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preparation of cinnamic acid

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. Preparation of 4-Ethoxy-cinnamic Acid. 142 149, 1981. preparation of cinnamic acids from aromatic aldehydes and aliphatic carboxylic acids in the presence of sodium borohydride. This example illustrates the use of pyridine as a catalyst and mineral oil as a diluent. No. 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. While clinical efficacy of the suppository has been reported, few studies have been carried out to clarify the preparation procedure and pharmacokinetics of the suppository. Hereinafter, by the term "acetic acid derivative" is meant either a single salt or combinations of salts of acetic acid. Cinnamic acid is obtained: By heating benzaldehyde with acetic anhydride at 180C. 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. 48-81830 (1973). STAUFFER CHEMICAL COMPANY WESTPORT, CT A CORP OF, ASSIGNMENT OF ASSIGNORS INTEREST. An improvement in the above described process is reported in Japanese Pat. The process of the present invention is carried out in an inert atmosphere such as nitrogen. 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. STAUFFER CHEMICAL COMPANY WESTPORT, CT A CORP OF, Free format text: To 40 grams (0.4 mole) of anhydrous potassium acetate in a 250 milliliter 3-necked flask under nitrogen were added 16.1 grams (0.10 mole) of benzal chloride and 0.5 milliliter of pyridine. This example shows the effect of using pyridine as a catalyst without the addition of an inert diluent. interaction between benzaldehyde and acetic anhydride in presence of acetate ion and a hydronium ion yields, cinnamic acid and acetic acid.1,2. 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 process uses an inert diluent to increase the stirrability of the reaction mixture and uses an amine derivative as a catalyst. Kirk Othmer, Encyclopedia of Chem. A process according to claim 3 wherein said halogenated benzal derivative is benzal chloride. Aim: To prepare cinnamic acid from benzaldehyde. The mixture is then diluted with water and basified using a known amount of caustic. The present invention relates to an improved process for the production of cinnamic acid. Acetonitrile at HPLC grade was... 2.2. 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 yield of cinnamic acid was 45 percent. 7. 142-149, 1981. In one embodiment of the invention, the halogenated benzal derivative and the acetic acid derivative are reacted together in the presence of an amine catalyst. After extraction and washing procedures, a 55 percent yield of cinnamic acid was obtained. The amount of catalyst can range from about 2 to about 10 percent by weight of the halogenated benzal derivative. Fisher esterification is a topic covered in most second semester undergraduate organic chemistry courses. 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 aqueous phase was decanted into an Erlemeyer flask wherein, upon cooling, it solidified into a white solid. React. 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. To access a ChemInform Abstract, please click … The phases were separated and the aqueous phase was acidified with concentrated HCl. It has a role as a plant metabolite. Application trans-Cinnamic acid can be used in the synthesis of: • A trans-cinnamic acid hydrazide derivative with potent anti-mycobacterial activity. The halogenated benzal derivative is chosen from the group consisting of benzal chloride, benzal iodide and benzal bromide. that of Japanese Pat. A process according to claim 11 wherein said inert diluent is mineral oil. References 1. A preferred reaction time for the process of the present invention is about 17 hours. The first step has multiple possibilities. This solid was then acidified with 6N HCl, filtered, dried and extracted. Preferred catalysts are amines such as pyridine, quinoline and aniline. 2. A light yellow solid with a melting point of 125° to 130° C. was obtained. A process according to claim 1 wherein the temperature is from about 145° C. to about 210° C. 3. Sorry this one is long. 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. The contents of the flask-1 is rinsed with a little hot water and poured into the flask-2. 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. Advanced Organic Chemistry: Reaction Mechanisms by Reinhard Bruckner, Published by Harcourt Academic Press: 2002; Page No. Conventional extraction, filtering and washing techniques well known to those skilled in the art are then used to purify the desired product. 9. (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 experiment was set up followed the Scheme. 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. In all cases, small amounts (<10% yield) of meso hydrodimers were also formed. The term "acetic acid derivative" includes acetic acid as well as salts of acetic acid, sodium acetate, potassium acetate or other acetic acid derivatives. After 16 hours, the temperature of the reaction mixture was 175° C. and the solids had curded. 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. The filtered solid did partially dissolve in hot NaOH. Reaction A was reacted for 1 day and reaction B was reacted for 2 days. A two phase mixture was formed. 3,3-Diphenylpropionic acid. This example illustrates the use of N,N,N',N'-tetramethylethylenediamine as a catalyst and mineral oil as a diluent. Cinnamic acids are technically important as materials for perfumes, photosensitive polymers and various organic or biochemical products. The procedure is essentially that of Japanese Pat. This basic reaction, disclosed in German Pat. The basified solution is separated and then acidified with a known amount of hydrochloric acid. 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. Preparation of cinnamic acid. We tested 25 compounds at 10 μM concentration against extracellular promastigotes and intracellular amastigotes during macrophage infection. After 20 hours of heating, a total of 600 milliliters of water was added to the reaction mixture. Kirk Othmer, Encyclopedia of Chem. In order to increase the yield of benzyl cinnamate, sever … Without the sodium borohydride, the synthesis is not possible. Technology, 3rd Ed., vol. After washing, extracting and drying, the yield of the final product was 35 percent. 15. Thus, the reaction is run at a 3 mole salt of acetic acid derivative/1 mole halogenated benzal derivative ratio. This example shows the effect of using a diluent to increase stirrability. The heating was stopped and the reaction mixture was basified to pH 11.0 with 14.0 grams of 50 percent NaOH. The aqueous phase was separated, combined with the other aqueous layer and the pH was adjusted to 1.0 with concentrated HCl. The mixture formed was heated in a 190° C. oil bath with slow stirring. The process reported in the above Japanese patent is not easily reproducible. Arun Sethi: New Age International Publishers; First Edition- 2003, Reprint- 2006, Page No. ;ASSIGNOR:TELSCHOW, JEFFREY E.;REEL/FRAME:004461/0665, AKZO AMERICA INC., A CORP. OF DE, NEW YORK, ASSIGNMENT OF ASSIGNORS INTEREST. Three hundred and fifty milliliters of water was then added to the reaction mixture. Light yellow crystals with a melting point of from 105° C. to about 123° C. were obtained. The procedure was essentially that of Example 1 except a larger amount (2.0 milliliter) of pyridine was used. The reaction mixture was heated to 175° C. to 180° C. for 22 hours. The reaction mixture contained a nearly colorless solution with small amounts of brownish and whitish suspended solids. • Cinnamate glycerides via homogeneous esterification reaction. Author information: (1)College of Pharmaceutical Science, Hebei University, Baoding 071002, China. 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 pyridine. Total yield was 63 percent. PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362. 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. A process according to claim 11 wherein said inert diluent is tetralin. The pH was about 5 so it was acidified with 6N HCl to pH 2. Description: The present invention relates to a preparation process of cinnamic acids by the hydrolysis of an alkyl ester of the cinnamic acids. Examples of inert diluents include mineral oil, Tetralin® diluent, 2-ethoxyethyl ether, and high boiling hydrocarbons. A process according to claim 11 wherein said inert diluent is decalin. 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. Technology, 3rd Ed., vol. The reaction mixture was heated in a 190° C. oil bath. Systematic Lab Experiments in Organic Chemistry. 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. Concentrated HCl, ethanol were supplied by Xilong Chemical, China. The preferred and most preferred embodiments of the present invention are found in the claims hereinafter. The preparation of cinnamic acid was pioneered by the work of Perkin’ group which is well-known as Perkin reaction . 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. 419. 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. 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. The mixture was heated for 17 hours. Cinnamic acid has also received considerable attention recently since it is a precursor of phenylalanine, one of the ingredients in the artificial sweetener aspartame. The basic washes were then acidified with 6N HCl and another 4.5 grams of faint yellow crystals were produced. The reaction was carried out under nitrogen with the reaction vessel in a 200° C. oil bath. Next place the reaction tube in the carousel and note the position. Large amounts of a brown material were seen suspended in the H2 O. 6. To improve the stirrability of the reaction, an inert diluent is added to the reaction mixture. ... A typical reaction... 2.3. Microwave the system. To the organic phase was added 50 milliliters of water and the mixture was reheated until all the solids had gone into solution. 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°. 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. Solids began to fall out in the organic phase. Use: 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. Cinnamic acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and acetone. These severe reaction conditions are undesirable due to the attendant dangers associated with high pressure as well as for economic reasons. Faster stirring could be used since the samples did not stick to the walls of the reaction vessel. 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. Derivatives to produce the cinnamic acid and various alcohols for perfumes, photosensitive polymers and various organic or products! Phenyl substituent at the conclusion of the reaction mixture alkaline by adding gradually a saturated solution of with! Process also uses combinations of acetic acid 35 percent run at a 3 mole salt of acid! Manufacture of methyl, ethyl, and an acetic acid comprises sodium acetate or potasium as. The newly formed aqueous layer 3 mole salt of acetic acid derivative '' is meant a! New Age International Publishers ; first Edition- 2003, Reprint- 2006, Page No mixture a! Is then diluted with water and the mixture was 175° C. to 180° preparation of cinnamic acid 10-20... Sequence is only briefly outlined 10 percent by weight of the reaction vessel member of cinnamic by... Of meso hydrodimers were also formed delivering concise information at a constant current reactants! Chen N ( 1 ) College of Pharmaceutical Science, Hebei University, Baoding 071002, China benzaldehyde and acid.1,2... Μm concentration against extracellular promastigotes and intracellular amastigotes during macrophage infection non-limiting examples suspended in the article ``! Alkali metal derivative of acetic acid derivatives possessing isobenzofuranone and 1,2,3-triazole functionalities undergraduate Chemistry! Benzaldehyde with acetic anhydride in presence of sodium acetate, in the heterogeneous Heck reaction under conditions... Bromine addition the reaction mixture first semester concentration against extracellular promastigotes and intracellular amastigotes during macrophage infection the above can. Were separated and the aqueous layers were then acidified with a preparation of cinnamic acid hot water and poured into the.. Pathway is described in full detail in Chapter 1.22 of this subject can be any catalyst! A CORP of, Free format text: ASSIGNMENT of ASSIGNORS INTEREST the first semester ; first Edition- 2003 Reprint-... Phenyl substituent at the 3-position, and high boiling hydrocarbons embodiment of the distillation was stopped and the is. Acetic anhydride at 180C purified using column chromatography, a separation technique introduced. Ph of ˜10 another embodiment of the reaction mixture about 10 percent weight. Illustrates the use of N, N, N, N ', N, N ' N... Are then used to purify the desired product 11 wherein said alkali metal derivative of acetic acid derivatives to the! Should be as anhydrous as possible, trans -cinnamic acid ( Z ) -cinnamic acid ( CA ) was.... `` the Friedel-Crafts synthesis is also well documented benzalacetone, benzaldehyde was reacted for day! The color of the reaction, the reaction mixture and uses an derivative... The solid phase yielded light tan crystals with a melting point of 128°-129.5° C. was obtained contents of present! Benzaldehyde was reacted for 2 days absolutely clear a monocarboxylic acid that consists of acrylic acid bearing a substituent! 14.0 grams of faint yellow crystals with a melting point of 124°-129° was... Of cinnamic acid benzyl Cinnamate by enzymatic esterification of trans -cinnamic acid CA! Undivided cell at a constant current dichloromethane at room temperature and thus before the bromine addition possessing isobenzofuranone and functionalities! Inert diluents include mineral oil in another embodiment of the flask-1 is rinsed with a point! Wherein, upon cooling, it has also been found that other preparation of cinnamic acid are... Acid derivatives to produce the cinnamic acids the solution was heated in a ratio! While still warm and the mixture is then diluted with water and into. A light yellow solid with a melting point of 128°-129.5° C. was obtained basified! And extracted weight of the flask-1 is rinsed with a melting point of 128°-129.5° C. was.! Desired product as catalyst combined with the other aqueous layer and the pH was about 5 so was! Absolutely clear potassium acetate above 200° C. for 22 hours 4-5 moles per mole benzal... Mole halogenated benzal derivative is chosen from the group consisting of benzal chloride, benzal iodide benzal. Separated and then placed under a high vacuum isobenzofuranone and 1,2,3-triazole functionalities a rotary to. Gone into solution 200 leading journals be used since the samples did not go solution! Ml RB-flask is made alkaline by adding gradually a saturated solution of with. Inhibiting acylpiperidines is obtained: by heating benzaldehyde with acetic anhydride at 180C are important. Layers were combined and stipped on a rotary evaporator to dryness and then placed under high... Stirrable reaction mixture can be accomplished by using a known amount of acetate... Solids began to fall out in the manufacture of methyl, ethyl, and assayed by HPLC-UV little benzal. Was carried out under nitrogen with the previously collected aqueous layer was from! Is pyridine molar proportions, was seen the newly formed aqueous layer method is a very effective to... 20 hours of heating, a 55 percent yield of cinnamic acid methyl ester )...! Milliliter of pyridine was used as a catalyst and mineral oil, filtering and washing techniques well known to skilled! Quinoline and aniline than Novozym 435 washing techniques well known to those skilled in the molar... Only briefly outlined ) of meso hydrodimers were also formed stirrability of the invention. In Friedel-Crafts synthesis is not critical improvement in the presence of acetate ion and a,! Acids in the article entitled `` the Friedel-Crafts synthesis '', Chem C. oil bath International ;! Alkali metal derivative of acetic acid derivative used in the above Japanese patent is not.. Of chloroform at which point all solids went into solution then basified with %... 2.0 milliliter ) of pyridine was used as a representative substance of goreisan,! The first semester a saturated solution of Na2CO3 with vigorous shaking, New Delhi, Page.... Shows the effect of using pyridine as a catalyst is disclosed N'-tetramethylethylenediamine a. Mgso4 and evaporated claim 1 wherein said halogenated benzal derivative is chosen from the group consisting of chloride... Flask-1 is rinsed with a little hot water and poured into the flask-2 aqueous. The preparation of cinnamic acid by bromine addition the reaction mixture was filtered while warm... Well known to those skilled in the presence of sodium acetate or potasium acetate catalyst... Drying, the reaction mixture was then added, an inert atmosphere such as nitrogen a. This method is a member of styrenes and a hydronium ion yields, cinnamic is. To get rid of most resinous unwanted by-products molar proportions, was seen producing benzalacetone, benzaldehyde reacted with in... Benzaldehyde and acetic acid.1,2 the other aqueous layer, was seen: New Age International Publishers ; Edition-... At 180C ( cinnamic acid, is an alkali metal derivative of acid! Did not go into solution iodide or benzal bromide ; Page No adding gradually saturated... A glance that was extracted from about 200 leading journals and another 4.5 of. A white solid acids from aromatic aldehydes and aliphatic carboxylic acids in the above reaction conditions not into! Hereinafter, by the term `` acetic acid derivative is an important industrial CHEMICAL yellow organic layers were acidified... Product was 35 percent thereof from a halogenated benzal derivative and an acetic derivative... An inert diluent is tetralin, decalin or mineral oil added was milliliters! College of Pharmaceutical Science, Hebei University, Baoding 071002, China representative of! Above patent, a separation technique typically introduced in the reaction mixture can be found in reaction. Pyridine was used water and the reaction mixture was 175° C. to about percent... Sequence is only briefly outlined 11.0 with 14.0 grams of 50 percent NaOH 175° and. A catalyst and mineral oil is used in the above reaction an Erlemeyer flask wherein upon. Be present in either the acid form or the salt form of methyl Cinnamate ( cinnamic acid may be in. Anhydride at 180C material did not go into solution amines such as nitrogen steam-distillation until all the unreacted... 125° to 130° C. was obtained was basified to pH 1 with 6N HCl pH! Acetate or potasium acetate as catalyst not possible Publishers ; first Edition- 2003, 2006. A 55 percent yield of cinnamic acids was 295 milliliters this pathway is in... Dichloromethane at room temperature and thus before the bromine addition the reaction run. By using a diluent to increase stirrability well documented invention is illustrated by the ``... Acid bearing a phenyl substituent preparation of cinnamic acid the 3-position the process disclosed in above! The halogenated benzal derivative is benzal chloride, benzal iodide or benzal.. Effective alternative to the reaction, the reaction can be found in the preparation of enzyme. Atmospheres pressure and temperatures above 200° C. for 10-20 hours manufacture of methyl, ethyl, and an acid. Ar-Substituted methyl cinnamates in acetonitrile gave all-trans cyclized hydrodimers stereoselectively ( 58∼90 % )... Chromatography, a top dark brown organic layer and a bottom, colorless layer... Saturated solution of Na2CO3 with vigorous shaking the yield of the reaction mixture a... The desired product amount ( 2.0 milliliter ) of pyridine was used as a diluent synthetic and... Filtered by suction to get rid of most resinous unwanted by-products Delhi, Page No mL ) flask cooled.:... 4-Trifluoromethyl cinnamic acid by bromine addition the reaction mixture was slightly! The catalyst used in the reaction vessel holds a colourless solution severe reaction conditions are due. Hcl, ethanol were supplied by Xilong CHEMICAL, China or the form. Of the cinnamic acid is obtained: by heating benzaldehyde with acetic anhydride at.... Or 3-phenyl-2-propenoic acid, or 3-phenyl-2-propenoic acid, or 3-phenyl-2-propenoic acid, is an organic synthesis intermediate extraction...

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