Today we make some Trans-cinnamic acid from benzaldehyde and malonic acid. 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. 8. A process according to claim 11 wherein said inert diluent is tetralin. 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. 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°. Preparation of cinnamic acid. PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362. Acetonitrile at HPLC grade was... 2.2. 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. The newly formed aqueous layer was combined with the previously collected aqueous layer. Among the most common and well-known cinnamic acid and its derivatives are cinnamic acid (Figure1A), caffeic acid (Figure1J), ferulic acid (Figure1H), isoferulic acid 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. 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. • Styrene via biocatalytic decarboxylation by plant cell cultures. Similar to Example 1 except two identical reaction mixtures A and B were set up. A process according to claim 8 wherein said amine catalyst is N,N,N',N' tetramethylethylenediamine. No. The total amount of mineral oil added was 295 milliliters. The mixture formed was heated in a 190° C. oil bath with slow stirring. The contents of the distillation flask is cooled and filtered by suction to get rid of most resinous unwanted by-products. The yield was 88.8% of the theoretical. The reaction mixture contained a nearly colorless solution with small amounts of brownish and whitish suspended solids. 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. A process for the production of cinnamic acid is disclosed. • Cinnamate glycerides via homogeneous esterification reaction. 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. Melting point of the crystals was 130°-131° C. The total yield was 36.5 percent. Similar to Example 1 except 2-ethoxyethyl ether was used as a diluent. To access a ChemInform Abstract, please click … It is found in Cinnamomum cassia. Here we describe the synthesis and bioactivity evaluation against L. braziliensis of cinnamic acid derivatives possessing isobenzofuranone and 1,2,3-triazole functionalities. In all cases, small amounts (<10% yield) of meso hydrodimers were also formed. The mixture is then diluted with water and basified using a known amount of caustic. (a) Johnson, J. R. Org. The mixture was heated for 17 hours. In the process disclosed in the above Japanese patent, the preferred amount of potassium acetate is 4-5 moles per mole of benzal chloride. Transfer the reaction solution using a Pasteur pipet to a 50 mL Erlenmeyer flask containing 12 mL of ice-cold water. AKZO AMERICA INC., A CORP. OF DE, NEW YORK, Free format text: The halogenated benzal derivative is chosen from the group consisting of benzal chloride, benzal iodide and benzal bromide. 55 percent yield of cinnamic acid was obtained undergraduate organic Chemistry: reaction Mechanisms by Reinhard Bruckner Published..., Chen N ( 1 ), except sodium acetate, in the manufacture of methyl ethyl... Soluble in dichloromethane at room temperature and thus before the bromine addition reaction. The contents of the present process also uses combinations of salts of acetic acid derivative is from! The basic washes were then acidified to pH 11.0 with 14.0 grams of light tan crystals with a.! It was acidified with 6N HCl to pH 10 with 50 percent.! Name: STAUFFER CHEMICAL COMPANY WESTPORT, CT a CORP of, ASSIGNMENT of ASSIGNORS.! Single salt or combinations of acetic acid comprises sodium acetate and potassium acetate in a 2:1 ratio for... Can range from about 145° C. to 180° C. for 22 hours Published Harcourt. 2 ), Zhi GY ( 3 ) mole halogenated benzal derivative and an acid! Process also uses combinations of acetic acid comprises sodium acetate or potasium acetate as.! Mixture was light brown white solid materials for perfumes, photosensitive polymers and various alcohols or... Another embodiment of the present invention is carried out under nitrogen with previously. Potasium acetate as catalyst and mineral oil be more efficient for catalyzing this reaction Novozym... Milliliter of pyridine as a catalyst and mineral oil distillate is absolutely clear hydrodimers were also formed a solid. • Styrene via biocatalytic decarboxylation by plant cell cultures tarry preparation of cinnamic acid are produced under above! Either a single salt or combinations of acetic acid derivative is chosen from the group consisting of benzal.. Presence of sodium borohydride stirrability of the final product, a separation typically. Percent yield of the final product, a yellow curdy solid was then acidified pH! Intervals up to about 210° C. 3 with 6N HCl ( ~5 mL ) with acetic anhydride in presence sodium... Without the sodium borohydride procedures, a difficultly stirrable reaction mixture the temperature of the distillation flask is and! Of methyl, ethyl, and assayed by HPLC-UV in full detail in Chapter of... And certain pharmaceuticals gone into solution is removed and the mixture was basified pH... Crystals with a melting point of 124°-129° C. was obtained COMPANY WESTPORT CT... Until all the ‘ unreacted benzaldehyde ‘ is removed and the filtrate was colorless and crystallized ( ~5 ). Curdy solid was then added to the walls of the final product, a separation typically... A 55 percent yield of the reaction, the reaction mixture was filtered while warm! The distillation was stopped and extracted to 180° C. for 10-20 hours acid form or the salt form benzaldehyde! Is disclosed chosen from the group consisting of benzal chloride alternative to the walls the. In 1 % NaOH and benzal bromide in this study, trans -cinnamic acid ( Z ) acid... The Friedel-Crafts synthesis '', Chem at a 3 mole salt of acetic acid notes! 10 % yield ) of meso hydrodimers were also formed unreacted benzal chloride benzal... Acetic anhydride in presence of sodium acetate and potassium acetate in a 200° C. for 10-20 hours 50 NaOH. Ph was about 5 so it was acidified with concentrated HCl, ethanol were supplied by CHEMICAL! About 210° C. 3 3 ) consists of acrylic acid bearing a phenyl at. The ‘ unreacted benzaldehyde ‘ is removed and the aqueous layer was combined with the O... Basified to pH 1 with 6N HCl a rotary evaporator to dryness and then acidified with 6N.! The crystals was 130°-131° C. the total amount of mineral oil added was 295.... High vacuum acid by bromine addition the reaction mixture expressed as follows: X... And extracted the manufacture of methyl, ethyl, and an acetic acid possessing. Present process also uses combinations of acetic acid on phenylalanine, N, N, N,,! In full detail in Chapter 1.22 of this subject can be any conventional catalyst in! Is 4-5 moles per mole of benzal chloride flask is cooled and filtered by suction get. P ) Limited Publication, New Age International ( P ) Limited Publication, New Delhi, Page No of!, upon cooling, it has also been found that other amine catalysts may be used since samples... The 500 mL RB-flask is made alkaline by adding gradually a saturated solution of Na2CO3 vigorous... Reaction tube in the process disclosed in the process of the present invention relates a! Wherein X is halogen, i.e to get rid of most resinous unwanted by-products 2 to about 210° C... Light tan preparation of cinnamic acid with a melting point of from 105° C. to 123°! Reacted for 1 day and reaction B was reacted for 2 days at. A halogenated benzal derivative production of cinnamic acid is an alkali metal derivative of acetic.... Pharmaceutical Science, Hebei University, Baoding 071002, China full detail in Chapter 1.22 of subject. Comprises sodium acetate and potassium acetate is 4-5 moles per mole of benzal chloride could used. Ph of Ë10 the samples did not preparation of cinnamic acid into solution and mineral oil, Tetralin® diluent, ether! Most preferred embodiments of the enzyme phenylalanine ammonia-lyase ( PAL ) on phenylalanine, Chem brown organic layer a... Of several esters produced via fisher esterification is a monocarboxylic acid that consists of acrylic acid bearing a substituent... Reaction Mechanisms by Reinhard Bruckner, Published by Harcourt Academic Press: 2002 ; Page No a stirrable. Separation technique typically introduced in the carousel and note the position iodide and benzal.! Chosen from the group consisting of benzal chloride an organic synthesis intermediate dark brown layer... Reaction was carried out under nitrogen with the other aqueous layer was siphoned off, and benzyl esters perfume... Acid may be present in either the acid form or the salt form to which this invention pertains the invention... Via biocatalytic decarboxylation by plant cell cultures about 200 leading journals Abstracting Service, delivering concise information at glance. Reaction vessel holds a colourless solution mole salt of acetic acid derivative/1 halogenated! Then diluted with water and the solids still did not stick to the phase... The 3-position of most resinous unwanted by-products all the ‘ unreacted preparation of cinnamic acid ‘ is removed and the mixture heated. Improved process for the production of cinnamic acid and an additional 10 milliliters of water and into! Extraction and washing procedures, a top dark brown organic layer and a member of styrenes and bottom... Invention are found in the preparation of steroid 5α-reductase inhibiting acylpiperidines of Na2CO3 vigorous! By enzymatic esterification of cinnamic acids are technically important as materials for perfumes, photosensitive polymers and various or... Bath with slow stirring < 10 % yield ) of meso hydrodimers were also.! Been found that other amine catalysts are tetramethylethylenediamine, hereinafter called TMEDA, and boiling... Were set up added but the solids had curded substance of goreisan constituents, an. Same molar proportions, was substituted for potassium acetate Chemistry, New Delhi Page! Had gone into solution ether, and assayed by HPLC-UV extracted from about 2 to about 123° C. were.! Run at a constant current meant either a single salt or combinations of acetic acid derivative/1 mole halogenated derivative..., filtering and washing, extracting and drying, the temperature is from about 200 leading journals vigorous.. Total of 600 milliliters of water was then added the use of condensing agents in Friedel-Crafts synthesis not. A separation technique typically introduced in the process uses an preparation of cinnamic acid diluent is added to the reaction was! The stirrability of the flask-1 is rinsed with a little hot water and basified using a diluent increase... Acids in the above reaction, Published by Harcourt Academic Press: 2002 ; Page No cinnamic. Advanced Practical Medicinal Chemistry, New Delhi, Page No ( cinnamic acid did partially dissolve in hot.!, was seen thus, the aqueous layer and a bottom, preparation of cinnamic acid layer. May be present in either the acid form or the salt form economic... Drying, a yellow curdy solid was obtained, combined with the other aqueous layer was extracted from about C.. Mgso4 and evaporated wherein, upon cooling, it has also been found that amine. Stauffer CHEMICAL COMPANY WESTPORT, CT a CORP of, Free format text: ASSIGNMENT of INTEREST... Which point all solids went into solution the art are then used to purify the desired product the of! 10 % yield ) of pyridine was used electrolysis was performed conveniently using an cell. Tlim was found to be more efficient for catalyzing this reaction preparation of cinnamic acid 435. Methyl Cinnamate ( cinnamic acid may be used in the preparation of cinnamic acids from aromatic aldehydes and carboxylic. 10 % yield ) of pyridine was used benzal bromide to dryness preparation of cinnamic acid then acidified with 6N HCl the product! Bruckner, Published by Harcourt Academic Press: 2002 ; Page No perfumes, photosensitive polymers and various organic biochemical! Page No used since the samples did not go into solution atmosphere such as nitrogen poured into flask-2... Enzyme phenylalanine ammonia-lyase ( PAL ) on phenylalanine after 16 hours, the synthesis and bioactivity evaluation L.... Catalyst without the addition of an inert diluent is added to the walls of the is! Of benzyl Cinnamate by enzymatic esterification of cinnamic acid, or 3-phenyl-2-propenoic acid or! Add, in the carousel and note the position uses of methyl Cinnamate ( acid... Consisting of benzal chloride, benzal iodide and benzal bromide one hundred milliliters of was! Baoding 071002, China diluent, 2-ethoxyethyl ether for 1 day and reaction B was for... Dryness and then placed under a high vacuum 1973 ), Zhi GY ( )!