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Format: 1 online resource (282 pages)

ISBN: 978-0-12-821027-7 , 9780128210260

Content: Addition, Elimination and Substitution: Markovnikov, Hofmann, Zaitsev and Walden: Discovery and Development discusses foundational reactions in organic chemistry and their major protagonists, contributions to synthesis, and history. Hofmann, Zaitsev, and Markovnikov are introduced, along with their major discoveries and contributions to organic chemistry. The history of controversies around Markovnikovs Rule are addressed. The book introduces Waldens original demonstration of configuration inversion, then discusses bimolecular elimination reactions, regioselective addition reactions, regiospecific alkene synthesis, and the development of modern reactions with configuration inversion.

Note: Front Cover -- ADDITION, ELIMINATION AND SUBSTITUTION: MARKOVNIKOV, HOFMANN, ZAITSEV AND WALDEN -- ADDITION, ELIMINATION AND SUBSTITUTION: MARKOVNIKOV, HOFMANN, ZAITSEV AND WALDEN: DISCOVERY AND DEVELOPMENT -- Contents -- Copyright -- ONE - Introduction: Organic Chemistry in the Nineteenth Century -- A 19th-century chronology of organic chemistry -- Atomic theory: a brief history -- Theories of organic chemistry -- Organic radicals: Theory of substitutions -- Theory of types -- Valence and the structural theory of organic chemistry -- References -- TWO - Vladimir Vasil'evich Markovnikov and his rule for addition -- Vladimir Vasil'evich Markovnikov (1837-1904) -- The education of the chemist -- With Kolbe at Leipzig -- Markovnikov's return to Kazan -- Markovnikov's resignation from Kazan -- Professor and head at Novorossiisk University -- Markovnikov's move to Moscow -- Markovnikov's initial work in Moscow -- Markovnikov, the Sanitation Guru: The Russo-Turkish war -- Markovnikov and cycloalkanes -- A new direction: petroleum chemistry -- Markovnikov's ouster from his professorship -- References -- THREE - Markovnikov's rule: history and development -- The first decades: early challenges to the validity of the rule -- Louis Henry -- Arthur Michael -- Yuliya (Julia) Vsevolodovna Lermontova -- Morris Selig Kharasch -- What is in a name? Markovnikov and anti-Markovnikov -- References -- FOUR - Aleksandr Mikhailovich Zaitsev and his empirical rule for elimination -- Aleksandr Mikhailovich Zaitsev (1841-1910) -- In Western Europe -- 1863: faux pas and recovery -- Theoretician no more: the synthetic organic chemist emerges -- Sulfur compounds in Marburg -- The return to Kazan -- Moving into leadership of the Kazan Chemical School -- Scientific work as professor at Kazan -- The genesis of Zaitsev's rule -- The feud -- Alkene oxidation. , Zaitsev's later career and legacy -- Awards and honors -- Zaitsev's legacy -- Yegor Yegorovich Wagner (Vagner) (1849-1903) -- Sergei Nikolaevich Reformatskii (1860-1934) -- Aleksandr Yerminingel'dovich Arbuzov (1877-1968) -- References -- FIVE - August Wilhelm von Hofmann and Hofmann's rule for elimination -- August Wilhelm von Hofmann (1818-92)4,5 -- Family connections -- Student years: Giessen -- Hofmann's career -- Bonn: docent and extraordinary professor, 1845 -- The Royal College of Chemistry: director, 1845-65 -- The University of Berlin: Professor, 1865-92 -- Hofmann's chemistry -- Coal-tar chemistry: aniline and aniline dyes -- Perkin and aniline dyes (mauveine) -- Alkylation of amines: the "Ammonia Type" -- Halogenation of amines and amides -- The Hofmann-Löffler-Freytag reaction -- The Hofmann rearrangement -- The Hofmann elimination92 -- References -- SIX - Paul Walden and the Walden inversion -- Introduction -- Paul Walden (Pauls Valdens, Pavel Ivanovich Val'den) -- Education -- Student years at the Polytechnic Institute (the Polytechnicum) -- Graduate studies and first academic appointments -- Leader at the Riga Polytechnic Institute -- Professor and Rector -- Consulting within the empire -- The Imperial Academy of Sciences in St. Petersburg -- World War I: evacuation of Riga -- Rostock -- Walden's scientific career as an independent researcher -- Research in physical chemistry -- Handbuch der Stereochemie -- Research in organic chemistry -- The Walden inversion and the Walden cycle -- Walden in the Third Reich -- Walden in retirement -- Walden, the historian of chemistry -- Afterword -- References -- SEVEN - Mechanistic studies -- Early mechanistic and stereochemical investigations -- Elimination reactions -- Hofmann elimination -- Zaitsev elimination -- Addition reactions -- The beginnings of modern mechanistic studies. , The key early players -- Nikolai Aleksandrovich Menshutkin (1842-907) -- Edward David Hughes -- Christopher Kelk Ingold -- The origin of physical organic chemistry: Menshutkin's kinetic studies -- Effects of reactant structure on the rate of esterification -- The Menshutkin reaction -- Classifying substitution and elimination mechanisms: Hughes and Ingold -- SN2 substitution and the Walden inversion: a stereochemical enigma -- Elimination reactions with base -- E2 elimination -- Electrophilic addition to alkenes -- Lowry-Brønsted acids -- Markovnikov hydration without rearrangement -- Kharasch and the "peroxide effect" -- Halogens and similar nonacidic electrophiles -- Isotope effect evidence for the mechanisms of elimination -- References -- EIGHT - Development of highly regioselective addition reactions of alkenes and alkynes -- Factors affecting reaction regiochemistry: the alkene -- Mechanisms of carbocation stabilization -- Using the Hammett σ+ parameter as a predictor of regiochemistry -- Silicon and tin as directing groups in electrophilic addition reactions of alkenes -- The Hosomi-Sakurai reaction -- Heteroatom-stabilized electrophilic carbocations: The Prins, Mannich, and Mukaiyama reactions -- The Prins reaction -- The Mannich reaction -- The Mukaiyama addition reactions -- Carbocation rearrangements in synthesis -- Anti-Markovnikov additions to alkenes -- Hydroboration of alkenes -- Hydrometallations of alkynes -- Hydroalumination -- Hydrozirconation of alkynes -- References -- NINE - Development of highly regiospecific alkene syntheses: elimination and its substitutes -- Introduction -- Steric effects of alkoxide anion bases -- β-Eliminations not involving deprotonation: reductive elimination -- Elimination during Wolff-Kishner and related reactions4 -- The Bamford-Stevens and Shapiro reactions -- The Bamford-Stevens reaction. , The Shapiro reaction -- The Wharton reaction -- Alkenes by 1,3-elimination and extrusion -- The Ramberg-Bäcklund reaction -- Where do we stand now? -- References -- TEN - Inversion of configuration in modern synthesis -- Introduction -- Effects of solvent on the mechanism and rates of nucleophilic substitutions -- Aprotic dipolar solvents -- Phase transfer catalysis -- SN2 displacement driven by the formation of a phosphoryl group -- Phosphine-based halogenating reagents -- The Mitsunobu reaction -- Immobilized Mitsunobu reagents41,42 -- The substoichiometric Mitsunobu reaction -- The Toy and Taniguchi variants -- A bona fide totally catalytic variant: the Aldrich variant -- Changing the paradigm: the Denton variant -- Thioethers directly from alcohols -- References -- Index -- A -- B -- C -- D -- E -- F -- G -- H -- I -- K -- L -- M -- N -- O -- P -- R -- S -- T -- U -- V -- W -- Z -- Back Cover.

Additional Edition: Print version: Lewis, David E. Addition, Elimination and Substitution: Markovnikov, Hofmann, Zaitsev and Walden San Diego : Elsevier,c2022

Language: English

Keywords: History.