Experiment 2: Two Step Synthesis of Ethyl 4-Methoxycinnamate
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Malonic Acid
SIGMA-ALDRICH sigma-aldrich.com Material Safety Data Sheet Version 4.1 Revision Date 09/20/2012 Print Date 03/13/2014 1. PRODUCT AND COMPANY IDENTIFICATION Product name : Malonic acid Product Number : M1296 Brand : Sigma-Aldrich Supplier : Sigma-Aldrich 3050 Spruce Street SAINT LOUIS MO 63103 USA Telephone : +1 800-325-5832 Fax : +1 800-325-5052 Emergency Phone # (For : (314) 776-6555 both supplier and manufacturer) Preparation Information : Sigma-Aldrich Corporation Product Safety - Americas Region 1-800-521-8956 2. HAZARDS IDENTIFICATION Emergency Overview OSHA Hazards Toxic by inhalation., Harmful by ingestion., Irritant GHS Classification Acute toxicity, Inhalation (Category 5) Acute toxicity, Oral (Category 4) Skin irritation (Category 3) Serious eye damage (Category 1) GHS Label elements, including precautionary statements Pictogram Signal word Danger Hazard statement(s) H302 Harmful if swallowed. H316 Causes mild skin irritation. H318 Causes serious eye damage. H333 May be harmful if inhaled. Precautionary statement(s) P280 Wear protective gloves/ eye protection/ face protection. P305 + P351 + P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. HMIS Classification Health hazard: 2 Flammability: 1 Physical hazards: 0 NFPA Rating Health hazard: 2 Fire: 1 Sigma-Aldrich - M1296 Page 1 of 7 Reactivity Hazard: 0 Potential Health Effects Inhalation Toxic if inhaled. Causes respiratory tract irritation. Skin Harmful if absorbed through skin. Causes skin irritation. Eyes Causes eye irritation. Ingestion Harmful if swallowed. 3. COMPOSITION/INFORMATION ON INGREDIENTS Synonyms : Propanedioic acid Formula : C3H4O4 Molecular Weight : 104.06 g/mol Component Concentration Malonic acid CAS-No. -
Step Formation Constants of Some Malonato Lanthanide Chelate Species Marvin Lee Adolphson Iowa State University
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1969 Step formation constants of some malonato lanthanide chelate species Marvin Lee Adolphson Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Physical Chemistry Commons Recommended Citation Adolphson, Marvin Lee, "Step formation constants of some malonato lanthanide chelate species " (1969). Retrospective Theses and Dissertations. 3809. https://lib.dr.iastate.edu/rtd/3809 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. 70-13,563 ADOLPHSON, Marvin Lee, 1941- STEP FORMATION CONSTANTS OF SOME MÀLONATO LANTHANIDE CHELATE SPECIES. Iowa State University, Ph.D., 1969 Chemistiy, physical University Microfilms, Inc., Ann Arbor, Michigan THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED STEP FORMATION CONSTANTS OF SOME MALONATO LANTHANIDE CHELATE SPECIES by Marvin Lee Adolphson A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Physical Chemistry Approved; Signature was redacted for privacy. In/Charge of Major Work Signature was redacted for privacy. Signature was redacted for privacy. Iowa State University Ames, Iowa 1969 ii TABLE OF CONTENTS Page INTRODUCTION 1 COMPUTATIONS 4 EXPERIMENTAL DETAILS 15 EXPERIMENTAL RESULTS 35 DISCUSSION 56 SUMMARY 88 BIBLIOGRAPHY 89 ACKNOWLEDGMENT S 94 APPENDIX 95 1 INTRODUCTION The motivations for this research were fourfold. -
Knoevenagel Condensation
Knoevenagel condensation The Knoevenagel condensation (pronounced [ˈknøːvənaːɡl̩ ]) Knoevenagel condensation reaction is an organic reaction named after Emil Knoevenagel. It is a Named after Emil Knoevenagel modification of the aldol condensation.[1][2] Reaction type Coupling reaction A Knoevenagel condensation is a nucleophilic addition of an active Identifiers hydrogen compound to a carbonyl group followed by a dehydration reaction in which a molecule of water is eliminated (hence Organic knoevenagel- condensation). The product is often an α,β-unsaturated ketone (a Chemistry condensation conjugated enone). Portal RSC ontology RXNO:0000044 ID In this reaction the carbonyl group is an aldehyde or a ketone. The catalyst is usually a weakly basic amine. The active hydrogen component has the form[3] Z–CH2-Z or Z–CHR–Z for instance diethyl malonate, Meldrum's acid, ethyl acetoacetate or malonic acid, or cyanoacetic acid.[4] Z–CHR1R2 for instance nitromethane. where Z is an electron withdrawing functional group. Z must be powerful enough to facilitate deprotonation to the enolate ion even with a mild base. Using a strong base in this reaction would induce self-condensation of the aldehyde or ketone. The Hantzsch pyridine synthesis, the Gewald reaction and the Feist–Benary furan synthesis all contain a Knoevenagel reaction step. The reaction also led to the discovery of CS gas. Contents Doebner modification Scope Weiss–Cook reaction See also References Doebner modification The Doebner modification of the Knoevenagel condensation. Acrolein and malonic acid react in pyridine to give trans-2,4-pentadienoic acid with the loss of carbon dioxide. With malonic compounds the reaction product can lose a molecule of carbon dioxide in a subsequent step. -
Crystallization of Malonic and Succinic Acids on Sams: Toward the General Mechanism of Oriented Nucleation on Organic Monolayers†
pubs.acs.org/Langmuir © 2009 American Chemical Society Crystallization of Malonic and Succinic Acids on SAMs: Toward the General Mechanism of Oriented Nucleation on Organic Monolayers† Boaz Pokroy,‡ Victoria Fay Chernow, and Joanna Aizenberg* School of Engineering and Applied Sciences, Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138. ‡ Current address: Department of Materials Engineering, Israel Institute of Technology, Haifa 32000, Israel. Received July 25, 2009. Revised Manuscript Received September 2, 2009 Self-assembled monolayers (SAMs) were shown to induce very specific oriented growth of simple organic and inorganic crystals. Here we present a detailed study of the mechanism by which SAMs control the oriented nucleation by examining a more complex case of crystallization of bifunctional organic molecules. Malonic and succinic acids were grown on the SAMs of HS(CH2)10CO2H and HS(CH2)11CO2H supported on gold films. Each SAM induced a very controlled, specific orientation of the crystals. The preferred nucleating planes always exhibited an alignment of one of the carboxylic acid groups in the molecules of the growing crystal with the carboxylic acid groups on the surface of the SAMs. These results suggest that the translation of the structural information through the interface occurs by stereochemical registry such that the functional groups in the SAM play the role of an oriented surrogate layer for the nucleating crystal. These findings are very important to the understanding of the underlying principles by which various organic surfaces;and most probably also biological templates;control the crystallization process. Introduction templates to control the formation of both organic and inorganic An understanding of crystal nucleation and growth and the materials. -
Knoevenagel Condensation Reaction Catalysed by Agro-Waste Extract As a Greener Solvent Catalyst
ORIGINAL ARTICLE Org. Commun. 14:1 (2021) 81-91 Knoevenagel condensation reaction catalysed by agro-waste extract as a greener solvent catalyst Krishnappa B. Badiger and Kantharaju Kamanna * Peptide and Medicinal Chemistry Research Laboratory, Department of Chemistry, Rani Channamma University, P-B, NH-4, Belagavi 591 156, India (Received January 22, 2021; Revised March 15, 2021; Accepted March 18, 2021) Abstract: This paper present a novel Knoevenagel reaction protocol for the condensation of aromatic/heteroaromatic aldehydes with malononitrile to give α, β–unsaturated benzylidene derivatives. The main focus of this work is to reveal the usability of agro-waste extracts as a catalyst in the Knoevenagel condensation. The present protocol proceeds efficiently for various substituted aromatic and heterocyclic aldehydes in the Knoevenagel reactions. In addition, the present method describes direct isolation of the formed products without using organic solvent extraction gave good yields product. Keywords: one-pot reaction; green chemistry; solvent-free; Knoevenagel condensation reaction; malononitrile; room temperature. ©2021 ACG Publication. All right reserved. 1. Introduction The carbon-carbon bond formation via Knoevenagel condensation1-3 is one of the most important routes repeated in the synthetic organic chemistry and allows the production of various active pharmaceutical molecules.4 Figure 1. Structure of biologically potent benzylidinemalononitrile derivatives * Corresponding author:E-Mail: [email protected] The article was published -
Metabolomics of Metformin's Cardioprotective Effect in Acute
Sys Rev Pharm 2021;12(3):100-109 A multifaceted revieMw jouernatl ian thbe fioeld lofophamrmaciycs Of Metformin's Cardioprotective Effect In Acute Doxorubicin Induced- Cardiotoxicity In Rats Lubna Zuhair Abdul Karim *, Inam Sameh Arif **, Fouad A. Al Saady *** *Pharmacist, Department of Pharmacology and Toxicology, College of Pharmacy, Mustansiriyah University, M.Sc. program, Iraq. **Assist.Prof., Department of Pharmacology and Toxicology, College of Pharmacy, Mustansiriyah University, Iraq. *** Assist. Prof., Department of pharmaceutical chemistry, College of Pharmacy, Mustansiriyah University, Iraq. Corresponding author: Lubna Zuhair Abdul Karim *e-mail: [email protected] ABSTRACT Doxorubicin (DOX) is a powerful anticancer agent with sever cardiotoxic side Keywords: metabolomics, cardiotoxicity, doxorubicin, cardioprotection, effect which limits the clinical use. Metformin (MET) is antihyperglycemic drug metformin. with potential cardioprotective effect via AMP-activated protein kinase (AMPK) (increases fatty acid oxidation, decreases the production of ROS, maintaining Correspondence: energy homeostasis and apoptosis). Metabolomics technology deals with Lubna Zuhair Abdul Karim systematic study of chemical fingerprints of metabolite profiles. Different *Pharmacist, Department of Pharmacology and Toxicology, College of Pharmacy, metabolic processes can be identified which will give information of any change Mustansiriyah University, M.Sc. program, Iraq. in the metabolic profile of tissues as well as of biofluids after drug -
Microwave-Assisted Urea Catalyzed Knoevenagel Condensation of Aldehydes with = Light Brown Solid, M.P
Available online at www.banglajol.info Bangladesh J. Sci. Ind. Res. 55(2), 159-164, 2020 purification. The Chemicals 4-fluorobenzaldehyde (98%), 2-(4-nitrophenylmethylene)malononitrile (3a): yield 90%, 2-(4-Hydroxyphenylmethylene)malononitrile (3f): yield CDCl3) δ(ppm): 8.32(s, 1H), 8.01(d, J=8.4, 2H), 7.22(d, Furthermore, the treatment of aldehyde such as acknowledge the University Research Centre, SUST for Yang Y, Dong ODW, Pan W, Zhang J and Liu Q (2006), Wang C, Li Guishen S, Li G, Feng J, Li S and Xiaolu (2001), 4-hydroxybenzaldehyde (98%), 4-nitrobenzaldehyde yellowish white solid, m.p. 158-159 , (lit.160 (Sun Qi et 96%, yellow solid, m.p. 171-172 , (lit. 189-190 ( Sun J=8.4, 2H), 6.38(s, 1H, N-H), 6.11(s, 1H, N-H) . cinnamaldehyde with ethylcyanoacetate also give financial support. Facile and clean synthesis of α-alkenoyl Synthesis of 5-alkylene barbituric acid in solventless 2 Qi et al 2005 ); IR (KBr): υ (cm-1): 3354(-OH), olefinic compounds 3i under similar conditions (Table ketene-(S,S)-acetal via the aldol condensation under microwave irradiation, Chin. J. Org. Chem. (98%), 2-nitrobenzaldehyde (98%), 3-nitrobenzaldehyde al 2005)); IR (KBr): υmax: 3039(sp C-H), 2231 (C≡N), 1604 max (98%), 4-chlorobenzaldehyde (97%) and cyanoacetamide (C=C) and 1521 and 1344(N-O) cm℃-1; 1H NMR℃ (400 MHz, 3030(sp2 C-H), 2227(C≡N), and℃ 1670(C=C) cm℃-1; 1H 2-cyano-3-(4-nitrophenyl)acrylamide (3l): yield 85%, 1, Scheme 1). Both electron-rich and References reactions in water, Tetrahedron 62: 10-111. -
APPENDIX G Acid Dissociation Constants
harxxxxx_App-G.qxd 3/8/10 1:34 PM Page AP11 APPENDIX G Acid Dissociation Constants § ϭ 0.1 M 0 ؍ (Ionic strength ( † ‡ † Name Structure* pKa Ka pKa ϫ Ϫ5 Acetic acid CH3CO2H 4.756 1.75 10 4.56 (ethanoic acid) N ϩ H3 ϫ Ϫ3 Alanine CHCH3 2.344 (CO2H) 4.53 10 2.33 ϫ Ϫ10 9.868 (NH3) 1.36 10 9.71 CO2H ϩ Ϫ5 Aminobenzene NH3 4.601 2.51 ϫ 10 4.64 (aniline) ϪO SNϩ Ϫ4 4-Aminobenzenesulfonic acid 3 H3 3.232 5.86 ϫ 10 3.01 (sulfanilic acid) ϩ NH3 ϫ Ϫ3 2-Aminobenzoic acid 2.08 (CO2H) 8.3 10 2.01 ϫ Ϫ5 (anthranilic acid) 4.96 (NH3) 1.10 10 4.78 CO2H ϩ 2-Aminoethanethiol HSCH2CH2NH3 —— 8.21 (SH) (2-mercaptoethylamine) —— 10.73 (NH3) ϩ ϫ Ϫ10 2-Aminoethanol HOCH2CH2NH3 9.498 3.18 10 9.52 (ethanolamine) O H ϫ Ϫ5 4.70 (NH3) (20°) 2.0 10 4.74 2-Aminophenol Ϫ 9.97 (OH) (20°) 1.05 ϫ 10 10 9.87 ϩ NH3 ϩ ϫ Ϫ10 Ammonia NH4 9.245 5.69 10 9.26 N ϩ H3 N ϩ H2 ϫ Ϫ2 1.823 (CO2H) 1.50 10 2.03 CHCH CH CH NHC ϫ Ϫ9 Arginine 2 2 2 8.991 (NH3) 1.02 10 9.00 NH —— (NH2) —— (12.1) CO2H 2 O Ϫ 2.24 5.8 ϫ 10 3 2.15 Ϫ Arsenic acid HO As OH 6.96 1.10 ϫ 10 7 6.65 Ϫ (hydrogen arsenate) (11.50) 3.2 ϫ 10 12 (11.18) OH ϫ Ϫ10 Arsenious acid As(OH)3 9.29 5.1 10 9.14 (hydrogen arsenite) N ϩ O H3 Asparagine CHCH2CNH2 —— —— 2.16 (CO2H) —— —— 8.73 (NH3) CO2H *Each acid is written in its protonated form. -
A Previously Undescribed Pathway for Pyrimidine Catabolism
A previously undescribed pathway for pyrimidine catabolism Kevin D. Loh*†, Prasad Gyaneshwar*‡, Eirene Markenscoff Papadimitriou*§, Rebecca Fong*, Kwang-Seo Kim*, Rebecca Parales¶, Zhongrui Zhouʈ, William Inwood*, and Sydney Kustu*,** *Department of Plant and Microbial Biology, 111 Koshland Hall, University of California, Berkeley, CA 94720-3102; ¶Section of Microbiology, 1 Shields Avenue, University of California, Davis, CA 95616; and ʈCollege of Chemistry, 8 Lewis Hall, University of California, Berkeley, CA 94720-1460 Contributed by Sydney Kustu, January 19, 2006 The b1012 operon of Escherichia coli K-12, which is composed of tive N sources. Here we present evidence that the b1012 operon seven unidentified ORFs, is one of the most highly expressed codes for proteins that constitute a previously undescribed operons under control of nitrogen regulatory protein C. Examina- pathway for pyrimidine degradation and thereby confirm the tion of strains with lesions in this operon on Biolog Phenotype view of Simaga and Kos (8, 9) that E. coli K-12 does not use either MicroArray (PM3) plates and subsequent growth tests indicated of the known pathways. that they failed to use uridine or uracil as the sole nitrogen source and that the parental strain could use them at room temperature Results but not at 37°C. A strain carrying an ntrB(Con) mutation, which Behavior on Biolog Phenotype MicroArray Plates. We tested our elevates transcription of genes under nitrogen regulatory protein parental strain NCM3722 and strains with mini Tn5 insertions in C control, could also grow on thymidine as the sole nitrogen several genes of the b1012 operon on Biolog (Hayward, CA) source, whereas strains with lesions in the b1012 operon could not. -
Green Chemistry – Aspects for the Knoevenagel Reaction
2 Green Chemistry – Aspects for the Knoevenagel Reaction Ricardo Menegatti Universidade Federal de Goiás Brazil 1. Introduction Knoevenagel condensation is a classic C-C bond formation reaction in organic chemistry (Laue & Plagens, 2005). These condensations occur between aldehydes or ketones and active methylene compounds with ammonia or another amine as a catalyst in organic solvents (Knoevenagel, 1894). The Knoevenagel reaction is considered to be a modification of the aldol reaction; the main difference between these approaches is the higher acidity of the active methylene hydrogen when compared to an -carbonyl hydrogen (Smith & March, 2001). Figure 1 illustrates the condensation of a ketone (1) with a malonate compound (2) to form the Knoevenagel condensation product (3), which is then used to form the ,-unsaturated carboxylic compounds (3) and (4) (Laue & Plagens, 2005). R R R O O O O H O O O + base hydrolysis H O O O O R R (1) (2) (3) (4) Fig. 1. An example of the Knoevenagel reaction. Subsequent to the first description of the Knoevenagel reaction, changes were introduced using pyridine as the solvent and piperidine as the catalyst, which was named the Doebner Modification (Doebner, 1900). The Henry reaction is another variation of the Knoevenagel condensation that utilises compounds with an -nitro active methylene (Henry, 1895). The general mechanism for the Knoevenagel reaction, which involves deprotonation of the malonate derivative (6) by piperidine (5) and attack by the formed carbanion (8) on the carbonyl subunit (9) as an aldol reaction that forms the product (10) of the addition step is illustrated in Fig. -
Route of Knoevenagel Reaction from Conventional Method to Greener Methods
IOSR Journal of Environmental Science, Toxicology and Food Technology (IOSR-JESTFT) e-ISSN: 2319-2402,p- ISSN: 2319-2399.Volume 9, Issue 12 Ver. I (Dec. 2015), PP 52-55 www.iosrjournals.org Route of Knoevenagel Reaction from Conventional method to Greener methods Dr. Leena H. Sarkar Department of Chemistry, J.V.M’s Degree College, Airoli, Navi Mumbai 400 708, India. Abstract: In the past few years, classic methods of synthesis have been replaced by newer methods of synthesis involving principles of Green Chemistry given by Anastas and Warner leading to environmentally safer products and processes and reducing pollution and thus making the environment greener. In this review article I have compared old classical method of Knoevenagel reaction with greener methods for a more sustainable, pollution free future society. Key Words: Green chemistry, Knoevenagel reaction, solvent free reactions, sustainable chemistry, use of ultrasound radiations, catalysis, microwave chemistry and use of ionic liquids. I. Introduction The Knoevenagel [1] reaction is considered to be a modification of the aldol reaction [2]. It is named after Emil Knoevenagel. It is a condensation reaction of aldehydes or ketones 1 with active methylene compounds 2 in presence of base like ammonia or another amine or piperidine as a catalyst in organic solvents to yield α,β-unsaturated carbonyl compounds 3 (Fig. 1) which serve as intermediates in various reactions and compounds of medicinal interest [3-7]. Group attached to methylene group must be powerful enough to facilitate deprotonation to form enolate ion, even with a mild base. Fig. 1: Conventional method of Knoevenagel synthesis II. -
Production of Malonic Acid Through the Fermentation of Glucose
University of Pennsylvania ScholarlyCommons Department of Chemical & Biomolecular Senior Design Reports (CBE) Engineering 4-20-2018 Production of Malonic Acid through the Fermentation of Glucose Emily P. Peters University of Pennsylvania, [email protected] Gabrielle J. Schlakman University of Pennsylvania, [email protected] Elise N. Yang University of Pennsylvania, [email protected] Follow this and additional works at: https://repository.upenn.edu/cbe_sdr Part of the Biochemical and Biomolecular Engineering Commons Peters, Emily P.; Schlakman, Gabrielle J.; and Yang, Elise N., "Production of Malonic Acid through the Fermentation of Glucose" (2018). Senior Design Reports (CBE). 107. https://repository.upenn.edu/cbe_sdr/107 This paper is posted at ScholarlyCommons. https://repository.upenn.edu/cbe_sdr/107 For more information, please contact [email protected]. Production of Malonic Acid through the Fermentation of Glucose Abstract The overall process to produce malonic acid has not drastically changed in the past 50 years. The current process is damaging to the environment and costly, requiring high market prices. Lygos, Inc., a lab in Berkeley, California, has published a patent describing a way to produce malonic acid through the biological fermentation of genetically modified easty cells. This proposed technology is appealing as it is both better for the environment and economically friendly. For the process discussed in this report, genetically modified Pichia Kudriavzevii yeast cells will be purchased from the Lygos lab along with the negotiation of exclusive licensing rights to the technology. The cells will be grown in fermentation vessels, while being constantly fed oxygen, glucose and fermentation media. The cells will excrete malonic acid in the 101 hour fermentation process.