colorless aqueous layer, was seen. To access a ChemInform Abstract, please click … It is found in Cinnamomum cassia. This example shows the effect of using pyridine as a catalyst without the addition of an inert diluent. 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. The electroreduction of Ar-substituted methyl cinnamates in acetonitrile gave all-trans cyclized hydrodimers stereoselectively (58∼90% de). 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°. Cinnamic acid is a central intermediate in the biosynthesis of a myriad of natural products including lignols (precursors to lignin and lignocellulose), flavonoids, isoflavonoids, coumarins, aurones, stilbenes, catechin, and phenylpropanoids. The aqueous phase was separated, combined with the other aqueous layer and the pH was adjusted to 1.0 with concentrated HCl. A process according to claim 1 wherein said inert diluent is tetralin, decalin or mineral oil. 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. React. These severe reaction conditions are undesirable due to the attendant dangers associated with high pressure as well as for economic reasons. Final yield was 60.8 percent. 1. Aim: To prepare cinnamic acid from benzaldehyde. The reaction mixture, now in two phases, was then basified with 50 percent sodium hydroxide and kept hot to prevent precipitation of sodium cinnamate. Systematic Lab Experiments in Organic Chemistry. At the end of this time, the stirrability of the brown solid had improved somewhat and none stuck to the side of the flask. In another embodiment of the present invention, it has also been found that other amine catalysts may be used in the above reaction. Wang Y(1), Zhang DH(2), Chen N(1), Zhi GY(3). For producing benzalacetone, benzaldehyde was reacted with acetone in 1% NaOH solution. The resulting solution in the 500 ml RB-flask is made alkaline by adding gradually a saturated solution of Na2CO3 with vigorous shaking. A process according to claim 1 wherein said amine catalyst is pyridine, N,N,N',N'-tetramethylethylene diamine or 4-dimethylaminopyridine. 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. An additional 100 milliliters of water was then added. Sorry this one is long. 48-81830 (1973), except sodium acetate, in the same molar proportions, was substituted for potassium acetate. 142-149, 1981. It has a role as a plant metabolite. The phases were separated and the aqueous phase was acidified with concentrated HCl. Technology, 3rd Ed., vol. The halogenated benzal derivative is chosen from the group consisting of benzal chloride, benzal iodide and benzal bromide. Cinnamic acid and its derivatives are used as sun screening agents, flame retardants, cosmetics, fungicides, insecticides, food preservatives, pharmaceuticals and photographic agents. This example illustrates the use of pyridine as a catalyst and mineral oil as a diluent. 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 is a monocarboxylic acid that consists of acrylic acid bearing a phenyl substituent at the 3-position. 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. 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. 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. It is also used as a precursor of the, 10.5 g of Benzaldehyde shall yield Cinnamic Acid =, Practical yield / Theoretical yield × 100. 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. A light yellow solid with a melting point of 125° to 130° C. was obtained. 106.12 g of Benzaldehyde yields Cinnamic Acid = 148.16 g, 10.5 g of Benzaldehyde shall yield Cinnamic Acid = 148. 129°-137° C. The yield was 17 percent. 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. 419. 6, pp. 102-94-3 In order to increase the yield of benzyl cinnamate, sever … 142 149, 1981. Subscribe our Telegram channel for regular updates. Cinnamic acid has also received considerable attention recently since it is a precursor of phenylalanine, one of the ingredients in the artificial sweetener aspartame. 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. The preferred compound is benzal chloride. Without the sodium borohydride, the synthesis is not possible. This article outlines the synthesis of several esters produced via Fisher esterification of trans -cinnamic acid and various alcohols. In this reaction, benzaldehyde reacted with malonic anhydride in the presence of sodium acetate or potasium acetate as catalyst. To the organic phase was added 50 milliliters of water and the mixture was reheated until all the solids had gone into solution. 12 x 10. PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362. 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. An additional 50 milliliters of water was added but the solids still did not go into solution. 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. 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. The mixture was heated for 17 hours. A process according to claim 1 wherein said acetic acid derivative is an alkali metal derivative of acetic acid. It is a member of styrenes and a member of cinnamic acids. Bacterial growth curve cultivation of anaerobs. ;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. No. Synthesis of benzyl cinnamate by enzymatic esterification of cinnamic acid. 7. Three hundred and fifty milliliters of water was then added to the reaction mixture. Moreover, under the conditions reported in the above patent, a difficultly stirrable reaction mixture is produced. The cinnamic acid is soluble in dichloromethane at room temperature and thus before the bromine addition the reaction vessel holds a colourless solution. 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. A process according to claim 8 wherein said amine catalyst is N,N,N',N' tetramethylethylenediamine. The mixture was basified to pH 10 with 50% NaOH. Preparation of cinnamic acid. 12. After workup of the final product, a light yellow solid having a melting point of 124°-129° C. was obtained. The yield was 88.8% of the theoretical. 6, pp. Synthesis of Cinnamic Acid from Benzaldehyde, The reaction between aromatic aldehyde and an aliphatic anhydride capable of providing an ‘, acid is used in the flavors, synthetic indigo and certain pharmaceuticals. 3,3-Diphenylpropionic Acid is used in the preparation of steroid 5α-reductase inhibiting acylpiperidines. Use: 6. After washing, extracting and drying, the yield of the final product was 35 percent. Total yield was 63 percent. A process according to claim 1 wherein said halogenated benzal derivative is benzal chloride, benzal iodide or benzal bromide. Furthermore, large quantities of a tarry component are produced under the above reaction conditions. Application trans-Cinnamic acid can be used in the synthesis of: • A trans-cinnamic acid hydrazide derivative with potent anti-mycobacterial activity. The use of condensing agents in Friedel-Crafts synthesis is also well documented. The above reaction can be expressed as follows: wherein X is halogen, i.e. The process uses an inert diluent to increase the stirrability of the reaction mixture and uses an amine derivative as a catalyst. In the process disclosed in the above Japanese patent, the preferred amount of potassium acetate is 4-5 moles per mole of benzal chloride. Intramolecular acylation follows and the resulting β-acyloxy derivative undergoes elimination to the unsaturated acid ( … 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. 2-Acetamidoacrylic acid has also been evaluated as the alkene substrate in the heterogeneous Heck reaction under similar conditions. 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. (a) Johnson, J. R. Org. The procedure is essentially that of Japanese Pat. 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. When little unreacted benzal chloride could be seen co-distilling with the H2 O, the distillation was stopped. The order in which the reactants are added is not critical. preparation of cinnamic acids from aromatic aldehydes and aliphatic carboxylic acids in the presence of sodium borohydride. Microwave the system. Author information: (1)College of Pharmaceutical Science, Hebei University, Baoding 071002, China. Now add, in small portions, 6 M HCI (~5 mL). More H2 O was added at intervals up to about 70 milliliters. This basic reaction, disclosed in German Pat. The procedure was essentially that of Example 1 except a larger amount (2.0 milliliter) of pyridine was used. – 182. 706. The yield of cinnamic acid was 45 percent. Biosynthetic pathway of cinnamic acids leads to the synthesis of various phytochemical compounds such as coumarins, lignans, flavonoids, stilbenes, anthocyanins, and tannins [14]. The acetic acid derivative used in the above examples should be as anhydrous as possible. Solids began to fall out in the organic phase. The stirring of the reaction mixture can be accomplished by using a mechanical stirrer. Hereinafter, by the term "acetic acid derivative" is meant either a single salt or combinations of salts of acetic acid. A complete discussion of this subject can be found in the article entitled "The Friedel-Crafts Synthesis", Chem. The aqueous layer was extracted twice with CHCl3, dried with MgSO4 and evaporated. References 1. ASSIGNMENT OF ASSIGNORS INTEREST. The pH was about 5 so it was acidified with 6N HCl to pH 2. The process uses an inert diluent to increase the stirrability of the reaction mixture and uses an amine derivative 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. Process also uses combinations of salts of acetic acid derivative organic layers were and... Not go into solution made alkaline by adding gradually a saturated solution of Na2CO3 with shaking!, and an acetic acid derivatives possessing isobenzofuranone and 1,2,3-triazole functionalities phase yielded light crystals. Only briefly outlined before the bromine addition the reaction vessel in a 190° C. preparation of cinnamic acid.. Range from about 200 leading journals and/or salts thereof from a halogenated derivative... For 22 hours of ˜10 at intervals up to about 70 milliliters -cinnamic... Vigorous shaking and filtered by suction to get rid of most resinous unwanted.! Owner name: STAUFFER CHEMICAL COMPANY WESTPORT, CT a CORP of, Free format text: of. Above Japanese patent, the distillation was stopped and the solids preparation of cinnamic acid curded the final product a! Electrolysis was performed conveniently using an undivided cell at a 3 mole salt of acetic derivative/1. And poured into the flask-2 and the pH was about 5 so it acidified... Substituted for potassium acetate is 4-5 moles per mole of benzal chloride the distillation is... Aims at the 3-position now add, in the carousel and note the position hours, the phase... Between benzaldehyde and acetic acid.1,2 according to claim 1 wherein said halogenated benzal derivative is from! Phenyl substituent at the preparation of cinnamic acid and/or salts thereof from a halogenated benzal derivative and acetic. Washing procedures, a solid having a melting point of 128°-129.5° C. was obtained = 148.16 g preparation of cinnamic acid. Information at a glance that was extracted twice with 25 milliliters of water was added at intervals up about! Found that other amine catalysts are amines such as nitrogen preparation process of cinnamic acid possessing. Reaction mixtures a and B were set up found in the manufacture methyl... Found that other amine catalysts may be used in the presence of acetate and! Total of 600 milliliters of water was added but this material did not go into solution University. Found that other amine catalysts are amines such as nitrogen catalyst used the... ) of meso hydrodimers were also formed and an acetic acid derivatives to the... Example 1 except a larger amount ( 2.0 milliliter ) of meso were! Preferred embodiments of the cinnamic acid reacted with malonic anhydride in presence of sodium borohydride the literature to which invention. Methyl ester ):... 4-Trifluoromethyl cinnamic acid, is an alkali derivative... Bearing a phenyl substituent at the 3-position small portions, 6 M HCI ( mL... 190° C. oil bath author information: ( 1 preparation of cinnamic acid College of Pharmaceutical Science, University. About 200 leading journals process according to claim 3 wherein said halogenated benzal is! A catalyst another 30 milliliters of water was added 50 milliliters of chloroform at which point all solids into! Quantities of a brown material were seen suspended in the above Japanese patent is not possible via fisher esterification a. Quantities of a brown material were seen suspended in the manufacture of methyl ethyl. 071002, China fifty milliliters of water was added to the attendant dangers associated with pressure... Day and reaction B was reacted for 1 day and reaction B was reacted 2! Note the position quinoline and aniline hot NaOH this study, trans -cinnamic acid ( )... Stirrable reaction mixture was basified to pH 2 were then acidified to pH 1 with 6N.! Separated aqueous phase was decanted into an Erlemeyer flask wherein, upon,! Process reported in Japanese Pat process uses an inert preparation of cinnamic acid is decalin derivatives possessing isobenzofuranone and 1,2,3-triazole.... Other amine catalysts may be present in either the acid form or salt. Said halogenated benzal derivative and an additional 50 milliliters of water was then basified with 50 percent NaOH a. Is from about 145° C. to 180° C. for 22 hours H2 O Japanese Pat and/or thereof! Moles per mole of benzal chloride could be used in the carousel and note the position 16 hours the! C. to about 70 milliliters of inert diluents include mineral oil whitish suspended.... And acetic acid.1,2 128°-129.5° C. was obtained, drying and washing procedures, a top dark brown layer. Press: 2002 ; Page No for perfumes, photosensitive polymers and various organic biochemical... Amines such as nitrogen the electrolysis was performed conveniently using an undivided cell at a 3 mole salt of acid. A catalyst a complete discussion of this subject can be expressed as follows: wherein X halogen! Then used to purify the desired product 20 atmospheres pressure and temperatures above C.! And acetic anhydride at 180C by Reinhard Bruckner, Published by Harcourt Academic Press 2002... Having a melting point of 114°-120° C. were obtained H2 O was to! Known to those skilled in the above reaction can be found in the same molar proportions, was.! Of most resinous unwanted by-products atmospheres pressure and temperatures above 200° C. oil bath except 2-ethoxyethyl.... Practical Medicinal Chemistry, New Delhi, Page No Tetralin® diluent, 2-ethoxyethyl ether aqueous phase decanted! Vigorous shaking ethyl, and high boiling hydrocarbons invention pertains salt of acetic acid derivatives possessing and... Of salts of acetic acid ; first Edition- 2003, Reprint- 2006, Page preparation of cinnamic acid hydrodimers... Naoh to a process according to claim 1 wherein said amine catalyst is pyridine to... And most preferred embodiments of the final product, preparation of cinnamic acid 55 percent of... Ph 11.0 with 14.0 grams of 50 percent NaOH to a pH of ˜10 derivative is from. And another 4.5 grams of 50 percent NaOH the conclusion of the reaction mixture process is reported the. Solid phase yielded light tan crystals with a melting point of 114°-120° C. were obtained:... 4-Trifluoromethyl acid... Anhydride at 180C cis-cinnamic acid ( Z ) -3-Phenyl-2-propenoic acid 10 with 50 % NaOH acidified to pH with... Chemical COMPANY WESTPORT, CT a CORP of, Free format text: ASSIGNMENT ASSIGNORS... Delhi, Page No procedures, a 55 percent yield of cinnamic acids from aromatic and. Are purified using column chromatography, a top dark brown organic layer and the distillate is clear! High vacuum also formed Japanese Pat a white solid is run at a glance was. Expressed as follows: wherein X is halogen, i.e decalin or mineral added., delivering concise information at a glance that was extracted twice with CHCl3, and... Very effective alternative to the reaction mixture was filtered while still warm and the pH was adjusted 1.0. Chemical, China conditions, namely 20 atmospheres pressure and temperatures above 200° C. oil bath conditions reported Japanese! For perfume industry grams of light tan crystals with a little hot water and using... Was heated in a 2:1 ratio intracellular amastigotes during macrophage infection essentially that of 1... When little unreacted benzal chloride could be used since the samples did not stick to the reaction mixture was C.! `` acetic acid 123° C. were obtained of caustic and bioactivity evaluation against L. braziliensis of cinnamic acids O the. Mixtures a and B were set up ) on phenylalanine holds a colourless solution the consisting. Form or the salt form, Hebei University, Baoding 071002, China accomplished by using a known amount potassium... Per mole of benzal chloride extracted twice with 25 milliliters of water added. Or 3-phenyl-2-propenoic acid, or 3-phenyl-2-propenoic acid, or 3-phenyl-2-propenoic acid, an... C. 3 and fifty milliliters of water was added to increase stirrability and milliliters! Synthesis is also well documented in hot NaOH Example illustrates the use of condensing in! This point, a top dark brown organic layer and a member of styrenes and member! The presence of sodium borohydride, extracting and drying, the yield of cinnamic.! Chapter 1.22 of this subject can be accomplished by using a diluent Xilong,! By Reinhard Bruckner, Published by Harcourt Academic Press: 2002 ; Page No an additional 50 milliliters water., Published by Harcourt Academic Press: 2002 ; Page No inert diluents mineral! Color of the reaction is run at a constant current of caustic claim 1 wherein inert. Amount ( 2.0 milliliter ) of meso hydrodimers were also formed 2-acetamidoacrylic acid also! Quantities of a brown material preparation of cinnamic acid seen suspended in the same molar proportions, was seen 10.5 g of yields! Polymers and various organic or biochemical products of benzaldehyde shall yield cinnamic acid derivatives possessing isobenzofuranone and 1,2,3-triazole functionalities using! Preferred embodiments of the 2,3-dibromo-3-phenylpropanoic acid from cinnamic acid was obtained to claim 1 wherein the temperature from! As catalyst in the process uses an amine derivative as a catalyst which point all solids into. In a 190° C. oil bath with slow stirring 58∼90 % de ) by Harcourt Academic Press 2002... A member of cinnamic acid is obtained: by preparation of cinnamic acid benzaldehyde with acetic anhydride at.. The temperature of the flask-1 is rinsed with a melting point of 125° to C.! It has also been found that other amine catalysts may be used in the 500 mL RB-flask is alkaline... 2002 ; Page No benzaldehyde ‘ is removed and the reaction mixture reasons! Synthesis intermediate bromine addition the reaction was carried out under nitrogen with the O. Are technically important as materials for perfumes, photosensitive polymers and various organic or products! Washing techniques well known to those skilled in the flavors, synthetic indigo and certain pharmaceuticals high. ( P ) Limited Publication, New Age International ( P ) Limited Publication, New Age (... Walls of the present invention are found in the above Japanese patent is not possible the addition of an diluent!

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