50611/'72, Japanese Patent Laid-Open No. 1a) and its simple derivatives are widely represented in plants. For instance, these processes are methods of preparing cinnamic acid and its derivatives from benzaldehydes as a main raw material by Perkin reaction, Knoevenagel reaction or Claisen condensation (as described in, for example, Organic Reactions, vol. The yield was 88.8% of the theoretical. For instance, these processes are methods of preparing cinnamic acid and its derivatives from benzaldehydes as a main raw material by Perkin reaction, Knoevenagel reaction or Claisen condensation (as described in, for example, Organic Reactions, vol. The purpose of this study was to develop a sensitive method for quantifying cinnamic acid in human plasma using UPLC–ESI–MS/MS. As a result, it has been found that a cinnamic acid of excellent quality can be favorably obtained by a process embodying the invention employing alkali hydrolysis in a heterogeneous binary-phase liquid system; the aqueous solvent being free of organic solvents; followed by acidifying the resultant aqueous alkaline solution so that the pH value of the solution obtained by the reaction was not more than a specific value. Both methods gave products in similar yields. The procedure of Example 6 was repeated except 17.6 grams (0.1 mol) of ethyl cinnamate was used in place of methyl cinnamate. It is found in Cinnamomum cassia. Consequently, cinnamic acid obtained was 13.9 grams and the yield was reduced to 93.8%. The cell pellet was washed twice with 25 mM potassium phosphate buffer of pH 7.0 and resuspended in the same buffer. The resultant slurry having concentration of 3.4% by weight was cooled to room temperature and measured pH to give a value of about 2. R² and R3 may be the same or different groups and represent respectively hydrogen or alkyl of l to 6 carbon atoms. 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. Cinnamic acid and its derivatives have a numerous potential applications in many different fields such as pharmacy, organic “building blocks”, and corrosion inhibitors. For producing benzalacetone, benzaldehyde was reacted with acetone in 1% NaOH solution. On conducting the acidification reaction of this invention, the continuous reaction may optionally be started after previously charging the sufficient quantity of aqueous solution of the mineral acid for stirring the reactant. Therefore the method of this invention is technically very advantageous for preparing the cinnamic acid. : 133 oC) was first melted and heated in an oven at 180 oC for 30 minutes. generation. The formed suspension had pH of approximately 1.5 after cooling to room temperature. 0000000016 00000 n When the acidification of aforementioned aqeuous alkaline solution is conducted either by adding the aqueous alkaline solution into mineral acid or by continuously charging the aqueous alkaline solution and said mineral acid into the reaction vessel so as to keep the pH value at not more than the specific value in the mixture obtained by acidifying and continuously discharging the product, this method can decrease the quantity of water in use, and thus the amount of product produced per unit volume of the reaction vessel can be increased, the environmental problems on drainage is mitigated, the loss of the product by dissolving in the drainage is reduced and the cinnamic acids having an excellent qualify can be obtained in good efficiency. Furthermore, the use of organic solvents described in the prior art results in the loss due to dissolving of desired product into the solvents and hence cause the reduction of yield. Publication: 2006-04-26. As a concrete method, for example, from a flooding port equipped on the reaction vessel, the suspension may be discharged by an overflow mode, or may also be discharged by use of a pump. This novel approach allows the preparation of various cinnamic acids in good to high yields (up to 81%). TRMK2 cells grown on cinnamic acid were harvested at mid-logarithmic growth phase by centrifugation at 8000 rpm (10 min at 4 °C). OBJECTIVE: To prepare cinnamic acid derivatives-g-CTS and to study its antioxidation activity. A 300 ml separable flask was charged with 16.2 grams (0.10 mol) of methyl cinnamate, and a solution of 4.3 grams of 97 wt.% sodium hydroxide in 140 grams of water. concentrations of carvacrol and cinnamic acid below 20 mM could be used to inhibit microbial growth on fresh-cut fruit destined for storage under chill conditions. 1c), 4‐hydroxycinnamic acid (p‐coumaric acid, Fig. Cinnamic acid was separated using water containing 0.005% (v/v) formic acid and acetonitrile as a mobile phase by gradient elution at a flow rate 0.2 mL/min, equipped with a HALO-C18 column (2.1 × 100 mm, 2.7 μm). The cinnamate esters include, for example, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, ethyl α-methyl-β-phenylacrylate, methyl α-propyl-β-chlorophenylacrylate, methyl β-3,4-dimethoxyphenylacrylate, methyl β-4-methoxyphenylacrylate and benzyl cinnamate. One of the simplest and most efficient and environmentally benign methods for cinnamic acid synthesis is based on the Knoevenagel condensation of diethylmalonate with benzaldehyde catalyzed by mixed oxides of Mg/Al, Mg–Al + Ln (Ln = Dy, Gd), or Li/Al as shown in Fig. trans-Cinnamaldehyde and eugenol were purchased from ChromaDex. 33 0 obj<>stream Therefore the acidification reaction of the alkali cinnamate solution is suitably carried out by maintaining the system always in acidic conditions, that is, at the pH value of not more than 4 and preferably not more than 3. There are cis and a trans isomer exist naturally in a number … Furthermore, the solvents used for the extraction should be recovered in the industrial application. The electroreduction of Ar-substituted methyl cinnamates in acetonitrile gave all-trans cyclized hydrodimers stereoselectively (58∼90% de). METHOD: The ability of catching oxygen of the products and raw material were determined through two methods, Marklund method and trace pyrogallic acid method, with autoxidation reaction of … 0 0000007639 00000 n The suspension of the cinnamic acid formed by the acidification of this invention is continuously discharged, and optionally, it may be discharged intermittently. trans -Cinnamic acid (TCD, also known as trans --pheny-lacrylic acid) is one of the main chemical constituents of cinnamon which belongs to plant Lauraceae [, ]. 2004 Apr;42(4):207-10. The procedure of Example l was repeated except 64 grams of water were used in the hydrolysis. It has a role as a plant metabolite. Ref. I have already done a Doebner reaction using using benzaldehyde and malonic acid. For the hydrolysis reaction of the cinnamate ester with aqueous solution of the alkali, any operation can be applied which includes a batchwise or semi-batchwise operation of charging both components in a lump or separately into the reaction vessel and a continuous operation of continuously charging these components. In the process of this invention, the cinnamic acids can be precipitated by acidifying the resultant aqueous alkaline solution with mineral acid so that the reaction mixture forms a slurry or suspension. 12736/'85). A round bottomed flask having an overflow port of about 20 mm in diameter in the middle of the vessel (the volume below the port was about 130 ml) was respectively equipped with a stirrer, an electrode of pH meter, a discharge orifice of tube pump capable of delivering 25 wt.% aqueous sulfuric acid solution at a constant flow rate, and an orifice of hot dropping funnel containing aqueous alkaline solution of sodium cinnamate. Cinnamic Acid is a white crystalline organic compound with the chemical formula C6H5CHCHCO2H.Cinnamic Acid is slightly soluble in water and is soluble in many organic solvents.Cinnamic Acid is classified as an unsaturated carboxylic acid, which is an organic compound that contains a carboxyl group (C(O)OH). x�b```"V� >�c`��0p4�)00. Preparation of cell free extract and enzyme assays. Various synthetic methods have been used for the preparation of cinnamic acid and its For producing benzalacetone, benzaldehyde was reacted with acetone in 1% NaOH solution. Cinnamate esters are always formed as an intermediate in such processes as Claisen condensation which used benzaldehyde and acetate esters, a method of using benzene or its derivatives and acrylate esters as the raw materials, and a method of employing styrene or its derivatives, carbon monoxide, alcohol and oxygen as the raw materials. Curve calibration pre-pared from standar solution of trans-cinnamic acid containing 0.5-2.5 µg/mL. The yield was 88.8% of the theoretical. Sodium hydroxide or potassium hydroxide is preferably employed among these compounds. Then the resultant aqueous alkaline solution of sodium cinnamate having concentration of 13.1% by weight was transferred to a hot dropping funnel kept at 80°C. In the method of this invention, alcohols generated in the course of the hydrolysis reaction may optionally be recovered, for example, by distilling from the system during or after the reaction. Hence the cinnamic acid having good quality can be obtained efficiently and in good yield. So this is the main drawback of 31 0 obj<> endobj The purpose of this study was to develop a sensitive method for quantifying cinnamic acid in human plasma using UPLC–ESI–MS/MS. Some embodiments of the invention will now be described in greater detail. It has a role as a plant metabolite. Vigorous stirring is more effective for the acidification. Preferably the whole binary-phase system is substantially free of organic solvents. The mixture was reacted at 80°C for 15 minutes with vigorous stirring. The quantity of cinnamic acid produced was 116 g/&litre to one liter of water used, and about 700 g/&litre to the unit volume of reaction vessel. 0000007341 00000 n An aqueous alkaline solution of sodium cinnamate was obtained by the same method as described above. 133°C. R4 represents unsubstituted or substituted alkyl group.). by the' Stuart-method ' of heating o-chlorobenzaldehyde with malonic acid and glacial acetic acid. Cinnamic acid is a monocarboxylic acid that consists of acrylic acid bearing a phenyl substituent at the 3-position. On the hydrolysis of cinnamate esters with an acid catalyst a long reaction time is generally required because of a low reaction rate. J Chromatogr Sci. Besides in embodiments of this invention, the aqueous alkaline solution of the alkali cinnamate obtained by the alkali hydrolysis of the cinnamic acid ester can be acidified at a high concentration, the quantity of products per unit volume of the reaction vessel can be increased, the quantity of water in use can be reduced, the environmental problems of drainage can be mitigated and the loss by dissolving the products into the drainage can be decreased. 5570/'84 and 23661/'85). It is well-known that Verley-Doebner modification is a high efficient method for the preparation of cinnamic acid derivaties, especially with the compounds containing electron-donating subtituents at para position in aromatic ring. To the obtained aqueous alkaline solution of sodium cinnamate having concentration of 7.7% by weight were added in a lump 1240 ml of aqueous sulfuric acid solution containing 0.35 mol of sulfuric acid. The procedure of Example 10 was repeated except the dropwise addition rate of aqueous sulfuric acid solution was reduced and pH of the reaction mixture was kept at 5 in acidification. 0000001009 00000 n And the materials may be fed continuously or intermittently at a certain rate. In the category of phytochemicals that can be found in food, there are : . The yield was low though. The procedure of Example 6 was repeated except 0.102 mol of hydrochloric acid was used in place of 0.053 mol of sulfuric acid in acidification. In the operation of adding the mineral acid into the aqueous solution of alkali cinnamate, however, the reaction mixture often forms a slurried liquid having a high viscosity. Perkin's method was first applied to m-bromobenz-aldehyde by Miller and Rohde (1890) who, after heating the Perkin mixture at 140-50° for as many as twenty hours, obtained a 73% yield of m-bromo-cinnamic acid. Consequently cinnamic acid thus obtained was 14.6 grams (98.5% yield) and had purity of above of 99.9%. The electrolysis was performed conveniently using an undivided cell at a constant current. So this is the main drawback of very low. On the other hand, the alkali hydrolysis is, as described above, commonly carried out in a homogeneous system employing the aqueous mixture of organic solvents. In order to afford high yield of the cinnamic acid in the method of this invention, the alkali cinnamate and the mineral acid are required to react so as to keep the pH value at not more than 4 and preferably at not more than 3 in the solution after ending the acidification reaction. 8, 1952, pages 421-423, Georg Thieme Verlag, Stuttgart, Stuart, Ian Alexander (40 Basinghall Street, GB). Chemical Properties monoclinic crystals The cinnamate esters mentioned above can be prepared by various methods. 0000017832 00000 n The reaction time depends upon reaction temperature and pressure and is preferably in the range of 1 to 120 minutes, and more preferably 3 to 30 minutes. Consequently cinnamic acid thus obtained was 14.4 grams (97.2% yield) and had purity of above 99.9%. 0000004005 00000 n 0000003521 00000 n The concentration of cinnamic acid in the reaction vessel was about l0 wt.%. The solution was distilled at about 100°C, a fraction of 98 to 99°C was collected, and 17.8 grams of methanol were recovered as an aqueous solution. Also , what can be done to convert cinnamic acid to phenyl propionic acid? 0000000736 00000 n & Terms of Use. l, 217 (1942)), and from benzene or its derivatives and acrylate esters as raw materials (as described in, for example, Japanese Patent Publication No. A 3 &litre flask equipped with a stirrer was charged with 100.0 grams (0.617 mol) of methyl cinnamate and 1260 grams of aqueous solution containing 25.9 grams (0.647 mol) of sodium hydroxide and vigorously stirred for 15 minutes at 80°C. As a result a homogeneous solution cannot be formed and in the extreme cases the operation is substantially inhibited as a result of solidification. The term continuous operation mentioned herein is different from what is called batchwise operation in which raw materials are charged in a lump and discharged after ending the reaction. Cinnamic acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and acetone. aldehyde and an aliphatic carboxylic acid in order to obtain cinnamic acids is possible under certain conditions, through a new direct synthesis. Consequently, cinnamic acid obtained was 14.5 grams (97.9% yield) and had purity of above 99.9%. In this paper design and synthesis of a scaffold comprising primaquine (PQ) motif and cinnamic acid derivatives (CADs) bound directly (compounds 3a–k) or via a spacer (compounds 7a–k) are reported. 0000001218 00000 n Blacklight irradiation the Besides a method has also been proposed recently wherein styrene or its derivatives are reacted with carbon monoxide, alcohol and oxygen in the presence of a catalyst (as described in Japanese Patent Publication Nos. The same reaction procedure as in Example l was carried out except 230 grams of water was used in hydrolysis. The benzalacetone was further oxidized with sodium hypochlorite to give 88.2% of cinnamic acid, m.p. Herein, we report a simple, dependable, and scalable preparation method for CBDA-4 (Scheme 1). 31 22 102614/'74). tional method; mangiferin, jateorrhizine, palmatine, berberine, cinnamic acid, and cinnamaldehyde were all ordered from the National Institute for the Control of Pharmaceutical and Biological Products (Beijing, China). The quantity of alkali in use is at least one equivalent to the cinnamate ester. Primaquine-Cinnamic Acid Conjugates of the Amide ... Two methods for the preparation of amides 3a k were applied: acid chlorides 4 (method A) and benzotriazolides 2 (method B) were used as the activated CAD intermediates. The aqueous alkaline solution of sodium cinnamate thus obtained was added slowly under stirring into 200 ml of aqueous sulfuric acid solution containing 0.056 mol of sulfuric acid. It is also desirable to provide a method of preparing a cinnamic acid by starting the hydrolysis of the cinnamate ester with the alkali in the heterogeneous binary-phase liquid system, followed by acidifying the resultant alkaline solution with the mineral acid through an improved method. For producing benzalacetone, benzaldehyde was reacted with acetone in 1% NaOH solution. The procedure of Example l was repeated except 2100 grams of water in the hydrolysis and 200 grams of aqueous sulfuric acid solution containing 0.08 mol of sulfuric acid were used in acidification. It is preferably in the range of 2 to 15% by weight. Therefore, to avoid aforesaid problems in the batchwise or semi-batchwise operation, the alkaline solution of alkali cinnamate is preferably added into the mineral acid. conditions, through a new direct synthesis. It can also inhibit melanoma and proliferation and promote di erentiation of cancer cell in In a process embodying this invention, the hydrolysis of the cinnamic acid ester with the alkali can be started in the heterogeneous binary-phase liquid system with the aqueous solvent in the absence of organic solvents. The operation may be intermittent with a suitable interval so long as the operation does not make this invention invalid. Therefore, procedures such as extraction and concentration are required for the isolation of desired products. In the extreme cases the stirring is inhibited. The cinnamic acid is soluble in dichloromethane at room temperature and thus before the bromine addition the reaction vessel holds a colourless solution. It is desirable to provide an industrial method of preparing a cinnamic acid by the hydrolysis of a cinnamate ester with an alkali. The yield was 88.8% of the theoretical. It is found in Cinnamomum cassia. 0000003232 00000 n Herein, we report a simple, dependable, and scalable preparation method for CBDA-4 (Scheme 1). These new matrices (sinapic, ferulic and caffeic acids) are cinnamic acid derivatives that have several pratical advantages over the nicotinic acid matrices previously used. 59927/'83, USP 3783140 and 3922299). 0000004081 00000 n Naturally occurring compounds from this group include, among others: cinnamic acid, cinnamaldehyde (Fig. Cinnamic acid thus obtained was 14.6 grams (98.5% yield) and had purity of more than 99.9% according to analysis. The procedure of Example l was repeated except 6.9 grams of 85% potassium hydroxide was used in place of sodium hydroxide in hydrolysis. Introduction. 2.5 Industrial preparations of cinnamic acid derivatives There are numerous methods for the preparation of cinnamic acid derivatives, but industrially it is prepared from 1, 1, 1, 3- tatrachloro-3-p-phenylpropane by using CCl4 as a solvent, which may be destroy the ozonosphere and is harmful to the human body. Hydroxycinnamic acids (hydroxycinnamates) are a class of aromatic acids or phenylpropanoids having a C 6 –C 3 skeleton. UNIV ZHEJIANG. It was then dissolved in a small amount of DMF and added into ice water with stirring. The partial purified cinnamic acid is obtained after column chromatography application. It is a member of styrenes and a member of cinnamic acids. The reaction pressure is normally atmospheric and yet in some cases slightly decreased or increased pressure is effective. As a result the product is deteriorated in quality and the yield tends to decrease. The absorbance was measured at … 0000010308 00000 n Privacy Policy Background and objective: Periodontitis is the chronic destructive disease of the periodontium, which causes severe inflammation in the tissues. For example, quantity of the raw materials can be set so as to obtain the pH value of not more than 4 after the reaction. Consequently cinnamic acid thus obtained was 14.5 grams (97.9%) and had purity of above 99.9%. 1b), cinnamyl alcohol (Fig. A high-performance liquid chromatographic method for the determination of cinnamic acid in Cinnamomi ramulus and paeoniflorin in Paeoniae radix was established. In these cases, however, acidification must be performed in a low concentration, involving a large amount of water, e.g. The procedure of Example l was repeated except 0.112 mol of hydrochloric acid was used in place of 0.056 mol of sulfuric acid in acidification. 1. trans -Cinnamic acid (TCD, also known as trans --pheny-lacrylic acid) is one of the main chemical constituents of cinnamon which belongs to plant Lauraceae [, ]. While excessive quantity of water leads to the reduction of yield. The procedure of Example l0 was repeated except 19 wt.% hydrochloric acid was used in place of 25 wt.% sulfuric acid and pH was kept at not more than 3 in the reaction vessel in acidification. Perkin's method was first applied to m-bromobenz-aldehyde by Miller and Rohde (1890) who, after heating the Perkin mixture at 140-50° for as many as twenty hours, obtained a 73% yield of m-bromo-cinnamic acid. Therefore it becomes difficult to conduct the acidification of aqueous solution of the alkali cinnamate with the mineral acid in a high concentration and the amount of products produced per unit volume of the reaction vessel is reduced. The cinnamate esters useful for the practice of the process of this invention comprise those of the following formula: (wherein n is an integer of l to 5, R1 is hydrogen or at least one kind of substituent on the aromatic ring and represents, for example, halogen, hydroxyl, alkyl of l to 4 carbon atoms or alkoxy of l to 4 carbon atoms. Stenotrophomonas sp. The aqueous alkaline solution of sodium cinnamate thus obtained was poured into a hot funnel which was previously kept at 80°C. is acid possessesantibacterial,elevatedwhitebloodcell,cholagogue, and anticancer e ects [] . The concentration outside of this range cannot sufficiently achieve the object of this invention. That is, the yield of the product reduces at less than 1% by weight, while a highly concentrated slurry is formed at more than 20% by weight and causes insufficient stirring, incomplete reaction and deterioration in the purity of product. The cell pellet was washed twice with 25 mM potassium phosphate buffer of pH 7.0 and resuspended in the same buffer. ), our alternative uses aliphatic carboxylic acids instead of the corresponding anhydrides. Vigorous stirring is effective for the process of this invention because the hydrolysis reaction of the alkyl cinnamate with the alkali starts in the heterogeneous binary-phase liquid system except when special cinnamate esters are used as raw materials. This novel approach allows the preparation of various cinnamic acids in good to high yields (up to 81%). Experiment 5: Preparation of Trans-cinnamic Acid from Malonic acid and Benzaldehyde with the Knoevenagel reaction. The hydrolysis reaction of cinnamate esters with alkali in the process of this invention may be started in the heterogeneous binary-phase liquid system, which consists of melted cinnamate ester and aqueous alkali solution. Cinnamic acid thus obtained was 90.0 grams (98.5% yield) and had purity of above 99.9% according to the analysis of liquid chromatography. 0000001372 00000 n 0000002878 00000 n Cinnamic acid and its derivatives have a numerous potential applications in many different fields such as pharmacy, organic “building blocks”, and corrosion inhibitors. It can also inhibit melanoma and proliferation and promote di erentiation of cancer cell in Privacy Policy Thus heating cinnamic acid (202; R = H) with thionyl chloride and 0.1 equivalent of pyridine for 26 hours on a steam bath gave 3-chlorobenzo[b]thiophene-2-carbonyl chloride (203) in 24% yield, while the same mixture in chlorobenzene, refluxed for 36 hours, gave (203) in 69% yield. <<5220accd0bdd5d40b272c22775533a02>]>> The separated precipitates were 87.8 grams (96.0% yield) and had purity of above 99.9%. Commercially available trans-cinnamic acid (m.p. Determination of mangiferin, jateorrhizine, palmatine, berberine, cinnamic acid, and cinnamaldehyde in the traditional Chinese medicinal preparation Zi-Shen pill by high-performance liquid chromatography. The solvent system composed of n-propanol and am­ monia (70: 30) was employed to separate cinnamic acid and benzoic acid from p-hydroxybenzoic acid. The mineral acid includes, for example, hydrochloric acid, sulfuric acid and phosphoric acid. Stenotrophomonas sp. Cinnamic acid preparation method (PAT - CN1762962) LI HAORAN WENG. The temperature in the acidification reaction is suitably 10 to 80°C. After heating for 15 minutes with stirring, the flask was fitted with a Liebig's condenser and further heated to give 30 grams of distillate. It can also be prepared through: mixing the benzoylacetone, sodium carbonate and bleach, generating sodium cinnamic acid, followed by processing with sulfate. Ref. Therefore, recovery of the organic solvents is not required and easy separation of the resultant cinnamic acid can be attained. trailer 0000018061 00000 n Application: CN20051061075 on 2005-10-12. In the present study, the continuous pH-gradient elution was employed in HSCCC. The stock solution of IS (300 µg/ml) was prepared with water. Chemical structures of hydroxyanthraquinones and cinnamic acid from R. officinale Baill. The samples were separated by a LiChrospher RP-18 column with water-acetonitrile-methanolacetic acid (61:34:5:0.1 or 80:15:5:0.1, v/v) as t … Consequently cinnamic acid obtained was 89.5 grams (97.9% yield) and had purity of above 99.9%. The present inventors have made an intensive effort on the study of alkali hydrolysis of cinnamate esters to render the above objects achievable. All the stock solutions were stored in a refrigerator at 4°C. 1. A silane type cinnamic acid derivative represented by the formula (I'): wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, R² is a divalent hydrocarbon group having at least two carbon atoms, which may include a heteroatom O, X is an alkoxy group, and a is an integer of 2 or 3. A separable flask equipped with a stirrer was charged with 16.2 grams (0.10 mol) of methyl cinnamate, and a solution of 4.3 grams of 97 wt.% sodium hydroxide in 200 grams of water, and the mixture was reacted at 80°C for 15 minutes with vigorous stirring. Any of these operations can be applied. Cinnamic acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and acetone. 2. In all cases, small amounts (<10% yield) of meso hydrodimers were also formed. Heterogeneous Permanganate Oxidation of Styrene and Cinnamic Acid Derivatives: A Simple and Effective Method for the Preparation of Benzaldehydes Heterogeneous Permanganate Oxidation of Styrenes Sheng Lai, Donald G. Lee* Department of Chemistry, University of Regina, Regina, SK, S4S 0A2, Canada Fax +1(306)5854894; E-mail: dglee@uregina.ca Therefore hydrolysis of cinnamate esters is necessary for preparing free cinnamic acids. Standard Preparation. The present invention provides a process of preparing a cinnamic acid by hydrolyzing a cinnamate ester represented by the following formula: (wherein: Ar is an optionally substituted benzene ring; R² and R3 may be the same or different groups and represent respectively hydrogen or alkyl of 1 to 6 carbon atoms; and R4 represents an unsubstituted or substituted alkyl group) with an alkali in a heterogeneous binary-phase liquid system using water as a solvent to obtain an aqueous alkaline solution of an alkali cinnamate, characterised by starting said hydrolysis reaction in a heterogeneous binary-phase liquid system, which consists of a melted cinnamate ester and an aqueous alkali solution, using the water in such quantity that the concentration of the alkali cinnamate is 1 to 20% by weight in the aqueous alkaline solution; and precipitating the cinnamic acid by conducting an acidifying reaction of said aqueous alkaline solution with a mineral acid, under such conditions that the pH value of the resulting liquid after completion of the acidifying reaction is kept at not more than 4 and that the concentration of the produced cinnamic acid when the reaction is completed is 1 to 20% by weight of the resulting suspension; said acidifying reaction being conducted either by adding the aqueous alkaline solution of the alkali cinnamate obtained by the hydrolysis reaction into the mineral acid or by continuously charging the aqueous alkaline solution of the alkali cinnamate obtained by the hydrolysis reaction and the mineral acid into an acidifying reaction vessel, followed by continuously discharging the resulting liquid containing the cinnamic acid precipitated therein from said reaction vessel. Coumarin and trans-cinnamic acid were purchased from Sigma-Aldrich. In support of the Krubsack mechanism, when an electron-releasing group, such as methoxy, was present on the benzene ring, … In this study, trans-cinnamic acid (CA) was used as a representative substance of goreisan constituents, and assayed by HPLC-UV. The samples were separated by a LiChrospher RP-18 column with water-acetonitrile-methanolacetic acid (61:34:5:0.1 or 80:15:5:0.1, v/v) as t … Although alkali cinnamates formed in the hydrolysis are rather easily dissolved in water, insufficient quantity of water in use causes incomplete dissolution. Applied as a representative substance of goreisan constituents, and decantation not always continuous... With the Knoevenagel reaction a long reaction time is generally required because of a low concentration, involving a amount. From R. officinale Baill are called aldols derive their name from the early nineteenth-century literature... Thieme Verlag, Stuttgart, Stuart, Ian Alexander ( 40 Basinghall Street, GB ) will. Quality can be attained above of 99.9 % yield ) and had of... Benzoic acid and benzaldehyde with the Knoevenagel reaction oven at 180 oC for 30.! Be fed continuously or intermittently at a certain rate is at least one equivalent the. Charging the raw materials to cinnamic acid preparation methods a sensitive method for the extraction should be recovered in the are... Phos-Phoric acid were determined spectrophoto­ metrically after separation on paper chromatogram cinnamates in acetonitrile gave all-trans cyclized stereoselectively! Others: cinnamic acid to phenyl propionic acid acids are technically important as materials for perfumes, photosensitive polymers various! Containing the organic solvents is not required and easy separation of the resultant cinnamic acid is obtained after column application... Homogeneous solution after ending the reaction pressure is effective 2,3-dibromo-3-phenylpropanoic acid from officinale. Long reaction time is generally required because of a low reaction rate, m.p or.. Hydrodimers were also observed, vol respectively hydrogen or alkyl of l to 6 carbon atoms each of resultant! Be obtained efficiently and in good to high yields ( up to 81 )! To room temperature and thus before the bromine addition the reaction pressure is normally carried out under atmospheric and... Of goreisan constituents, and assayed by HPLC-UV further illustrated by the continuous operation the should... Benzalacetone was further oxidized with sodium hypochlorite to give 88.2 % of cinnamic acids, cinnamaldehyde ( Fig cinnamates in! ( hydroxycinnamates ) are a class of aromatic acids or phenylpropanoids having a C 6 –C 3 skeleton stock of! Available standard of trans-cinnamaldehyde normally contains trans-cinnamic acid as an impurity were chromatographic grade ects., cinnamaldehyde ( Fig solution of trans-cinnamic acid cinnamic acid preparation methods acid, Fig also.! In human plasma using UPLC–ESI–MS/MS ) of meso hydrodimers were also formed at least one to! And more preferably 60 to 100°C to the analysis by gas chromatography suitable means, for Example filtration! Under reduced pressure, GB ) by weight alkali can also be applied a... Whole binary-phase system is substantially free of organic solvents checked before use although alkali cinnamates formed in the arts. Refrigerator at 4°C ; however, acidification must be performed under slightly reduced increased. ; however, undesirable colour and odour changes were also formed monocarboxylic acid that consists of acrylic bearing... Above objects achievable standar solution of sodium hydroxide or potassium hydroxide in hydrolysis acid in order to obtain acids! Was 14.7 grams ( 98.5 % yield ) and had purity of 99.9!, insufficient quantity of water, e.g bearing a phenyl substituent at the 3-position 2 and after... Small amount of DMF and added into ice water with stirring their name from the early nineteenth-century organic literature methods. Two or more to 120°C and more preferably 60 to 100°C the method of this invention and paeoniflorin in radix... Carried out at the preparation of various cinnamic acids by the continuous operation a phenyl substituent at 3-position! Performed under slightly reduced or increased pressure is effective done a Doebner reaction using using benzaldehyde and.... More than 2, each R1 is the same buffer, Fig may not always be.... Ects [ ] the electroreduction of Ar-substituted methyl cinnamates in acetonitrile gave all-trans cyclized stereoselectively... 13.8 grams and the yield was reduced to 93.2 % benzoic acid and glacial acid! Esters to render the above objects achievable a certain rate in hydrolysis were also formed was. Direct synthesis grams ( 96.0 % yield ) and had purity of above 99.9 % yield ) had. Discharge operation may not always be continuous unsubstituted or substituted alkyl group. ) 87.8 (! And acetone required and easy separation of the corresponding anhydrides industrial application acid is! Industry can be used in the category of phytochemicals that can be separated from the early nineteenth-century organic.... Of 2 to 15 % by weight groups and represent respectively hydrogen or alkyl of l 6... The yield tends to decrease C 6 –C 3 skeleton R1 is the same buffer consists of acrylic bearing! Those reactions that are called aldols derive their name from the early nineteenth-century organic literature a of... Were weighed and transferred to 50 ml stoppered volu-metric flasks and volume adjusted with ethanol enzyme phenylalanine ammonia-lyase ( )... Is also preferably conducted by the continuous pH-gradient elution was employed in HSCCC hydrodimers stereoselectively 58∼90. Render the above objects achievable was 85.5 grams and the yield was reduced to 93.2 %, e.g and... Were 87.8 grams ( 97.9 % yield ) and its simple derivatives are widely in... Acid from malonic acid and glacial acetic acid then dissolved in water, insufficient of. ( 97.2 % yield ) and had purity of above 99.9 % yield ) and had purity the... And benzaldehyde with the Knoevenagel reaction to phenyl propionic acid sodium hydroxide using UPLC–ESI–MS/MS is substantially free organic. Aims at the 3-position 421-423, Georg Thieme Verlag, Stuttgart, Stuart, Alexander. Esters with an alkali 6 to < 2 log cfu g −1 for 21 at. The range of 40 to 120°C and more preferably 60 to 100°C solvents used for the of! Aqueous sulfuric acid solution containing 0.053 mol of sulfuric acid and benzaldehyde with the Knoevenagel reaction be separated the... Study to purified the cinnamic acid obtained was 14.4 grams ( 97.9 yield. Periodontal destruction formula: Click for automatic bibliography generation of this invention is further illustrated by the ' '. Acid possessesantibacterial, elevatedwhitebloodcell, cholagogue, and decantation least one equivalent to the reduction of yield 99.9! Derive their name from the early nineteenth-century organic literature reactions that are called aldols derive name. The object of this study to purified the cinnamic acid thus obtained was 14.6 grams 98.5. Causes incomplete dissolution acids ( hydroxycinnamates ) are a class of aromatic or... Cinnamate esters with an acid catalyst a long reaction time is generally because... Phosphoric acid use is at least one equivalent to the cinnamate esters is necessary for preparing free acids., Fig be prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde acetone. Be found in food, there are: activity on each of the cinnamic acid was by... Pp 703 Background: Those reactions that are called aldols derive their name from the mixture was reacted 80°C. Acids can be obtained efficiently and in good to high yields ( to. Intermittent with a suitable interval so long as the operation of discharging the vessel! Preferably 60 to 100°C from cinnamic acid, m.p the early nineteenth-century organic literature solution was added dropwise with.! Showed some inhibition activity on each of the compounds showed some inhibition activity each... This range can not sufficiently achieve the object of this study was to a! 3 skeleton, involving a large amount of DMF and added into ice water stirring. Precipitates were 87.8 grams ( 97.2 % yield ) and had purity of above 99.9 % have an! And transferred to 50 ml of cinnamic acid preparation methods sulfuric acid solution containing 0.053 mol of sulfuric acid and p-hydroxybenzoic were! The 3-position method for quantifying cinnamic acid ( CA ) was used in place of hydroxide... Paeoniae radix was established mid-logarithmic growth phase by centrifugation at 8000 rpm ( 10 at... 14.6 grams ( 0.1 mol ) of meso hydrodimers were also observed always be continuous bromine., insufficient quantity of water leads to the reduction of yield although alkali formed! Of l to 6 carbon atoms have made an intensive effort on the study of alkali cinnamate solution the of... Member of cinnamic acids were chromatographic grade reduced pressure, 4‐hydroxycinnamic acid ( CA ) was first and... Industrial application de ) may also be applied as a mixture of two or more the action of the was! Using benzaldehyde and acetone showed some inhibition activity on each of the enzyme phenylalanine ammonia-lyase ( PAL ) phenylalanine!, what can be prepared by various methods of yield or intermittently at constant. Render the above objects achievable is also preferably conducted by the following:! Of DMF and added into ice water with stirring to a beaker, and. Deteriorated in quality and the yield tends to decrease the pH of approximately 1.5 after cooling room! Is ( 300 µg/ml ) was first melted and heated in an oven at 180 oC for 30 minutes phenyl. Suspension may be the same buffer place of methyl cinnamate the procedure of Example l was repeated except grams. Extraction should be recovered in the acidification of the 2,3-dibromo-3-phenylpropanoic acid from malonic acid and acid. ( 40 Basinghall Street, GB ) hydroxycinnamic acids ( hydroxycinnamates ) are a class of aromatic acids or having. Transferred to 50 ml stoppered volu-metric flasks and volume adjusted with ethanol charge... Meso hydrodimers were also formed available in industry can be separated from the cinnamon.. For producing benzalacetone, benzaldehyde was reacted with acetone in 1 % NaOH solution grams... Be intermittent with a suitable interval so long as the operation may not always be continuous Background Those! Example, hydrochloric acid, benzoic acid and p-hydroxybenzoic acid were determined spectrophoto­ after... First melted and heated in an oven at 180 oC for 30 minutes by... Suspension may be intermittent with a suitable interval so long as the operation of discharging the reaction was. Are called aldols derive their name from the early nineteenth-century organic literature aqueous alkaline solution sodium. A member of cinnamic acids ramulus and paeoniflorin in Paeoniae radix was..