bluuebunny/crossref_metadata_2025 huggingface dataset:
Resource Allocation After a Nuclear Detonation Incident: Unaltered Standards of Ethical Decision Making
Authors: Caro J. Jaime , DeRenzo Evan G. , Coleman C. Norman , Weinstock David M. , Knebel Ann R.
Published: March 2011

This article provides practical ethical guidance for clinicians making decisions after a nuclear detonation, in advance of the full establishment of a coordinated response. We argue that the utilitarian maxim of the greatest good for the greatest number, interpreted only as “the most lives saved,” needs refinement. We take the philosophical position that utilitarian efficiency should be tempered by the principle of fairness in making decisions about providing lifesaving interventions and palliation. The most practical way to achieve these goals is to mirror the ethical precepts of routine clinical practice, in which 3 factors govern resource allocation: order of presentation, patient's medical need, and effectiveness of an intervention. Although these basic ethical standards do not change, priority is given in a crisis to those at highest need in whom interventions are expected to be effective. If available resources will not be effective in meeting the need, then it is unfair to expend them and they should be allocated to another patient with high need and greater expectation for survival if treated. As shortage becomes critical, thresholds for intervention become more stringent. Although the focus of providers will be on the victims of the event, the needs of patients already receiving care before the detonation also must be considered. Those not allocated intervention must still be provided as much appropriate comfort, assistance, relief of symptoms, and explanations as possible, given the available resources. Reassessment of patients' clinical status and priority for intervention also should be conducted with regularity.

(Disaster Med Public Health Preparedness. 2011;5:S46-S53)
Using the Model of Resource and Time-Based Triage (MORTT) to Guide Scarce Resource Allocation in the Aftermath of a Nuclear Detonation
Authors: Casagrande Rocco , Wills Nick , Kramer Elizabeth , Sumner Louise , Mussante Mark , Kurinsky Rachel , McGhee Patrick , Katz Luba , Weinstock David M. , Coleman C. Norman
Published: March 2011

Conventional triage algorithms assume unlimited medical resource availability. After a nuclear detonation, medical resources are likely to be particularly limited, suggesting that conventional triage algorithms need to be rethought. To test various hypotheses related to the prioritization of victims in this setting, we developed the model of resource- and time-based triage (MORTT). This model uses information on time to death, probability of survival if treated and if untreated, and time to treat various types of traumatic injuries in an agent-based model in which the time of medical practitioners or materials can be limited. In this embodiment, MORTT focuses solely on triage for surgical procedures in the first 48 hours after a nuclear detonation. MORTT determines the impact on survival based on user-selected prioritization of victims by severity or type of injury. Using MORTT, we found that in poorly resourced settings, prioritizing victims with moderate life-threatening injuries over victims with severe life-threatening injuries saves more lives and reduces demand for intensive care, which is likely to outstrip local and national capacity. Furthermore, more lives would be saved if victims with combined injury (ie, trauma plus radiation >2 Gy) are prioritized after nonirradiated victims with similar trauma.

(Disaster Med Public Health Preparedness. 2011;5:S98-S110)
Legal Considerations in a Nuclear Detonation
Authors: Sherman Susan E.
Published: March 2011

This article summarizes public health legal issues that need to be considered in preparing for and responding to nuclear detonation. Laws at the federal, state, territorial, local, tribal, and community levels can have a significant impact on the response to an emergency involving a nuclear detonation and the allocation of scarce resources for affected populations. An understanding of the breadth of these laws, the application of federal, state, and local law, and how each may change in an emergency, is critical to an effective response. Laws can vary from 1 geographic area to the next and may vary in an emergency, affording waivers or other extraordinary actions under federal, state, or local emergency powers. Public health legal requirements that are commonly of concern and should be examined for flexibility, reciprocity, and emergency exceptions include liability protections for providers; licensing and credentialing of providers; consent and privacy protections for patients; occupational safety and employment protections for providers; procedures for obtaining and distributing medical countermeasures and supplies; property use, condemnation, and protection; restrictions on movement of individuals in an emergency area; law enforcement; and reimbursement for care.

(Disaster Med Public Health Preparedness. 2011;5:S65-S72)
Tracking Deaths Related to Hurricane Ike, Texas, 2008
Authors: Zane David F. , Bayleyegn Tesfaye M. , Hellsten John , Beal Ryan , Beasley Crystal , Haywood Tracy , Wiltz-Beckham Dana , Wolkin Amy F.
Published: March 2011

Background: On September 13, 2008, Hurricane Ike, a category 2 storm with maximum sustained winds of 110 mph, made landfall near Galveston, Texas. Ike produced a damaging, destructive, and deadly storm surge across the upper Texas and southwestern Louisiana coasts. Thirty-four Texas counties were declared disaster areas by the Federal Emergency Management Agency; 15 counties were under mandatory evacuation orders. To describe causes of death associated with this hurricane and identify prevention strategies during the response and recovery phases, the Texas Department of State Health Services (DSHS) monitored mortality data in 44 counties throughout the state. This report summarizes Ike-related deaths reported by Texas medical examiners, justices of the peace (coroners), forensic centers, public health officials, and hospitals.

Methods: Based on the Centers for Disease Control and Prevention (CDC) disaster-related mortality surveillance form, DSHS developed a state-specific 1-page form and collected (optimally daily) data on demographic, date and place of death, and cause and circumstance of deaths. A case was defined as any death that was directly or indirectly related to Ike among evacuees, residents, nonresidents, or rescue personnel in the declared disaster counties, counties along the Texas Gulf coast or counties known to have evacuation shelters occurring September 8, 2008, through October 13, 2008. Analyzed data were shared with the state emergency operation center and the CDC on a daily basis.

Results: The surveillance identified 74 deaths in Texas as directly (10 [14%]), indirectly (49 [66%]), or possibly (15 [20%]) related to Ike. The majority of deaths (n = 57) were reported by medical examiners. Deaths occurred in 16 counties of the 44 counties covered by the surveillance. The majority of deaths occurred in Harris and Galveston (28 [38%] and 17 [23%]), respectively. The deceased ranged in age from younger than 1 year to 85 years, with an average age of 46 years (median 50 years); 70% were male. Of the 74 deaths, 47 (64%) resulted from injuries, 23 (31%) from illnesses, and 4 (5%) were undetermined. Among the injuries, carbon monoxide poisoning (13 [18%]) and drowning (8 [11%]) were the leading causes of injury-related deaths. Cardiovascular failure (12 [16%]) was the leading cause of illness-related deaths.

Conclusions: Defining the relation of death to hurricane using an active mortality surveillance system is possible. The active mortality surveillance form used in Ike provided valuable daily information to DSHS, state emergency management officials, and the CDC regarding the characteristics of deaths in the state. Most of the Ike-related deaths were caused by injury (direct and indirectly related) such as carbon monoxide poisonings and drowning and may have been preventable by educating the public.

(Disaster Med Public Health Preparedness. 2011;5:23-28)
Assessment of the Efficacy of the First Water System for Emergency Hospital Use
Authors: Long Sharon C. , Olstadt Jeremy
Published: March 2011

Objective: The First Water Responder B package water treatment device was evaluated for its ability to reduce the levels of spiked indicators and pathogens (Escherichia coli, MS2 coliphage, murine adenovirus, and Cryptosporidium oocysts) in a surface water to partially evaluate its appropriateness to be used to provide safe drinking water to hospitals during emergency situations.

Methods: Lake water was collected in 50-L carboys and spiked with selected indicators and pathogens (E coli, MS2 coliphage, murine adenovirus, and Cryptosporidium oocysts) at 2 different spike levels (low and high). This water was treated using the First Water Responder B, and the microorganisms were enumerated before and after treatment using US Environmental Protection Agency and Standard Methods. Microbial removal efficiencies were compared with Environmental Protection Agency guidelines.

Results:E coli spikes ranged from 2.9 to 1059 colony-forming units (CFU)/100 mL with removals to below detection limits (1 CFU/100 mL) to 2.8 CFU/100 mL or 0.98 to 3.5 log10 reductions. MS2 coliphage spikes ranged from 3 plaque-forming units (PFU) to 837 PFU/100 mL with removals to below detection limits (1 PFU/100 mL) to 11.7 PFU/100 mL or 0.65 to 1.9 log10 reductions. Murine adenovirus spikes ranged from 203 to 8410 most probable number (MPN) of infectious units/100 mL with removals to below detection limits (23 MPN infectious units/100 mL) to 1370 MPN infectious units/100 mL or 0.79 to >1.2 log10 reductions. Cryptosporidium parvum oocyst spikes ranged from 52 to 853 oocysts per liter with removals to below detection limits (<1 oocyst per liter) to 0.3 oocysts per liter or >2.2 to 3.4 log10 reductions.

Conclusions: Although the First Water system could remove a significant portion of the spiked organisms, it is recommended that this point-of-use system be coupled with chemical disinfection in a multiple-barrier approach to provide water of the highest reasonably achievable quality for hospital use in emergency situations.

(Disaster Med Public Health Preparedness. 2011;5:29-36)
The
A
rndt‐
E
istert Synthesis
Authors: Bachmann W. E. , Struve W. S.
Published: March 2011

The Arndt‐Eistert synthesis is a procedure for converting an acid to its next highest homolog or to a derivative of the homologous acid, and an ester and an amide. The synthesis, which is applicable to both, aliphatic and aromatic acids involves the following three operations; formation of the acid chloride; reaction of the acid chloride with diazomethane to yield a diazoketone; and rearrangement of the diazoketone in the presence of suitable reagents and a catalyst (colloidal silver, platinum, copper). An acid is formed in the presence of water, and ester is produced in an alcohol, and am amide results when ammonia or an amine is used.
Chloromethylation of Aromatic Compounds
Authors: Fuson Reynold C. , McKeever C. H.
Published: March 2011

The replacement of a hydrogen atom by a chloromethyl group in a single operation has come to be known as chloromethylation. The process is illustrated by its earliest example, a synthesis of benzyl chloride carried out by Grassi and Maselli. This chapter is limited to nuclear chloromethylation of aromatic compounds. Typical procedures are given and an attempt is made to indicate the scope and limitations of the reaction.
The
B
ucherer Reaction
Authors: Drake Nathan L.
Published: March 2011

The Bucherer reaction is the reversible conversion of a naphthylamine to a naphthol in the presence of an aqueous sulfite or bisulfite. It has proved to be of value in the synthesis of naphthalene derivatives, particularly in the manufacture of dye intermediates. In certain instances it is conveniently used in the preparation of naphthols from naphthylamines, in others it is employed for the reverse transformation, the synthesis of naphthylamine from naphthols. A second reaction has been extended to the synthesis of certain alkyl and aryl aminonaphthalenes.
TheElbs Reaction
Authors: Fieser Louis F.
Published: March 2011

Diaryl ketones having a methyl or methylene substituent adjacent to the carbonyl group often suffer cyclodehydration when submitted to pyrolysis and afford a certain amount of the corresponding anthracene derivative. The reaction is usually carried out by heating the ketone without catalyst or solvent at the reflux temperature or at a temperature in the range of 400‐450 degrees until the water is no longer evolved. The main hydrocarbon reaction product may not be that normally expected based on the starting material. A product of the Elbe condensation usually require extensive purification. The mechanism of the condensation is not known.
TheClemmensen Reduction
Authors: Martin Elmore L.
Published: March 2011

The replacement of the oxygen atoms of the carbonyl group in an aldehyde or ketone by two hydrogen atoms through the use of amalgamated zinc and hydrochloric acid was first employed in 1913 by Clemmensen and is know as the Clemmensen method of reduction. The process has been applied to a large number of aldehydes and ketones as a step in the synthesis of polynuclear hydrocarbons and alkylated aromatic compounds. It has also played an important role in the elucidation of the structures of highly complex natural products. The wide use of this method has resulted in the development of several modifications of the original procedure.
The Acetoacetic Ester Condensation and Certain Related Reactions
Authors: Hauser Charles R. , Hudson Boyd E.
Published: March 2011

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.
The
M
annich Reaction
Authors: Blicke F. F.
Published: March 2011

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

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

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

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

The 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

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

The 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

Arsonic 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

Since 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

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

This 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

In 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

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

The 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

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

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

Benzoins 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

p‐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

In 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

The 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

A 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

An 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

The 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

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

The 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

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

The 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

The 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

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

The 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.
The Halogen‐Metal Interconversion Reaction with Organolithium Compounds
Authors: Jones Reuben G. , Gilman Henry
Published: March 2011

The reaction of an organic halide with an organometallic compound in which the metal and the halogen atoms exchange laces is known as the halogen‐metal interconversion reaction. Numerous studies have established the fact that the halogen‐lithium interconversion is a general and widely applicable reaction. Many organic halides do not react satisfactorily with metallic lithium to form RLi compounds or with metallic magnesium to form Grignard reagents. However, the desired organolithium compound often can be obtained by a halogen‐metal Interconversion reaction. The halogen‐metal interconversion greatly extends the utility of organolithium and Grignard‐type reactions.
The Preparation of Thiazoles
Authors: Wiley Richard H. , England D. C. , Behr Lyell C.
Published: March 2011

Thiazoles have become increasingly important in pharmaceutical, biochemical and technical fields. Commercially important compounds that contain the thiazole ring are the mercaptothiazoles, which are valuable as rubber accelerators, and for penicillins and thiamin, for example. Certain thiazole derivatives show great promise as intermediates in the synthesis of amino acids. This chapter summarizes information on the methods of preparation of the thiazoles, but is restricted to those in which the thiazole ring is not part of a condensed system.
Reductions by Lithium Aluminum Hydride
Authors: Brown Weldon G.
Published: March 2011

Lithium aluminum hydride is a useful and convenient reagent for the selective reduction of various polar functional groups. It is used in diethyl ether solution, less commonly in higher boiling ethers, following the conventional procedures for syntheses employing the Grignard reagents, which the hydride closely resembles in its general pattern of behavior. The reaction proceeds with extraordinary rapidity and is relatively free of side reactions. The types of organic compounds reduced by lithium aluminum hydride and the nature of the products are detailed in this chapter. Functional groups not reduced are discussed.
ThePechmann Reaction
Authors: Sethna Suresh , Phadke Ragini
Published: March 2011

H. v. Pechman found that coumarin derivatives are formed when malic acid or beta‐ketonic esters are condensed with phenols in the presence of concentrated sulfuric acid. This reaction is commonly known s the Pechmann reaction. It has found extensive use. Simonis and co‐workers used phosphorus pentaoxide as the condensing agent in place of sulfuric acid and demonstrated that with the same reactants chromones rather than coumarins resulted. The condensation of a phenol and beta‐ketonic ester in the presence of phosphorus pentaoxide is sometimes called the Simonis reaction, but it is actually a variation of the Pechmann reaction and is considered in this chapter. Other condensing agents that have been used, for example, are phosphorus oxychloride, phosphoric acid, zinc chloride and others. These are discussed in the chapter. By condensing appropriately substituted phenols and beta‐ketonic esters, coumarins can be synthesized with substituents either in the benzene nucleus in the heterocyclic ring or both. The course of this reaction depends on three factors; nature of the phenol, of the beta‐ketonic ester, and the condensing agent.
TheSkraup Synthesis of Quinolines
Authors: Manske Richard H. F. , Kulka Marshall
Published: March 2011

Konigs first synthesized quinoline in 1879 by passing allylaniline over heated litharge. Shortly after he prepared quinoline by heating the condensation product of aniline and acrolein, thus anticipating the classical Skraup synthesis. This synthesis involves a series of reactions brought about by heating a primary aromatic amine, in which at least one position ortho to the amino group is unsubstituted, with glycerol, sulfuric acid, and an oxidizing agent. The product is a quinoline containing only those substituents that were originally present in the aromatic amine. Quinolines substituted in the hetero ring may be obtained by a modified Skraup synthesis in which a substituted acrolein or a vinyl ketone is used in place of glycerol.
Hydrogenolysis of Benzyl Groups Attached to Oxygen, Nitrogen, or Sulfur
Authors: Hartung Walter H. , Simonoff Robert
Published: March 2011

The benzyl group and a variety of substituted benzyl groups attached to an oxygen atom as in alcohols, ethers, acetals, or esters; to an amino nitrogen atom; or to a sulfur atom in thio ethers may be removed as toluene, or the corresponding substituted toluene, by hydrogenolysis. Other chemical and catalytic methods have been employed to bring about these debenzylations. It is the purpose of this chapter to give illustrations of both types of debenzylations so that their usefulness may be appreciated.
Epoxidation and Hydroxylation of Ethylenic Compounds with Organic Peracids*One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.
Authors: Swern Daniel
Published: March 2011

Oxiranes and alpha‐glycols can be prepared from olefins by a variety of methods. One of the most important and generally applicable of these is the oxidation of ethylenic compounds with organic peracids. Depending on the peracid employed and/or operating conditions either an oxirane or an alpha‐glycol can be obtained in good yield. It is important to note that the oxidation step both in epoxidation and hydroxylation reactions with organic peracids is the conversion of the olefin to the oxirane.
Catalytic Hydrogenation of Esters to Alcohols
Authors: Adkins Homer
Published: March 2011

In the presence of suitable catalysts esters react with hydrogen to form alcohols. The reaction is reversible, the relative concentrations of esters and alcohols at equilibrium being determined by the temperature and particularly by the pressure of hydrogen. The conversion of esters to alcohols may proceed either by hydrogenation or by hydrogenolysis. There is no experimental basis for the choice of one hypothesis over another, the use of the term hydrogenation in this chapter is matter of convenience and does not imply a choice of mechanism. The catalyst most suitable for the preparation of alcohols from esters by reacting with hydrogen under pressure is copper chromium oxide. This chapter deals almost exclusively with this catalyst, However, certain other catalysts of limited usefulness are considered.
The Acylation of Ketones to Form β‐Diketones or β‐Keto Aldehydes
Authors: Hauser Charles R. , Swamer Frederic W. , Adams Joe T.
Published: March 2011

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.
TheSommelet Reaction
Authors: Angyal S. J.
Published: March 2011

The Sommelet reaction is the process whereby aldehydes are produced from alkyl halides by the action of hexamine. The reaction is essentially a conversion of an amine into an aldehyde, a process in itself that is not particularly useful because aldehydes are frequently more readily available than the corresponding primary amines, It is fortunate therefore that the required amines can be prepared by the interaction of alkyl halides with hexamine, i.e., with the same reagent that serves to convert the amines into aldehdyes, It is this combined form that was discovered by Sommelet.

The Sommelet reaction, when started with a halide, proceeds in three stages: (1) formation of a hexaminium salt; (2) hydrolysis of this salt to an amine and its methylene derivative; and (3) formation of an aldehdye (the Sommelet reaction proper).
The Synthesis of Aldehydes from Carboxylic Acids
Authors: Mosettig Erich
Published: March 2011

The Rosenmund reduction of acid chlorides to the corresponding aldehydes was discussed in volume 4 of this series. There are a number of other less direct methods by which carboxylic acids can be converted into aldehydes and the purpose of this chapter is to consider the more useful of these procedures. Three of these methods, the hydrolytic decomposition of Reissert's compounds, the method of Grundmann, and the reductive desulfurization of thiol esters require acid chlorides as intermediates and in the respect are competitive with the Rosenmund reduction of acid chlorides. In the fourth method method, the McFadyen and Stevens synthesis, acid chlorides may be used for the preparation of the intermediate acyl hydrazides. Two additional methods, (Sonn and Muller, and Stephen) are based on the intermediate imido chlorides. These methods listed appear to be the one ones developed to the point where further discussion is profitable.