RODD'S CHEMISTRY OF CARBON COMPOUNDS VOLUME I PART BPDF电子书下载

Chapter 4．Monohydric Alcohols,their Ethers and Esters＆by J．G．BUCHANAN,N．A．HUGHES AND G．A．SWAN 1

Introduction 1

1．Monohydric alcohols 3

a．Saturated alcohols,paraffin alcohols or alkanols,CnH2n+1OH 3

(ⅰ)Formation and preparation of alcohols 5

(ⅱ)Interconversion of primary,secondary and tertiary alcohols 12

(ⅲ)Properties and re-actions 13

(ⅳ)Individual alcohols 16

1．Methyl alcohol 16

2．Ethyl alcohol 18

3．Propyl alcohols 24

4．Butyl alcohols 25

5．Amyl alcohols 27

6．Higher saturated alcohols 30

b．Derivatives of saturated alcohols 33

(ⅰ)Alkoxides 33

(ⅱ)Halogenohydrins;Halogenoalkanols 34

(ⅲ)Nitro-alkanols 37

c．Unsaturated alcohols 38

(ⅰ)Olefinic alcohols or alkenols,CnH2n-1OH 38

(ⅱ)Alcohols CnH2n-3OH 42

(ⅲ)Alcohols CnH2n-5OH 44

(ⅳ)Alcohols CnH2n-7OH 45

(ⅴ)Alco-hols CnH2n-9OH 46

(ⅵ)Alcohols CnH2n-11OH 46

(ⅶ)More highly unsaturated alcohols 46

2．Ethers 46

a．Saturated ethers;dialkyl ethers,(CnH2n+1)2O 46

b．Substituted dialkyl ethers 49

(ⅰ)Halogenoalkyl ethers 49

(ⅱ)Nitrodialkyl ethers 50

c．Unsaturated ethers 50

3．Alkyl peroxides 52

a．Alkyl hydroperoxides,RO·OH 53

b．Dialkyl peroxides,RO·OR＇ 54

4．Esters of mineral or inorganic acids 54

a．Esters of boric acid,trialkyl orthoborates 55

b．Esters of silicic acid,tetra-alkoxysilanes 56

c．Esters of nitrous acid,alkyl nitrites 57

d．Esters of nitric acid 58

(ⅰ)Alkyl nitrates 58

(ⅱ)Alkylene nitrosates,alkyl nitrosonitrates 60

e．Esters of phosphorous acid,alkyl phosphites and related compounds 60

f．Esters of phosphoric acid,alkyl phosphates and related compounds 63

g．Esters of sulphurous acid and related compounds 66

h．Esters of sulphuric acid and related compounds 68

i．Esters of hypochlorous and perchloric acids 71

Chapter 5．Sulphur Analogues of the Alcohols and their Derivatives＆by H．GOLDWHITE 73

Introduction 73

1．Thiols,mercaptans,or alkyl hydrosulphides 74

2．Sulphides or thio-ethers 78

a．Dialkyl sulphides,alkylthioalkanes 78

b．Olefinic sulphides,dialkenyl sulphides or thioethers,alkenylthio-alkenes 80

c．Acetylenic sulphides,ethynyl thioethers or alkylthioalkynes 81

3．Derivatives of alkanesulphenic acids 82

4．Dialkyl disulphides or alkyldithioalkanes 83

5．Alkyl polysulphides 84

6．Alkylthiosulphuric acids 84

7．Sulphonium compounds 85

8．Dialkyl sulphoxides or alkylsulphinylalkanes 86

9．Alkanesulphinic acids 87

10．Sulphones 88

11．Alkanesulphonic acids and derivatives 90

12．Alkanethiosulphonic acids 92

Chapter 6．Nitrogen Derivatives of the Aliphatic Hydrocarbons＆by H．GOLDWHITE 93

1．Nitro-and nitroso-compounds 93

a．Nitroalkanes and related compounds 93

(ⅰ)Nitroalkanes or nitroparaffins 93

(ⅱ)Halogenonitroalkanes or halogenonitroparaffins 100

b．Nitro-olefins or nitroalkenes 102

c．Dinitroalkanes or dinitroparaffins 104

d．Polynitroalkanes 106

e．Nitrosoalkanes and derivatives 107

f．Nitronitrosoalkanes,pseudonitroles and nitrolic acids 110

(ⅰ)pseudo-Nitroles or meso-nitronitrosoparaffins 110

(ⅱ)Nitrolic acids 111

2．Amines and quaternary ammonium compounds 111

a．Alkylamines 111

(ⅰ)Occurrence and methods of preparation of amines 112

(ⅱ)Properties and reactions of amines 121

(ⅲ)Individual amines 129

b．Halogen-substituted alkylamines 130

c．Nitroalkylamines 132

d．Quaternary ammonium compounds 133

e．Unsaturated amines and ammonium compounds 135

3．N-Substituted derivatives of the alkylamines 137

a．N-Halogenoalkylamines 137

(ⅰ)Preparation 137

(ⅱ)Properties and reactions 138

(ⅲ)Individual compounds 139

b．N-Oxygen derivatives of the alkylamines 139

(ⅰ)Alkylhydroxylamines 139

(ⅱ)Trialkylamine oxides 142

c．N-Sulphur derivatives of the alkylamines 144

d．Boron,silicon,phosphorus,arsenic,and antimony derivatives of alkylamines 147

e．Derivatives of alkylamines with a nitrogen-nitrogen linkage 148

(ⅰ)Nitramines(nitroamines) 148

(ⅱ)Nitrosoamines(nitrosamines) 150

(ⅲ)Alkylhydrazines 151

(ⅳ)Alkylazoxyalkanes 154

(ⅴ)Alkylazo-alkanes 155

(ⅵ)Diazoalkanes 156

(ⅶ)Alkyl azides 162

(ⅷ)Di-alkyltriazenes(diazoaminoalkanes) 163

(ⅸ)Tetra-alkyl-2-tetrazenes 163

(ⅹ)Hexa-alkyltetrazanes 164

Chapter 7．Aliphatic Organometallic and Organometalloidal Compounds＆by C．B．MILNE AND A．N．WRIGHT 165

1．Introduction 165

(ⅰ)History and development of organometallic chemistry 165

(ⅱ)Nomen-clature 166

(ⅲ)Carbon-metal bonding 166

(ⅳ)General methods of prep-aration of organometallic compounds 169

(ⅴ)General physical proper-ties of organometallic compounds 172

(ⅵ)Reactivity of metal-carbon bonds 172

(ⅶ)Reactions of metal and metalloid alkyls 173

2．Group ⅠA:Lithium,sodium,potassium,rubidium,caesium 175

a．Lithium 175

b．Other metals of Group ⅠA 178

3．Group ⅡA:Beryllium,magnesium,calcium,strontium,barium;Group ⅡB:Zinc,cadmium,mercury 179

a．Beryllium 179

b．Magnesium 180

(ⅰ)Magnesium dialkyls 180

(ⅱ)Organomagnesium halides 181

c．Calcium,strontium and barium 188

d．Zinc 188

e．Cadmium 189

f．Mercury 190

(ⅰ)Mercury dialkyls 191

(ⅱ)Alkylmercury oxides,hydroxides and halides 191

4．Group ⅢB:Boron,aluminium,gallium,indium,thallium 192

a．Boron 192

(ⅰ)Trialkylboranes 193

(ⅱ)Alkyl-and dialkyl-boranes;alkylboron hydrides 196

(ⅲ)Alkylboron halides 196

(ⅳ)Alkylboronic acids and dialkylborinic acids 197

b．Aluminium 197

(ⅰ)Preparation of organo-aluminium compounds 198

(ⅱ)Properties of organo-aluminium compounds 200

(ⅲ)Reactions of organo-aluminium compounds 200

c．Gallium 204

(ⅰ)Gallium alkyls 204

(ⅱ)Alkylgallium halides 205

(ⅲ)Alkylgallium hydrides 205

d．Indium 206

e．Thallium 206

5．Group ⅣB:Silicon,germanium,tin,lead 207

a．Silicon 208

(ⅰ)Tetra-alkylsilanes 210

(ⅱ)Alkylsilicon halides 211

(ⅲ)Alkylsilanes with Sill groups;alkylsilicon hydrides 211

(ⅳ)Alkylsilanes with other substituents 212

b．Germanium,tin,lead 214

(ⅰ)Tetra-alkyl derivatives 214

(ⅱ)Alkylhalogeno derivatives 216

(ⅲ)Trialkylmetal hydroxides 217

(ⅳ)Alkylmetal hydrides 217

(ⅴ)Alkali metal derivatives 218

(ⅵ)Compounds with metal-metal bonds 218

6．Group ⅤB:Phosphorus,arsenic,antimony,bismuth 218

a．Phosphorus 219

Derivatives of tervalent phosphorus:(ⅰ)Phosphines 220

(ⅱ)Diphos-phines 222

(ⅲ)Alkylphosphonous dihalides and dialkylphosphinous halides 223

(ⅳ)Phosphonous acids 225

(ⅴ)Esters of phosphonous and phosphinous acids 226

Derivatives of quinquevalent phosphorus:(ⅵ)Phosphine oxides 226

(ⅶ)Diphosphine dioxides 227

(ⅷ)Alkylphosphonic dihalides and di-alkylphosphinic halides 228

(ⅸ)Alkylphosphonic acids and dialkyl-phosphinic acids 229

(ⅹ)Esters of phosphonic and phosphinic acids 230

(ⅹⅰ)Alkylhalogenophosphoranes 231

(ⅹⅱ)Quaternary phosphonium compounds 232

b．Arsenic 232

Derivatives of tervalent arsenic:(ⅰ)Alkylarsines 232

(ⅱ)Diarsines 233

(ⅲ)Polyarsines 233

(ⅳ)Halides 234

(ⅴ)Alkylarsine oxides 234

Derivatives of quinquevalent arsenic:(ⅵ)Alkyls 235

(ⅵ)Halides 235

(ⅷ)Trialkylarsine oxides 236

(ⅸ)Alkylarsonic acids 236

(ⅹ)Dialkyl-arsinic acids 236

c．Antimony 236

Derivatives of tervalent antimony:(ⅰ)Mono-and di-alkylstibines 237

(ⅱ)Trialkylstibines 237

(ⅲ)Halides 238

(ⅳ)Alkylstibine oxides 238

(ⅴ)Compounds containing Sb-Sb bonds 238

Derivatives of quinquevalent antimony:(ⅵ)Penta-alkyls 238

(ⅶ)Quaternary stibonium salts 239

(ⅷ)Trialkylstibine dihalides 239

(ⅸ)Dialkylstibine trihalides 239

(ⅹ)Trialkylstibine oxides 239

(ⅹⅰ)Dialkylstibinic acids 239

(ⅹⅱ)Alkylstibonic acids 239

d．Bismuth 240

(ⅰ)Bismuth(Ⅲ)hydrides 240

(ⅱ)Bismuth(Ⅲ)alkyls 240

(ⅲ)Bismuth(Ⅲ)monohalides and dihalides 240

7．Group ⅥB:Selenium,tellurium,polonium 241

a．Selenium 241

(ⅰ)Alkaneselenols 241

(ⅱ)Alkylselenoalkanes,dialkylselenides 242

(ⅲ)Alkyldiselenoalkanes,dialkyl diselenides 242

(ⅳ)Acids 243

(ⅴ)Selenocarbonyl compounds 243

(ⅵ)Organoselenium halides 243

(ⅶ)Alkylseleninylalkanes,dialkylselenoxides 244

b．Tellurium 244

(ⅰ)Alkanetellurols 244

(ⅱ)Alkyltelluroalkanes,dialkyl tellurides 244

(ⅲ)Organotellurium halides 245

(ⅳ)Dialkyltelluroxides(alkyltellurinyl-alkanes)and alkyltellurinic acids(tellurinoalkanes) 245

c．Polonium 245

8．Transition metals 246

Metal-ligand bonding 246

Nomenclature 247

a．Compounds with metal bonded to one carbon atom in an aliphatic compound or radical 248

(ⅰ)Group ⅢA 249

(ⅱ)Group ⅣA:Titanium(zirconium,hafnium) 249

(ⅲ)Group ⅤA:(Vanadium,niobium,tantalum) 250

(ⅳ)Group ⅥA:Chromium,molybdenum,tungsten 250

(ⅴ)Group ⅦA:Manganese,(Technetium),Rhenium 251

(ⅵ)Group Ⅷ:Iron,ruthenium,osmium 253

(ⅶ)Group Ⅷ:Cobalt,(Rhodium),(Iridium) 254

(ⅷ)Group Ⅷ:Nickel,palladium,platinum 255

(ⅸ)Group ⅠB:Copper,silver,gold 257

b．Compounds with metal bonded to two carbon atoms in an aliphatic compound or radical 260

(ⅰ)Transition metal olefin complexes 260

(ⅱ)Alkyne derivatives 263

c．Compounds with metal bonded to three carbon atoms in an aliphatic compound or radical 270

d．Compounds with metal bonded to four carbon atoms in an aliphatic compound or radical 273

(ⅰ)Non-conjugated diene complexes 273

(ⅱ)Conjugated diene com-plexes 274

Bibliography 277

INDEX 279