DOCSLIB.ORG

The Condensation of Aldehydes with Malonic Acid in the Presence of Organic Bases

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Condensation of Aldehydes with Malonic Acid in the Presence of Organic Bases THE CONDENSATION OF ALDEHYDES WITH MALONIC ACID IN THE PRESENCE OF ORGANIC BASES. Part II. The Condensation of Salicylaldehyde. BY AzI~I< ALl KHAN, 1VI.SC., P. N. KURIEN, M.SC., AND K. C. PANDYA, M.A., P~.D., D.I.C., Cl, emieal Laboratory, St. John's College, Agra. Received Decembe~ 8, 1934. KNO~VENAGELI (1898) brought about the condensation of salicylaldehyde with malonic acid in the presence of a minimum quantity of piperidine, with tile formation of coumarin-carboxylic acid. Butt 2 reported (1925) a conden- sation " in presence of piperidine in pyridine solution" with a poor yield of o-coumaric acid. In Part I of this series, it has been shown (Kurien, Pandya and Surange, 3 193~) that (I) the simpler aromatic aldehydes could be condensed with malonic acid in the presence of pyridine alone and without the piperidine, the base, the acid and the aldehyde being in equimolar proportions, and the yields, under suitable conditions, could be up to 96% of theory; that (2) under the same conditions the aromatic hydroxy-aldehydes, including salicylaldehyde, showed no condensation at all; but that (3) the condensation did occur, with yields up to 57~ of coumarin-carboxylic acid, if traces, instead of molecular quantities, of pyridine were used ; and that, lastly, in the condensations of other aldehydes also the trace of pyridine was equally, if not more, efficacious (piperonal giving 100% yield, in contrast with the 76% reported by Dutt2). In the present paper the study of this condensation is extended to the use of other organic bases in place of piperidine or pyridine, such as have not been hitherto tried, viz., lutidine, quinoline, iso-quinoline, a-naptho- quinoline, quinaldine, cinchonine, dimethylaniline, diethylaniline, benzyl- methylaniline, acridine and methylacridine : the aldehyde being in all cases salicylaldehyde. A preliminary experiment, under conditions of maximum yield with pyridine, but without the use of any base or another reagent, was tried. It 1 Knoevenagel, Bet., ]898, 31, 2585. 2 Butt, Jour. Ind. Chem. See., ]925, 1, 298, 300. S Kurien, Pandya and Surange, Jour. Ind. Chem. Soc., ]934, 11,823. 440 T,~e Cozdemaiion o/ AMe@des 441 showed that salicylaldehyde and malonie acid alone, on heating :[or five hours at 100 ~ C. and then keeping overnight, reacted with the formation of the usual coumarin-carboxylic acid (m.p. 187-188~ but the yield was only 11% of the theory. A detailed examination with varying molecular proportions of lutidine added to the acid and the aldehyde, was undertaken. The observations (Table I) show that there is no condensation when the base is from 1 to 0.2 mole. Indeed, when full molar proportions are tried, carbon dioxide is given out as soon as heating is started. As this never happens when the condensation results in the formation of coumarin-carboxylic acid, it is clear that, if there is any condensation in this case, the product should be either eoumarin or o-comnaric acid. None of these is, however, to be found at the end, while the reaction mixture gives back ahnost all the aldehyde, the base and acetic acid. When the base was in lesser proportion, the usual condensation-product made its appearance in increasing amounts till under the most favourable conditiorts, the yield rose to 74%(Table I). The other bases were used on the same principle, the product in all cases being the same coumarin-carboxylic acid, which, though slightly and differently coloured, was always pure enough to give tile same melting point and good analysis. The yields are comparable, in many cases favourably, with the figures obtained by Dalal and Dutt ~ who employed molecular quantities of bases with aldehydes. Though salicylaldehyde does not occur in their table, it is remarkable that methyl- acridine gives them with benzaldehyde their lowest yield (1-3%), and the same base gives us with salieylaldehyde our highest (77%). Knoevenagel thinks that the aldehyde combines first with the base piperidine which then reacts with malonic acid. It has been found while the experiments described in Part I were in progress, that pyridine and malonic acid when warmed together in molecular proportions gave a white solid product which analysis showed to be pyridine malonate and which, after isolation, could also be used irt condensations with benzaldehyde. Ouinoline malonate has also been obtained in the same way and decomposes just above its melting-point, 90 ~ C., giving off carbon dioxide, acetic acid and the base. When, however, it is mixed with salieylaldehyde, the decomposition starts even at 50 ~ C. As the temperature of the condensation is higher, 80 ~ C. or so, no condensation is thus possible. The decomposition is avoided when malonic ester is used in place of 4 Dalal and:Dutt, ,lmtr. fnd. Chem. Soc., 1932, 9, 309. 442 Azhar Ali Khan and others the acid, and then, as other investigations to be reported in Part III show, the condensations take place even when 0.5 mole. of the base is present. Experimental. Condensatio.~ ~,it.hout a base.--5 grams malonie acid (Sch. Kahl Baum, pure for scientific purposes, dried at 100 ~ C., and kept in a desiccator) and 6 c.c. of salicylaldehyde (Merck, pure synthetic) were mixed and kept in a dry flask on the water-bath at I00 ~ C. for 5 hours and then left overnight to cool. The product, acidified with hydrochloric acid, was steam-distilled till the remaining aldehyde was removed. Tile contents of the flask were taken out and cooled; crystals separated, which on drying and after a recrystallisation from alcohol, melted at 187-188 ~ C. The yield was 11% (Table I). Condensations with lutidir~e.--The same experiment was repeated with different proportions of purified and redistilled lutidine and later with different conditions of heating, etc. (Tables I and II). The highest yield was 74%, obtained with 0.05 mole. (0-25 c.c.) of lutidine, on heating at 800 C. for 12 hours and then keeping it for a week at the ordinary temperature. Condensations with quir~oline.--The acid and the aldehyde were heated together on a water-bath till the acid passed in solution. The base was then added and the mixture kept at laboratory temperature (15-20 ~ C.) for some time and then heated on water-bath for definite time (Table III). Condensations in the presence of the remaining bases were carried out in the same way, the results and details are given in Tables IV and V (isoquinoline in Table IV and all the bases in Table V). The identity of the product was confirmed not only by comparison with known samples, but also by analysis. The equivalent weight (by titration against standard baryta) was 190- 5. Found : C, 62.6~ I-I, 3.19% ; C10H604 requires 190-0, 63-1%, and 3-25 % respectively. The ComlemaXion of ZlMe@des 443 TABLE I. Temp. of Quantity of Base Time of Yield Yield hea~ing h eating Remarks % C. I-Iours Grams C.CS. M ol. Prop. 0.00 0'00 i00 ~ 5 Kept, over- 1 11 night after heating. 2 0.05 O'O1 2.8 31 3 0.1 0.02 4.1 45 4 0.15 0.03 5,1 56 5 0.2 0.04 4.5 50 6 0"25 0.05 4.5 50 7 0-5 0,1 2.3 25 8 0.5 0.1 ~ 6 2.2 24 9 0.5 0.1 2.3 25 10 0"5 0.1 2.1 23 11 1.0 0.2 ~ 5 0 0 12 2"0 0.4, 0 0 13 3.0 0.6 0 0 14 4"0 0.8 0 0 15 5-0 1"0 0 0 16 0.25 0.05 Kept for 7 5.3 58 days after heating. 17 0.25 0.05 60 ~ 10 Kept over- 4.5 50 night after heating. 18 0.25 0-05 60 ~ 12 4.8 53 19 0.25 O.O5 60 ~ 15 4.8 53 20 0'25 0-05 80 ~ 12 6 66 21 0"25 0.05 80 ~ 15 6 66 22 0.25 O. 05 80 ~ 12 Kept for 7 6.6 74 days after heating. 444 Azhar Ali Khan and others TABLE II. Quantity of Base of Temp. Time Time of Yield C. heating keeping % C.(~S. Mol. Prop. Hours 1 0.5 0.1 60 ~ 10 15 days 66 2 0"25 0.05 100 ~ 5 30 3 0.25 0.05 60 ~ 10 5 ~ 50 4 0-25 0.05 800 10 5 ~ 66 5 0-25 0.05 80 ~ 10 64 TABL~ III. Quantity of Base Temp. Time of Yield Yield C. heating Grams % }Iours C.C8, ~ol. Prop. 1 0"05 O. 008 100 ~ 5 2.8 31 2 0-1 O. 016 4-5 50 3 0.15 O. 02-i 4.8 53 4 0.2 O. 032 4.5 50 5 0"25 0.04 4.5 50 6 0.5 0.08 2-5 28 7 1 0.16 1.0 11 8 2 0.32 0.0 0 9 3 0.48 0-0 0 10 4 0.64 0.0 0 11 6.4 1 0.0 0 12 0-25 0.04 80 ~ 11 6.0 66 The Condensation o/./1/de/ ydes 445 TABLE IV. Quantity of Base Time of t_ Temp. Yield Yield C. heating Grams % C.CS. Mol. Prop. 1tours 1 0.]5 0.024 I00 ~ 5 4.5 50 2 0.2 0,032 4.5 50 3 0.25 0.04 77 4.8 52 4 0.5 0.08 3 33 5 0'25 0.04 80 ~ 12 6 66 TABLE V.
Load more

Recommended publications
  • Cv1p0149.Pdf
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • Multicatalytic, Asymmetric Michael/Stetter Reaction Of
    Multicatalytic, asymmetric Michael/Stetter reaction SPECIAL FEATURE of salicylaldehydes and activated alkynes Claire M. Filloux, Stephen P. Lathrop, and Tomislav Rovis1 Department of Chemistry, Colorado State University, Fort Collins, CO 80523 Edited by David W. C. MacMillan, Princeton University, Princeton, NJ, and accepted by the Editorial Board May 30, 2010 (received for review March 22, 2010) We report the development of a multicatalytic, one-pot, asymmetric Ar Ar Michael/Stetter reaction between salicylaldehydes and electron- N H deficient alkynes. The cascade proceeds via amine-mediated OO 3 OTMS (20 mol %) Me HO Me Michael addition followed by an N-heterocyclic carbene-promoted Me Me 1 Ar = 3,5-(CF3)2C6H3 O intramolecular Stetter reaction. A variety of salicylaldehydes, dou- + O O BF4 N bly activated alkynes, and terminal, electrophilic allenes participate 2 Me 5 Me in a one-step or two-step protocol to give a variety of benzofura- NNC F 4a 6 5 One-Pot Two - Po t none products in moderate to good yields and good to excellent (10 mol %) 93% yield 46% yield NaOAc (10 mol %) 85:15:<1:<1 dr 5:1 dr enantioselectivities. The origin of enantioselectivity in the reaction 86% ee 58% ee CHCl3, 23 C is also explored; E∕Z geometry of the reaction intermediate as well as the presence of catalytic amounts of catechol additive are O found to influence reaction enantioselectivity. O Me * O Me ∣ ∣ catalysis organic synthesis tandem catalysis Me 6 ascade catalysis has garnered significant recent attention Scheme 1. Multicatalytic Michael/Benzoin cascade. Cfrom the synthetic community as a means to swiftly assemble CHEMISTRY complex molecules from simple starting materials with minimal benzofuranones.
    [Show full text]
  • Note to Users
    NOTE TO USERS This reproduction is the best copy available Synthetic Approaches to Coniochaetones A & B Leo James Patrick Martyn A thesis submitted in conformity with the requirements for the degree of Master of Science Graduate Department of Chemistry University of Toronto @ Copyright by Leo James Patrick Martyn 1999 National Library Bibliothèque nationale * of Canada du Canada Acquisitions and Acquisitions et Bibliographie Services seMces bibliographiques 395 Wellington Street 395, nie Wellington OltawaûN KIAW OnawaON K1AW Canada Canada The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant à la National Library of Canada to Bibliothèque nationale du Canada de reproduce, loan, distribute or seU reproduire, prêter, distribuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or electronic formats. la forme de microfiche/film, de reproduction sur papier ou sur format électronique. The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts fiom it Ni la thèse ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation. Abstract Several routes to the synthesis of coniochaetones A and B, two natural products isolated from a liquid culture of Coniochaeta soccardoi,' were explored. Two different pathways which we believe will eventually lead to the synthesis of coniochaetones A and B have been focused upon. Utilizing a mode1 senes, key intermediates for each synthetic route have been synthesized and characterized.
    [Show full text]
  • Synthesis and Antidepressant Activity of Some New Coumarin Derivatives
    Scientia Pharmaceutica (Sci. Pharm.) 74, 193-216 (2005) O Osterreichische Apotheker-Verlagsgesellschafl m. b. H., Wien, Printed in Austria Synthesis and Antidepressant Activity of Some New Coumarin Derivatives Nehad A. Abdel-Latif Natural Compounds Department, National Research Centre, Dokki, Cairo, Egypt; E-mail: [email protected] Abstract The coumarin-3-cinnamoyl derivatives 2a-d were prepared via Claisen- Schmidt condensation of 3-acetylcoumarin 1 with different aromatic aldehydes. Cycloaddition reaction of 2b,e with guanidine and thiourea yielded the corresponding aminopyrmimidine 3a,b and thioxypyrimidine derivatives 4a,b, respectively. Compounds 4a,b were condensed with chloroacetic acid or 3- bromopropionic acid to yield coumarin 3-thiazolo-pyrimidine 5a,b and thiazinopyrimidine 6a,b derivatives, respectively. Compounds 4a,b were condensed with chloroacetic acid and aromatic aldehyde to yield the aryl methylene derivatives 7a,b which could be prepared directly by condensation of compounds 5a,b with aromatic aldehydes. Compounds 2a-e were condensed with malononitrile or ethyl cyano acetate in presence of ammonium acetate to yield cyanopyridine 8a,b and cyanopyridone 9a- d derivatives, respectively, which were prepared by condensation of 3- acetylcoumarin 1, malononitrile or ethylcyanoacetate and aromatic aldehydes in presence of ammonium acetate. Condensation of compounds 2a,b,e with o-phenylenediamine in refluxing ethanol led to the formation of 10a-c as intermediate, followed by cleavage by thermolysis to benzimidazole derivative 11 along with compounds 12a-c as mixture, which were obtained directly by fusion of a,&unsaturated ketones 2 with o- phenylene diamine at 200-220°C, while compound 11 could be prepared in pure form by fusion of 1 with o-phenylene diamine at the same temperature.
    [Show full text]
  • Part I: Synthesis of Functionalized Bile Acids Towards The
    PART I: SYNTHESIS OF FUNCTIONALIZED BILE ACIDS TOWARDS THE CONSTRUCTION OF STEROIDAL MACROCYCLES. PART II: EVALUATION AND EXPANSION OF A MODULAR CARD GAME FOR TEACHING ORGANIC CHEMISTRY A DISSERTATION IN Chemistry and Pharmaceutical Sciences Presented to the Faculty of the University of Missouri-Kansas City in partial fulfillment of the requirements for the degree DOCTOR OF PHILOSOPHY by CHRISTOPHER ANTON KNUDTSON B.S., Saint Louis University 2004 M.S., Kansas University 2011 Kansas City, Missouri 2019 © 2019 CHRISTOPHER ANTON KNUDTSON ALL RIGHTS RESERVED PART I: SYNTHESIS OF FUNCTIONALIZED BILE ACIDS TOWARDS THE CONSTRUCTION OF STEROIDAL MACROCYCLES. PART II: EVALUATION AND EXPANSION OF A MODULAR CARD GAME FOR TEACHING ORGANIC CHEMISTRY Christopher A. Knudtson, Candidate for the Doctor of Philosophy Degree University of Missouri-Kansas City, 2019 ABSTRACT In Part I, the synthesis of chenodeoxychoic acid (CDCA) derivatives towards the construction of unique chemical architectures are reported. Building on previously described methods, CDCA based macrocycles with inner cavities have been synthesized and characterized. Attempts toward oxa-Michael coupling of CDCA monomers to form sulfonate ester linked dimmers is described. CDCA was also functionalized with terminal alkynes (pentynyl, hexynyl, and heptynyl) and aryl iodide and cyclized to from the respective macrocycles. These have been coupled together via oxygen-free Sonogashira reaction conditions to form large barrel-like steroidal architectures. These structures were investigated by 1H NMR, 13 C NMR spectroscopy, and HR-MS, and MALDI-TOF spectroscopy. In part II a game to teach organic chemistry, ChemKarta was evaluated as a teaching tool. Analysis of an undergraduate class’s impressions of the game showed that Chemkarta was an easy to learn and enjoyable game, but the amount of information in the game could be overwhelming for some students.
    [Show full text]
  • Trusscore Chemical Resistance Chart
    Chemical Resistance Chart Table courtesy of JENSEN INERT PRODUCTS, INC. Resistance Material E = Excellent G = Good F = Fair PVC = Polyvinylchloride N = Not Recommended This information, based on experience to date, is believed to be reliable. It is intended as a guide for use at your own discretion and risk. All indications refer to room temperature. Chemical PVC Chemical PVC Acetaldehyde G Calcium Hypochlorite G Acetamide N Carbazole N Acetic Acid, 5% E Carbon Disulfide N Acetic Acid, 50% E Carbon Tetrachloride G Acetone E Chlorine E Aluminum Hydroxide E Chloroacetic Acid F Ammonia E Chloroform N Ammonium Hydroxide E Chromic Acid E Ammonium Oxalate E Citric Acid G n-Amyl Acetate F Cresol N Amyl Chloride N Cyclohexane G Aniline N Chemical PVC Chemical PVC Decalin E Benzaldehyde N o-Dichlorobenzene G Benzene N p-Dichlorobenzene N Benzoic Acid, Sat. E Diethyl Benzene N Benzyl Acetate F Diethyl Ether F Boric Acid E Diethyl Ketone N Bromine G Diethyl Malonate G Bromobenzene F Dimethyl Formamide F n-Butyl Acetate N sec-Butyl Alcohol G Chemical PVC Butyric Acid G Ether F Ethyl Acetate F Chemical PVC Ethyl Benzene N Nitric Acid, 50% G Ethyl Benzoate N Nitric Acid, 70% F Ethyl Butyrate N Nitrobenzene N Ethyl Chloride, Liquid N n-Octane F Ethyl Cyanoacetate NF Orange Oil F Ethyl Lactate F Ethylene Chloride N Chemical PVC Ethylene Glycol E Perchloric Acid G Ethylene Oxide F Perchloroethylene N Phenol, Crystals F Chemical PVC Phosphoric Acid, 1-5% E Fluorine N Phosphoric Acid, 85% E Formic Acid, 50% G Potassium Hydroxide E Formic Acid, 90-100% F Propane Gas E Fuel Oil E Propylene Glycol F Gasoline G Propylene Oxide F Glycerine E Chemical PVC Chemical PVC Resorcinol F n-Heptane F Salicylaldehyde F Hexane G Sulfuric Acid, 1-6% E Hydrochloric Acid, 1-5% E Sulfuric Acid, 20% E Hydrochloric Acid, 35% G Sulfuric Acid, 60% E Hydrofluoric Acid, 4% G Sulfuric Acid, 98% N Hydrofluoric Acid, 48% G Sulfur Dioxide, Liq.
    [Show full text]
  • United States Patent Office Patented Jan
    United States Patent Office Patented Jan. 23, 1968 1. 2 3,365,500 Therefore, from what information appears in the litera HYDROXYBENZALDEHYDE PROCESS ture, there would seem to be little advantage to be gained Donald F. Pontz, Midland, Mich., assignor to The Dow by using aqueous ethyl alcohol as a solvent in the prepara Chemical Company, Midland, Mich., a corporation of tion of Salicylaldehyde by this method. There is nothing Delaware to incline a chemist to investigate other alcoholic solvents No Drawing. Filed Jan. 21, 1964, Ser. No. 339,104 as the means by which improved results might be obtained. 5 Claims. (C. 260-600) Consequently, it is surprising and unexpected to find that aqueous methanol used as the solvent medium for the preparation of Salicylaldehyde by the Reimer-Tiemann ABSTRACT OF THE DISCLosURE 10 reaction provides both better combined yields of hy In the Reimer-Tiemann reaction wherein phenol is droxyaldehydes and sharply reduced tar formation as com reacted with chloroform and an alkali metal base to make pared to the results obtained by using either water or salicylaldehyde and p-hydroxybenzaldehyde, improved aqueous ethyl alcohol as the reaction solvent. By using yields of total aldehydes and decreased tar formation are as the Solvent aqueous methanol containing from about obtained when the reaction medium is aqueous methanol 5 10% to about 75% by weight of methanol, the yield of of 10-75 percent by weight concentration as compared Salicylaldehyde is at least as good as that obtained with to reactions run in water alone or in aqueous ethanol. The Water or aqueous ethyl alcohol and the yield of the improvement in total aldehyde yield is due principally to valuable p-hydroxybenzaldehyde is considerably better.
    [Show full text]
  • Fluorescent Iridium(III) Coumarin-Salicylaldehyde Schiff Base Compounds As Lysosome-Targeted Antitumor Agents
    Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2020 Fluorescent Iridium(III) Coumarin-salicylaldehyde Schiff Base Compounds as Lysosome-Targeted antitumor agents Cong Liu, Xicheng Liu*, Xingxing Ge, Qinghui Wang, Lei Zhang, Wenjing Shang, Yue Zhang, XiangAi Yuan, Laijin Tian, Zhe Liu*, Jinmao You Institute of Anticancer Agents Development and Theranostic Application, The Key Laboratory of Life-Organic Analysis and Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China. *Corresponding authors (Email): [email protected] (X. C. Liu); [email protected] (Z. Liu) Supporting Information Experimental Section .....................................................................................................................2 Synthesis.........................................................................................................................................6 Figures S1-S16..........................................................................................................................7 Tables S1-S9...................................................................................................................................24 1 EXPERIMENTAL SECTION NMR Spectrum NMR spectra were acquired in 5 mm NMR tubes at 298 K on Bruker DPX 500 (1H NMR: 500.13 MHz; 13C NMR: 126 MHz; 19F NMR: 471 MHz) spectrometers. 1H NMR chemical shifts were internally referenced
    [Show full text]
  • Role of Nicotinamide and Salicylaldehyde on Some Growth Parameters in Wheat
    ©Verlag Ferdinand Berger & Söhne Ges.m.b.H., Horn, Austria, download unter www.biologiezentrum.at Phyton (Austria) Vol. 29 Fasc. 1 33-40 16. 5. 1989 Role of Nicotinamide and Salicylaldehyde on Some Growth Parameters in Wheat Youssef A. H. MOHAMED, Ahmed SHARAF EL-DIN & El-Sayed FODA With 3 Figures Received January 13, 1988 Key words: Nicotinamide, salicylaldehyde, growth, wheat, Triticum. Summary MOHAMED Y. A. H., SHARAF EL-DIN A. & FODA E. 1989. Role of nicotinamide and salicylaldehyde on some growth parameters in wheat. - Phyton (Austria) 29 (1): 33-40, with 3 figures. - English with German summary. The effect of 1(T4 and 1CT5 M nicotinamide and salicylaldehyde was shown in favour of the increase in root and shoot length. The area of the leaf in plants treated with nicotinamide increased and the width decreased. Salicylaldehyde exerted neu- tral effect on leaf. Both growth regulators increased the level of total soluble carbohydrates and total soluble proteins throughout the overall age of the plant and in the different plant organs. As a result of these growth regulators application, DNA quantities decreased in the root and stem and increased in the leaf, while inhibition of RNA synthesis was observed. Zusammenfassung MOHAMED Y. A. H., SHARAF EL-DIN A. & FODA E. 1989. Der Einfluß von Nikotinamid und Salicylaldehyd auf einige Wachstumsparameter bei Weizen. - Phyton (Austria) 29 (1): 33-40, mit 3 Figuren. - Englisch mit deutscher Zusammen- fassung. 10"4 und 10~5 M Nikotinamid und Salicylaldehyd begünstigten das Längen- wachstum von Wurzel und Sproß. Die Blattfläche nikotinamidbehandelter Pflanzen nahm zu, während deren Breite abnahm.
    [Show full text]
  • Synthetic and Meschanistic Studies of The
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by South East Academic Libraries System (SEALS) APPLICATIONS OF THE BAYLIS-HILLMAN REACTION IN THE SYNTHESIS OF COUMARIN DERIVATIVES A thesis submitted in fulfilment of the requirements for the degree DOCTOR OF PHILOSOPHY of RHODES UNIVERSITY by MUSILIYU AYODELE MUSA M.Sc (Lagos) Department of Chemistry Rhodes University Grahamstown January 2002 ABSTRACT The reaction of specially prepared salicylaldehyde benzyl ethers with the activated alkenes, methyl acrylate or acrylonitrile, in the presence of the catalyst, DABCO, has afforded Baylis-Hillman products, which have been subjected to conjugate addition with either piperidine or benzylamine. Hydrogenolysis of these conjugate addition products in the presence of a palladium-on-carbon catalyst has been shown to afford the corresponding 3-substituted coumarins, while treatment of O-benzylated Baylis- Hillman adducts with HCl or HI afforded the corresponding 3-(halomethyl)coumarins directly, in up to 94%. The 3-(halomethyl)coumarins have also been obtained in excellent yields (up to 98%) and even more conveniently, by treating the unprotected Baylis-Hillman products with HCl in a mixture of AcOH and Ac2O, obtained from tert-butyl acrylate and various salicylaldehydes. The generality of an established route to the synthesis of coumarins via an intramolecular Baylis-Hillman reaction, involving the use of salicylaldehyde acrylate esters in the presence of DABCO, has also been demonstrated. Reactions between the 3-(halomethyl)coumarins and various nitrogen and carbon nucleophiles have been shown to proceed with a high degree of regioselectivity at the exocyclic allylic centre to afford 3-substituted coumarin products.
    [Show full text]
  • Summary: Synthesis of Salicylaldehyde and Its Applications Twghs Kap Yan Directors’ College Introduction
    Summary: Synthesis of Salicylaldehyde and its Applications TWGHs Kap Yan Directors’ College Introduction Salicylaldehyde (SA) (C6H4CHO-2-OH) is a useful aromatic organic chemical. It is a common reactant for many synthesis, such as cyclic organic compounds like coumarin and organic ligand such as salan ligand. Salicylaldehyde is also crucial to our daily lives. In A. Ravin’s medical publication, it is mentioned that SA can be used for detection of ketonuria in medical treatment. It also serves as a chelating agent with heavy metal ions such as Copper(II) ion, which is applicable to colorimetric analysis of the concentration of heavy metal ions in water sample. SA is also a precursor in total synthesis of coumarin (C9H6O2), which is a white organic crystal with antibacterial activities. However, salicylaldehyde is not commonly stored in secondary schools’ laboratories. People can only buy a relatively large amount of salicylaldehyde with high price from chemical suppliers. In our research project, we used a simple one-pot reaction to synthesize salicylaldehyde from phenol (C6H5OH), sodium hydroxide (NaOH) and chloroform (CHCl3) which are available in school laboratory. The synthesis, separation and identification are carried under a normal secondary school laboratory without using advanced laboratory devices and apparatus. Meanwhile, several applications of salicylaldehyde were also investigated, for instance the synthesis of coumarin, metal complex chelation and the medical detection of ketonuria. Figure 1: Chemical structure of salicylaldehyde Figure 2: Appearance of salicylaldehyde Part 1: Synthesis By Reimer-Tiemann Reaction, phenol reacts with chloroform to form SA under refluxing for 1 hour in 65℃ water bath. This method is simple to carry out with a relatively high yield of SA obtained (~30%).
    [Show full text]
  • Bis(Salicylidene)Ethylenediamine(Salen) and Bis(Salicylidene)Ethylenediamine-Metal Complexes: from Structure to Biological Activity
    Journal of Analytical & Pharmaceutical Research Bis(Salicylidene)Ethylenediamine(Salen) and Bis(Salicylidene)Ethylenediamine-Metal Complexes: from Structure to Biological Activity Abstract Review Article Schiff bases and their metal complexes have occupied a central role in the Volume 3 Issue 6 - 2016 development of co-ordination chemistry as evidenced by the vast number, ease and flexibility of the synthetic procedure, diverse properties, and use as biologically active compounds as antitumor, antibacterial, antifungal and other miscellaneous Department of Industrial Chemistry, Ebonyi State University, biological applications. Many reports have demonstrated that Salen and Salen- Nigeria metal complexes are highly active against several diseases, including cancer. The thrust of this review work is to evaluate the structural nature of Salen and assess *Corresponding author: Felix Sunday Nworie, Department the biological applications thereof. of Industrial Chemistry, Ebonyi State University, PMB 053 Abakaliki, Ebonyi State, Nigeria, Tel: +2348034813342; Keywords: Schiff base; Salen; Metal salen; Biological applications; Structural Email: characterization Received: October 31, 2016 | Published: December 15, 2016 Abbreviations: C: Carbon; N: Nitrogen; DMSO: Dimethylsulphoxide; PXRD: Powder X-ray Diffractometer; the elimination of the hemiaminal (carbinolamine) hydroxyl SOD: Superoxide Dismutase; Cu: Copper; Zn: Zinc; Fe: Iron; groupconditions, (dehydration there is unavailabilitystep) [5]. of sufficient protons to catalyze Cr: Chromium; Mn:
    [Show full text]