CONTENTS

Preface 111 Introduction V one ACETYLENIC COMpqUNDS: STRUCTURE AND IMPORTANT PROPERTIES

Physic'al Properties 1.1. Bond Lengths and Arrangement of Electrons 2 1.2. Molecular Radii 3 1.3. Solubility of 4 1.4. Solubility of in Donor Solvents 4 2. Chemical Properties of Acetylenic Compounds 5 2.1. Acetylenes as Hydrogen-bonding Acids 5. 2.2. Acetylenes as Hydrogen-bondirig Bases 6 2.3. Intermolecular Association of Ethynyl Groups 7 2.4. Donor Capacity of Acetylenes 7 3. Structure and Acidity 8 4. Sources of Data on Other Properties 10 References 10

two EXPERIMENT AL AIDS 12

.1. Safe Handling of Acetylene and Acetylenic Compounds 12 ~.1. Atmospheric Pressure 12 1.2. Elevated Pressure 13 .2. Laboratqry Purification of Cylinder Acetylene 13 3. Detection, Analysis and Identification of Acetylenic Com- pounds 14 3.1. Analysis by Gas-Liquid Chromatography 14 3.2. Infrared Absorption 14 .3:3. Nuclear Magnetic Resonance Spectra 16 References 19 three PREPARATION OF ACETYLENIC COMPOUNDS BY ELIMINATION REACTIONS 22 1. Tertiary and Secondary 23 2. ~rylacetylenes 24 viii CONTENTS

3. Diacetylenes 25 4. Polyfluoroacetylenes 25 4.1. 3,3,3-Trifluorol?ropyne 25 4.2. Hexafluoro-2-butyne 27 4.3. Symmetrical Polyfluoroalkylacetylenes 27 5. Enynes 28 5.1. Vinylacetylene 28 5.2. Isoalkenylacetylenes 28 5.3. Other enynes 28 6. 29 7. Aldehydes and 29 8. Aminobutynes 31 9. (X-Acetylenic 31 10. (X-AcetylenicAcids 32 11. Acetylenic Tin Compounds 33 12. Acetylenic 35 12.1. Alkyl1-Ethynyl and 1-Alkynyl Ethers 35 12.2. Benzyl1-Alkynyl Ethers 36 12.3. Bis (l-acetylenic) Ethers 36 12.4. Dialkynyl Ethers 37 13. Ethynyl and 1-Alkynyl Thioethers and Selenoethers 37 13.1. Ethynyl and 1-Alkynyl Thioethers 37 13.2. RSC=CSR. 38 13.3. Alkenyl Alkynyl Thio- and Selenoethers 38 13.4. Dialkynyl Thioethers 39 14. 1-Aminoacetylenes 40 15. Ethynylimidazoles 41 References 42

four SUBSTITUTION OF ACETYLENIC HYDROGEN BY OTHER ELEMENTS 45 PART ONE- ACETYLIDESAND ACETYLENIC GRIGNARDREAGENTS-PREPARATION AND REACTIONS 46 1. 46 1.1. Preparation in Liquid Ammonia 46 1.2. Preparation in Inert Organic Diluents 47 1.3. Reactions of Sodium Acetylide 50 2. Sodium Derivatives of Substituted Acetylenes 53 2.1. Sodium Derivatives of Acetylenic Hydrocarbons- Preparation and Reactions 53 3. Sodium Derivatives of Diacetylene 59 3.1. Sodium Diacetylides 59 3.2. Reactions of Monosodium Diacetylide 59 3.3. Reactions of Disodium Diacetylide 59 3.4. Reactions of Sodium Methoxyvinylacetylene 59 4. Acetylide I, 60 4.1. Preparation of Lithium Acetylide- Ethylenediamine Complex 60 4.2. Reaction of Lithium Acetylide-Ethylenediamine with (J)-Fluoroalkyl Halides 60 5. Lithium Derivatives of Substituted Acetylenes 61 5.1. Reaction of Lithium with l-Alkenes to form

Lithium Alkynylides 61

5.2. Lithium Alkynylides in Dioxane 62 5.3. Reaction of Lithium Alkynylides with (J)-Chloroalkyl Bromides 64 5.4. Reaction of Lithium Alkynylides with (J)-Bromo Alkanols and (J)-Bromo Acids 65 5.5. Reaction of Monolithium Dialkynylides with (J)-Bromo Acids 66 5.6. Relative Acidity of Fluorenyl and Acetylenic Hydrogen; Competitive Reactions of Lithium Derivatives 66 5.7. Reaction of Lithium Alkynylides with Disulfides to Form Alkynyl Thioethers 67 5.8. Reaction of Lithium Alkynylides with Sulfur and Acyl Bromides to Form l-Acylthio-l-alkynes 68 5.9. Lithium l-Alkoxyalkynylides and Their Reactions 69 5.10. Lithium Ethylthioethynylide and Its Reactions 69 5.11. Lithium Vinylthioethynylide 70 5.12. Lithium Ethylselenoethyne 70 6. Calcium Carbide 70 7. Grignard Reagents of Acetylenes 71 7.1. Acetylene 71 7.2. Grignard Reagents of Substituted Acetylenes 71 7.3. Reactions of Grignard Reagents of Substituted Acetylenes 75 7.4. Grignard Reagents of Diacetylenes 80 7.5. Acetylenic Zinc Grignard Reagents 81 References . 81 PART TWO-COPPER, SILVER, ZINC, CADMIUM AND MERCURIC DERIvAnvES OF ACETYLENES 84

1. Copper 84 .1.1. Cuprous Acetylide 84 x CONTENTS

1.2. Cupric Acetylide 85 1.3. Uses of Heavy Metal Acetylides RS 1.4. Complexes of Cuprous Derivatives of Substituted Acetylenes 86 1.5. Reactions of Cuprous Derivatives of Substituted Acetylenes with Aromatic Halides 86 2. Cuprous-Catalyzed of Acetylenes 93 3. Silver Acetylides 96 4. Zinc-Copper Couples 96 5. Zinc Acetylides 97 6. Cadmium Acetylides 97 7. Mercuric Acetylides 98 7.1. Application of Mercuric Acetylides 99 7.2. Preparation of 1- Nitrosoacetylenes 99 References 99

PART THREE-BORON, ALUMINUM, GALLIUM, THALLIJJM, SILICON AND GERMANIUM COMPOUNDS OF ACETYLENES 100

1. Boron Compounds of Acetylenes 100 1.1. Alkynylboronates 100 1.2. Other Boron-Acetylenic Compounds 102 2. Aluminum Compounds of Acetylenes 102 2.1. Reaction of Dialkylaluminum Chlorides with Sodium Vinylacetylide 102 2.2. Reaction of Alkylaluminum Compounds with Terminal Acetylenes 102 2.3. Reaction of Aluminum Hydrides with Terminal Acetylenes 104 2.4. Reaction of Sodium Aluminum Hydride with Terminal Acetylenes 10~ 3. Gallium Compounds of Acetylenes-Reaction of Gallium Alkyls and Alkyl Hydrides with Acetylenes 105 4. Thallium Compounds of Acetylenes 106 5. Silicon Compounds of Acetylenes 106 5.1. Ethynylsilanes 106 5.2. Silicon-Enyne Compounds 106 5:3. Silicon-Acetylenic Carbinol Compounds 107 5.4. Silylacetylenes as Bactericides and Fungicides 108 6. Germanium Compounds of Acetylenes 108 6.1. Ethynylgermanes 1.08 6.2. Germanium Compounds of Substituted Acetylenes 108 References 10Q CONTENTS xi

PART FOUR-TIN, ARSENIC, BISMUTH, ANTIMONY AND LEAD DERIVATIVESOF ACETYLENICCOMPOUNDS 111

1. Background 111 2. Organotinacetylenes 111 2.1. Reaction of Organotin Halides with Metal Acetylides or Grignard Reagents 111 2.2. Reaction of Acetylenes with Trisubstituted Tin Oxides 114 2.3. Reaction of Acetylenes with Trisubstituted Tin Hydroxides 115 3. Organoarsenicacetylenes 115 4. Organobismuthacetylenes 116 5. Organoantimonyacetylenes 117 6. Organoleadacetylenes 117 7. Uses 119 References 120

PART FIVE-ACETYLENIC NITROGEN , PHOSPHORUS AND TELLURIUM COMPOUNDS 121

Compounds with Nitrogen Attached Directly to Acetylenic Carbon 121 1.1. Preparation of l-Aminoacetylenes (Yneamines) 121 1.2. Preparation of 1-Acetylenic Diazonium Compounds 121 1.3. Reactions of l-Aminoacetylenes 122 2. Compounds with Phosphorus Attached to Acetylenic Carbon 124 2.1. Introduction 124 2.2. 1-Acetylenic Phosphines 125 2.3. Triethynylphosphine, Arsine and Stibine 129 2.4. Tertiary Acetylenic Phosphine Sulfides 130 2.5. Acetylenic Phosphites 130 3. Acetylenic p-Phosphines 131 4. Propargylphosphonates and Allenylphosphonates 131 5. Acetylenic Tellurium Compounds 132 References 133

PART SIx-I-HALOACETYLENES 134 1. Pr~paration of I-Haloacetylenes 134 1.1. Chloroacetylene 134 1.2. Dichloroacetylene 134 1.3. Fluoroacetvlene 135 CONTENTS xii

1.4. Bromoacetylene 135 1.5. Difluoroacetylene 135 1.6. Other Haloacetylene Compounds 136 2. 1-Bromo-Substituted Acetylenes 136 3. Mono- and Dihalodiacetylenes 136 4. Reactions of 1-Haloacetylenes 137 4.1. Cyclizations 137 4.2. Nucleophilic Displacement of Halogen 138 4.3. Discussion of Nucleophilic Substitution at Acetylenic Carbon (or Halogen) 139 5. Acetylenic and Ethylenic Iodonium Salts 141 References 142

five ETHYNYLATION AND ALKYNYLATION 144 PART ONE-ETHYNYLAtlON AND ALKYNYLATIONUSING SToICHIo- METRICAMOUNTS OF BASEAS CONDENSINGAGENT 146

1. Stoichiometric KOH Ethynylations and Alkynylations 146 1.1. Atmospheric Pressure 146 1.2. Stoichiometric KOH Ethynylation under Pressure 147 1.3. Ethynylation of Aldehydes 147 1.4. Ethynylation of Ketene 149 1.5. Ethynylation of Tropinone 149 1.6. Tetraarylbutynediols and Their Reduction to Cumulenes 150 1.7. Liquid Phase Ethynylation System 150 1.8. Stereochemistry of KOH Ethynylation 150 1.9. Exchange Reactions 151 1.10. Alkynylations Using Diynes-Skipped Diynes 152 1.11. Alkynylations Using Other Acetylenic Hydrocarbons 153 1.12. "Alkynylations" Using Acetylenic Carbinols 153 2. "Semicatalytic" KOH Ethynylation and Alkynylation 155 2.1. Polar Organic Solvents 155 2.2. Ammonia as Solvent 156 2.3. Semicatalytic Reaction of Diacetylene with Ketones in Aqueous NaOH 163 References 163 PART TW0--ETHYNYLATION AND ALKYNYLATION BY ALKALI METAL ACETYLIDES 166 1 Rack2round 166 2. Ethynylation by Sodium Acetylide and Lithium Acetylide in Ammonia 166 2.1. Aldehydes 166 2.2. Cyclopropyl Alkyl Ketones 167 2.3. Methylheptenone 167 2.4. Terpene Ketones 168 2.5. Bicyclic Terpene Ketones 169 2.6. Pyridyl Ketones 170 2.7. Spiroketones 171 2.8. Benzotropones 172 2.9. Thioketones 172 2.10. Stereochemistry of Sodium Acetylide Ethynylations 175 3. Semicatalytic Ethynylation of by Sodium Acetylide-Acetylene 175 4. Preparation of Acetylenic Diols and Reduction of the Diols to Cumulenes 176 5. Reactions of Sodium and Lithium Alkynylides with Simple Carbonyl Compounds 182 5.1. Lithium Propynylide (Preparation of Vitamin A Aldehyde) 182 5.2. Ethynylation and Alkynylation of Xanthone and Thioxanthones 184 5.3. Reaction of Sodium Vinylacetylide with Hydroxyketones 186 5.4. Reaction of Sodium Methoxyvinyl Acetylide with Carbonyl Compounds 187 5.5. Preparation and Reactions of Disodium Diacetylide 187 5.6. Alkali Metal Chloroacetylides 189 6. Ethynylation and Alkynylation in Organic Diluents 192 6.1. Ethynylation by Sodium Acetylide 192 6.2. Ethynylation by Lithium Acetylide Ethylenediamine 192 6.3. Reaction of Lithium Alkynylides with Paraformaldehyde 194 6.4. Lithium Chloropropynylides 194 7. Complex Aluminum Alkynylides as Alkynylating Reagents 195 References 195

PARTTHREE-ETHYNYLA TIONAND ALKYNYLATION BY ACETYLENIC GRIGNARD REAGENTS 197 .1. Background 197 xiv CONTENTS

2 Acetylene Monogrignard Reagent 197 3 Acetylene Digrignard Reagent 198 4 Alkynyl Grignard Reagents 199 5 Aralkynyl Grignard Reagents 200 Aralkynylation with Zinc "Grignard " Reagents 201 6 7 Aluminum Propargyl "Grignard" Reagent 201 8 Grignard Reagents of Heterocyclic Compounds 201 8.1. Reaction of Ethynylfuran and Tetrahydropyran Grignards 201 8.2. Reaction of Thiophenemagnesium Iodide with Tetrolaldehyde 202 9 Grignard Reagents of Acetylenic Ethers 202 10 Grignard Reagents of Acetylenic Thioethers 203 11 Grignard Reagents of Enynes and Diynes 204 References 205

PART FOUR-CATALYTIC ETHYNYLATIONREACTIONS 207 1. Background 207 2. Cuprous Acetylide Catalysts 207 3. Catalytic Ethynylation of Formaldehyde in Organic Solvents 4. Other Cuprous Acetylide-Catalyzed Ethynylation Reactions 5. Vapor Phase Catalytic Ethynylation of Acetone Over Bases 209 6. Catalytic Reaction of Orthoesters with Acetylenes 211 6.1. Synthesis of Acetals 211 6.2. Synthesis of Ketals 212 6.3. Synthesis of Acetylenic Orthoesters 212 References

PART FIVE-ETHYNYLATION AND ALKYNYLATION OF DICARBONYL COMPOUNDS 213

1. Background 213 2. Dialdehydes 213 3. Diketones 214 3.1. Ethynylation of Cyclohexanediones 214 3.2. Alkynylation of Cyclohexanedione 216 4. o-Quinones 216 4.1. Ethynylation 216 4.2. Alkynylation 218