Thiazole and its Derivatives. Part One

Автор(ы):Metzger J. V.
06.10.2007
Год изд.:1979
Описание: All discussion of chemical properties is complemented by tables in which all the known derivatives are inventoried and characterized by their usual physical properties. This information should be of particular value to organic chemists in identifying natural or synthetic thiazoles. Two brief chapters concern mesoionic thiazoles and selenazoles. Finally, an important chapter is devoted to cyanine dyes derived from thiazolium salts, completing some classical reviews on the subject and discussing recent developments in the studies of the reaction mechanisms involved in their synthesis.
Оглавление:
Thiazole and its Derivatives. Part One — обложка книги.
PART ONE
Introduction [1]
I. Properties and Reactions of Thiazole [5]
  J. V. METZGER and E. J. VINCENT, with the collaboration of J. CHOUTEAU and G. MILLE
II. Genera] Synthetic Methods for Thiazole and Thiazolium Salts [165]
  G. VERNIN
III. Alkyl, Aryl, Axalkyl, and Related Thiazole Derivatives [337]
  J. P. AUNE, H. J. M. DOU, and J. CROUSIER
IV. Thiazolecarboxylic Acids, Thiazolecarboxaldehydes, and Thiazolyl Ketones [519]
  R. MEYER
V. Halo- and Nitrothiazoles [565]
  L. FORLANI and P. E. TODESCO
Subject Index [587]

PART TWO
General Introduction to Protomeric Thiazoles
  M. CHANON
VI. Aminothiazoles and Their Derivatives
  R. BARONE, M. CHANON, and R. GALLO
VII. Mercaptothiazoles, Hydrorythiazoles, and Their Derivatives
  C. ROUSSEL, M. CHANON, and R. BARONE Subject Index

PART THREE
VIII. Mesoionic Thiazoles
  M. BEGTRUP and C. ROUSSEL
IX. Cyanine Dyes Derived from Thiazolmm Salts
  H. LARIVE and R. DENNILAULER
X. Selenazole and Derivatives
  R. GUGLIELMETTI
Subject Index Cumulative Author Index

I. Properties and Reactions of Thiazole [5]
      C. Rhodanine [19]
      D. 2-Mercaptothiazoie [21]
      E. 2-Aminothiazole [22]
    4. Preparation [24]
    5. Theoretical Model. Electronic Structure [26]
      A. Influence of Substituents [42]
  II. Physical Properties [45]
    1. Geometrical Structure [45]
    2. Ultraviolet Absorption Spectroscopy [46]
      A. Quaternary Sails [50]
      B. Phosphorescence Spectra [50]
    3. Photoelectron Spectroscopy [51]
    4. Infrared Absorption and Raman Diffusion [53]
      A. Numbering, Activity, and Nomenclature of ihe Vibrations [53]
      B. Assignments [56]
      C. Thiaaole Derivatives [63]
    5. Nuclear Magnetic Resonance [66]
    6. Mass Spectrometry [81]
    7. Electronic Paramagnetic Resonance Spectromeiry [84]
    8. Thermodynamic Data [85]
    9. Magnetic Susceptibility [89]
    10. Dipole Moment [89]
    11. Refracttvity [90]
  III. Chemical Reactivity [90]
    1. Theoretical Aspects [90]
    2. Basicity [91]
    3. Additions 10 the Thiazole Sysiem [94]
    4. Electrophilic Substitution [99]
    5. Free Radical Substitution [108]
    6. Nucleophiltc Substitution [113]
      A. Hydrogen-Deuterium Exchange Reactions [113]
      B. Hydrogen-Metal Exchange Reactions [119]
      C. Nucleophilic Animation [124]
    7. Thiazole as an Electron Donor [125]
      A. Quaternary ThiazoHum Salts Formation [125]
      B. Thiazole Complexes with Metal Atoms [126]
    8. Miscellaneous Reactions [130]
      A. Oxidation [130]
      B. Reduction [132]
      C. Ring Cleavage [134]
      D. Photochemically Induced Transformations [136]
      E. Ring Expansion to 1,4-Thiazines [139]
  IV. Effects of the Thiazole Ring on Substituents [143]
    1. Alkylthtazoles [143]
    2. a-Chloroethylthiazoles [146]
    3. Halothiazoles [147]
    4. Hydroxy-, Mercapm-, and Aminoihiazoles [147]
  V. Linear Free-Energy Relationships [147]
  VI. References [149]
II. General Synthetic Methods for Thiazole and Thiazolium Salts GASTON VERNIN [165]
Laboraloin de CkimU Organiquc, Faculte des Sciences el Techniques de Saint-Jerome, Marseille, France
    1. Introduction [166]
  I. Various Types of Thiazole Ring Closure [167]
  II. Thiazoles from a-Halocarbonyl Compounds and Derivatives. Hantzsch's Synthesis, and Related Condensation (Type I) [169]
    1. Reaction with Thioamides [169]
      A. Chloroacetaldehyde and Derivatives (Thiazole and its 2-Monosubstituied Derivatives [169]
      B. Higher a-Haloaldehydes (5- and 2,5-Disubsiituied Thiazoles) [172]
      С a-Haloketones and Derivatives [175]
      D. Hantzsch's Synthesis Mechanism [209]
    2. Reaction with N-Substituted Thioamides (Thiazolium Salts) [211]
    3. Reaction with Thiourea [213]
      A. a-Halocarbonyl Compounds and Derivatives: 2-Aminothiazoles [213]
      B. Mechanism [232]
    4. Reaction with JV-Substituted Thioureas [232]
      A. N-Monosubstituted Thioureas [232]
      B. Dithiobiuret [244]
      С. N,N-Disubstituted Thioureas [244]
      D. Thiosemicarbazides and Thiosemicarbazones [249]
    5. Reaction with Salts and Esters of Thiocarbamic Acid: 2-Hydroxythiazoles and Derivatives [258]
    6. Reaction with Salts and Esters of Dithiocarbamic Acid: 2-Mercaptothiazole Derivatives and 2-Thiazolyl Sulfides [260]
      A. 2-Mercaptothiazole Derivatives [260]
      B. 2-Thiazolyl Sulfides [266]
      C. Mechanism [269]
  III. Thiazoles from Rearrangement of the a-Thiocyanatoketones (Type Ib) [271]
    1. Acid or Alkaline Hydrolysis [271]
    2. Action of Dry Hydrogen Halides [273]
    3. Action of Labile Sulfur [276]
    4. Action of Labile Nitrogen [278]
  IV. Thiazoles from Acylaminocarbonyl Compounds and Phosphorus Pentasulfide and Related Condensations (Gabriel's Synthesis (Type III) [278]
  V. Thiazoles from a-Aminonitriles (Cook-Heilbron's Synthesis) (Type II) [284]
    1. Salts and Esters of Dithioacids: 5-Aminothiazole Derivatives and Related Condensations [284]
    2. Carbon Disulfide: 2-Mercapto-5-aminothiazole Derivatives [286]
    3. Carbon Oxysulfide: 2-Hydroxy-5-aminothiazole Derivatives [288]
    4. Isothiocyanates: 2,5-Diaminothiazole Derivatives [289]
  VI. Thiazoles from Nitriles and o-Mercaptoketones or Acids: 2,4-Disubstituted and 4-Hydroxythiazole Derivatives [291]
    1. (?)-Mercapioketones. [291]
    2. (?)-Mercaptoacids: 4-Hydroxythiazole Derivatives [293]
    3. 2,4-Diaminothiazoles from (?)-Halonitriles and Thiourea [296]
  VII. Miscellaneous Reactions [297]
    1. 2-Aminothiazole Derivatives [297]
    2. 4-Aminothiazole Derivatives [301]
    3. 5-Hydroxythiazole Derivatives [303]
    4. 4,5-Dihalogenothiazoles and 2,4,5-Trihalogenothiazoles [304]
    5. 4-Tosylthiazoles [305]
    6. Alkylthiazoles [305]
    7. Cyanothiazoles [306]
    8. Miscellaneous [306]
  VIII. Thiazoles from Other Heterocyclic Compounds [308]
    1. Thiazoles from (?)-3-Thiazoles [308]
    2. Thiazoles from Oxazoles [309]
    3. Thiazoles from Isothiazoles [310]
  IX. References [310]
III. Alkyl, Aryl, Aralkyl, and Related Thiazole Derivatives JEAN PIERRE AUNE [337]
Institut de-petroleochimie et de Synoast Organiqut Industrielle, Marseille, France
HENRI JEAN-MARIE DOU
Laboratoire deChimie Org unique A, Centre Scientijique de Saint-Jerome, Marseille, France
JACQUELINE CROUSIER
Laboratoirt de Chimie de materiaux, Centre Scitntifiquc de Saint-Charles, Marseille, France
  I. Synthesis [339]
    1. Replacement of a Ring Substituent by Hydrogen [339]
    2. Dehydrogenation of Thiazolines [340]
    3. Reactivity of Side-Chain Functional Substhuents [340]
    4. Isotopic Synthesis [342]
  II. Nuclear Magnetic Resonance [342]
    1. Chemical Shifts and Coupling Constants [342]
      A. Chemical Shifts [342]
      B. Coupling Constants [344]
    2. Correlations with Electron Densities [344]
    3. 13C Chemical Shifts and Coupling Constants [345]
  III. Mass Spectrometry [347]
    1. Alkylthiazoles [348]
    2. Arylthiazoles [349]
  IV. Infrared Spectroscopy [349]
    1. C-H Vibrations [349]
    2. Combination Vibrations of the -(?) Modes [351]
    3. Vibrations of the Thiazole Ring [351]
  V. Ultraviolet Spectroscopy [352]
    1. Alkylthiazoles [352]
    2. Styrylthiazoles [353]
    3. Arylthiazoles [353]
    4. Charge-Transfer Complexes [354]
  VI. Basicity and pK(?) [355]
  VII. Other Physicochemical Studies [357]
    1. Viscosity and Diffusion [357]
    2. Thermodynamic Properties [357]
    3. Theoretical Calculations [357]
  VIII. Gas-Liquid and Thin-Layer Chromatography [358]
    1. Gas-Liquid Chromatography [358]
    2. Thin-Layer Chromatography [362]
  IX. Radical Reactivity [364]
    1. Free-Radical Reactivity of Thiazoles [364]
      A. Reactivity with Aryl Radicals [364]
      B. Influence of Radical Source and Medium [366]
      C. Reactivity of the Conjugate Acid of Thiazole [368]
      D. Comparison of Free-Radical Reactivity with Theoretical Calculations [370]
    2. Thiazolyl Radicals [370]
      A. Electron Spin Resonance [373]
    3. Photochemical Rearrangement [374]
      A. Alkylthiazoles [374]
      B. Arylthiazoles [376]
  X. Nucleophiiic Reactivity [378]
    1. Organomagnesium Compounds [378]
    2. Organolithium Compounds [378]
    3. Dimerization [379]
    4. Isotopic Effect [379]
  XI. Electrophilic Reactivity [380]
    1. Alkylthiazoles [380]
      A. Halogenation [380]
      B. Mercuration [380]
      C. Nitration [381]
    2. Arylthiazoles [382]
  XII. Reactivity of the Nitrogen Atom [386]
    1. Quatemization [386]
      A. Steric Effects of Substituents at the 2- and 4-Positions [386]
      B. Effect of a Group Adjacent to an Ortho-Substituent [389]
      C. Electronic Effects of 5-Substituents [390]
      D. Quaternization of Arylthiazoles [391]
    2. Thiazole N-Oxides [392]
    3. Metallic Complexes of Thiazoles [392]
  XIII. Condensation on the Methyl Group [392]
    1. Reactions with 2-Alkyl Groups [392]
    2. Reaction with the Hydrogen Atom at the 2-Position [393]
  XIV. Substituent Effects [393]
  XV. Applications [395]
    1. Natural Flavors [395]
    2. Polymers [395]
      A. Polymerization by Total Synthesis of the Thiazole Ring [396]
      B. Polymerization through a Substituent on the Thiazole Ring [397]
      C. Copolymerization with Dienes [398]
      D. Study of Different Monomers [398]
    3. Biological and Pharmacological Uses of Thiazoles [399]
  XVI. Tables of Products [400]
    AlkylthJazoles
      Table III-62 2-Alkylthiazoles [402]
      Table III-63 4-Alkylthiazoles [403]
      Table III-64 5-Alkylthiazoles [403]
    DialkyI and TriaUylthiazoles
      Table III-65 2,4-Dialkylthiazoles [404]
      Table III-66 2,5-Dialkylthiazoles [406]
      Table III-67 4.5-Dialkylthiazoles [407]
      Table III-68 2,4,5-Trialkylthiazoles [408]
    Arvtthiazoles
      Table III-69 2-Arylthiazoles [409]
      Table III-70 4-Arylthiazoles [410]
      Table III-71 5-Arylthiazoles [410]
    Diraryi- and Triarylthiazoles
      Table III-72 2,4-Diarylthiazoles [410]
      Table III-73 2,5-Diarylthiazoles [411]
      Table III-74 4,5-Diarylthiazoles [411]
      Table III-75 2,4.5-Triarylthiazoles [411]
    ArytolkyltbiazoJes
      Table III-76 2-Aryl-4-alkylthiazoles [412]
      Table III-77 2-Alkyl-4-arylthiazoles [412]
      Table III-78 2-Aryl-5-alkylthiazoles [413]
      Table III-79 2-Alkyl-5-arylthiazoles [413]
      Table III-80 4-Aryl-5-alkylthiazoles [413]
      Table III-81 4-Alkyl-5-arylthiazoles [413]
      Table III-82 Dialkyl-arylthiazoles [414]
      Table III-83 Alkyl-diarylthiazoles [414]
    Alkenynhiazotes
      Table III-84 2-Position [415]
      Table III-85 4-Position [416]
      Table III-86 5-Position [416]
      Table III-87 2-Position with a heterocyclic group [417]
      Table III-88 4-Position with a heterocyclic group [419]
    Aralkylthiazoles
      Table III-89 2-AraIkylthiazoles [419]
      Table III-90 4-Aralkylthiazoles [420]
      Table III-91 5-Aralkylthiazoles [420]
    Aralkylthiazoles with One Snbstituent on the Aryl Group
      Table III-92 2-Aralkylthiazoles with one subsiiruent on the aryl group [421]
      Table III-93 4-Aralkylthiazoles with One substituent on the aryl group [422]
      Table III-94 5-Aralkylthiazoles with one substituent on the aryl group [422]
    Arylthhuoles with Snbstitoenfc on the Aryl group
      Table III-95 2-Arylthiazoles with one substituent on the aryl group [422]
      Table III-96 2-Arylthiazoles with two substituents on the aryl group [424]
      Table III-97 4-Arylthiazoles with one substituent on the aryl group [424]
      Table III-98 4-Arylthiazoles with substituents on the aryl group [426]
      Table III-99 5-Arylthiazoles with one substituent on the ary] group [426]
    Diarylthiazoles with Substituents on the Aryl Groups
      Table III-100 2,4-Diarylthiazoles with substituents on the aryl groups [427]
      Table III-101 2,5-Diarylthiazoles with substituents on the aryl groups [428]
      Table III-102 4,5-Diarylthiazoles with substituents on the aryl groups [428]
    Alkyltniazoles with One Function on the Alkyl Group
      Table III-103 2-Alkylthiazoles with one function on the alky] group [429]
      Table 111-104 4-Alkylthiazoles with one function on the alkyl group [439]
      Table III-105 5-Alkylthiazoles with one function on the alkyl group [452]
    Thiazoles Substituted by Poryhmctional Groups
      Table III-106 Thiazoles substituted by one polyfunctional group [460]
      Table III-107 Thiazoles substituted by several polyfunctional groups [464]
    Thiazotyrthiazoles
      Table III-108 2-Thiazolylthiazoles [468]
      Table III-109 4-ThiazolyIthiazoles [468]
      Table III-110 5-Thiazolylthiazoles [469]
      Table III-111 Benzothiazolylthiazoles [469]
    Thiazoles Substituted by One Heterocyclic Group
      Table III-112 Furylthiazoles [469]
      Table III-113 Thienylthiazoles [470]
      Table III-114 Pyrolyl and benzopyrrolyl thiazoles [471]
      Table III-115 Oxazolylthiazoles [471]
      Table III-116 Thiazolidinyl and thiazolynylthiazoles [472]
      Table III-117 Imidazolyl and benzimidazolylthiazoles [473]
      Table III-118 1,3,4-Oxadiazolylthiazoles [476]
      Table III-119 Triazolinylthiazoles [476]
    Pyridytthiazoles
      Table III-120 2-PyridyIthiazoles [477]
      Table III-121 4-Pyridylthiazoles [478]
      Table III-122 5-Pyridylthiazoles [478]
      Table III-123 2,4-Dipyridylthiazoles [478]
    Thiazoles Substituted by Several Heterocydic Groups
      Table III-124 Thiazoles substituted by several heterocyclic groups [479]
    Thiazoles Substituted by Heterocydic Groups Nonadjaccnt to the Thiazole Ring
      Table III-125 Thiazoles substituted by heterocyclic groups nonadjacent to the thiarole ring [481]
    Nonadjacent Dnhiazoles
      Table III-126 Nonadjacent dithiazoles [482]
    Miscellaneous Substituted Thiazoles
      Table III-127 Miscellaneous substituted thiazoles [487]
  XVII. References [492]
IV. Thiazolecarboxylic Acids, Thiazolecarboxaldehydes, and Thiazolyl Ketones ROGER MEYER [519]
Laboratoirc de Chimie Physique Organique, Facalte ties Sciences et Techniques de Saint-Jerome, Marseille, France
  I. Tniazolecarboxylic Acids [520]
    1. Syntheses [520]
      A. Ester Hydrolysis [520]
      B. Oxidation [521]
      C. Carbonating Organometallic Compounds [522]
      D. Other Methods [522]
    2. Properties and Reactions [522]
      A. Acidity [522]
      B. Decarboxyiation [523]
      C. Reduction [524]
    3. Functional Derivatives [525]
      A. Esters [525]
      B. Thiazolecarboxylic Acid Chlorides [528]
      C. Thiazolecarboxamides [529]
      D. Thiazolecarboxylic Acid Hydrazides [530]
      E. Cyanothiazoles [531]
  II. Thiazolecarboxaldehydes [532]
    1. Syntheses [532]
    2. Reactions [534]
  III. Thiazolyl Ketones [535]
    1. Syntheses [535]
    2. Reactions [537]
      A. Reduction [537]
      B. Oxidation [537]
      C. Reactions of Condensation and Others [537]
  IV. Tables of Compounds [538]
  V. References [557]
V. Halo- and Nitrothiazoles L. FORLANI and P. E. TODESCO [565]
Istituto di Chimica Organica, Universita. Bologna, Italy
  I. Monohalogenothiazoles [565]
    1. Preparative Methods [565]
    2. Properties [567]
      A. Nucleophilic Substitution Reactions on Halogenothiazoles [567]
      B. Substituent Effect on the Reactivity of Halogenothiazoles [571]
      C. Other Reactions of Halogenothiazoles [573]
  II. Polyhalogenothiazoles [575]
    1. Preparative Methods [575]
    2. Properties [576]
  III. Mononitrothiazoles [576]
    1. Preparative Methods [576]
    2. Properties [577]
  IV. Polynitrothiazoles [578]
  V. Halogenonitrothiazoles [578]
    1. Preparative Methods [578]
    2. Properties and Reactivity [578]
  VI. References [582]
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