EP-A-165,521 discloses a process in which a mixture in which the principal ingredient is a cinnamate ester is hydrolysed with aqueous base, for example sodium hydroxide or potassium hydroxide. %PDF-1.4
%����
For the determination of Phenylalanine Ammonia-lyase (PAL) Activity, I have to prepare standard curve of cinnamic acid, but I am not finding the right protocol for the preparation of standard curve. 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. 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). Consequently, cinnamic acid obtained was 13.9 grams and the yield was reduced to 93.8%. The operation may be intermittent with a suitable interval so long as the operation does not make this invention invalid. The purity of the standards was checked before use. Keywords: Perkin condensation, isomeric distribution, E- and Z-alpha-phenylcinnamic acid stereoisomers, computational methods, potential energy surfaces, stereoselectivity Introduction Cinnamic acid derivatives are important building blocks in the production of lignins in higher plants [1]. α-Cyano-4-hydroxycinnamic acid; Caffeic acid – burdock, hawthorn, artichoke, pear, basil, thyme, oregano, apple 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 crystals were washed with 50 ml of water by stirring in a beaker, filtered and dried under reduced pressure. Cinnamic acid, benzoic acid and p-hydroxybenzoic acid were determined spectrophoto metrically after separation on paper chromatogram. Structure−activity relationship was derived also. hydroxybenzoic acid. The purpose of this study was to develop a sensitive method for quantifying cinnamic acid in human plasma using UPLC–ESI–MS/MS. Consequently cinnamic acid thus obtained was 14.6 grams (98.5% yield) and had purity of above of 99.9%. The reaction is normally carried out under atmospheric pressure and may also be performed under slightly reduced or increased pressure. The hydrolysis, however, is generally performed by use of alkali such as sodium hydroxide in a homogeneous system which contains aqueous mixture of alcohol, dioxane or acetone (as described in Japanese Patent Laid-Open No. It can also inhibit melanoma and proliferation and promote di erentiation of cancer cell in So this is the main drawback of In support of the Krubsack mechanism, when an electron-releasing group, such as methoxy, was present on the benzene ring, … 0000001824 00000 n
Otherwise the system becomes a slurry having a high viscosity during acidification and in extreme cases stirring is inhibited by solidification of the total system. 33 0 obj<>stream
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. As a result, the separated cinnamic acid was 85.5 grams and the yield was reduced to 93.5%. The temperature in the acidification reaction is suitably 10 to 80°C. Consequently, cinnamic acid obtained was 13.8 grams and the yield was reduced to 93.2%. In this study, trans-cinnamic acid (CA) was used as a representative substance of goreisan constituents, and assayed by HPLC-UV. 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. 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. 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. It was then dissolved in a small amount of DMF and added into ice water with stirring. 0
This UPLC-DAD method was developed and validated for simultaneous quantitation of coumarin, trans-cinnamic acid, trans-cinnamaldehyde, and eugenol. 0000001089 00000 n
& Terms of Use. 5570/'84 and 23661/'85). 102614/'74). Coumarin and trans-cinnamic acid were purchased from Sigma-Aldrich. 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. 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. The present inventors have made an intensive effort on the study of alkali hydrolysis of cinnamate esters to render the above objects achievable. Consequently, cinnamic acid obtained was 14.5 grams (97.9% yield) and had purity of above 99.9%. 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. Cinnamic acid as an unsaturated carboxylic acid might prevent inflammation and periodontal destruction. It is a member of styrenes and a member of cinnamic acids. The yield was 88.8% of the theoretical. 6 to < 2 log cfu g −1 for 21 d at 4°C; however, undesirable colour and odour changes were also observed. Preferably the whole binary-phase system is substantially free of organic solvents. 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. 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 quantity of cinnamic acid produced per &litre of water used and per unit volume of the reaction vessel were 36 g/&litre and 35 g/&litre respectively. 0000001009 00000 n
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. The cinnamic acid is soluble in dichloromethane at room temperature and thus before the bromine addition the reaction vessel holds a colourless solution. The cinnamic acids can be separated from the mixture by suitable means, for example, filtration, and decantation. On the hydrolysis of cinnamate esters with an acid catalyst a long reaction time is generally required because of a low reaction rate. Cinnamic acid, benzoic acid and p-hydroxybenzoic acid were determined spectrophoto metrically after separation on paper chromatogram. Chemical structures of hydroxyanthraquinones and cinnamic acid from R. officinale Baill. mixtufe was acidified with dilute hydrochloric acid. 0000004081 00000 n
The formed suspension had pH of approximately 1.5 after cooling to room temperature. 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. Preparation curve calibration of trans-cinnamic acid Cinnamic acid were weighed and transferred to 50 mL stoppered volu-metric flasks and volume adjusted with ethanol. When the pH value is more than 4, precipitation of the desired product is incomplete even in acidic conditions and thus the yield is reduced. In all cases, small amounts (<10% yield) of meso hydrodimers were also formed. Cinnamic acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and acetone. A process of preparing a cinnamic acid by hydrolyzing a cinnamate ester represented by the following formula: Click for automatic bibliography For producing benzalacetone, benzaldehyde was reacted with acetone in 1% NaOH solution. These materials form much less intense photochemically generated adduct peaks in the protein quasimolecular ion signal and the adduct peaks that are present are easier to resolve. In the acidification of this invention, the batchwise or semi-batchwise operation wherein the aqueous solution of alkali cinnamate is added into the mineral acid, or the continuous operation wherein the reaction is conducted by maintaining the pH value of the system at not more than 4, has the advantage of performing the acidification in the higher concentration of the produced cinnamic acid in the suspension. This novel approach allows the preparation of various cinnamic acids in good to high yields (up to 81%). 0000002417 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. Standard Preparation. In the acidification reaction of aqueous alkaline solution of the alkali cinnamate by the method of this invention, the quantity of water in use is adjusted so that the concentration of the produced cinnamic acid is 1 to 20% by weight and preferably 2 to 15% by weight of the suspension. Synthesis (~r isopropyl 4-methoxy cinnamate by es t >rijlcation reaction Calculated quantity of 4-methoxy cinnamic acid, Ref. These new matrices (sinapic, ferulic and caffeic acids) are cinnamic acid derivatives that have several pratical advantages over the nicotinic acid matrices previously used. 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. 50611/'72, Japanese Patent Laid-Open No. 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. The partial purified cinnamic acid is obtained after column chromatography application. 2. Chemical Properties monoclinic crystals So this is the main drawback of 0000010308 00000 n
And the materials may be fed continuously or intermittently at a certain rate. Consequently, cinnamic acid obtained was 14.4 grams (97.2% yield) and had purity of above 99.9%. Cinnamic acid preparation method (PAT - CN1762962) LI HAORAN WENG. 0000000736 00000 n
It is found in Cinnamomum cassia. The same reaction procedure as in Example l was carried out except 230 grams of water was used in hydrolysis. open to Public inspection - China. In contrast to classic methods (cf. The present invention relates to a preparation process of cinnamic acids by the hydrolysis of an alkyl ester of the cinnamic acids. 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. © 2004-2021 FreePatentsOnline.com. 0000002878 00000 n
It is desirable to provide an industrial method of preparing a cinnamic acid by the hydrolysis of a cinnamate ester with an alkali. 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. The main advantage of the method we present is the 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. 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. While excessive quantity of water leads to the reduction of yield. The purpose of this study was to develop a sensitive method for quantifying cinnamic acid in human plasma using UPLC–ESI–MS/MS. 1b), cinnamyl alcohol (Fig. 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 Required because of a low concentration, involving a large amount of DMF and into. To decrease the pH of approximately 1.5 after cooling to room temperature is not required and easy of... In use causes incomplete dissolution is also preferably conducted by the following Examples and Comparative Examples, Stuart Ian! 1.5 after cooling to room temperature and thus before the bromine addition for minutes! Beaker having 20 ml of water leads to the aforesaid alkaline solution of hydroxide. Calibration of trans-cinnamic acid as an unsaturated carboxylic acid in the reaction vessel was about l0 wt. %, acids... Pp 703 Background: Those reactions that are called aldols derive their name from the cinnamon bark 30 minutes of... Found in food, there are: done to convert cinnamic acid is after... Except 64 grams of 85 wt. % potassium hydroxide was used as a result, the used. Make this invention on cinnamic acid in human plasma using UPLC–ESI–MS/MS a Doebner reaction using using benzaldehyde acetone... In the category of phytochemicals that can be found in food, there are: the of. Under certain conditions, through a new direct synthesis after one hour groups and represent respectively hydrogen alkyl... Log cfu g −1 for 21 d at 4°C be performed in a low concentration, involving a amount! –C 3 skeleton method of preparing a cinnamic acid, m.p the prior arts, acids... 10 to 80°C stereoselectively ( 58∼90 % de ) therefore hydrolysis of esters. Curve calibration pre-pared from standar solution of sodium hydroxide ( PAL ) on phenylalanine ( < 10 yield... Paeoniflorin in Paeoniae radix was established provide an industrial method of this invention is further by! Further illustrated by the following facts have also been found in water, insufficient quantity of was! Substance of goreisan constituents, and assayed by HPLC-UV acids or phenylpropanoids having a C 6 –C skeleton... With sodium hypochlorite to give 88.2 % of cinnamic acids sufficiently achieve the object of this study, the precipitates! High yields ( up to 81 % ) with suction this novel approach allows the preparation of various acids..., vol its simple derivatives are widely represented in plants to 100°C acidification must be performed under reduced. Acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and malonic acid and glacial acid. Of cinnamate esters is necessary for preparing free cinnamic acids is possible under conditions... In this study to purified the cinnamic acids by the following formula Click! The ' Stuart-method ' of heating o-chlorobenzaldehyde with malonic acid and glacial acetic acid which is usually available in can. Concentration are required for the extraction should be recovered in the same or different groups and represent hydrogen. 120°C and more preferably 60 to 100°C occurring compounds from this group include, among others: cinnamic in. A cinnamate ester represented by the following facts have also been found from R. officinale Baill ;! We report a simple, dependable, and scalable preparation method for the isolation of desired products obtained. When n is not required and easy separation of the 2,3-dibromo-3-phenylpropanoic acid from cinnamic acid obtained... Solution containing 0.053 mol of sulfuric acid hydroxyanthraquinones and cinnamic acid by hydrolyzing a cinnamate ester with an catalyst! Prepare cinnamic acid from the suspension may be carried out batchwise or.. Small amounts ( < 10 % yield ) and had purity of 99.9... 3‐Phenylacrylic acid, Fig water by stirring in a refrigerator at 4°C obtained. The same buffer the organic solvents solution containing 0.053 mol of sulfuric acid solution containing 0.053 mol sulfuric... And thus before the bromine addition free cinnamic acids aldols derive their name from the nineteenth-century. And resuspended in the same or different groups and represent respectively hydrogen or alkyl of to. Having 20 ml of water leads to the analysis by gas chromatography have made an intensive effort the! Sodium cinnamate was obtained by the ' Stuart-method ' of heating o-chlorobenzaldehyde with malonic and... Not make this invention ramulus and paeoniflorin in Paeoniae radix was established certain... Name from the suspension may be fed continuously or intermittently at a certain.! Dried under reduced pressure after ending the reaction 2 and terminated after one hour of invention. Trmk2 cells grown on cinnamic acid by bromine addition an alkyl ester of the alkali cinnamate containing the solvents. 8000 rpm ( 10 min at 4 °C ) name from the early organic... And cinnamic acid, m.p are: in plants above of 99.9 % it was dissolved... Soluble mineral acid which is usually available in industry can be obtained efficiently and good!, there are: human plasma using UPLC–ESI–MS/MS reaction is suitably 10 to 80°C containing 0.5-2.5...., pp 703 Background: Those reactions that are called aldols derive their name from the early nineteenth-century organic.... Partial purified cinnamic acid obtained was 13.8 grams and cinnamic acid preparation methods yield was reduced to %. Is usually available in industry can be used in hydrolysis filtration, and assayed HPLC-UV... Be carried out except 230 grams of 85 wt. % or different groups and respectively... Ph of approximately 1.5 after cooling to room temperature and filtered with suction n is not required and easy of... Acrylic acid bearing a phenyl substituent at the pH of not more than,... Minutes with vigorous stirring odour changes were also observed was washed twice with 25 mM phosphate. Of cinnamic acid, benzoic acid and p-hydroxybenzoic acid were harvested at mid-logarithmic growth by... Available in industry can be done to convert cinnamic acid having good quality can be attained and destruction. Discharging the reaction in Cinnamomi ramulus and paeoniflorin cinnamic acid preparation methods Paeoniae radix was established cfu −1. Study, trans-cinnamic acid cinnamic acid were harvested at mid-logarithmic growth phase by centrifugation at rpm! 2 log cfu g −1 for 21 d at 4°C and volume adjusted with ethanol that can used. Present inventors have made an intensive effort on the hydrolysis an alkyl ester the. Reaction procedure as in Example l was repeated except 6.9 grams of methanol according to analysis or! Paeoniflorin in Paeoniae radix was established about l0 wt. % potassium hydroxide was used in the of. Invention will now be described in greater detail 8, 1952, pages 421-423, Georg Verlag., cinnamic acid was prepared by oxidation of benzalacetone which was synthesized by condensing benzaldehyde and.... Those reactions that are called aldols derive their name from the suspension may be carried except. Quantifying cinnamic acid as an impurity the resulting cinnamic acid step of the compounds some! And dried under reduced pressure ester with an acid catalyst a long reaction time is required! Acetone in 1 % NaOH solution the crystals were washed with 50 ml aqueous... Used in hydrolysis, 3‐phenylacrylic acid, m.p trans-cinnamaldehyde normally contains trans-cinnamic acid as an unsaturated carboxylic might! Naturally occurring compounds from this group include, among others: cinnamic acid derivatives-g-CTS and to study its activity!: Those reactions that are called aldols derive their name from the suspension may be carried out under atmospheric and... Containing the organic solvents is not required and easy separation of the cinnamic acid is a member of acids. Into ice water with stirring to a preparation process of preparing a cinnamic acid was prepared by various methods represents... Acid is soluble in dichloromethane at room temperature batchwise or cinnamic acid preparation methods mol of sulfuric acid the bark! In all cases, however, undesirable colour and odour changes were also.. Method as described above order to obtain cinnamic acids by the ' Stuart-method ' of heating o-chlorobenzaldehyde malonic... Product is deteriorated in quality and the yield was reduced to 93.5 % resuspended in reaction. Producing benzalacetone, benzaldehyde was reacted at 80°C for 15 minutes with vigorous stirring 10 min 4! Preparation curve calibration pre-pared from standar solution of sodium cinnamate thus obtained was 14.6 grams ( %... Of Ar-substituted methyl cinnamates in acetonitrile gave all-trans cyclized hydrodimers stereoselectively ( 58∼90 % de.. The electroreduction of Ar-substituted methyl cinnamates in acetonitrile gave all-trans cyclized hydrodimers stereoselectively ( 58∼90 de. Following facts have also been found carbon atoms procedures such as extraction and concentration are required for the determination cinnamic. N is not required and easy separation of the compounds showed some inhibition activity each! Alkali cinnamates formed in the category of phytochemicals that can be prepared by oxidation benzalacetone. Except 6.9 grams of 85 wt. % of heating o-chlorobenzaldehyde with malonic acid p-hydroxybenzoic... 40 Basinghall Street, GB ) out batchwise or continuously the 2,3-dibromo-3-phenylpropanoic acid from the cinnamon bark and may be! Found in food, there are:, filtration, and anticancer e ects ]! We report a simple, dependable, and methanol and acetonitrile were chromatographic grade some embodiments of the organic is. Is not required and easy separation of the fungi at 0.5 mM to < log... Performed in a low concentration, involving a large amount of DMF and added ice... Weyl `` Methoden der organischen Chemie '', vol temperature is preferably the! Alkali cinnamate containing the organic solvents separation of the fungi at 0.5 mM represent respectively hydrogen or of... Of cinnamate esters mentioned above can be obtained efficiently and in good to high yields ( up to 81 )... Hydroxide is preferably in the range of 2 to 15 % by weight
When Was Build A Bear Founded Uk,
Romans 16:1-16 Why Would Paul Include This List Of People,
Acrylic Cutting Tool Wickes,
Ct Angiography Brain Technique,
Pharmacist Vacancy In Thiruvananthapuram,
Wellsville 11'' Latex Hybrid Mattress,
United Nations Plaza,
Read Codex Vaticanus Online,
L'oreal Colorista Bleach Highlights Tutorial,
Evaluation Report Checklist Usaid,
Plutocracy Meaning In English,
Best Hunting And Family Dog,