《RODD'S CHEMISTRY OF CARBON COMPOUNDS VOLUME I PART B》

Chapter 4．Monohydric Alcohols,their Ethers and Esters＆by J．G．BUCHANAN,N．A．HUGHES AND G．A．SWAN1

Introduction1

1．Monohydric alcohols3

a．Saturated alcohols,paraffin alcohols or alkanols,CnH2n+1OH3

(ⅰ)Formation and preparation of alcohols5

(ⅱ)Interconversion of primary,secondary and tertiary alcohols12

(ⅲ)Properties and re-actions13

(ⅳ)Individual alcohols16

1．Methyl alcohol16

2．Ethyl alcohol18

3．Propyl alcohols24

4．Butyl alcohols25

5．Amyl alcohols27

6．Higher saturated alcohols30

b．Derivatives of saturated alcohols33

(ⅰ)Alkoxides33

(ⅱ)Halogenohydrins;Halogenoalkanols34

(ⅲ)Nitro-alkanols37

c．Unsaturated alcohols38

(ⅰ)Olefinic alcohols or alkenols,CnH2n-1OH38

(ⅱ)Alcohols CnH2n-3OH42

(ⅲ)Alcohols CnH2n-5OH44

(ⅳ)Alcohols CnH2n-7OH45

(ⅴ)Alco-hols CnH2n-9OH46

(ⅵ)Alcohols CnH2n-11OH46

(ⅶ)More highly unsaturated alcohols46

2．Ethers46

a．Saturated ethers;dialkyl ethers,(CnH2n+1)2O46

b．Substituted dialkyl ethers49

(ⅰ)Halogenoalkyl ethers49

(ⅱ)Nitrodialkyl ethers50

c．Unsaturated ethers50

3．Alkyl peroxides52

a．Alkyl hydroperoxides,RO·OH53

b．Dialkyl peroxides,RO·OR＇54

4．Esters of mineral or inorganic acids54

a．Esters of boric acid,trialkyl orthoborates55

b．Esters of silicic acid,tetra-alkoxysilanes56

c．Esters of nitrous acid,alkyl nitrites57

d．Esters of nitric acid58

(ⅰ)Alkyl nitrates58

(ⅱ)Alkylene nitrosates,alkyl nitrosonitrates60

e．Esters of phosphorous acid,alkyl phosphites and related compounds60

f．Esters of phosphoric acid,alkyl phosphates and related compounds63

g．Esters of sulphurous acid and related compounds66

h．Esters of sulphuric acid and related compounds68

i．Esters of hypochlorous and perchloric acids71

Chapter 5．Sulphur Analogues of the Alcohols and their Derivatives＆by H．GOLDWHITE73

Introduction73

1．Thiols,mercaptans,or alkyl hydrosulphides74

2．Sulphides or thio-ethers78

a．Dialkyl sulphides,alkylthioalkanes78

b．Olefinic sulphides,dialkenyl sulphides or thioethers,alkenylthio-alkenes80

c．Acetylenic sulphides,ethynyl thioethers or alkylthioalkynes81

3．Derivatives of alkanesulphenic acids82

4．Dialkyl disulphides or alkyldithioalkanes83

5．Alkyl polysulphides84

6．Alkylthiosulphuric acids84

7．Sulphonium compounds85

8．Dialkyl sulphoxides or alkylsulphinylalkanes86

9．Alkanesulphinic acids87

10．Sulphones88

11．Alkanesulphonic acids and derivatives90

12．Alkanethiosulphonic acids92

Chapter 6．Nitrogen Derivatives of the Aliphatic Hydrocarbons＆by H．GOLDWHITE93

1．Nitro-and nitroso-compounds93

a．Nitroalkanes and related compounds93

(ⅰ)Nitroalkanes or nitroparaffins93

(ⅱ)Halogenonitroalkanes or halogenonitroparaffins100

b．Nitro-olefins or nitroalkenes102

c．Dinitroalkanes or dinitroparaffins104

d．Polynitroalkanes106

e．Nitrosoalkanes and derivatives107

f．Nitronitrosoalkanes,pseudonitroles and nitrolic acids110

(ⅰ)pseudo-Nitroles or meso-nitronitrosoparaffins110

(ⅱ)Nitrolic acids111

2．Amines and quaternary ammonium compounds111

a．Alkylamines111

(ⅰ)Occurrence and methods of preparation of amines112

(ⅱ)Properties and reactions of amines121

(ⅲ)Individual amines129

b．Halogen-substituted alkylamines130

c．Nitroalkylamines132

d．Quaternary ammonium compounds133

e．Unsaturated amines and ammonium compounds135

3．N-Substituted derivatives of the alkylamines137

a．N-Halogenoalkylamines137

(ⅰ)Preparation137

(ⅱ)Properties and reactions138

(ⅲ)Individual compounds139

b．N-Oxygen derivatives of the alkylamines139

(ⅰ)Alkylhydroxylamines139

(ⅱ)Trialkylamine oxides142

c．N-Sulphur derivatives of the alkylamines144

d．Boron,silicon,phosphorus,arsenic,and antimony derivatives of alkylamines147

e．Derivatives of alkylamines with a nitrogen-nitrogen linkage148

(ⅰ)Nitramines(nitroamines)148

(ⅱ)Nitrosoamines(nitrosamines)150

(ⅲ)Alkylhydrazines151

(ⅳ)Alkylazoxyalkanes154

(ⅴ)Alkylazo-alkanes155

(ⅵ)Diazoalkanes156

(ⅶ)Alkyl azides162

(ⅷ)Di-alkyltriazenes(diazoaminoalkanes)163

(ⅸ)Tetra-alkyl-2-tetrazenes163

(ⅹ)Hexa-alkyltetrazanes164

Chapter 7．Aliphatic Organometallic and Organometalloidal Compounds＆by C．B．MILNE AND A．N．WRIGHT165

1．Introduction165

(ⅰ)History and development of organometallic chemistry165

(ⅱ)Nomen-clature166

(ⅲ)Carbon-metal bonding166

(ⅳ)General methods of prep-aration of organometallic compounds169

(ⅴ)General physical proper-ties of organometallic compounds172

(ⅵ)Reactivity of metal-carbon bonds172

(ⅶ)Reactions of metal and metalloid alkyls173

2．Group ⅠA:Lithium,sodium,potassium,rubidium,caesium175

a．Lithium175

b．Other metals of Group ⅠA178

3．Group ⅡA:Beryllium,magnesium,calcium,strontium,barium;Group ⅡB:Zinc,cadmium,mercury179

a．Beryllium179

b．Magnesium180

(ⅰ)Magnesium dialkyls180

(ⅱ)Organomagnesium halides181

c．Calcium,strontium and barium188

d．Zinc188

e．Cadmium189

f．Mercury190

(ⅰ)Mercury dialkyls191

(ⅱ)Alkylmercury oxides,hydroxides and halides191

4．Group ⅢB:Boron,aluminium,gallium,indium,thallium192

a．Boron192

(ⅰ)Trialkylboranes193

(ⅱ)Alkyl-and dialkyl-boranes;alkylboron hydrides196

(ⅲ)Alkylboron halides196

(ⅳ)Alkylboronic acids and dialkylborinic acids197

b．Aluminium197

(ⅰ)Preparation of organo-aluminium compounds198

(ⅱ)Properties of organo-aluminium compounds200

(ⅲ)Reactions of organo-aluminium compounds200

c．Gallium204

(ⅰ)Gallium alkyls204

(ⅱ)Alkylgallium halides205

(ⅲ)Alkylgallium hydrides205

d．Indium206

e．Thallium206

5．Group ⅣB:Silicon,germanium,tin,lead207

a．Silicon208

(ⅰ)Tetra-alkylsilanes210

(ⅱ)Alkylsilicon halides211

(ⅲ)Alkylsilanes with Sill groups;alkylsilicon hydrides211

(ⅳ)Alkylsilanes with other substituents212

b．Germanium,tin,lead214

(ⅰ)Tetra-alkyl derivatives214

(ⅱ)Alkylhalogeno derivatives216

(ⅲ)Trialkylmetal hydroxides217

(ⅳ)Alkylmetal hydrides217

(ⅴ)Alkali metal derivatives218

(ⅵ)Compounds with metal-metal bonds218

6．Group ⅤB:Phosphorus,arsenic,antimony,bismuth218

a．Phosphorus219

Derivatives of tervalent phosphorus:(ⅰ)Phosphines220

(ⅱ)Diphos-phines222

(ⅲ)Alkylphosphonous dihalides and dialkylphosphinous halides223

(ⅳ)Phosphonous acids225

(ⅴ)Esters of phosphonous and phosphinous acids226

Derivatives of quinquevalent phosphorus:(ⅵ)Phosphine oxides226

(ⅶ)Diphosphine dioxides227

(ⅷ)Alkylphosphonic dihalides and di-alkylphosphinic halides228

(ⅸ)Alkylphosphonic acids and dialkyl-phosphinic acids229

(ⅹ)Esters of phosphonic and phosphinic acids230

(ⅹⅰ)Alkylhalogenophosphoranes231

(ⅹⅱ)Quaternary phosphonium compounds232

b．Arsenic232

Derivatives of tervalent arsenic:(ⅰ)Alkylarsines232

(ⅱ)Diarsines233

(ⅲ)Polyarsines233

(ⅳ)Halides234

(ⅴ)Alkylarsine oxides234

Derivatives of quinquevalent arsenic:(ⅵ)Alkyls235

(ⅵ)Halides235

(ⅷ)Trialkylarsine oxides236

(ⅸ)Alkylarsonic acids236

(ⅹ)Dialkyl-arsinic acids236

c．Antimony236

Derivatives of tervalent antimony:(ⅰ)Mono-and di-alkylstibines237

(ⅱ)Trialkylstibines237

(ⅲ)Halides238

(ⅳ)Alkylstibine oxides238

(ⅴ)Compounds containing Sb-Sb bonds238

Derivatives of quinquevalent antimony:(ⅵ)Penta-alkyls238

(ⅶ)Quaternary stibonium salts239

(ⅷ)Trialkylstibine dihalides239

(ⅸ)Dialkylstibine trihalides239

(ⅹ)Trialkylstibine oxides239

(ⅹⅰ)Dialkylstibinic acids239

(ⅹⅱ)Alkylstibonic acids239

d．Bismuth240

(ⅰ)Bismuth(Ⅲ)hydrides240

(ⅱ)Bismuth(Ⅲ)alkyls240

(ⅲ)Bismuth(Ⅲ)monohalides and dihalides240

7．Group ⅥB:Selenium,tellurium,polonium241

a．Selenium241

(ⅰ)Alkaneselenols241

(ⅱ)Alkylselenoalkanes,dialkylselenides242

(ⅲ)Alkyldiselenoalkanes,dialkyl diselenides242

(ⅳ)Acids243

(ⅴ)Selenocarbonyl compounds243

(ⅵ)Organoselenium halides243

(ⅶ)Alkylseleninylalkanes,dialkylselenoxides244

b．Tellurium244

(ⅰ)Alkanetellurols244

(ⅱ)Alkyltelluroalkanes,dialkyl tellurides244

(ⅲ)Organotellurium halides245

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

c．Polonium245

8．Transition metals246

Metal-ligand bonding246

Nomenclature247

a．Compounds with metal bonded to one carbon atom in an aliphatic compound or radical248

(ⅰ)Group ⅢA249

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

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

(ⅳ)Group ⅥA:Chromium,molybdenum,tungsten250

(ⅴ)Group ⅦA:Manganese,(Technetium),Rhenium251

(ⅵ)Group Ⅷ:Iron,ruthenium,osmium253

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

(ⅷ)Group Ⅷ:Nickel,palladium,platinum255

(ⅸ)Group ⅠB:Copper,silver,gold257

b．Compounds with metal bonded to two carbon atoms in an aliphatic compound or radical260

(ⅰ)Transition metal olefin complexes260

(ⅱ)Alkyne derivatives263

c．Compounds with metal bonded to three carbon atoms in an aliphatic compound or radical270

d．Compounds with metal bonded to four carbon atoms in an aliphatic compound or radical273

(ⅰ)Non-conjugated diene complexes273

(ⅱ)Conjugated diene com-plexes274

Bibliography277

INDEX279