Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR008.03
C. Hauser, F. W. Swamer, J. T. Adams
{"title":"The Acylation of Ketones to Form β‐Diketones or β‐Keto Aldehydes","authors":"C. Hauser, F. W. Swamer, J. T. Adams","doi":"10.1002/0471264180.OR008.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR008.03","url":null,"abstract":"Under certain conditions, a ketone having an alpha-hydrogen atom may be acylated with an ester, an acid anhydride, or an acid chloride to form a β-ketone or, when the acylating agent is a formic ester, a β-keto aldehyde. The process consists in the replacement of an alpha-hydrogen atom of the ketone by an acyl group. The reaction involves a carbon-carbon condensation. The acylation of ketones with esters has generally been effected by means of a basic reagent, such as sodium, sodium ethoxide, etc. The acylation of ketones to form β-diketones may also occur with acid anhydrides by means of an acidic reagent boron trifluoride. In this chapter the basic reagent and boron trifluoride methods of acylation are considered separately. They are compared with other methods. \u0000 \u0000 \u0000Keywords: \u0000 \u0000acylation; \u0000ketones; \u0000β-ketones; \u0000β-aldehdyes; \u0000basic reagents; \u0000boron trifluoride; \u0000comparison of methods; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"177 1","pages":"59-196"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77867633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR008.06
H. Gilman, J. W. Morton
{"title":"The Metalation Reaction with Organolithium Compounds","authors":"H. Gilman, J. W. Morton","doi":"10.1002/0471264180.OR008.06","DOIUrl":"https://doi.org/10.1002/0471264180.OR008.06","url":null,"abstract":"The term metalation denotes the replacement of hydrogen by metal to yield a true organometallic compound. The replacement of hydrogen by metal in a compound such as acetoacetic acid is not generally classed as a metalation reaction in this sense because the resulting salt is not a typical organometallic compound. This distinction is matter of degree. The ability to yield ortho priducts, usually unmixed with para or other isomers, distinguishes the metalation reaction from the more familiar types of substitutions and makes possible the preparation of many products not readily available by other routes. The derivative most commonly prepared from a metalation product has been the carboxylic acid, made by the reaction of the lithium compound with carbon dioxide. This reaction is useful in the study of metalation products because the usual metalating agents, the alkyllithium compounds, yield volatile acids which are easily separated from the acids of higher molecular weight obtained from the metalated products themselves. \u0000 \u0000 \u0000Keywords: \u0000 \u0000metalation reaction; \u0000organolithium compounds; \u0000hydrocarbons; \u0000halides; \u0000amines; \u0000ammonium salts; \u0000sulfur compounds; \u0000ethers; \u0000phenols; \u0000alcohols; \u0000experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"1 1","pages":"258-304"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75135984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR001.04
M. T. Leffler
{"title":"The Amination of Heterocyclic Bases by Alkali Amides","authors":"M. T. Leffler","doi":"10.1002/0471264180.OR001.04","DOIUrl":"https://doi.org/10.1002/0471264180.OR001.04","url":null,"abstract":"Heterocyclic bases such as pyridine and quinoline and their derivatives react with metal amides to yield amino derivatives. For example, pyridine is converted to 2-aminopyridine by the action of sodium amide; an intermediate metal derivative is formed, and this is hydrolyzed to the free amine. It has been suggested that the initial step in the reaction is the addition of the metal amide to the CHNgroup; the resulting product is then transformed to the metal derivative of the amine, either through intramolecular rearrangement or through decomposition to the amino compound and sodium hydride to give the metal derivative. \u0000 \u0000 \u0000Keywords: \u0000 \u0000amination; \u0000heterocyclic bases; \u0000alkali amides; \u0000solvents; \u0000temperature; \u0000mole ratio; \u0000general precautions; \u0000experimental conditions","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"22 1","pages":"91-104"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75731994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR022.02
G. Posner
{"title":"Substitution Reactions Using Organocopper Reagents","authors":"G. Posner","doi":"10.1002/0471264180.OR022.02","DOIUrl":"https://doi.org/10.1002/0471264180.OR022.02","url":null,"abstract":"Carbon-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. \u0000 \u0000 \u0000Keywords: \u0000 \u0000substitution reactions; \u0000organocopper reagents; \u0000organic substrate; \u0000stereochemical stability; \u0000dimerization; \u0000structure; \u0000alcohol derivatives; \u0000epoxides; \u0000experimental procedures; \u0000organometallic compounds; \u0000synthetic utility","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"11 1","pages":"253-400"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82076622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR010.03
E. Bergmann, D. Ginsburg, R. Pappo
{"title":"The Michael Reaction","authors":"E. Bergmann, D. Ginsburg, R. Pappo","doi":"10.1002/0471264180.OR010.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR010.03","url":null,"abstract":"The Michael condensation in its original scope is the addition of an addend or donor containing an alpha-hydrogen atom in the system OCCH to a carbon-carbon double bond that forms part of a conjugated system of the general formula CCCO 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. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Michael reaction; \u0000side reaction; \u0000adduct; \u0000bridged intermediates; \u0000cyclopropane derivatives; \u0000Michael condensation; \u0000ketones; \u0000esters; \u0000cycloalkanones; \u0000cycloalkenes; \u0000Robinson's modification; \u0000aromatic rings systems; \u0000rings; \u0000pyrroles; \u0000piperidines; \u0000pyrrolizidines; \u0000amino salts; \u0000experimental conditions","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"28 1","pages":"179-556"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79721347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR011.02
P. Smith, D. Baer
{"title":"The Demjanov and Tiffeneau‐Demjanov Ring Expansions","authors":"P. Smith, D. Baer","doi":"10.1002/0471264180.OR011.02","DOIUrl":"https://doi.org/10.1002/0471264180.OR011.02","url":null,"abstract":"The reaction of aminomethylcycloalkanes with nitrous acid to produce cycloalkanols in which the ring is larger by one carbon atom is known as the Demjanov rearrangement. The first example of this type of ring expansion was encountered in 1901, but was not recognized until 1903 when cyclopentanol was identified as one of the products formed from cyclobutanemethylamine. Since that time the reaction has extended to rings of many sizes. Olefins almost invariably accompany the alcohols that are formed. The Demjanov rearrangement includes within its scope the rearrangements that occur when acyclic amines are treated with nitrous acid as well as other ring expansion detailed in this chapter. The Tiffeneau-Demjanov ring expansion is used here to designate ring enlargements by pinacolic deamination. This ring expansion can be made the key step in the conversion of a cyclic alcohol or ketone into its next ring homolog. \u0000 \u0000 \u0000Keywords: \u0000 \u0000Demjanov ring expansions; \u0000Tiffeneau -Demjanov ring expansion; \u0000ring sizes; \u0000unsaturated rings; \u0000heterocyclic rings; \u0000bicyclic systems; \u0000polycyclic systems; \u0000Experimental procedures","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"11 1","pages":"157-188"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84147194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR018.03
V. Dave, E. Warnhoff
{"title":"The Reactions of Diazoacetic Esters with Alkenes, Alkynes, Heterocyclic and Aromatic Compounds","authors":"V. Dave, E. Warnhoff","doi":"10.1002/0471264180.OR018.03","DOIUrl":"https://doi.org/10.1002/0471264180.OR018.03","url":null,"abstract":"After the first unsuccessful attempt of Curtius in 1884 to affect the reaction of ethyl diazoacetate with toluene other researchers studied the reaction. Later, Buchner and Curtius treated several aromatic, olefinic, and acetylenic compounds with diazoacetic esters to form cyclopropanes. Since then the reactions of diazoacetates with various unsaturated compounds have been studied. The carbalkoxy carbenes are of interest since they are believed to be intermediates in higher temperature thermal and photochemical reactions of diazoacetates. \u0000 \u0000 \u0000Keywords: \u0000 \u0000diazoacetic esters; \u0000alkenes; \u0000alkynes; \u0000hetercyclic compounds; \u0000aromatic compounds; \u0000benzene; \u0000derivatives; \u0000stereochemistry; \u0000polynuclear aromatics; \u0000experimental conditions; \u0000preparation","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"2 1","pages":"217-401"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83411737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR001.09
C. Hauser, B. E. Hudson
{"title":"The Acetoacetic Ester Condensation and Certain Related Reactions","authors":"C. Hauser, B. E. Hudson","doi":"10.1002/0471264180.OR001.09","DOIUrl":"https://doi.org/10.1002/0471264180.OR001.09","url":null,"abstract":"The acetoacetic ester condensation consist in the reaction in the presence of certain bases, of an ester having hydrogen on the alpha carbon atom with a second molecule of the same ester or with another ester to form a beta-ketoester. The bases capable of effecting such reactions include sodium alkoxides, triphenylmethylsodium, sodium amide, certain Grignard reagents. Metallic sodium effects certain condensations, the sodium, alkoxide which is formed in the reaction mixture probably serves as the active condensing agents. The classical example of the acetoacetic ester reaction is the formation of acetoacetic ester itself by the condensation of ethyl acetate by means of sodium ethoxide. \u0000 \u0000 \u0000Keywords: \u0000 \u0000acetoacetic ester; \u0000condensation; \u0000side reactions; \u0000Dieckmann reaction; \u0000acylation; \u0000esters; \u0000acid chlorides; \u0000sodium; \u0000experimental conditions","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"61 1","pages":"266-302"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80913990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR002.08
E. Jackson
{"title":"Periodic Acid Oxidation","authors":"E. Jackson","doi":"10.1002/0471264180.OR002.08","DOIUrl":"https://doi.org/10.1002/0471264180.OR002.08","url":null,"abstract":"Periodic acid oxidation is applicable to compounds having two hydroxyl groups or hydroxyl and an amino group attached to adjacent carbon atoms and is characterized by the cleavage of the carbon-carbon bond. Carbonyl compounds in which the carbonyl group is adjacent to a second carbonyl or hydroxyl group are oxidized also In reactive compounds containing the amino-alcohol structure, the amino group may be primary or secondary. Oxidation has been reported to occur with a number of compounds which contain nitrogen, but possess no alpha-amino-alcohol structure. \u0000 \u0000 \u0000Keywords: \u0000 \u0000periodic acid; \u0000oxidation; \u0000aqueous solution; \u0000oxidation; \u0000methylgylcosides; \u0000alginic acid; \u0000acetyl glucosylamine; \u0000starch; \u0000side chain; \u0000dihydroxystearic acid; \u0000glycerol benzyl ether; \u0000experimental conditions; \u0000ethanol","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"104 1","pages":"341-375"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82741550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic ReactionsPub Date : 2011-03-15DOI: 10.1002/0471264180.OR002.02
A. L. Henne
{"title":"The Preparation of Aliphatic Fluorine Compounds","authors":"A. L. Henne","doi":"10.1002/0471264180.OR002.02","DOIUrl":"https://doi.org/10.1002/0471264180.OR002.02","url":null,"abstract":"Reactions of four types have been used for introducing fluorine atoms in to aliphatic molecules. These are listed below in the order of their practical importance at the present time. \u0000 \u0000 \u0000 \u0000Interaction of organic halides or polyhalides with inorganic fluorides \u0000 \u0000 \u0000 \u0000 \u0000Addition of hydrogen fluoride to olefins and acetylene \u0000 \u0000 \u0000 \u0000 \u0000Direct fluorination of saturated compounds or additions of fluorine to unsaturated compounds \u0000 \u0000 \u0000 \u0000 \u0000Replacement of the hydroxyl group of alcohols. \u0000 \u0000 \u0000 \u0000 \u0000These reactions are discussed in this chapter. \u0000 \u0000 \u0000 \u0000 \u0000 \u0000Keywords: \u0000 \u0000aliphatic fluorine compounds; \u0000hydrogen fluoride; \u0000silver; \u0000mercury; \u0000polyhalides; \u0000unsaturated compounds; \u0000fluorination; \u0000organic halides; \u0000direct fluorination; \u0000mercury; \u0000inorganic fluorides","PeriodicalId":19539,"journal":{"name":"Organic Reactions","volume":"85 1","pages":"49-93"},"PeriodicalIF":0.0,"publicationDate":"2011-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89364911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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