Organic chemistry principles and industrial practice

목차 (Table of Contents)

• CONTENTS
• Preface = XV
• What the Experts Say about this Book = XIX
• 1 How Petroleum is converted into Useful Materials : Carbocations and Free Radicals are the Keys = 1
• 1.1 The Conflicting Uses for Petroleum : The Chemical Industry and the Internal Combustion Engine = 1
• 1.2 How do we achieve these Two Objectives? By Using two different Kinds of Cracking : One depends on Free Radicals and the Other on Carbocations = 2
• 1.3 What is in Petroleum? = 3
• 1.4 The Historical Development of Steam Cracking = 4
• 1.5 What was Available before Thermal and Steam Cracking? = 6
• 1.6 Acetylene was Widely Available before Steam Cracking and Exceptionally Useful but Everyone wanted to replace this Dangerous Industrial Intermediate. Happily, Double Bonds replaced Triple Bonds = 6
• 1.7 Petroleum yields Ethylene and lays the Groundwork for a New Kind of Chemical Industry = 8
• 1.8 But What about that Thirsty Internal Combustion Engine? The Development of Catalytic Cracking = 8
• 1.9 Discovery of the Proper Catalyst for Catalytic Cracking : From Natural Synthetic Zeolites = 10
• 1.10 Let's compare the Mechanisms of Steam and Catalytic Cracking : Free Radicals versus Carbocations = 12
• 1.11 How are Free Radicals formed in Steam Crackers, and What do they do? = 12
• 1.12 Now let's look at Catalytic Cracking and the Essential Role of Carbocations and their Ability to rearrange the Structure of Organic Molecules = 15
• 1.13 What's going on inside those Zeolite Pores? = 16
• 1.14 Why do Steam Cracking and Catalytic Cracking produce such Different Results. Or, in Other Words, Why do Carbocations and Free Radicals behave so Differently? = 19
• 1.15 Summary = 20
• Study Guide Problems for Chapter 1 = 21
• 2 Polyethylene, Polypropylene and the Principles of Stereochemistry = 23
• 2.1 The Thermodynamics of Addition Polymerization : the Competition between Enthalpy and Entropy = 23
• 2.2 Polyethylene is formed via a Free Radical Polymerization that involves the Classic Steps of all Chain Reactions : Initiation, Propagation, and Termination = 24
• 2.3 Attempted Free Radical Polymerization of Propylene. It fails because of Resonance Stabilization of Allylic Radicals = 27
• 2.4 So How is Polypropylene made? Organometallic Chemistry can do what Free Radical Chemistry cannot. And the Big Surprise is the Role of Stereochemistry and Specifically Chirality. This is Something No One suspected = 29
• 2.5 There are More Kinds of Polyethylene than the One produced by the Free Radical Chain Mechanism = 29
• 2.6 What have we learned from the Organometallic Method for Polymerizing Ethylene that leads to the Possibility of Polymerizing Propylene? = 32
• 2.7 Do the Methyl Groups on Every Third Carbon on Each Individual Polypropylene Chain all have to be on the Same Side of the Chain? = 34
• 2.8 What do the Opposite "Faces" of Propylene have to do with the Formation of Isotactic Polypropylene by the Ziegler-Natta Catalyst? = 35
• 2.9 From the Ziegler-Natta Catalyst to Single-site Catalysts : Creating a Catalyst with a Precisely Known Structure that can Polymerize Propylene to an Isotactic Polypropylene = 36
• 2.10 How does this Small Molecule Analog of the Ziegler-Natta Catalyst polymerize Popylene? = 38
• 2.11 An Interesting Story concerning Industrial Conflict = 40
• 2.12 Summary = 41
• Study Guide Problems for Chapter 2 = 42
• 3 The Central Role of Electrophilic Aromatic Substitution = 45
• 3.1 Materials derived from Ethylene, Propylene and Benzene are All Around Us = 45
• 3.2 The Carbon Atoms in Ethylene, Propylene and Benzene find their Way into Polystyrene, Polycarbonate, and Epoxy Resin = 46
• 3.3 Industrial Synthesis of the Building Blocks of Polystyrene, Polycarbonate, and Epoxy Resin = 47
• 3.4 How Isopropylbenzene is Industrially produced and the Struggle to reduce the Di- and Triisopropylbenzene Byproducts = 49
• 3.5 How Ethylbenzene is produced Industrially = 52
• 3.6 Zeolites and Ethylbenzene = 52
• 3.7 How does the Zeolite Catalyst repress the Formation of Di- and Triethylbenzene? = 54
• 3.8 So Why are Zeolites not used for the Formation of Cumene? = 54
• 3.9 What Role does Cumene play in the Production of Epoxy Resin and Polycarbonate? = 56
• 3.10 How Phenol and Acetone react together to form an Isomeric Mixture of the Intermediate HO$$C_6$$H₄C(CH₃)₂OH, which then goes on to form Isomers of Bisphenol A = 56
• 3.11 We continue Our Backward Path. How are Phenol and Acetone formed from Cumene? = 59
• 3.12 A Remarkable Rearrangement = 60
• 3.13 Summary = 62
• Study Guide Problems for Chapter 3 = 64
• 4 From Nucleophilic Chemistry to Crosslinking, with a Side Trip to Glycerol, in the Synthesis of Commercially Important Plastics = 67
• 4.1 The Structure and Use of Epoxy Resins = 67
• 4.2 Epoxy Coatings and their Curing(Crosslinking) and Pot Life = 68
• 4.3 The Molecular Source of the Toughness of Epoxy Resin = 71
• 4.4 With Epichlorohydrin and Bisphenol A We are only One Step, a Nucleophilic Step, from Epoxy Resin. It all depends on the Reactivity of the Epoxide Ring = 71
• 4.5 Just as for Formation of Epoxy Resin, Curing of Epoxy Resin also involves Nucleophilic Chemistry and the Reactivity of the Epoxide Ring = 74
• 4.6 How Epichlorohydrin is synthesized from Allyl Chloride by a Classic Double Bond Addition Reaction followed by Formation of an Epoxide = 76
• 4.7 How is Allyl Chloride produced industrially from Propylene? = 77
• 4.8 A Less Temperature-dependent Way to make Epichlorohydrin = 79
• 4.9 A Final Note about Epoxy Resins = 80
• 4.10 What did the Original Shell Method for producing Epichlorohydrin have to do with Glycerol? The Answer is Alkyd Resins and this will teach Us More about Crosslinking and also introduce Nucleophilic Acyl Chemistry = 80
• 4.11 The Earliest Production of Glycerol arose from Production of Soap = 86
• 4.12 What Commercial Uses exist for Glycerol? = 87
• 4.13 The Role of Glycerol in Dynamite, and the Nobel Prize = 88
• 4.14 Glycerol plays a Role in the Production of Polyurethanes : Nucleophilic Chemistry and Crosslinking = 89
• 4.15 Polyurethanes are a Product of the Chemical Reactivity of Isocyanates = 90
• 4.16 A Route to Chemically Crosslinked Polyurethanes = 92
• 4.17 Polyether Polyols are widely used for forming Crosslinked Polyurethanes. There are many Variations on this Theme = 93
• 4.18 What About the Foamed Structure of the Polyurethane? Addition of a Small Amount of Water is a Common Answer = 94
• 4.19 Let's return again to Bisphenol A and learn about an Entirely Different Kind of Plastic, Polycarbonate, which is Very Different from Epoxy, Alkyd Resins and Polyurethanes = 95
• 4.20 How Polycarbonates are synthesized and the Unwelcome Role of Phosgene = 96
• 4.21 Is there a Future in the Chemical Industry for a Chemical as Dangerous as Phosgene? = 99
• 4.22 A few Remarks about the Double Meaning of Chloride as a Leaving Group = 99
• 4.23 Summary = 101
• Study Guide Problems for Chapter 4 = 103
• 5 The Nylon Story = 107
• 5.1 What was the World of Polymers like When Carothers entered the Picture? = 107
• 5.2 What did Carothers do at DuPont? = 109
• 5.3 Carothers' Work at DuPont had Enormous Consequences for both DuPont and the Chemical Industry? = 111
• 5.4 The Similarities and Distinctions of the Various Polyamides that make up the Family of Nylons = 112
• 5.5 The Industrial Route to Adipic Acid and Hexamethylene Diamine : the Precursors of Nylon 6,6. Benzene is the Source = 116
• 5.6 Hexamethylene Diamine from 1,3-Butadiene. Improving a Route to a New Kind of Rubber led to a Better Way to synthesize Hexamethylene Diamine : Industry and the Principle of Thermodynamic versus Kinetic Control of Reaction Products = 119
• 5.7 The Role of Acrylonitrile in the Production of Nylons = 122
• 5.8 From the Dicarboxylic Acid and the Diamine to Nylon? = 125
• 5.9 Nylons made from a Single Monomer : Nylon 6 = 127
• 5.10 Another Nylon made from a Single Monomer : Nylon 11 = 129
• 5.11 Summary = 132
• Study Guide Problems for Chapter 5 = 134
• 6 Competition for the Best Industrial Synthesis of Methyl Methacrylate = 137
• 6.1 Economic and Environmental Factors are Driviing Forces for Industrial Innovation = 137
• 6.2 Plexiglas™ = 137
• 6.3 The Classical Route to Methyl Methacrylate involves the Essential Role of Cyanohydrins, which can be Easily Converted to Unsaturated Carboxylic Acids = 139
• 6.4 Problems in the Classical Approach to Synthesis of Methyl Methacrylate = 142
• 6.5 What New Possibilities exist for Replacing the Old Process? Can the Ammonium Bisulfate Disposal Problem be Solved? = 143
• 6.6 The Mitsubishi Gas Chemical Company Approach to improving the Synthesis of Methyl Methacrylate = 144
• 6.7 The Double Bond still has to be Introduced to form the Final Methyl Methacrylate Product = 146
• 6.8 Can Things still be Improved Further? = 146
• 6.9 From Isobutene to Methyl Methacrylate : Mitsubishi Rayon versus Asahi = 147
• 6.10 How Environmental Reasons stopped the Use of Tetraethyllead as an Octane Improver in Gasoline leading to its Replacement with Methyl Tertiary Butyl Ether(MTBE). But MTBE is synthesized from Isobutene, which could have blocked the Supply of Isobutene for Production of Methyl Methacrylate. But Environmental Concerns about MTBE have caused it to lose Favor as an Octane Improver in Gasoline therefore releasing Isobutene for Production of Methyl Methacrylate. A Story of the Ups and Downs of the Chemical Industry - What a Ride! = 148
• 6.11 A Competitive Process for the Synthesis of Methyl Methacrylate based on Ethylene = 150
• 6.12 A Competitive Process for Synthesis of Methyl Methacrylate based on Propylene = 151
• 6.13 A Possible Commercial Synthesis of Methyl Methacrylate starting from Methyl Acetylene = 152
• 6.14 Summary = 153
• Study Guide Problems for Chapter 6 = 155
• 7 Natural Rubber and Other Elastomers = 157
• 7.1 Introduction to Rubber = 157
• 7.2 Why are Some Materials Rubbery? = 158
• 7.3 The Conformational Basis of Elasticity = 158
• 7.4 How does the Structure of Natural Rubber fit into the Theoretical Picture of Elasticity drawn above? = 160
• 7.5 Let's take a Short Diversion from Elastomers = 162
• 7.6 Elastomers require Essentially Complete Recoverability from the Stretched State. The Story of Vulcanization and How Sulfur supplies this Characteristic to Hevea Rubber = 163
• 7.7 What happens When Sulfur and Natural Rubber are mixed and heated? = 164
• 7.8 Hypalon : an Elastomer that can be Crosslinked without the Presence of Double Bonds = 167
• 7.9 Many Synthetic Elastomers are produced by the Chemical Industry. In Every Case the Physical Principles are Identical to those at Work in Natural Rubber and the Essential Characteristic of an Elastomer must be present, that is, a Crosslinked Flexible Polymer Chain = 170
• 7.10 What Kinds of Polymer Properties will preclude Elastomeric Behavior? What Kinds of Polymers could be called Anti-elastic? = 177
• 7.11 Physical Interactions among Polymer Chains can be used to form Elastomers with Unique Properties. How the Polymeric Glassy State can act as a Physical Crosslin = 177
• 7.12 Variations on the Block Theme produce Thermoplastic Polyurethane Elastomers including Spandex(Lycra™), the Elastic Fiber. Here, the Crosslinks involve a Kind of Physical Interaction, which is Different from Glass Formation = 183
• 7.13 Spandex : A Possible Synthesis = 185
• 7.14 Ionomers : Yet Another Approach to Reversible Crosslinking = 188
• 7.15 Summary = 190
• Study Guide Problems for Chapter 7 = 191
• 8 Ethylene and Propylene : Two Very Different Kinds of Chemistry = 195
• 8.1 Ethylene and Propylene = 195
• 8.2 The Industrial Importance of Ethylene and Propylene = 195
• 8.3 Ethylene Oxide and Propylene Oxide are Very Large Volume Industrial Intermediates derived from Ethylene and Propylene but must be Industrially Synthesized in Entirely Different Ways = 197
• 8.4 The Production of Propylene Oxide without using Chlorine = 198
• 8.5 Why did Dow maintain the Hypochlorous Route to Propylene Oxide? = 201
• 8.6 Before We continue to investigate the Difference in the Industrial Chemistry of Ethylene and Propylene, let's take a Diversion from the Main Theme of the Chapter. Why are Ethylene Oxide and Propylene Oxide so Important to the Chemical Industry? We find out by adding Water = 201
• 8.7 Any Process that could produce Ethylene Glycol without Oligomeric Products would be Highly Desirable = 204
• 8.8 We've seen the problems arising from the allylic hydrogens in propylene. Does the Reactivity of these Hydrogens bestow any Advantages? = 204
• 8.9 The Importance of Polyacrylic Acid and its Esters = 204
• 8.10 The Importance of Acrylonitrile and Polyacrylonitrile = 206
• 8.11 How was Arylonitrile produced in the "Old Days" before the "Propylene Approach" took over? = 209
• 8.12 How was Acrylic Acid produced in the "Old Days" before the "Propylene Approach" took over? = 209
• 8.13 An Early Example of Transition Metal Catalysis led to a Direct Route from Acetylene to Acrylic Acid = 211
• 8.14 The Oxidation of Propylene to Acrylic Acid and to Acrylonitrile shuts down all Previous Processes. The Catalyst is the Key, but the Allylic Hydrogens are Essential = 212
• 8.15 Summary = 217
• Study Guide Problems for Chapter 8 = 218
• 9 The Demise of Acetaldehyde : A Story of How the Chemical Industry Evolves = 221
• 9.1 An Interesting Example of Shutdown Economics = 221
• 9.2 An Aspect of the Evolution of the Chemical Industry that begins with World War Ⅰ = 223
• 9.3 The Aldol Condensation leads to n-Butanol = 224
• 9.4 Reactivity Principles associated with the Aldol Condensation = 226
• 9.5 Pentaerythritol and other Polyhydric Alcohols synthesized via Aldol Condensations = 229
• 9.6 A Prominent "Plasticizer" is synthesized via an Aldol Condensation = 232
• 9.7 The Grandfather Molecule of the Aldol Condensation is Acetaldehyde. How was and is Acetaldehyde produced? = 234
• 9.8 A Palladium-based Process, the Wacker Reaction, shuts down all Older Industrial Methods to Acetaldehyde = 236
• 9.9 Hydroformylation - Another Triumph for Transition Metals = 238
• 9.10 How is the Other Product, Acetic Acid, which formerly was made from Acetaldehyde, now produced? = 243
• 9.11 Summary = 244
• Study Guide Problems for Chapter 9 = 246
• 10 Doing Well by Doing Good = 249
• 10.1 Many Companies in the Chemical Industry have been Amazed to Learn that Replacement of Dangerous and／or Toxic Chemicals Leads not only to Safety, but also to Greater Profit = 249
• 10.2 What's the Problem with Acetylene? First, it is Explosive = 249
• 10.3 What Else is Wrong with Acetylene? = 251
• 10.4 What is the Precise Chemical Nature of these Carbide Salts? = 252
• 10.5 Is Acetylene derived from Calcium Carbide of Commercial Importance? = 254
• 10.6 Large-scale Production of Acetylene = 255
• 10.7 How was Acetylene Used to Produce Industrial Intermediates? = 258
• 10.8 Replacing Acetylene with Ethylene and Zinc with Palladium for the Production of Vinyl Acetate = 260
• 10.9 What is Valuable about Vinyl Acetate? = 262
• 10.10 Replacing Acetylene with Ethylene for the Production of Vinyl Chloride = 265
• 10.11 The Production of 1,4-Butynediol shows an Entirely Different Face of Acetylene Reactivity = 268
• 10.12 Phosgene and Chlorine - the Poison Gases of World War Ⅰ. Can their Replacement for Industrial Processes by Safer Chemicals also be an Example of "Doing Well by Doing Good?" = 273
• 10.13 Is there a Way to Eliminate Phosgene in the Industrial Synthesis of Polycarbonate? = 274
• 10.14 Let's look at Another Competition, the Production of Methyl Methacrylate, in Terms of Cash and Finance Costs = 281
• 10.15 Reducing the Use of Chlorine in Industrial Processes = 282
• 10.16 HCN is a Dangerous Chemical Hastening its Replacement in the Synthesis of Methyl Methacrylate, as we have seen. But its Exquisite Reactivity has Fostered its Use in Other Processes and Particularly in a Potential Process for Getting rid of Ammonium Sulfate as a Byproduct in the Synthesis of Nylon 6 = 283
• 10.17 Routes to Caprolactam that Avoid Production of Ammonium Sulfate = 284
• 10.18 Summary = 287
• Study Guide Problems for Chapter 10 = 289
• An Epilogue - The Future = 293
• Index = 297