bluuebunny/crossref_metadata_2025_split huggingface dataset:
The
M
annich Reaction
Authors: Blicke F. F. 
Published: March 2011

Abstract
The Mannich reaction consists in the condensation of ammonia or a primary or secondary amines, usually as the hydrochloride, with formaldehyde and a compound containing at least one hydrogen atom of pronounced reactivity. The essential feature of the reaction is the replacement of the active hydrogen atom by an aminomethyl or substituted aminomethyl group. The product from acetophenone, formaldehyde, and a secondary amine salt is an example. The product to be expected from a Mannich reaction involving an ammonium salt is a primary amine. The mechanism of the Mannich reaction has not been established.
The
J
acobsen Reaction
Authors: Smith Lee Irvin 
Published: March 2011

Abstract
The migration of an alkyl group or a halogen atom in a sulfonic acid derived from a polyalkylbenzene, a halogenated polyalkylbenzene, or a polyhalogenated benzene is known as the Jacobsen reaction. The migrations of the Jacobsen reaction may be divided into two general types, intramolecular in which the migrating group moves from one position to another in the same molecule; and intermolecular in which there is a transfer of one or more groups from one molecule to from one molecule to another. In most cases migration of both types occur simultaneously. An important characteristic of the reaction is the migration of the alkyl groups to vicinal positions.
The Formation of Cyclic Ketones by IntramolecularAcylation
Authors: Johnson William S. 
Published: March 2011

Abstract
The cyclizations of gamma‐phenylbutyric acid (I) to tetralone‐1 (II) and of beta‐phenylpropionic acid (III) to hydrindone‐1 (IV) exemplify a type of intramolecular acylation which has served as an important tool in the synthesis of polycyclic hydroaromatic and aromatic compounds, Such ring closures have been effected by a variety of methods, generally involving either the direct cyclodehydration of the acids or the cyclodehydrohalogenation of the acid chlorides by an intramolecular Freidel‐Crafts reaction. This chapter presents a discussion of these methods and the various problems involved in the formation of cyclic ketones by the ring closure of aryl‐substituted aliphatic acid.
The Preparation of Unsymmetrical Biaryls by the Diazo Reaction and the Nitrosoacetylamine Reaction
Authors: Bachmann Werner E. , Hoffman Roger A. 
Published: March 2011

Abstract
The amino group of aromatic amines can be replaced by aryl groups with the formation of unsymmetrical biaryl by two general procedures: (1) by reaction of the aryldiazo hydroxide or acetate with aromatic compounds and (2) by reaction of the nitrosoacetylamine with aromatic compounds, In general the aromatic compounds must be a liquid for no solvent has been found which will not be attacked by the reactive intermediates which are formed in these reactions. Diazo and nirosoacetykeamine reactions are discussed.
Replacement of the Aromatic Primary Amino Group by Hydrogen*National Research Fellow, 1942–1943. Present address, Purdue University.
Authors: Kornblum Nathan 
Published: March 2011

AbstractThe replacement of an aromatic primary amino group by hydrogen is usually effected by the reduction of the diazonium salt derived from the amine. It is evident that the success of the deamination process is a function of the completeness of diazotization as well as of the reduction. Diazonium compounds have been treated with a great variety of reducing agents some of which have become incorporated into procedures for replacing the diazo group by hydrogen. The important process involve reduction by: alcohols, hypophosphorous acid, alkaline formaldehyde, stabilization of the diazonium salt with naphthalene‐1,5‐disulfonic acid followed by treatment with zinc or copper, sodium stannite, stannous chloride or sodium sulfate reduction to hydrazine from which the hydrocarbon is obtained by oxidation.
Periodic Acid Oxidation
Authors: Jackson Ernest L. 
Published: March 2011

AbstractPeriodic 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.
The Resolution of Alcohols
Authors: Ingersoll A. W. 
Published: March 2011

AbstractThe resolution of nearly one hundred and fifty alcohols and phenols are recorded in the literature. Practically every known method of resolution has been applied to these classes of substances and several methods of considerable utility have been developed. This chapter gives a description and evaluation of results obtained to date. A brief statement of the underlying principles and the main steps of the procedure for all the important methods of resolution are included.
The Preparation of Aromatic Arsonic and Arsinic Acids by the Bart, Bechamp, and Rosenmund Reactions
Authors: Hamilton Cliff S. , Morgan Jack F. 
Published: March 2011

AbstractArsonic acids may be regarded as derived from orthoarsenic acid, by replacement of one of the hydroxyl groups with an organic residue, the arsenic acids are similarly derived by replacement of the two hydroxyl groups. The preparation of aromatic arsenic acids is described in this chapter. The most widely used is the Bart reaction, which involves the interaction of a diazonium salt with an inorganic arsenic compound. Arsenic acids are also obtained as by‐products in the Bechamp synthesis. In the Rosenmund synthesis, salts of arsenic acids are obtained by treatment of aryl halides with sodium or potassium arsenite.
The Alkylation of Aromatic Compounds by the Friedel‐Crafts Method
Authors: Price Charles C. 
Published: March 2011

AbstractSince the discovery by Friedel and Crafts that aluminum chloride catalyzes the condensation of alkyl and acyl halides with various aromatic compounds to effect substitution of an alkyl or acyl group for more or more hydrogen atoms of the aromatic compound, this reaction has been greatly extended in scope with respect to alkylating or acylating agents and catalysts. The use of aluminum chloride as a catalyst was studied by Thomas. Aspects of this study appeared in an earlier volume of this series. The present discussion is limited to the direct alkyl, cycloalky, or aralkyl residues containing no functional groups into various aromatic compounds under various catalysts, such as e.g., aluminum trichloride, zinc dichloride, and hydrogen fluoride. The alkylating agents include olefins, highly strained cycloparaffins, polyalkylbenzenes, alkyl halides, alcohols, esters, of inorganic and organic acids, and ethers. The aromatic compound may be e.g., a hydrocarbon, an aryl chloride, or bromide, a mono‐or polyhdrydric phenol or its ether. The Friedel‐Crafts process is frequently the most useful method for the introduction of an alkyl group.
Preparation of Ketenes and Ketene Dimers*Present address, M. W. Kellogg Co., 225 Broadway, New York, N. Y.
Authors: Hanford W. E. , Sauer John C. 
Published: March 2011

Abstract
Ketenes contain the functional group CCO. They have been classified as aldoketenes and ketoketenes. The ketenes are prepared by modifications of the general methods for the synthesis of olefins. The ketenes are much more reactive than simple olefins, however, and are more likely to enter into combination with the reagents from wich they are prepared or with solvents used or into self‐condensation to yield dimers or polymers, Many of the aldoketenes, which are generally more reactive than ketoketenes, have not been isolated as the pure monomers. The dimers of aldoketenes have some of the properties of ketenes and some are useful.
Direct Sulfonation of Aromatic Hydrocarbons and their Halogen Derivatives
Authors: Suter C. M. , Weston Arthur W. 
Published: March 2011

AbstractThis chapter deals with the direct replacement of the hydrogen atoms in aromatic hydrocarbons, and their halogen derivatives by sulfonic acid, sulfonyl chloride, and sulfonyl fluoride groups. These sulfonations are more convenient and much more commonly used than indirect synthetic methods such as those that involve the reaction of an aryl halide with a sulfite, the oxidation of a disulfide, thiol, or sulfinic acid, or the conversion of a diazonium salt into a sulfonic acid. The reagents most used for direct sulfonation are sulfuric acid, sulfur trioxide in an inert solvent, in sulfuric as oleum, or an addition product with pyridine or dioxane, Chlorosulfonic acid, its salts and its anhydride and flurosulfonic acid. Combinations of reagents have been used.
The Hofmann Reaction*Present address, Rutgers University, New Brunswick, N. J.
Authors: Wallis Everett S. , Lane John F. 
Published: March 2011

AbstractIn the Hofmann reaction an amide is converted to an amine of one less carbon atom by treatment with bromine or chlorine, and alkali. In effect, the carbonyl group of the amide is eliminated. The reaction is applicable to the preparation of amines from amides of aliphatic, aromatic, arylaliphatic, and hetereocyclic acids. The Hofmann reaction is generally carried out by dissolving the amide in a very slight excess of cold aqueous hypohalite solution, followed by rapid warming, A valuable modification consists in carrying out the reaction in an alcoholic solution, with subsequent hydrolysis of the urethan so obtained.
The
S
chmidt Reaction
Authors: Wolff Hans 
Published: March 2011

Abstract
The reaction between equimolar quantities of hydrazoic acid and carbonyl compounds in the presence of a strong mineral acid has become known as the Schmidt reaction It offers a convenient method for the preparation of amines from acids. Aldehydes yield nitriles and formyl derivatives of amines, and ketones yield amides. With hydrazoic acid in large excess, aldehdyes and ketones yield substituted tetrazoles. The reaction of carbonyl compounds with hydrazoic acid was first reported by Karl Friedrich Schmidt in 1923.
The Curtius Reaction
Authors: Smith Peter A. S. 
Published: March 2011

AbstractThe decomposition of acid azides to isocyanates and nitrogen is known as the Curtius rearrangement. The reaction is a preparative method for isocyanates, ureas, amides, and amines. When coupled with a hydrolytic step, the Curtius rearrangement becomes a practical procedure for replacing a carboxyl group by an amino group. The overall process of converting an acid through its azide to an amine is commonly referred to as the Curtius reaction. Acid azides are commonly prepared by treating hydrazides in cold, aqueous solution with nitrous acid. Azides can be rearranged in inert solvents, from which isocyanates can be isolated in the presence of water or alcohol., which will react with the intermediate to form urethans or ureas.
The
D
iels‐
A
lder Reaction with Maleic Anhydride*Present address, University of Southern California, Los Angeles, California.
Authors: Kloetzel Milton C. 
Published: March 2011

Abstract
The Diels‐Alder reaction consists in an addition of a compound containing a double or triple bond (usually activated by additional unsaturation in the alpha, beta‐position) to the 1,4‐positions of a conjugated dienes system with the formation of a six‐membered ring, Various dienes systems to dienophiles are described as typical examples of the Diels‐Alder reaction. A noteworthy feature of this reaction is the great variety of compounds that may serve as the dienophile. Among the most widely employed dienophiles are maleic anhydride and closely related dicarboxylic acid derivatives.
The
D
iels‐
A
lder Reaction Ethylenic and Acetylenic Dienophiles
Authors: Holmes H. L. 
Published: March 2011

Abstract
In addition to the reactions with malic anhydride and related compounds, conjugated dienes react by 1,4‐addition with olefinic and acetylenic compounds in which the unsaturated group is conjugated with one or more carbonyl or other unsaturated group. Even certain vinyls and allyl compounds have been found to function as dienophiles. Typical examples are the reactions of butadiene with acrolein beta‐nitrostyrene, allyl chloride, and acetylene‐dicarboxylic acid. The olefinic dienophiles yield cyclohexene derivatives and the acetylenic dienophiles lead to derivatives of 1,4‐dihydrobenzene.
The Synthesis of Benzoins*Present address: Sterling‐Winthrop Research Institute, Rensselaer, N.Y.†The invitation to write this chapter was extended to J. S. B., but circumstances compelled him to turn the work over to W. S. I., the second author's contribution being nominal.
Authors: Ide Walter S. , Buck Johannes S. 
Published: March 2011

AbstractBenzoins are aromatic alpha‐hydroxy ketones of the general formula, Ar'CHOHCOAr. Similar compounds containing aromatic heterocyclic nuclei are also classed as benzoins. The reactions for the preparation of benzoins are (1) the condensation of two molecules of an aromatic aldehyde in the presence of cyanide ion; (2) the conversion of an unsymmetrical benzoin into it into its isomer; (3) condensation of an aryl glyoxal with an aromatic hydrocarbon; (4) the reaction of an aryl Grignard reagent with mandelamide or mandelonitrile; (5) the reduction of a benzyl; (6) the reduction of an aromatic acid or its derivatives; (7) the introduction of a hydroxyl group into a desoxybenzoin; (8) and some miscellaneous reactions. These are the subject of this chapter
Synthesis of Benzoquinones by Oxidation*Present address: Department of Chemistry, University of California, Berkeley, Cal.
Authors: Cason James 
Published: March 2011

Abstractp‐Benzoquinone or quinone was discovered in 1838 as a product of the action of manganese dioxide in sulfuric acid on the natural product, quinic acid, However, benzoquinones generally prepared by the oxidation of disubstituted aromatic hydrocarbons derivatives having hydroxyl or amino groups in the ortho and para positions. The quinone results from the oxidation of hydroquinone, p‐aminophenol, or p‐phenylendiamine. Certain quinones are obtainable in moderate or fair yield by oxidation of starting materials containing only one hydroxyl or amino group as exemplified by the industrial production of quinine from aniline. Oxidation of phenols and amines constitutes the chief topic of discussion in this chapter.
The Rosenmund Reduction of Acid Chlorides to Aldehydes
Authors: Mosettig Erich , Mozingo Ralph 
Published: March 2011

AbstractIn the synthesis of complex molecules, particularly in connection with natural products, it is occasionally desirable to prepare an aldehyde when the readily available starting material is the corresponding acid. The Rosenmund reduction is probably the most useful method for application to a large number of aldehdyes of varied types. The Rosenmund reduction consists in the selective hydrogenation of an acid chloride in the presence of a suitable catalyst, usually supported palladium to the corresponding aldehyde.
TheWolff‐Kishner Reduction
Authors: Todd David 
Published: March 2011

AbstractThe oxygen atom of the carbonyl group in aldehdyes and ketones can be replaced by hydrogen by heating the semicarbazone, the hydrazone, or the azine in the presence of an alkaline catalyst. This reaction is known as the Wolff‐Kishner reduction. Two slightly different variations of the method were discovered independently by Kishner in 1911 and by Wolff in 1912. Though the Kishner method has the advantage of avoiding the necessity of a sealed tube, the Wolff method has been modified to obviate both this necessity and that of isolating the intermediate carbonyl derivative. This reduction is the subject of this chapter.
Cyanoethylation*Present address, Industrial Rayon Corporation, Cleveland, Ohio.
Authors: Bruson Herman Alexander 
Published: March 2011

AbstractA variety of organic and inorganic compounds possessing labile hydrogen atoms add readily to acrylonitrile with the formation of molecules containing a cyanoethyl grouping. This reaction is commonly know as cyanoethylation and resembles closely a Michael type of reaction. The cyanoethylation except with certain amines usually require the presence of an alkaline catalysts, e.g., hydroxides, alkoxides, hydrides, etc. The strongly basic quarternary ammonium hydroxides are particularly effective. The cyanoethylation of certain amines require and acidic catalyst. Many of the reactions are exothermic and require cooling to prevent excessive polymerization of the acrylonitrile. Inert solvents are helpful. Typical compounds involved in this reaction are discussed.
Preparation of Aromatic Fluorine Compounds from Diazonium Fluoborates
Authors: Roe Arthur 
Published: March 2011

AbstractAn excellent method for the introduction of fluorine into the aromatic nucleus, described by Balz and Schiemann, has been extensively extended. The method involves two steps, first, the preparation and solution of a dry diazonium fluoborate, and second, the controlled decomposition of this salt by heat to yield an aromatic fluoride, nitrogen, and boron trifluoride. This phenomenon which makes possible, the Schiemann reaction is the remarkable stability of the dry diazonium borofluoride. The overall yields are satisfactory and no special apparatus is necessary. The reaction may be carried out on a wide variety of amines. The effect of the Schiemann reaction on other groups present in the ring is discussed in detail.
The Friedel and Crafts Reaction with Aliphatic Dibasic Acid Anhydrides
Authors: Berliner Ernst 
Published: March 2011

AbstractThe Friedel‐Crafts reaction between an aliphatic dibasic anhydride and an aromatic group results in the formation of an aroyl fatty acid with the aroyl group situated at the last carbon atom of an aliphatic chain. Since the lowest know dibasic anhydride is succinic anhydride, the number of methylene groups between the carboxyl group and the carbonyl group cannot be less than two. Since the time of the original reaction, it has been extended to include substituted succinic and maleic anhydride, glutaric anhydride, and the polymeric anhydrides of higher dibasic acids. Such as adipic acid or sebacic acid. The basic and extended reactions are discussed in this chapter.
The
G
attermann‐
K
och Reaction*Present address, Institute of Medical Research, The Christ Hospital, Cincinnati, Ohio.
Authors: Crounse Nathan N. 
Published: March 2011

Abstract
The introduction of an aldehyde group into certain aromatic nuclei by means of carbon monoxide, hydrogen chloride, and an appropriate catalyst is know as the Gatterman‐Koch reaction. The catalyst commonly used is aluminum chloride with cuprous chloride as a carrier. The carrier is not necessary when high pressure is used. Gatterman discovered the reaction when he tried to extend the Friedel‐Crafts reaction to the hypothetical formyl chloride.
TheHoesch Synthesis*Present address, Fuld Bros, Inc.
Authors: Spoerri Paul E. , DuBois Adrien S. 
Published: March 2011

AbstractThe Hoesch synthesis consists in the condensation of a nitrile with a phenol, a polyhydric phenol, or a phenolic ether to form a hydroxyaryl or alkoxyaryl ketone. Usually, equimolar quantities of the reactants are dissolved in dry ether, preferably in the presence of a catalyst such as zinc chloride and dry hydrogen chloride is introduced. When phenols are used, imino ether hydrochlorides are sometimes formed as by‐products and represent the only product of the reaction. The Hoesch synthesis has proved to be the most convenient synthetic method for certain polyhydroxyacylphenones and polyhydroxybenzophenones. Among these hydroxy ketones are anthelmintics, antidiarrhetics, and antiseptics. Extensions of the Hoesch synthesis are covered in this chapter.
The
S
tobbe Condensation
Authors: Johnson William S. , Daub Guido H. 
Published: March 2011

Abstract
In 1893, Stobbe demonstrated that when a mixture of acetone and diethyl succinate was treated with sodium ethoxide the expected acetoacetic ester type of condensation to give beta‐diketo compound did not take place. The reaction of aldehydes or ketones with an ester of succinic acid to form alkylidenesuccinic acid, or isomers formed by a tautomeric shift of hydrogen, is known as the Stobbe condensation. One mole of metal alkoxide is required per mole of carbonyl compound and ester, and the primary product is the salt of the half‐ester.
The Preparation of 3,4‐Dihydroisoquinolines and Related Compounds by theBischler‐Napieralski Reaction
Authors: Whaley Wilson M. , Govindachari Tuticorin R. 
Published: March 2011

AbstractThe frequent occurrence of the isoquinoline nucleus in alkaloids has led to considerable interest in the synthesis of isoquinolone derivatives. Many methods have been developed, but only three have enjoyed popularity. One of them, the Bischler‐Napieralski reaction is discussed in this chapter. The reaction consists in the cyclodehydration of beta‐phenethylamides to 3,4‐dihydroisoquinolines by heating to high temperatures with phosphorus pentoxide or anhydrous zinc chloride. Yields were not given for the original reaction, but later studies proved that the yields were low. Modifications using lower temperatures and milder condensing agents improved the reaction. The most important variation was introduced by Picet and Gams, which eliminates the dehydrogenation step. The classical synthesis of papaverine by Pictet and Gams is discussed.
ThePictet‐Spengler Synthesis of Tetrahydroisoquinolines and Related Compounds
Authors: Whaley Wilson M. , Govindachari Tuticorin R. 
Published: March 2011

AbstractThe Pictet‐Spengler reaction, in its simplest form, consists in the condensation of a beta‐arylethylamine with a carbonyl compound to yield a tetrahydroisoquinolone and is a special example of the Mannich reaction. The condensation of phenethylamine with methylal in concentrated hydrochloric acid to form 1,2,3,4‐tetrahydroisoquinoline was achieved in 1911 by Pictet and Spengler. Their reaction has been applied to the synthesis of other ring systems. The theory that proteins are the parent substances of alkaloids was tested by Pictet, who heated casein with methylal and hydrochloric acid, obtaining a mixture of pyridine and isoquinoline bases. Most of the products were not definitely identified.
The Synthesis of Isoquinolines by the
P
omeranz‐
F
ritsch Reaction
Authors: Gensler Walter J. 
Published: March 2011

Abstract
Acid‐catalyzed cyclization of benzalaminoacetal results in the formation of the isoquinoline nucleus. This reaction, first reported by Pomeranz and Fritsch, has been used in the synthesis of a variety of isoquinoline compounds. The process is carried out in two stages. In step one, a condensation leads to the benzalaminacetal. In step two, a ring closure leads to the isoquinoline. An alternative route involves the condensation of the corresponding benzylamine witth glyoxal semiacetal. The yield of isoquinoline products varies widely. The Pomeranz‐Fritsch synthesis offers the possibility of preparing isoquinolines with the substituent groups in an orientation difficult to achieve with other methods.
The Oppenauer Oxidation
Authors: Djerassi Carl 
Published: March 2011

AbstractThe application of the reduction of aldehdyes and ketones has been reviewed in an earlier chapter (The Meerwin‐Pondorff‐Verley reduction). The reversible nature of the reaction was demonstrated by Verley, but it was not until 1937 that Oppenauer showed that unsaturated steroid alcohols could be oxidized to the corresoponding ketones in excellent yield using aluminum t‐butoxide. In the presence of a large amount of acetones. Acetone functions as the hydrogen acceptor and the large excess serves to shift the equilibrium into the desired direction. This reaction is called the Oppenauer reaction hand is useful in steroid chemistry. The Oppenauer oxidation employs mild conditions so it will undoubtedly find use in synthetic organic chemistry. The recent experimental modifications are discussed here.