bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Smiles and Related Rearrangements of Aromatic Systems
Authors: Truce William E. , Kreider Eunice M. , Brand William W. 
Published: March 2011

Abstract
In 1894, Henriques reported that bis(2‐hydroxy‐1‐naphthyl) sulfide was converted to an isomeric dibasic substance by treatment with alkaline ferricyanide and a subsequent reduction of the intermediate obtained. Hinsberg carried out a similar sequence of reactions with bis(2‐hydroxy 1 naphthyl) sulfone. The structures of the isomeric products of the two series were established by Smiles who recognized the occurrence of a novel intramolecular nucleophilic rearrangement.
This chapter surveys the reactions, which because of the extensive work of Smiles, have been called Smiles rearrangements. They may be characterized as intramolecular displacements at aromatic rings initiated by nucleophilic centers located two or three atoms distant from the functional group which is displaced.
The Reactions of Diazoacetic Esters with Alkenes, Alkynes, Heterocyclic and Aromatic Compounds
Authors: Dave Vinod , Warnhoff E. W. 
Published: March 2011

AbstractAfter the first unsuccessful attempt of Curtius in 1884 to affect the reaction of ethyl diazoacetate with toluene other researchers studied the reaction. Later, Buchner and Curtius treated several aromatic, olefinic, and acetylenic compounds with diazoacetic esters to form cyclopropanes. Since then the reactions of diazoacetates with various unsaturated compounds have been studied. The carbalkoxy carbenes are of interest since they are believed to be intermediates in higher temperature thermal and photochemical reactions of diazoacetates.
The Base‐Promoted Rearrangements of Quaternary Ammonium Salts
Authors: Pine Stanley H. 
Published: March 2011

AbstractThe based‐promoted rearrangements of quaternary ammonium salts can be divided into two categories. In the Stevens rearrangement one‐alkyl group migrates from the quaternary nitrogen group to the alpha carbon atom of a second alkyl group. The Somelet‐Hayser rearrangement involves migration to the ortho position of a benzyl quaternary ammonium salt. When structurally feasible, both rearrangements may occur simultaneously although experimental conditions markedly affect the competing pathways.
Conjugate Addition Reactions of Organocopper Reagents
Authors: Posner Gary H. 
Published: March 2011

AbstractAddition of an organometallic reagent to alpha,beta‐usaturated carbonyl compounds occurs in one or both of two modes: attack at the carbonyl function produces a 1,2 adduct, whereas reaction with the entire system gives a 1,4 adduct. Organoalkali metal reagents derived from unstabilized carbanions generally add across the carbonyl group, where as enolate and other stabilized anions usually undergo a Michael addition, introducing a carboalkyl group at the beta carbon. Grignard reagents normally give 1,2 adducts. The wide scope of these reagents has made conjugate addition of alkyl and aryl groups a useful reaction in organic synthesis. Copper‐promoted conjugate additions were generally effected by allowing an organomagnesium reagent and a alpha, beta‐ unsaturated carbonyl compound to react in the presence of a catalytic amount of copper salt. Studies since 1966 have shown that stoichiometric organocopper reagents in addition to their broad utility in coupling reactions with organic halides and in reaction with other substrates undergo unusually effective conjugate addition to a wide variety alpha,beta‐ unsaturated carbonyl substrates. Emphasis in this chapter is on stoichiometric organic copper reagents. Mechanism, scope, limitations, synthetic utility, and optimal conditions are considered.
TheThiele‐Winter Acetoxylation of Quinones
Authors: McOmie J. F. W. , Blatchly J. M. 
Published: March 2011

AbstractIn 1898, Johannes Thiele described the reaction of p‐benzoquinone with acetic acid in the presence of a small quantity of sulfuric acid to give 1,2,4‐triacetoxybenzene in 80% yield. Later Thiele and Winter described further experiments that showed both 1,2‐ and 1,4‐naphthoquinone gave 1,2,4‐triacetoxynaphthalene and that the same product was obtained when sulfuric acid was replaced by zinc chloride. Thiele‐Winter acetoxylation can be defined as the acid‐catalyzed reactions of quinones with acetic acid to give triacetoxy aromatic compounds. This reaction has been carried out on a large number of quinones and to this point there has been no review. Very little work has been done on the reaction of quinones with anhydrides other than acetic anhydride. Results of these studies are summarized. Reactions with other anhydrides are discussed.
Cyclopropanes from Unsaturated Compounds, Methylene Iodide, and Zinc‐Copper Couple
Authors: Simmons Howard E. , Cairns Theodore L. , Vladuchick Susan A. , Hoiness Connie M. 
Published: March 2011

AbstractThe reaction of the organozinc reagent prepared from methylene iodide and zinc‐copper couple with substituted unsaturated compounds has proved to be a versatile and convenient method for the synthesis of cyclopropanes. The synthesis is stereospecific with regard to the stereochemistry of the unsaturated compound and is usually free from serious side reactions; it can be carried out under mild conditions in diethyl and affords cyclopropanes often in good yields. This method can be easily adapted to large‐scale preparations. Two useful variations of the cyclopropanation reaction have appeared which involve the same or a similar organozinc intermediate: (1) diazomethane reacts with iodide in ether to form a reagent which converts unsaturated compounds to cyclopropanes; (2) methlyene iodide and diethyl zinc react in ether in the presence of unsaturated compounds to cyclopropanes. Processes are known in which a divalent carbon fragment adds to carbon‐carbon double bonds either as a free carbene or as an organometallic complex.
The Zinin Reduction of Nitroarenes
Authors: Porter H. K. 
Published: March 2011

AbstractThe Zinin reduction is a method for the reduction of nitroarenes by negative divalent sulfur. This versatile reaction can be carried out in the laboratory and for plant‐scale manufacture of aromatic amines when other reduction media are destructive to sensitive compounds or result in undesired side reactions. The first reaction, used by Zinin, was to prepare aniline from nitrobenzene. It has been of great importance in the preparation of aromatic amines. Refinements in technique and a better understanding of the reaction mechanism should make this method attractive for the preparation of a variety of amines.
Fluorination by Sulfur Tetrafluoride
Authors: Boswell G. A. , Ripka W. C. , Scribner R. M. , Tullock C. W. 
Published: March 2011

AbstractAlthough sulfur tetrafluoride is a remarkably versatile agent for selectively introducing fluorine atoms into organic compounds, its existence was doubted as late as 1950. A colorless gas boiling at ‐38o C, sulfur tetrafluoride was probably first made by treatment of sulfur with uranium hexafluoride and subsequently by the reaction of sulfur with cobalt(III) fluoride. Both products were of questionable purity. In 1950 sulfur tetrafluoride was unequivocally synthesized by electrical decomposition of trifluormethylsulfur pentafluoride. It was not until 1955 that gram amounts were prepared and thus making sulfur tetrafluoride a viable compound. This led the way for the discovery of its remarkable fluorinating ability. The ability of sulfur tetrafluoride to replace carbonyl oxygen selectively is probably the most useful synthetic application.
Modern Methods to Prepare Monofluoroaliphatic Compounds
Authors: Sharts Clay M. , Sheppard William A. 
Published: March 2011

AbstractOrganic fluorine chemistry has been important since the 1930s. The development of fluorine chemistry during World War II is well documented. Fluorine chemistry emerged in the 1950s because of three events:Large‐scale research designed to synthesize fluorine‐containing rockets was initiated.A fluorine atom at a specific site in a steroid molecule was found to enhance beneficial pharmacological effectsNew analytical techniques evolved (e.g., GC and NMR).There are eight reactions important for preparation of monofluoroaliphatic compounds.Halogen addition to alkenes and alkynesFluoroalkylamine reagent for replacement of a hydoxy group.Nitrosyl fluoride addition to an activated double bondHypofluorites for electrophilic fluorination.Inorganic and heteroatom fluorides for replacement of halogen, hydroxyl, or ester groupsHydrogen fluoride for additionPerchloryl fluoride for hydrogen replacementCondensation of a monolfluorinated organic compound.
Clemmensen Reduction of Ketones in Anhydrous Organic Solvents
Authors: Vedejs E. 
Published: March 2011

AbstractThe Clemmensen reduction of ketones and aldehydes using zinc and hydrochloric acid is the simplest direct method for converting the carbonyl group into a methylene group. Typically the carbonyl is refluxed for several hours with 40% hydrochloric acid, amalgamated zinc, and a water‐immiscible organic solvent such as tolurene. Because of these harsh conditions, reports of successful Clemmensen reduction of polyfunctional ketones have been rare. A milder procedure using dry hydrogen chloride in organic solvent extends the potential of this reaction. Other developments that define scope of both aqueous and anhydrous reduction conditions are discussed and an effort is made to compare the properties of possible reduction intermediates with other organozinc species.
The Acyloin Condensation
Authors: Bloomfield Jordan J. , Owsley Dennis C. , Nelke Janice M. 
Published: March 2011

AbstractThe acyloin condensation usually involves the reductive dimerization of a carboxylic ester, although acid chlorides and the anhydrides have been used. The reducing agent is in an alkali metal and the product is an ene‐diolate. Two gram‐atoms of metal are required for each mole of ester with the concomitant formation of a mole of akoxide and one‐half mole of the ene‐diolate. Oxidation of acyloins to diketoes can be accomplished by a variety of reagents. Acyloins can be reduced to ketones by various modifications of the Clemmenson technique. Under mild conditions the ketone will dominate. This chapter presents a complete picture of both the linear and cyclic acyloin condensation with particular emphasis on developments since 1960. The discussion is closely limited to the acyloin condensation and its modifications.
Alkenes from Tosylhydrazones
Authors: Shapiro Robert H. 
Published: March 2011

AbstractIn 1952, Bamford and Stevens observed that tosylhydrazones of aliphatic ketones yielded alkenes when treated with the sodium salt of ethylene glycol in boiling ethylene glycol. In addition to the alkene, molecular nitrogen, and p‐toluenesulfinate anion were produced. This chapter reviews such syntheses of alkenes from tosylhydrazones and the formation of cyclopropanes and acetylenes from tosylhydrazones because the several reactions involved are so closely interrelated. The four major reaction types are reviewed here: (1) base‐induced decomposition of tosylhydrazones in protic solvents and (2) in aprotic solvents (3) reactions of tosylhydrazones with alkyllithium reagents and (4) fragmentation reactions of alpha, beta‐epoxytosylhydrazones and analogous systems. Reactions 1 and 2 are called the protic and aprotic Bamford‐Stevens reaction.
Ester Cleavages
via
S

N

2‐Type Dealkylation
Authors: Mc Murry John 
Published: March 2011

Abstract
The cleavage of esters to furnish carboxylic acids is a common organic transformation that is usually carried out in a routine manner by acidic or basic hydrolysis. It often happens, however, particularly in the synthesis of natural products, that the substrate ester is sensitive to hydrolytic conditions. For such sensitive materials a number of mild, neutral methods of ester cleavage have been devised. Those methods that occur with displacement of carboxylate by SN2 dealkylation are the subject of this chapter.
Arylation of Unsaturated Compounds by Diazonium Salts (The
M
eerwein Arylation Reaction)
Authors: Rondestvedt Christian S. 
Published: March 2011

Abstract
The arylation of unsaturated compounds by diazonium salts with copper salt catalysis was first disclosed by Meerwein. Meerwein arylation proceeds best when the double bond is activated by an electron attracting groups such as carbonyl, cyano, aryl, vinyl, ethynyl or chloro. The net result is the union of the aryl group with the carbon atom beta to the activating group, either by substitution of a beta‐hydrogen atom of by addition of Ar and Cl to the double bond. The generally accepted mechanism of the reaction involves the aryl radical from the diazonium salt, though the manner of its formation and subsequent reaction is still controversial
Practical aspects of the oral new anticoagulants
Authors: DeLoughery Thomas G. 
Published: March 2011

AbstractAfter years of only oral vitamin K antagonists, there are new many new antithrombotic agents in development and on entering the marketplace. This review will analyze clinical trial results for these new agents—especially dibigatran, rivaroxaban, and apixiban. Also to be discussed are practical aspects of use of these new agents such monitoring, reversal, and use before procedures. Am. J. Hematol. 2011. © 2011 Wiley‐Liss, Inc.
Laboratory testing for cryoglobulins
Authors: Motyckova Gabriela , Murali Mandakolathur 
Published: March 2011

AbstractCryoglobulins are immunoglobulins that precipitate below 37°C and can cause multiorgan damage. There are three types of cryoglobulins: Type I (also called simple), which is mostly associated with monoclonal gammopathy and/or other hematologic disorders and Type II and Type III (known as mixed cryoglobulins), which are associated with infectious and systemic diseases. Testing for cryoglobulins is complicated by lack of reference range, standards, and stringency in maintaining testing temperature conditions. Identification of cryoprecipitate can be critical for patient care; therefore, correct testing conditions are crucial for reliable cryoglobulin testing. The patient's blood sample should be kept at 37°C initially to avoid premature precipitation of cryoglobulins and thereby decreasing the yield for subsequent identification. This could cause a false negative result. After warm centrifugation or warm cell precipitation, the clear serum is observed at 4°C for formation of cryoprecipitate. The cryoprecipitate is then washed in cold buffer, and the resulting precipitate is warmed to 37°C and subjected to further analysis by immunodiffusion and immunofixation. In addition to Meltzer's triad of purpura, weakness and arthralgias, cryoglobulinemias have protean manifestations involving skin, joints, kidney, nervous system, as well as the hematopoietic system. The management of cryoglobulinemia especially in patients with organ damage remains difficult. Treatment of cryoglobulinemia focuses on management of the underlying lymphoproliferative disorder or infectious or systemic causes. Medical management may also include corticosteroids and other immunosuppressive agents and plasmapheresis. Rituximab therapy seems to abrogate the aberrant B cell response. Am. J.Hematol. 86:500–502, 2011. © 2011 Wiley‐Liss, Inc.
No significant improvement in the outcome of patients with Waldenström's macroglobulinemia treated over the last 25 years
Authors: Kastritis Efstathios , Kyrtsonis Marie‐Christine , Hatjiharissi Evdoxia , Symeonidis Argiris , Michalis Eurydiki , Repoussis Panagiotis , Tsatalas Konstantinos , Michael Michael , Sioni Anastasia , Kartasis Zafiris , Stefanoudaki Ekaterini , Voulgarelis Michael , Delimpasi Sosana , Gavriatopoulou Maria , Koulieris Efstathios , Gika Dimitra , Vervesou Elissavet , Konstantopoulos Konstantinos , Kokkini Garyfalia , Zomas Athanasios , Roussou Paraskevi , Anagnostopoulos Nikolaos , Economopoulos Theofanis , Terpos Evangelos , Zervas Konstantinos , Dimopoulos Meletios A. 
Published: March 2011

AbstractThe treatment of Waldenström's macroglobulinemia (WM) has changed over the last decades, mainly because of the introduction of nucleoside analogues and of rituximab while novel agents such as bortezomib have been recently introduced. We performed an analysis to investigate whether the outcome of patients with WM has improved over the last years, compared to that of patients who started treatment before new drugs became widely available, especially as part of the frontline treatment. We analyzed 345 symptomatic patients with WM: 130 who initiated treatment before and 215 who started treatment after January 1, 2000. Patients who started treatment in the latter group were older and had more often elevated beta2‐microglobulin but the other characteristics were similar between the two groups. Most patients who started treatment before January 1, 2000 were treated upfront with alkylating agent‐based regimens and most patients who started treatment after January 1, 2000 received rituximab‐based regimens as initial treatment. Objective response (63 and 59%, respectively) and median overall survival, OS, (106.5 months for Group A and is estimated at 94 months for Group B, P = 0.327) were similar. There was also no difference regarding OS or cause specific survival (CSS) in each risk group according to IPSSWM. Our observation may be explained by the indolent course of WM in several patients and by the lack of profound cytoreduction in patients with high‐risk disease. Possible differences in the 15‐ or 20‐year survival rate between the two groups may be detected with further follow‐up of these patients. Am. J. Hematol. 2011. © 2011 Wiley‐Liss, Inc.
Integration of field and captive studies for understanding the behavioral ecology of the squirrel monkey (Saimirisp.)
Authors: Zimbler‐DeLorenzo Heather S. , Stone Anita I. 
Published: March 2011

AbstractCaptive and field studies both provide valuable and complementary information that lead to a better understanding of a species' behavioral ecology. Here, we review studies from wild, captive, and semi‐free ranging populations of squirrel monkeys (Saimirisp.), in order to (a) provide a more current (1985–2010) review ofSaimiribehavioral ecology and (b) illustrate that integrating data collected in a variety of settings is an effective approach to addressing ecological questions in primates. Captive environments, such as zoological facilities and research colonies, can be advantageous to researchers by allowing longitudinal studies of behavior and reproduction, as well as providing opportunities for gathering data on life history, because physiological and life history data are known for individual animals. Studies of field populations can provide contextual information regarding the adaptive nature of behaviors that are studied in captivity. Squirrel monkeys are small, neotropical primates that have extensively been used in captive research. As the last in‐depth review ofSaimiribiology was published in 1985 [Rosenblum & Coe, The squirrel monkey. New York: Academic Press], we review studies since conducted onSaimiriecology, life history, social behavior, reproduction, and conservation. Our review indicates that there is much variation in socioecology and life history traits betweenSaimirispecies and, surprisingly, also between populations of the same species studied at different locales. In addition, much is known about squirrel monkey reproductive physiology, basic ecology, and vocal communication, but data are still lacking in the fields of life history and some adaptive components and social behavior. In particular, longitudinal studies in the field would be particularly relevant for a genus with a slow life history such asSaimiri. Finally, few data (captive or wild) are available onS. ustusandS. vanzolinii, though at least one of these species is threatened. Am. J. Primatol. 73:607–622, 2011. © 2011 Wiley‐Liss, Inc.
Iron(III), cobalt(II) and copper(II) complexes bearing 8‐quinolinol encapsulated in zeoliteY for the aerobic oxidation of styrene
Authors: Yang Ying , Ding Hong , Hao Shijie , Zhang Ying , Kan Qiubin 
Published: March 2011

AbstractA series of Fe(III), Co(II) and Cu(II) complexes of 8‐quinolinol were encapsulated into the supercages of zeoliteY and characterized by X‐ray diffraction, SEM, N2 adsorption/desorption, FT‐IR, UV–vis spectroscopy, elemental analysis, ICP‐AES and TG/DSC measurements. The encapsulation was achieved by a flexible ligand method in which the transition metal cations were first ion‐exchanged into zeolite Y and then complexed with 8‐quinolinol ligand. The metal‐exchanged zeolites, metal complexes encapsulated in zeolite–Y plus non‐encapsulated homogeneous counterparts were all screened as catalysts for the aerobic oxidation of styrene under mild conditions. It was found that the encapsulated complexes always showed better activity than their respective non‐encapsulated counterparts. Moreover, the encapsulated iron complex showed good recoverability without significant loss of activity and selectivity within successive runs. Heterogeneity test for this catalyst confirmed its high stability against leaching of active complex species into solution. Copyright © 2011 John Wiley & Sons, Ltd.
Adsorption of Remazol Brilliant Violet‐5R reactive dye from aqueous solution by cocoa pod husk‐based activated carbon: kinetic, equilibrium and thermodynamic studies
Authors: Bello Olugbenga Solomon , Siang Tan Tong , Ahmad Mohd Azmier 
Published: March 2011

ABSTRACTThe adsorption of Remazol Brilliant Violet‐5R (RBV‐5R) reactive dye on cocoa pod husk activated carbon (CPHAC) was investigated in batch process. The effects of initial dye concentration, contact time, solution temperature and pH were evaluated. The equilibrium data were fitted into Langmuir, Freundlich, Temkin and Dubinin‐Radushkevich isotherm models. It was found that Freundlich model fitted the adsorption data most. The kinetic data were fitted into pseudo‐first‐order, pseudo‐second‐order, Elovich and intraparticle diffusion models. Adsorption of RBV‐5R dye on CPHAC was best described by pseudo‐second‐order kinetic model. The adsorption of RBV‐5R dye was favored at acidic pH. Thermodynamic parameters such as standard free energy ΔG0, standard enthalpy ΔH0 and standard entropy ΔS0 were calculated. The adsorption interaction of RBV‐5R reactive dye on the adsorbent was found to be feasible, spontaneous and endothermic. The adsorption process followed a physisorption mechanism. © 2011 Curtin University of Technology and John Wiley & Sons, Ltd.