bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Amination of Heterocyclic Bases by Alkali Amides*The Chichibabin Reactions.
Authors: Leffler Marlin T. 
Published: March 2011

AbstractHeterocyclic 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 CHNgroup; 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.
ThePerkin Reaction and Related Reactions
Authors: Johnson John R. 
Published: March 2011

AbstractIn 1868, W. H. Perkin described a synthesis of coumarin by heating the sodium salt of salicyaldehyde with acetic acid. Further study led to a new discovery for preparing cinnamic acid and its analogs by means of a synthesis of very general application, which became know as the Perkin reaction. In the course of study of unsaturated acids, Fittig made several important contributions to the mechanism of the Perkin reaction. Many studies have been made regarding this reaction and are described. The Perkin reaction may be regarded essential as the condensation of a carbonyl component A and an acid and dihydride‐salt combination B. The discussion here is a survey of the types of carbonyl components and acid anhydride salt combinations that can be used and of the yields obtained under favorable conditions.
The
F
ries Reaction
Authors: Blatt A. H. 
Published: March 2011

Abstract
The Fries reaction consists in the conversion of an ester of a phenol to an ortho‐ or para‐hydroxyketone, or a mixture of both, by treatment with aluminum chloride. Three different mechanisms for the fries rearrangement have received serious consideration.: the ester is assumed to react with aluminum chloride to give an acid chloride and a phenoxyaluminum chloride which combine to form a derivative of the hydroxyketone; one molecule of the phenyl ester is acylated by another molecule; the Fries reaction is considered ti be a true intramolecular rearrangement in which the acyl group shifts directly from the oxygen atom to the carbon atom of the ring.
TheClaisen Rearrangement
Authors: Tarbell D. Stanley 
Published: March 2011

AbstractAllyl ethers of enols and phenols undergo rearrangement to C‐allyl derivatives when heated to sufficiently high temperatures. The reaction, named after its discoverer (Claisen, 1912) was first observed when ethylO‐allylacetonacetate was subjected to distillation at atmospheric pressure in the presence of ammonium chloride. The allyl ethers of phenols rearrange smoothly at temperatures of about 200°C in the absence of catalysts, Allyl ethers ofortho‐disubstituted phenols rearrange to the correspondingp‐allyphenols. The only known example of para rearrangement accompanied by inversion is the reaction of alpha‐ethylallyl 2‐carbomethoxy‐6‐methylphenyl ether. These rearrangements are discussed in detail.
The Preparation of Aliphatic Fluorine Compounds
Authors: Henne Albert L. 
Published: March 2011

AbstractReactions 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.Interaction of organic halides or polyhalides with inorganic fluoridesAddition of hydrogen fluoride to olefins and acetyleneDirect fluorination of saturated compounds or additions of fluorine to unsaturated compoundsReplacement of the hydroxyl group of alcohols.These reactions are discussed in this chapter.
TheCannizzaro Reaction
Authors: Geissman T. A. 
Published: March 2011

AbstractThe reaction in which two aldehyde groups are transformed into the corresponding hydroxyl and carbonyl functions, existing separately or in combination as an ester, has been termed the Cannizzaro reaction. Here the discussion is restricted to the dismutation of two similar aldehyde groups into the corresponding alcohol and carboxylic salt function by means of aqueous or alcoholic and alkali. The conversion of benzaldehyde into a mixture of benzyl alcohol and sodium benzoate is an example.
Reduction with Aluminum Alkoxides
Authors: Wilds A. L. 
Published: March 2011

AbstractVerley and Meerwein and Schmidt discovered independently that an aldehyde can be reduced to the primary alcohol by treatment with aluminum ethoxide in the presence of ethanol. The reduction of the aldehyde occurs at the expense of an equivalent amount of ethanol which is oxdized to acetaldehyde. The reaction is reversible, but the equilibrium can be shifted to the point of complete reduction by removal of the acetaldehyde with a stream of hydrogen or nitrogen. This has the additional advantage of preventing side reactions such as aldol condensation between the original aldehdye and acetaldehyde. This method of reduction with aluminum chloride was found applicable to several aldehydes, but to only a few ketones of special types. This mild and specific method of reducing carbonyl compounds became know as the Meerwein‐Ponndorf‐Verley reduction Lund later studied the scope and limitations of the reaction.
The Willgerodt Reaction
Authors: Carmack Marvin , Spielman M. A. 
Published: March 2011

Abstract
The name of Conrad Willgerodt is associated with a group of closely related reactions which have a common feature the conversion of a carbonyl compound into an amide with the same number of carbon atoms. The original process involved the reaction of an appropriately substituted alkyl aryl ketone with an aqueous solution of yellow ammonium polysulfide at an elevated temperature to form an aryl‐substituted aliphatic acid amide, together with a smaller amount of the corresponding ammonium salt of the carboxylic acid. The Kindler variation promises to be more useful. It consists of heating a ketone with approximately equimolecular amounts of sulfur and dry amine.
Azlactones
Authors: Carter H. E. 
Published: March 2011

AbstractAzlactones may be considered the anhydrides of alpha‐acylamino acids. It is convenient to classify them into two groups, saturated and unsaturated, since the two types show characteristic differences in properties, Azlactones have been of interest mainly as intermediates in the synthesis of other compounds. Saturated azlactones are obtained most often from the corresponding amino acids used in preparing derivatives of those amino acids. Unsaturated azlactones, on the other hand, usually are prepared by condensing an aldehyde with an acylglycine and are used in the synthesis of the corresponding amino and keto acids. Four methods by which azlactones are prepared are discussed in this chapter.
Substitution and Addition Reactions of Thiocyanogen*Present address, School of Biological Sciences, The Medical School, University of Tennessee, Memphis, Tenn.
Authors: Wood John L. 
Published: March 2011

Abstract
The direct replacement of a hydrogen atom by a thiocyano group through the use of thiocyanogen is termed thiocyanation. This replacement reaction is limited practically to aromatic amines and phenols. Thiocyanogen reacts with olefinic and acetylenic linkage, the reagent adding to the unsaturated linkage. Thicyanogen reacts with compounds of other types. Thiocyanogen reacts with aromatic compounds that are highly susceptible to substitution with the introduction of a thiocyano groups. Thiocyanation of aromatic amines, phenols is discussed. Addition of thiocyanogen to olefins and acetylenes, and miscellaneous syntheses are also discussed.
The Preparation of Amines by Reductive Alkylation
Authors: Emerson William S. 
Published: March 2011

AbstractReductive alkylation is the term applied to the process of introducing alkyl groups into ammonia or primary or secondary amine by means of an aldehdye or ketone in the presence of a reducing agent. This chapter is limited to those reductive alkylations in which the reducing agent is hydrogen and a catalysts or nascent hydrogen, usually from a metal‐acid combination; most of these reductive alkylations have been carried out with hydrogen and a catalyst.
The Acyloins
Authors: McElvain S. M. 
Published: March 2011

Abstract
Acyloins arre alpha‐hydroxy ketones of the general formula, RCHOHCOR, in which R represents an aliphatic analog of benzoins. The term acyloin is commonly used as a class name for the symmetrical keto alcohols and the name of the individual compound is derived by adding the suffix “oin” to the stem name of the acid to which the acyloin corresponds, e.g., acetoin, butyoin, etc. The commonest method of preparation of those acyloins in which the alkyl groups are identical is the reaction of sodium with esters of aliphatic acids in inert solvents. Salts of enediols are produced in this reaction. Other methods of preparation are discussed.
The Synthesis of Acetylenes
Authors: Jacobs Thomas L. 
Published: March 2011

AbstractMany advances have been made in recent years in the methods for the synthesis of acetylenes and many compounds are now rather readily available in the pure state. Acetylene was first prepared by Davy, who treated acetylide with water. Propyne, the first substituted acetylene was obtained in 1861. At the present time alkynes are usually synthesized by the alkylation of sodium acetylide or substituted metallic acetylides, often in liquid ammonia and 1‐Alkynes are also obtained by dehydrohalogenation of suitable halides with sodium amide or in certain cases by ethanolic alkali. The present discussion will be limited to methods for the creation of a carbon‐carbon triple bond and to the alkylation of metallic acetylides.
The
D
iels‐
A
lder Reaction Quinones and Other Cyclenones*Present address, Chemistry Branch, Office of Naval Research.
Authors: Butz Lewis W. , Rytina Anton W. 
Published: March 2011

Abstract

Quinones and other cyclenones react by 1,4‐addition with conjugated dienes. A typical example is the reaction of butadiene with
p
‐benzoquinone yielding the diketohexahydronaphthalene. The direct synthesis of quinones with other cyclenones may be extended to provide a route to the preparation of fused‐ring aromatic systems. It is also possible to prepare fused‐ring ketones containing angular substituents. Diene syntheses described in this chapter may lead to the synthesis of compounds of steroidal structure. The stereochemcial configurations of Diels‐Alder addition products have been discussed elsewhere in this series, This problem is exceedingly complex with products described in this chapter and is impossible to predict stereochemical configurations of the adducts with any certainty.
The Leuckart Reaction
Authors: Moore Maurice L. 
Published: March 2011

AbstractThe Leuckart reaction is a process for reductive alkylation of ammonia or primary or secondary amines by certain aldehdyes and ketones, It is distinguished by the fact that the reduction is accomplished by formic acid or a derivative of formic acid and should be compared with reductive alkylation discussed elsewhere in this series. The reaction is carried out by heating a mixture of the carbonyl compound and the formic acid salt or formyl derivative of ammonia or the amine. Primary and secondary amines produced in the reaction often are obtained as the formyl derivatives and must be recovered by hydrolysis; tertiary amines are obtained as formate. Modifications of this reaction are discussed.
TheDarzens Glycidic Ester Condensation
Authors: Newman Melvin S. , Magerlein Barney J. 
Published: March 2011

AbstractThe Darzens glycidic ester condensation involves the condensation of an aldehdye and a ketone with an alpha‐halo ester to produce an alpha,beta‐epoxy ester (glycidic ester). The most frequently used condensing agents are sodium ethoxide and sodium amide. The glycidic esters are of interest primarily because they can be converted into aldehydes and ketones having a higher carbon content than the original aldehydes or ketones. This transformation occurs after hydrolysis to and decarboxylation of the epoxy acid and is accompanied by rearrangement when an aldehyde if formed. Darzens described another procedure which involves the reaction of aldehdyes and ketones with ethyl dichloracetate and dilute magnesium amalgam. Mechanisms of these reactions are discussed.
The Synthesis of Phosphonic and Phosphinic Acids
Authors: Kosolapoff Gennady M. 
Published: March 2011

AbstractThe phosphonic acids and the phosphinic acids may be regarded as derivatives of phosphoric acid in which one or two hydroxyls are replaced by organic radicals. Although individual phosphonic and phosphinic acids have been known for several decades, the syntheses of these two classes of compounds have not been well developed. This chapter is concerned only with the introduction of phosphorus‐containing functions, i.e, the synthesis of acids or their functional derivatives, which can be isolated and hydrolyzed to the acids.
The Preparation of Thiophenes and Tetrahydrothiophenes
Authors: Wolf Donald E. , Folkers Karl 
Published: March 2011

AbstractThiophenes and tetrahydrothiophenes are discussed as separate major divisions in this chapter because there are significant differences in the general methods by which these two similar types of compounds are prepared. The general reactions that lead to the formation of thiophenes may be segregated in the following five general classifications (1) Reaction of the 1,4‐difunctional compounds with sulfides; (2) reaction of unsaturated compounds with sulfides; (3) reaction of 1,2‐difunctional compounds with thiodiacetic acid and esters; (4) reaction of aryl methyl ketones with sulfides; (5) miscellaneous cyclization reactions. Similarly the reactions that form tetrahydrothiophenes may be grouped into four general classifications: (1) Reaction of 1,4‐difunctional compounds with sulfides; (2) Dieckmann cyclization; (3) Catalytic method; (4) miscellaneous methods. All of the above are discussed in this chapter.
Carbon‐Carbon Alkylations with Amines and Ammonium Salts
Authors: Brewster James H. , Eliel Ernest L. 
Published: March 2011

AbstractThis chapter is a review of those reactions of compounds containing labile amino groups in which a carbon‐carbon bond is formed by amine replacement as, for example, in the alkylation of diethyl malonate by 1‐dimethylamino‐3‐butanone. Attention has been given primarily to reactions of amines prepared by the Mannich reaction (Mannich bases), but for comparison, analogous reactions of simpler quaternary ammonium salts have been included.
ThevonBraun Cyanogen Bromide Reaction
Authors: Hageman Howard A. 
Published: March 2011

AbstractThe reaction of a tertiary amine with cyanogen bromide was first described in 1900 by Julius von Braun who elaborated the reaction to such an extent that it bears his name. Generally, a tertiary amine reacts with cyanogen bromide to yield an alkyl bromide and a disubstituted cyanamide. The direct conversion of secondary amines to disubstituted cyanamides with cyanogen bromide proceeds in low yield because some of the amine is converted to its hydrobromide. The material in this chapter is limited to a discussion of the reaction of tertiary amines with cyanogen bromide.
The Nitrosation of Aliphatic Carbon Atoms
Authors: Touster Oscar 
Published: March 2011

AbstractThe nitrosation reaction consists in the replacement of a hydrogen atom by the nitroso group with the formation of a nitroso or oximo derivative. With a few exceptions, the replacement of hydrogen on an aliphatic carbon atom requires the presence of an electron‐attracting groups adjacent to the carbon to be nitrosated. Acyl, aroyl, carbonyl, carboxy, carbalkoxyl, nitrogen, cyano, imino, and aryl groups may serve as activators. Monoketones are readily converted into alpha‐oximino ketones, whereas monoesters containing no other activating groups do not undergo the reaction. Victor Meyer discovered the reaction in 1873–1874.
The Synthesis of Ketones from Acid Halides and Organometallic Compounds of Magnesium, Zinc, and Cadmium
Authors: Shirley David A. 
Published: March 2011

AbstractThe synthesis of ketones from acid halides and organometallic compounds may be represented by the following equation:imageFreund fist observed the formation of ketones from simple acid chlorides and dimethyl‐ and diethyl‐zinc. Organometallic compounds of sodium, copper, magnesium, cadmium, mercury, aluminum, tin, and lead have also been found to give this reaction. Only organozinc, organocadmium, and organomagnesium reagents have been found to be generally useful for such syntheses, however. These reactions are reviewed in this chapter.
β‐Lactones
Authors: Zaugg Harold E. 
Published: March 2011

Abstractβ‐lactones contain a strained four membered heterocyclic ring. Consequently, they differ from the gamma and delta‐lactones both in the general methods available for their preparation and their chemical reactivity. Because of their high order of reactivity, only those β‐lactones with favorable physical properties can be isolated readily in pure form. The highly reactive β‐lactones are customarily prepared in order to transform them into other products. This chapter will consider, first the preparation of β‐lactones, and second, their reactions of synthesis value.
The Reaction of Diazomethane and its Derivatives with Aldehydes and Ketones
Authors: Gutsche C. David 
Published: March 2011

AbstractDiazomethane and its derivatives react with aldehdyes and ketones usually under very mild conditions to yield a variety of interesting and often useful products. The reaction is most often carried out by either allowing the carbonyl compound to react with an ethereal solution of the diazomethane derivative with or without the addition of a catalyst, or by treating a methanol solution of the carbonyl compound with a nitrosoalkylurethane in the presence of a base, Only the reactions of diazomethane and its alkyl and aryl derivatives are discussed in detail.
TheGattermann Synthesis of Aldehydes
Authors: Truce WIlliam E. 
Published: March 2011

AbstractGatterman developed two methods for introducing the aldehdye group into aromatic compounds. The first of these known as the Gatterman Koch reaction uses a mixture of carbon monoxide and hydrogen chloride in the presence of a mixture of anhydrous aluminum chloride and cuprous chloride. It is not adaptable to the preparation of aldehydes from phenols or phenolic ethers, however. The second method employs a mixture of hydrogen cyanide and hydrogen chloride with or without a catalyst and permits the introduction of an aldehdye group into phenols, naphthols, and their ethers under special conditions into aromatic hydrocarbons and related compounds. This chapter is concerned with the second method. The mechanism of the reaction appears to be complex and has not been fully elucidated. Details on the scope, limitations and alternative methods, as well as experimental tests, are detailed.
TheBaeyer‐VilligerOxidation of Aldehydes and Ketones
Authors: Hassall C. H. 
Published: March 2011

AbstractIn 1899, Bayer and Vlliger showed that the oxidation of alicyclic ketones, menthone, tetrahydrocarvone, and camphor with permono‐sulfuric acid led to the formation of lactones. Further studies using a variety of ketones or aldehydes and hydrogen peroxide or peracids in various media have established that the oxidation is of wide applicability. The oxidation, the Baeyer‐Villiger reaction, is the subject of this review. As the oxidation normally employs mild conditions, gives reasonable yields, and shows a high degree of selectivity, it has proved useful in a variety of both synthetic and degradative studies. Recent investigations have led to a better definition of favorable experimental conditions and have extended the scope of the reaction.
The Reaction of Halogens with Silver Salts of Carboxylic Acids
Authors: Wilson C.V. 
Published: March 2011

AbstractThe action of halogens with dry metallic salts, particularly silver salts of carboxylic acids has merited earlier reviews. It has been pointed out that the halogen used, the ratio of silver salt to halogen, and the presence or absence of other active materials, such as olefins, acetylenes, or readily substituted aromatic rings plays a determining the course of the reactions. Thus it is possible to produce an organic halide containing one less carbon atom than the original acid; esters derived from two molecules of the acid by the loss of one molecule of carbon dioxide; esters of 1,2‐diols or halohydrins; halogenated aromatic compounds; and halogenated acetylenes. These reactions are the subject of this chapter.
ThePschorr Synthesis and Related Diazonium Ring Closure Reactions
Authors: DeTar DeLos F. 
Published: March 2011

AbstractIn the middle 1890s, three groups of chemists independently discovered a new cyclization reaction of certain appropriately constituted diazonium salts. Fischer and Schmidt reported that an aqueous solution of 2‐benzylbenzenediazonium chloride furnished fluorene on heating. Graebe and Ullman reported that 2‐benzoylbenzenediazonium chloride yielded fluorenone and Staedel reported a somewhat similar result from the action of nitrous acid on 2,2'‐diaminbenozpehnone, a reaction that produced a little 1‐hydroxyfluorenone. Two years later, Robert Pschorr applied the ring closure reaction to the diazonium salt derived from trans‐2‐amino‐alpha‐phenylcinnamic acid to obtain phenanthrene‐9‐carboxylic acid. The principal utility of these cyclizations reactions has been the synthesis of substituted ring structures in which the positions of the substituents are known.
The Coupling of Diazonium Salts with Aliphatic Carbon Atoms
Authors: Parmerter Stanley M. 
Published: March 2011

AbstractA diazonium salt will couple with an aliphatic compound containing an activated carbon‐hydrogen bond. This discussion is limited to those reactions in which both the nitrogen atoms of the diazonium salts are retained in the resulting molecule. The discussion is further limited by the exclusion of coupling reactions, which occur with the elimination of a group from an activated methinyl compound, the Japp‐Klingemann reaction. These reactions are discussed in Chapter 2. Much of the early work with coupling was prompted by the desire to determine whether the products were of the azo or hydrazonestructure. It is difficult to establish the structures in such cases where the tautomeric forms are possible. It is generally considered that the hydrazone is the stable form.
The Japp‐Klingemann Reaction
Authors: Phillips Robert R 
Published: March 2011

Abstract
In an attempt to prepare an azo ester by coupling benzendiazonium chloride with ethyl‐2‐methylacetoacetate, Japp and Klingemann obtained a product, which was soon recognized as the phenylhydrazone of ethyl pyruvate. It thus appears that the acetyl group is displaced, actually the coupling product was unstable under the conditions of its formation, undergoing hydrolytic scission of the acetyl group and rearrangement of the azo structure. It was later discovered that, if the substituted acetoacetic ester was saponified and the cocoupling carried out on the sodium salt, the carboxylic function rather than the acetyl group, was lost and the product isolated was the phenylhydrazone of biacetyl. This reaction was extended to other systems containing methinyl groups.