Lecture 7 Imines, Hydrazones and Oximes
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Part I: Carbonyl-Olefin Metathesis of Norbornene
Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis……………………………………………………………. -
Pyramidalization/Twisting of the Amide Functional Group Via Remote Steric Congestion Triggered by Metal Coordination Chemical Science
Chemical Volume 8 Number 1 January 2017 Pages 1–810 Science rsc.li/chemical-science ISSN 2041-6539 EDGE ARTICLE Naoya Kumagai, Masakatsu Shibasaki et al. Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by Cite this: Chem. Sci.,2017,8,85 metal coordination† Shinya Adachi, Naoya Kumagai* and Masakatsu Shibasaki* For decades, the planarity of the amide functional group has garnered sustained interest in organic chemistry, enticing chemists to deform its usually characteristic high-fidelity plane. As opposed to the construction of amides that are distorted by imposing rigid covalent bond assemblies, we demonstrate herein the deformation of the amide plane through increased steric bulk in the periphery of the amide moiety, which is induced by coordination to metal cations. A crystallographic analysis revealed that the thus obtained amides exhibit significant pyramidalization and twisting upon coordination to the metals, Received 16th August 2016 while the amide functional group remained intact. The observed deformation, which should be Accepted 21st September 2016 attributed to through-space interactions, substantially enhanced the solvolytic cleavage of the amide, DOI: 10.1039/c6sc03669d Creative Commons Attribution 3.0 Unported Licence. providing compelling evidence that temporary crowding in the periphery -
Nitroso and Nitro Compounds 11/22/2014 Part 1
Hai Dao Baran Group Meeting Nitroso and Nitro Compounds 11/22/2014 Part 1. Introduction Nitro Compounds O D(Kcal/mol) d (Å) NO NO+ Ph NO Ph N cellular signaling 2 N O N O OH CH3−NO 40 1.48 molecule in mammals a nitro compound a nitronic acid nitric oxide b.p = 100 oC (8 mm) o CH3−NO2 57 1.47 nitrosonium m.p = 84 C ion (pKa = 2−6) CH3−NH2 79 1.47 IR: υ(N=O): 1621-1539 cm-1 CH3−I 56 Nitro group is an EWG (both −I and −M) Reaction Modes Nitro group is a "sink" of electron Nitroso vs. olefin: e Diels-Alder reaction: as dienophiles Nu O NO − NO Ene reaction 3 2 2 NO + N R h 2 O e Cope rearrangement υ O O Nu R2 N N N R1 N Nitroso vs. carbonyl R1 O O O O O N O O hυ Nucleophilic addition [O] N R2 R O O R3 Other reaction modes nitrite Radical addition high temp low temp nitrolium EWG [H] ion brown color less ion Redox reaction Photochemical reaction Nitroso Compounds (C-Nitroso Compounds) R2 R1 O R3 R1 Synthesis of C-Nitroso Compounds 2 O R1 R 2 N R3 3 R 3 N R N R N 3 + R2 2 R N O With NO sources: NaNO2/HCl, NOBF4, NOCl, NOSbF6, RONO... 1 R O R R1 O Substitution trans-dimer monomer: blue color cis-dimer colorless colorless R R NOBF OH 4 - R = OH, OMe, Me, NR2, NHR N R2 R3 = H or NaNO /HCl - para-selectivity ΔG = 10 Kcal mol-1 Me 2 Me R1 NO oxime R rate determining step Blue color: n π∗ absorption band 630-790 nm IR: υ(N=O): 1621-1539 cm-1, dimer υ(N−O): 1300 (cis), 1200 (trans) cm-1 + 1 Me H NMR (α-C-H) δ = 4 ppm: nitroso is an EWG ON H 3 Kochi et al. -
Empowering Alcohols As Carbonyl Surrogates for Grignard-Type Reactions
ARTICLE https://doi.org/10.1038/s41467-020-19857-9 OPEN Empowering alcohols as carbonyl surrogates for Grignard-type reactions Chen-Chen Li 1, Haining Wang1, Malcolm M. Sim1, Zihang Qiu 1, Zhang-Pei Chen1, Rustam Z. Khaliullin1 & ✉ Chao-Jun Li 1 The Grignard reaction is a fundamental tool for constructing C-C bonds. Although it is widely used in synthetic chemistry, it is normally applied in early stage functionalizations owing to 1234567890():,; poor functional group tolerance and less availability of carbonyls at late stages of molecular modifications. Herein, we report a Grignard-type reaction with alcohols as carbonyl surro- gates by using a ruthenium(II) PNP-pincer complex as catalyst. This transformation proceeds via a carbonyl intermediate generated in situ from the dehydrogenation of alcohols, which is followed by a Grignard-type reaction with a hydrazone carbanion to form a C-C bond. The reaction conditions are mild and can tolerate a broad range of substrates. Moreover, no oxidant is involved during the entire transformation, with only H2 and N2 being generated as byproducts. This reaction opens up a new avenue for Grignard-type reactions by enabling the use of naturally abundant alcohols as starting materials without the need for pre-synthesizing carbonyls. 1 Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, QC H3A 0B8, ✉ Canada. email: [email protected] NATURE COMMUNICATIONS | (2020) 11:6022 | https://doi.org/10.1038/s41467-020-19857-9 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-19857-9 n tandem with the significant advancements of biological and even be successfully applied in synergistic relay reactions29. -
Synthesis of Optically Pure Macroheterocycles with 2,6-Pyridinedicarboxylic and Adipic Acid Fragments from ∆3-Carene
Macrolides Paper Макролиды Статья DOI: 10.6060/mhc190660y Synthesis of Optically Pure Macroheterocycles with 2,6-Pyridinedicarboxylic and Adipic Acid Fragments from ∆3-Carene Marina P. Yakovleva,@ Kseniya S. Denisova, Galina R. Mingaleeva, Valentina A. Vydrina, and Gumer Yu. Ishmuratov Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, 450054 Ufa, Russia @Corresponding author E-mail: [email protected] Based on the available natural monoterpene ∆3-carene we have developed the synthesis of four optically pure macroheterocycles with ester and dihydrazide fragments through the intermediate 1-((1S,3R)-3-(2-hydroxyethyl- 2,2-dimethylcyclopropyl)propan-2-one using its [2+1]-interaction with dichloranhydrides of adipic or 2,6-pyridinedicarboxylic acids and [1+1]-condensation of the obtained α,ω-diketodiesters with dihydrazides of adipic or 2,6-pyridinedicarboxylic acids. The structure of new compounds was confirmed by IR and NMR spectroscopy and mass spectrometry. Keywords: 3-Carenes, ozonolysis, sodium hypochlorite, macroheterocycles with ester and dihydrazide fragments, [2+1] and [1+1] condensations, synthesis. Синтез оптически чистых макрогетероциклов со сложноэфирными и дигидразидными фрагментами адипиновой и 2,6-пиридиндикарбоновой кислот из D3-карена М. П. Яковлева,@ К. С. Денисова, Г. Р. Мингалеева, В. А. Выдрина, Г. Ю. Ишмуратов Уфимский Институт химии – обособленное структурное подразделение Федерального бюджетного научного учреждения Уфимского федерального исследовательского центра Российской академии -
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani To cite this version: Rim Mouselmani. Reduction of Organic Functional Groups Using Hypophosphites. Other. Univer- sité de Lyon; École Doctorale des Sciences et de Technologie (Beyrouth), 2018. English. NNT : 2018LYSE1241. tel-02147583v2 HAL Id: tel-02147583 https://tel.archives-ouvertes.fr/tel-02147583v2 Submitted on 5 Jun 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THESE de DOCTORAT DE L’UNIVERSITE DE LYON EN COTUTELLE AVEC L'UNIVERSITÉ LIBANAISE opérée au sein de l’Université Claude Bernard Lyon 1 École Doctorale de Chimie-École Doctorale des Sciences et Technologies Discipline : Chimie Soutenue publiquement le 07/11/2018, par Rim MOUSELMANI Reduction of Organic Functional Groups Using Hypophosphites Devant le jury composé de Mme. Micheline DRAYE Université Savoie Mont Blanc Rapporteure M. Mohammad ELDAKDOUKI Université Arabe de Beyrouth Rapporteur Mme. Emmanuelle SCHULZ Université Paris 11 examinatrice M. Abderrahmane AMGOUNE Université Lyon 1 Président M. Mahmoud FARAJ Université Internationale Libanaise examinateur Mme. Estelle MÉTAY Université Lyon 1 Directrice de thèse M. Ali HACHEM Université Libanaise Directeur de thèse M. Marc LEMAIRE Université Lyon 1 Membre invité M. -
Acetaldehyde Oxime Hazard Summary Identification
Common Name: ACETALDEHYDE OXIME CAS Number: 107-29-9 RTK Substance number: 0003 DOT Number: UN 2332 Date: March 1987 Revision: August 1998 ------------------------------------------------------------------------- ------------------------------------------------------------------------- HAZARD SUMMARY WORKPLACE EXPOSURE LIMITS * Acetaldehyde Oxime can affect you when breathed in and No occupational exposure limits have been established for by passing through your skin. Acetaldehyde Oxime. This does not mean that this substance * Contact can irritate the eyes and skin. is not harmful. Safe work practices should always be * Breathing Acetaldehyde Oxime can irritate the nose and followed. throat. * Acetaldehyde Oxime is a FLAMMABLE LIQUID and a * It should be recognized that Acetaldehyde Oxime can be FIRE HAZARD. absorbed through your skin, thereby increasing your exposure. IDENTIFICATION Acetaldehyde Oxime is a colorless liquid or crystalline WAYS OF REDUCING EXPOSURE (needle-like) solid. It is used to make other chemicals. * Where possible, enclose operations and use local exhaust ventilation at the site of chemical release. If local exhaust REASON FOR CITATION ventilation or enclosure is not used, respirators should be * Acetaldehyde Oxime is on the Hazardous Substance List worn. because it is cited by DOT. * Wear protective work clothing. * This chemical is on the Special Health Hazard Substance * Wash thoroughly immediately after exposure to List because it is FLAMMABLE. Acetaldehyde Oxime and at the end of the workshift. * Definitions are provided on page 5. * Post hazard and warning information in the work area. In addition, as part of an ongoing education and training HOW TO DETERMINE IF YOU ARE BEING effort, communicate all information on the health and safety hazards of Acetaldehyde Oxime to potentially EXPOSED exposed workers. -
Amide Activation: an Emerging Tool for Chemoselective Synthesis
Featuring work from the research group of Professor As featured in: Nuno Maulide, University of Vienna, Vienna, Austria Amide activation: an emerging tool for chemoselective synthesis Let them stand out of the crowd – Amide activation enables the chemoselective modification of a large variety of molecules while leaving many other functional groups untouched, making it attractive for the synthesis of sophisticated targets. This issue features a review on this emerging field and its application in total synthesis. See Nuno Maulide et al., Chem. Soc. Rev., 2018, 47, 7899. rsc.li/chem-soc-rev Registered charity number: 207890 Chem Soc Rev View Article Online REVIEW ARTICLE View Journal | View Issue Amide activation: an emerging tool for chemoselective synthesis Cite this: Chem. Soc. Rev., 2018, 47,7899 Daniel Kaiser, Adriano Bauer, Miran Lemmerer and Nuno Maulide * It is textbook knowledge that carboxamides benefit from increased stabilisation of the electrophilic carbonyl carbon when compared to other carbonyl and carboxyl derivatives. This results in a considerably reduced reactivity towards nucleophiles. Accordingly, a perception has been developed of amides as significantly less useful functional handles than their ester and acid chloride counterparts. Received 27th April 2018 However, a significant body of research on the selective activation of amides to achieve powerful DOI: 10.1039/c8cs00335a transformations under mild conditions has emerged over the past decades. This review article aims at placing electrophilic amide activation in both a historical context and in that of natural product rsc.li/chem-soc-rev synthesis, highlighting the synthetic applications and the potential of this approach. Creative Commons Attribution 3.0 Unported Licence. -
Microwave Assisted Synthesis, Spectral and Antimicrobial Evaluation of Hydrazones and Their Metal Complexes
Devendra Kumar et al. / Journal of Pharmacy Research 2012,5(2),830-834 Research Article Available online through ISSN: 0974-6943 http://jprsolutions.info Microwave assisted synthesis, spectral and antimicrobial evaluation of hydrazones and their metal complexes Devendra Kumar ,Shivani Singh,Neelam,Rubeena Akhtar Department of Chemistry, Institute of Basic Sciences,Dr. B. R. Ambedkar University, Khandari Campus, Agra-282002 Received on:19-12-2011; Revised on: 07-01-2012; Accepted on:28-01-2012 ABSTRACT Six new metal complexes of Co (II), Ni (II) and Cu (II) with bis-(furfuryl) adipic acid dihydrazone (FADH) and bis- (2-acetyl thiophene) adipic acid dihydrazone (2-ATADH) have been synthesized under microwave irradiation. The Microwave irradiation method was found remarkably successful and gave higher yield at less reaction time. All the synthesized compounds have been characterized by running their TLC for single spot, repeated melting point determinations, elemental analyses, IR, 1H-NMR and electronic spectral studies. The elemental analyses and spectral analysis results revealed their Metal: Ligand (1:1) stoichiometry. All the synthesized compounds have been screened in vitro for their antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa and also for their antifungal activity against Aspergillus niger and Candida albicans. Key words: Synthesis, Microwave irradiation, Spectral, Antibacterial, Antifungal. INTRODUCTION Over the last few years, there has been growing interest in the synthesis of Synthesis of diethyl adipate: 14.6 g (0.1M) adipic acid was dissolved in organic compounds under green or sustainable chemistry such as micro- 20 ml absolute alcohol. To this solution, 3ml conc. H2SO4 was added. The wave irradiation because of increasing environmental consciousness. -
Synthesis of Macrocyclic Bis-Hydrazone and Their Use in Metal Cations Extraction
International Scholarly Research Network ISRN Organic Chemistry Volume 2012, Article ID 208284, 8 pages doi:10.5402/2012/208284 Research Article Synthesis of Macrocyclic Bis-Hydrazone and Their Use in Metal Cations Extraction Farouk Kandil, Mohamad Khaled Chebani, and Wail Al Zoubi Department of Chemistry, Faculty of Science, University of Damascus, Damascus, Syria Correspondence should be addressed to Wail Al Zoubi, [email protected] Received 9 October 2011; Accepted 30 October 2011 Academic Editor: G. Li Copyright © 2012 Farouk Kandil et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Two new macrocyclic hydrazone Schiff bases were synthesized by reaction of succindihydrazide and adipdihydrazide with acetylacetone. Hydrazones have been characterized by elemental analyses and IR, mass, 1HNMR,and 13C NMR spectral data. Hydrazones have been studied by liquid-liquid extraction towards the s-metal ions (Li+,Na+,andK+)andd-metalions(Cu2+ and Cr3+) from aqueous phase to organic phase. The effect of chloroform and dichloromethane as organic solvents over the metal chlorides extraction was investigated at 25 ± 0.1◦C by using flame atomic absorption. We found differences between the two solvents in extraction selectivity. 1. Introduction Five dissymmetric tridentate Schiff base ligands contain- ing a mixed donor set of ONN and ONO were prepared by ff Hydrazones are special class of compounds in the Schi bases the reaction of benzohydrazide with the appropriate salicy- family. They are characterized by the presence of the follow- laldehyde and pyridine-2-carbaldehyde and characterized by ing FT-IR, 1HNMR,and13CNMR[13]. -
Detection of Phenethylamine, Amphetamine, and Tryptamine Imine By-Products from an Acetone Extraction
Detection of Phenethylamine, Amphetamine, and Tryptamine Imine By-Products from an Acetone Extraction Mary A. Yohannan* and Arthur Berrier U.S. Department of Justice Drug Enforcement Administration Special Testing and Research Laboratory 22624 Dulles Summit Court Dulles, VA 20166 [email: mary.a.yohannan -at- usdoj.gov] ABSTRACT: The formation of imine by-products from phenethylamines, amphetamines, and tryptamines upon an acetone extraction is presented. These imine by-products were characterized using GC/MSD and exhibited preferential cleavage at the α-carbon of the alkyl chain. Further characterization of the imine by-products of phenethylamine and tryptamine was done using IR and NMR. KEYWORDS: phenethylamine, tryptamine, imine, acetone, schiff base, drug chemistry, forensic chemistry In most forensic laboratories, the solvents used to extract at the α-carbon on the alkyl chain. In addition to GC/MS, the drugs are chosen based upon their solubility properties and their imines formed from phenethylamine base and tryptamine base ability to not interact with the drug. In fact, there are very few were characterized by Fourier transform-infrared spectroscopy publications where a solvent used to extract a drug reacts with (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. the drug and forms by-products [1-3]. This laboratory recently discovered that an additional Experimental component was formed when acetone was used to extract a Solvents, Chemicals, and Materials sample containing a known tryptamine. Analysis by gas Acetone was ACS/HPLC grade from Burdick and Jackson chromatography/mass spectroscopy (GC/MS) of the acetone Laboratories (Muskegon, MI). Phenethylamine base and extract yielded an extra peak in the total ion chromatogram that tryptamine base were obtained from Sigma-Aldrich Chemicals was approximately half the abundance of the known tryptamine (Milwaukee, WI). -
Chapter 18 Amines in Order for a Drug to Be Effective Orally, It Generally
Chapter 18 Amines In order for a drug to be effective orally, it generally has to be reasonable soluble in water so that it can be transported through the blood. Since amines are weak bases, they are often converted to salts with some acid and therefore may oral drugs have amine salts as part of their structure. One reason for their presence is that they confer some water solubility to the drug. The three-dimensional models show the shapes of amine molecules; notice the lone pair of electrons on nitrogen is not shown but affects the geometry about the nitrogen Primary, secondary and tertiary amines have 1, 2 or 3 alkyl groups attached to nitrogen. In these cases the alkyl group is the methyl In the IUPAC system, STEP 1 Name the longest carbon chain bonded to the N atoms as alkanamines by replacing e of the alkane name with amine. STEP 2 Number the carbon chain to locate the amine group and any substituents. N,N-Dimethylethanamine aminoethane 2-aminopropane 2-(N,N-dimethylamino)ethane 1-(N-methylamino)propane 2-(N-methylamino)butane Amines can also be names as groups attached to a hydrocarbon Aminobenzene is called aniline NH2 C H H C C C C H H C H NH2 NH2 NH CH3 Cl aniline 3-chloroaniline N-methylaniline aminobenzene 3-chloroaminobenzene N-methylaminobenzene Properties of amines The boiling points of amines are higher than alkanes of similar mass lower than alcohols of similar mass Amines are soluble in water if they have 1 to 5 carbon atoms; the N atom forms hydrogen bonds with the polar O—H bond in water An amine salt forms when an amine