bluuebunny/crossref_metadata_2025_split huggingface dataset:
TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.
Authors: Bergmann Ernst D. , Ginsburg David , Pappo Raphael 
Published: March 2011

AbstractThe Michael condensation in its original scope is the addition of an addend or donor containing an alpha‐hydrogen atom in the system OCCH to a carbon‐carbon double bond that forms part of a conjugated system of the general formula CCCO in an acceptor. The condensation takes place under the influence of alkaline reagents, typically alkali metal alkoxides. The range of addends is very broad. Typical acceptors are alpha, beta‐unsaturated aldehydes, keotnes, and acid derivatives. As an extension of the original scope, the Michael condensation has come to be understood to include addends and acceptors activated by groups other than carbonyl and carboxalkoxy. The wider scope is encompassed in this survey.
TheFavorskiĭ Rearrangement of Haloketones
Authors: Kende Andrew S. 
Published: March 2011

AbstractThe Favorskii rearrangement is the skeletal rearrangement of a alpha‐halogenated ketones in the presence of certain nucleophilic bases, such as hydroxides, alkoxides, or amines to give carboxylic acid salts, esters or amides, respectively. Monohaloketones undergo the reaction to yield derivatives of saturated acids having the same number of carbon atoms. In a similar manner, suitable dihaloketiones produce unsaturated carboxylic acids. Analogous rearrangements of trihaloketones can give rise to unsaturated halo acids. The Favorskii reaction has found application for the preparation of highly branched acyclic carboxylic acids. It is a preferred route to various 1‐cycloalkanecarboxylic acids and provides a direct method for ring contraction in simple alicyclic systems and in steroids.
Cyclobutane Derivatives from Thermal Cycloaddition Reactions*Contribution No. 2488 from the Gates and Crellin Laboratories of Chemistry. Supported in part by the National Science Foundation.
Authors: Roberts John D. , Sharts Clay M. 
Published: March 2011

AbstractPreparation of substituted cyclobutanes and cyclobutenes by cyclo‐addition reactions of alkene and alkyne has become an important synthetic reaction and where applicable is the method of choice for four‐membered carbon ring compounds. Such cycloadditons may be achieved thermally under autogeneous pressure in the presence of free‐radical inhibitors or photochemically by irradiation with visible or ultraviolet light. The establishment of cyclobutane structure proved an example of waxing and waning in the interpretation of organic reactions. Many studies were done and they are discussed. A breakthrough came with the discovery by DuPont that octafluorocyclobutane can be formed readily by thermal dimerization of tetrafluoroethylene. Several developments followed. The cycloaddition illustrates two important points. First, fluorinated alkenes may add to non‐fluorinated unsaturated compounds much more readily than they dimerize. Second, when fluorinated alkenes are given a choice between four‐ and six‐membered rings, as is possible with a conjugated diene, the formation of the four‐membered ring is favored. This chapter gives information on the various studies done on this reaction, The scope, limitations, and comparison of added reactivities are detailed.
The Synthesis of Aliphatic and Alicyclic Nitro Compounds
Authors: Kornblum Nathan 
Published: March 2011

AbstractThis chapter is concerned with the synthesis of nitro compounds in which the nitro group is on a saturated carbon atom. The most important methods available are as follows: 1. Treatment of alkyl halides with silver nitrite; 2. Reaction of allyl bromides and iodides with sodium nitrite; 3. Oxidation of amines; 4. Oxidation of oximes; 5. Nitration of active methylene compounds; 6, Nitration of active methylene compounds with nitric acid. These reactions are discussed and also noted are miscellaneous reactions of limited utility. Comparison of methods is given.
Synthesis of Peptides with Mixed Anhydrides
Authors: Albertson Noel F. 
Published: March 2011

AbstractA mixed acid anhydride, or mixed anhydride, is a dehydration product of two polyoxy acids. For a mixed anhydride to be of interest for peptide synthesis, one of the components must, in general, be an alpha‐acylamino acid. The nature of the second component acid may vary widely. In this chapter the term mixed anhydride will be used in a more general sense. In addition to conventional mixed anhydrides, from polyoxyacids, reference will be made to “mixed anhydrides” otherwise recognizable as acyl halides, ethers, esters, thiol esters, O‐acylisoureas and isoimides. This chapter is limited to a review of chemistry of the acyclic alpha‐amino acid mixed anhydrides, which the well‐know alpha‐acylamino acid chlorides and azides, which have been the subject of an excellent review. In general, discussion of the application of alpha‐acyllamino acid mixed anhydrides will be limited to non‐polymeric peptide bond formation and will not be concerned with acylations other than those that lead to a peptide bonds.
Desulfurization withRaney Nickel*The authors are indebted to Dr. Brian Green and Dr. John C. Knight for checking the final draft of this chapter.
Authors: Pettit George R. , van Tamelen Eugene E. 
Published: March 2011

AbstractThe conversion of an amine to an olefin by elimination of the nitrogen atom and an adjoining hydrogen atom is a useful procedure for degradation and synthesis. The Hofmann exhaustive methylation method has been used most often to bring about change, but other methods as the thermal decomposition of amine oxides and the pyrolysis of amine phosphates or acetyl or benzoyl derivative have often been employed to advantage. This chapter reviews the Hofmann elimination because of its extensive history. Alternative methods are considered.
Hydration of Olefins, Dienes, and Acetylenes
via
Hydroboration
Authors: Zweifel George , Brown Herbert C. 
Published: March 2011

Abstract
The hydroboration of olefins, dienes, and acetylenes involves the addition of a boron‐hydrogen bond to the carbon‐carbon multiple bond. This reaction provides a new, convenient route to the corresponding organoboranes and makes them readily available as intermediates in organic synthesis. One of the important reactions that the organoboranes undero is the rapid and essentially quantitative oxidation with alkaline hydrogen peroxide. The hydroboration of olefins involves a cis addition of the boron hydrogen bond, the boron atom becoming attached to the less substituted of the two olefinic carbon atoms of the double bond.
This chapter surveys the available information on the hydration of olefins, dienes, acetylenes, and their derivatives by the hydroboration‐oxidation procedure.
Formation of Carbon‐Hetero Atom Bonds by Free Radical Chain Additions to Carbon‐Carbon Multiple Bonds
Authors: Stacey F. W. , Harris J. F. 
Published: March 2011

AbstractFree‐radical chain addition to carbon‐carbon multiple bonds to form carbon‐hetero atom bonds is an important synthetic method of wide scope. Carbon‐halogen, carbon‐sulfur, carbon‐silicon, carbon‐germanium, carbon‐phosphorus, and carbon‐nitrogen bonds have been formed by this method, In this chapter, the mechanism, scope, limitations, and experimental conditions are treated for the addition reactions that lead to the formation of the six types of carbon‐hetero atom bonds mentioned above. Since the direction of addition of free radicals to carbon‐carbon multiple bonds is common to all classes reviewed here, it is briefly explained.
TheDieckmann Condensation (Including theThorpe‐Ziegler Condensation)
Authors: Schaefer John P. , Bloomfield Jordan J. 
Published: March 2011

AbstractThe Dieckman condensation is an acetoacetic ester condensation in which a dicarboxylic ester is cyclized to a beta‐ketonic ester through the action of a base. The dicarboxylic ester must have at least one alpha‐hydrogen atom and the carbalkoxy groups must be situated that cyclization will result in a 4‐membered ring or larger ring. Discovery and development of the reaction are generally credited to Dieckmann, who found that heating an adipic or a pimelic ester with sodium and a trace alcohol led to cyclization with formation of a cyclopentanone or a cyclohexanone. The Dieckmann condensation has proved useful for the preparation of a variety of carbocyclic and heterocyclic ketones and has been extended to the synthesis of 7 and 8‐membered rings.
The Aldol Condensation
Authors: Nielsen Arnold T. , Houlihan William J. 
Published: March 2011

AbstractThe aldol condensation takes its name from aldol (3‐hydroxybutanal) a name introduced by Wurtz who first prepared the beta‐hydroxy aldehyde from acetaldehdye in 1872. The aldol condensation includes reactions producing beta‐hydroxy aldehydes or beta‐hydroxy ketones by self condensations or mixed condensations of aldehydes and ketones as well as reactions leading to alpha, beta‐unsaturated aldehydes or alpha,beta‐unsaturated ketones formed by dehydration of intermediate beta‐aldols or beta‐ketals. The Claisen‐Schmidt condensation is most often taken to be the condensation of an aromatic aldehyde or ketone usually in the presence of a basic catalyst. The term aldol condensation has also been applied to many other condensations involving the reaction of an aldehyde or ketone. These condenations are discussed. The present review includes examples that are solely condensation reactions of aldehydes and ketones.
The Synthesis of Substituted Ferrocenes and other π‐Cyclopentadienyl‐Transition Metal Compounds
Authors: Bublitz Donald E. , Rinehart Kenneth L. 
Published: March 2011

AbstractThe discovery of dicyclopentadienyliron (ferrocene) in 1951 led to the development of an entirely new area of organometallic chemistry that of the pi‐metallohydrocarbons. Representative compounds are the pi‐metalloarenes such as dibenzenechromium, the pi‐methallopseudoarenes such as ferrocene, and the pi‐metalloolefin complexes such as butadiene iron tricarbonyl Since there is a great amount of literature available at this time, the treatment here is limited to three dimensions: to include only compounds containing cyclopentadienyl rings, of these to include only those which have shown to undergo aromatic substitution,reactions and within this group only synthetic aspects of their chemistry. This nearly restricts the discussion to syntheses of substituted ferrocenes.
The γ‐Alkylation and γ‐Arylation of Dianions of β‐Dicarbonyl Compounds
Authors: Harris Thomas M. , Harris Constance M. 
Published: March 2011

Abstract
It is well known that beta‐diketones can undergo condensations at the alpha‐methylene group with alkyl halides and certain other reagents though the intermediate formation of monoanions. For example, acetylacetone on treatment with an alkali metal or an alkali metal alkoxide or carbonate forms a mono‐anion which can be alkylated with alkyl halides. In 1958, Hauser and Harris reported that, if benzoylacetone or acetylacetone is first converted to the dipotassium salt. The salt undergoes alkylation and other carbon‐carbon condensations at the terminal methyl group rather than at the methylene group. Rapid alkylation was observed when the salts were treated with benzyl chloride and after acidification, the terminal monobenzylation derivatives were obtained in good yield. Dibenzylation was not observed. In this chapter alkylations of these and other beta‐ketones via dianions are surveyed. Other alkylations are also discussed. Arylations are included because alkylation and arylation are methods for directly converting beta‐homologs without increasing their functionality.
TheRitter Reaction
Authors: Krimen L. I. , Cota Donald J. 
Published: March 2011

AbstractThe formation of N‐substituted amides by the addition of nitriles to alkenes in the presence of concentrated sulfuric acid was first described by Ritter in 1948. The reaction has been extended to the addition of nitriles to a wide variety of compounds capable of forming a carbonium ion, and it constitutes the only really useful procedure for the preparation of amides of tertiary carbinamines. In its most general form, the Ritter reaction involves the nucleophilic addition of a nitrile to a carbonium ion in the presence of sulfuric acid. Attention has been given to reactions in which the carbonium ion is generated in sulfuric acid, or less commonly in sulfonic acids, phosphoric acids, or boron trifluoride. For comparison, analogous reactions, which are initiated by a nitrilium ion, formed from a nitrile and a Friedel‐Crafts catalyst, have been included in this chapter.
Formation of Carbon‐Carbon Bondsviaπ‐Allylnickel Compounds
Authors: Semmelhack Martin F. 
Published: March 2011

AbstractTransition metal complexes containing a planar three‐carbon ligand, the pi‐allyl group was first described in 1958 with the discovery of (pi‐1‐methylallyl)cobalt tricarbonyl. After this discovery, many other syntheses followed. This chapter deals with synthetic organic applications of pi‐allylnickel complexes. At this time, the study of this subject is in its infancy. The unifying aspect of pi‐allylnickel chemistry is the ability of the allyl ligand to form new carbon‐carbon bonds.
Oxidative Decarboxylation of Acids by Lead Tetraacetate
Authors: Sheldon Roger A. , Kochi Jay K. 
Published: March 2011

AbstractLead tetracetate, one of the most versatile oxidizing agents know in organic chemistry, is capable of reacting with a variety of common functional groups; its use in organic chemistry has been reviewed. The purpose of this chapter is to review the oxidative process involving the decarboxylation of acids, whereby carboxylic acids are converted to a variety of compounds depending on experimental conditions, e.g, solvent, structure of substrates, and presence of additives. The primary objective here is to evaluate critically the usefulness of this reaction in organic synthesis. Decarboxylation of alpha‐hydroxy and alpha‐amino acids by lead tetraacetate has been known for many years. Khararaschn and co‐workers reported exhaustive products studies of the decomposition of lead tetraacetate in acetic acid. Sodium acetate accelerates the reduction of lead tetraacetate but no carbon dioxides liberated. Mosher and Kahr also examined the thermal decomposition of various organic acids by lead tetraacetate. Since then many studies on the mechanism and synthetic utility of these reaction and its modifications have been reported.
Sensitized Photooxygenation of Olefins
Authors: Denny R. W. , Nickon A. 
Published: March 2011

AbstractSensitized photooxygenations of olefins have been extensively studied; they represent convenient methods for the introduction of oxygen at specific sites. When an aerated solution containing a monolefin, diene, or polyene, and a sensitizer is irradiated with light that can be absorbed by the sensitizer, oxygenated products are formed whose nature depends upon the structure of the substrate and the lability of the initial photoproducts under the reaction conditions. The ready reducibility of hydroperoxides to alcohols enhances the synthetic usefulness of these photoxygenations In this chapter, coverage is restricted to molecules with one or more carbon‐carbon double bonds.
The Synthesis of 5‐Hydroxyindoles by the
N
enitzescu Reaction
Authors: Allen George R. 
Published: March 2011

Abstract

The preparation of 5‐hydroxyindole derivatives by the reaction of benzoquinones with certain enamines was suggested by the work of Nenitzescu who reported that the parent quinone,
p
‐benzoquinone, reacts with ethyl 3‐aminocrotonate in boiling acetone to yield ethyl 5‐hydroxy‐2‐methylindole‐3‐carboxylate. The procedure was largely ignored until the 1950s when interest in melanin‐related substances and cognition of serotonin as a 5‐hydroxyindole derivative stimulated an exploration of this reaction.
TheClaisen andCope Rearrangements
Authors: Rhoads Sara Jane , Rebecca Raulins N. 
Published: March 2011

AbstractSince the first observation of a thermal rearrangement vinyl allyl ether to the corresponding homoallylcyclic carbonyl compound by Claisen in 1912, rearrangements of vinyl and aryl allylic ethers have been extensively studied and exploited for their synthetic value. The corresponding rearrangement of substituted 1,5‐hexadiene was first recognized by Cope in 1940 as the carbon analog of the Claisen rearrangement. Today it is recognized that such transformations fall within the general category of a [3,3] sigamtropic reaction and that considerable variation may be accommodated in the basic requirement of a system of six atoms with terminal unsaturated linkage. This chapter attempts to survey the vas t accumulation of Claisen and Cope rearrangements recorded since the first coverage in 1944.
Substitution Reactions Using Organocopper Reagents
Authors: Posner Gary H. 
Published: March 2011

AbstractCarbon‐carbon sigma‐bond formation one of the most fundamental operations in organic chemistry, is often accomplished by interaction of an organometallic reagent with an organic substrate having a suitable leaving group. Selective substitution of halogens and of alcohol derivatives by various hydrocarbon groups in many different types of organic substrates has been achieved most successfully using organocopper reagents. The wide scope and effectiveness of these reagents in coupling with halides and alcohol derivatives have made formation of the unsymmetrical coupling product R‐R' a useful reaction in organic synthesis, allowing efficient and specific substitution of X by alkyl, alkenyl, alkynyl, or aryl groups. Because selective coupling between organic substrate and organocopper reagent is usually achieved more effectively by stoichiometric than by catalytic organocopper reagents, and more effectively still by organocuprates(I) than by mono‐copper or by complexed organocopper reagents, the emphasis in this chapter is on organocuprates (I). Consideration is given to possible mechanisms of substitution reactions using organocopper reagents, to scope, limitations, and synthetic utility of these reactions, and to optimal experimental considerations for their application.
The
R
eformatsky Reaction
Authors: Rathke Michael W. 
Published: March 2011

Abstract
The Reformatsky reaction is the reaction of a carbonyl compound, usually an aldehyde or a ketone, with an alpha‐haloester in the presence of zinc metal to furnish, after hydrolysis, a β‐hydoxyester. Subsequent dehydration of the hydroxyester is commonly carried out to form an alpha, β‐unsaturated ester. This chapter summarizes some of the more important advances in the understanding and use of the Reformatsky reaction since the original chapter was published in volume 1 of this series.
Reduction and Related Reactions of α,β‐Unsaturated Carbonyl Compounds with Metals in Liquid Ammonia
Authors: Caine Drury 
Published: March 2011

Abstract

This chapter is concerned with the reduction and related reactions of alpha,beta‐unsaturated ketones by alkali and alkaline earth metals in liquid ammonia. Upon treatment with a metal in liquid ammonia (usually containing an ether co‐solvent) a simple alpha, beta‐unsaturated ketone is converted into the metal enolate corresponding to the saturated ketone. Research during the first half of the 20
th
Century revealed that a variety of organic compounds undergo reduction with metals in liquid ammonia but preparative metal‐ammonia reductions of alpha,beta‐unsaturated carbonyl compounds were apparently not described until 1951. In addition to affording a remarkable degree of stereoselectivity, many metal‐ammonia reductions of unsaturated carbonyl systems can be preformed in a variety of functional and protective groupings and the reaction is generally free of the rearrangements sometimes observed when chemical reduction methods are used. The unique features of metal‐ammonia reductions and related reaction have led to their wide application in total synthesis and transformations.
Homogeneous Hydrogenation Catalysts in Organic Synthesis
Authors: Birch A. J. , Williamson D. H. 
Published: March 2011

AbstractDuring recent years, studies of the activation of hydrogen by soluble catalysts have been intensely pursued. The scope of this chapter has been limited to those catalysts utilizing hydrogen gas in the reduction of organic substrates. The first hydrogenation of an organic molecule using a soluble catalyst rather than classical divided metal catalysts was reported in 1938. Other catalyst studies followed. Homogeneous and heterogenous catalysts employ a similar range of metals, but soluble complex catalysts are uniform and therefore show more clearly defined activity and selectivity. Variations of ligands in a soluble catalyst, resulting in arrange of properties, may be likened to poisoning of metal surfaces; but use of different ligands in theory makes possible precise control of a range of properties in soluble catalysts. Many developments are to come and with them the increasing utility of soluble catalyst in general organic synthesis.
Selenium Dioxide Oxidation
Authors: Rabjohn Norman 
Published: March 2011

AbstractSelenium dioxide has developed considerable stature since it was first reviewed in this series. Search for examples of oxidation by selenium dioxide or selenious acid is difficult because the terms are seldom indexed. Frequently it is difficult to decide whether selenium dioxide or selenious acid was the oxidizing agent employed in a reaction because it is impossible to determine if water was present. The determination is complex because the free acid or anhydride may react reversibly or irreversibly with various solvents such as alcohols or acids. To give selenium‐containing compounds of unknown structure which might be the real oxidizing gents. In this chapter, the practical aspects of oxidation with selenium dioxide are summarized. Mechanisms are treated in detail.
Echocardiography in Mice
Authors: Gao Shumin , Ho David , Vatner Dorothy E. , Vatner Stephen F. 
Published: March 2011

AbstractMurine models have been utilized with increasing frequency mainly due to availability of genetically engineered models. With advancement in high spatial and temporal resolution, echocardiography is used extensively for the evaluation of cardiovascular function in murine models of cardiovascular disease. This review summarizes the general applications and methods involved in echocardiography used to study mouse models for cardiovascular research, based on 20 years of experience in the authors' laboratory. The goal of this article is to provide a practical guide to the use of echo techniques in mice to evaluate cardiac systolic and diastolic function. Curr. Protoc. Mouse Biol. 1:71‐83. © 2011 by John Wiley & Sons, Inc.
Operating Modes of Sandwiched Light‐Emitting Electrochemical Cells
Authors: Lenes Martijn , Garcia‐Belmonte Germà , Tordera Daniel , Pertegás Antonio , Bisquert Juan , Bolink Henk J. 
Published: March 2011

AbstractLight‐emitting electrochemical cells (LECs) are promising lighting devices in which the redistribution of ionic charges allows for double electronic carrier injection from air‐stable electrodes. Uncertainties about the mode of operation are limiting the progress of these devices. Using fast (with respect to the current growth time) but resolutive electrical measurement techniques, the electronic transport mechanism in state‐of‐the‐art sandwiched devices can be monitored as a function of the operation time. The results indicate the formation of doped transport layers adjacent to the electrodes that reduces the extent of the central neutral light‐emitting layer where electronic transport is limited by space‐charge. Prolonged growth of the doped regions beyond that required for efficient injection should be prevented, as this decreases the efficiency and leads to low luminance devices.