《RODD‘S CHEMISTRY OF CARBON COMPOUNDS SECOND EDITION VOLUME Ⅰ PART C》求取 ⇩

Chapter 8．Aldehydes and Ketones＆by J．G．BUCHANAN,N．A．HUGHES,F．J．McQUILLIN AND G．A．SWAN1

1．Introduction1

2．Saturated aldehydes3

a．Aldehydes,alkanals,CnH2n+1CHO3

(ⅰ)Formation and preparation4

(ⅱ)Reactions of the aldehydes10

(ⅲ)Aldehydes in synthetic reactions14

(ⅳ)Individual compounds18

b．Halogen substitution products of the saturated aldehydes24

c．Nitro-aldehydes26

d．Aldehyde peroxides26

e．Ethers and esters of the aldehyde hydrates27

(ⅰ)Hemiacetals;I-alkoxyalkan-I-ols27

(ⅱ)Acetals;I,I-dialkoxyalka-nes28

(ⅲ)I,I-Dihalogenoalkanes,I-halogeno-I-hydroxyalkanes and I-alkoxy-I-halogenoalkanes30

(ⅳ)Carboxylic esters of the aldehyde hydrates31

(ⅴ)Aldehyde bisulphite compounds and aldehyde sulph-oxylates32

f．Sulphur derivatives of the saturated aldehydes33

(ⅰ)Alkane-I,I-dithiols34

(ⅱ)Thioaldehydes;alkanethials,polymeric thioaldehydes and their sulphones34

(ⅲ)Thioacetals;I,I-bisalkythio-alkanes and alkylidenesulphones;I,I-bisalkylsulphonylalkanes37

(ⅳ)Alkane-I,I-disulphonic acids39

g．Nitrogen-containing derivatives of the aldehydes40

(ⅰ)Compounds derived from aldehydes and ammonia40

(ⅱ)Compounds derived from aldehydes and alkylamines44

(ⅲ)Aldoximes45

(ⅳ)Azines and substituted hydrazones47

3．Unsaturated aldehydes48

a．Olefinic aldehydes;alkenals,CnH2n-1CHO48

b．Acetylenic aldehydes;alkynals,CnH2n-3CHO51

c．Di-and poly-olefinic aldehydes52

4．Saturated ketones52

a．Ketones;alkanones;oxoalkanes,CnH2nO52

(ⅰ)Methods of formation and preparation53

(ⅱ)Properties and re-actions58

(ⅲ)Individual ketones65

b．Halogen substitution products of the ketones70

c．Nitrosoketones71

d．Nitroketones71

e．Derivatives of the ketone hydrates72

(ⅰ)Ketone acetals;ketals;dialkoxyalkanes72

(ⅱ)Ketone halides72

(ⅲ)Ketone bisulphite compounds and sulphoxylates73

f．Sulphur analogues of the saturated ketones73

(ⅰ)Alkane-gem-dithiols73

(ⅱ)Thioketones,polymeric thioketones and their sulphones74

(ⅲ)Thioketals;bisalkylthioalkanes and derived sulphones75

g．Nitrogen analogues of the ketones76

(ⅰ)Nitro compounds76

(ⅱ)Compounds with ammonia76

(ⅲ)Com-pounds with alkylamines76

(ⅳ)Hydroxylamine derivatives;ketoxi-mes76

(ⅴ)Hydrazine derivatives78

(ⅵ)Ketone semicarbazones80

(ⅶ)Miscellaneous derivatives80

5．Unsaturated ketones and ketens81

a．Ketens,RR＇C:CO81

(ⅰ)Formation and preparation81

(ⅱ)Properties82

b．Olefinic ketones,CnH2n-1·CO·CnH2n+183

(ⅰ)Formation and preparation83

(ⅱ)Reactions84

c．Diolefinic ketones87

(ⅰ)Individual compounds87

(ⅱ)The action of ammonia on acetone,me-sityl oxide and phorone88

(ⅲ)Action of hydroxylamine and semicarba-zide on mesityl oxide and phorone89

d．Acetylenic ketones90

Chapter 9．Monobasic Carboxylic Acids＆by M．F．ANSELL AND R．H．GIGG92

1．Introduction92

2．Saturated monocarboxylic acids96

a．Formic acid and its derivatives96

(ⅰ)Formic acid96

(ⅱ)Metal formates100

(ⅲ)Halides of formic acid101

(ⅳ)Esters of formic acid(iormates)101

(ⅴ)Formamides102

(ⅵ)Hydrogen cyanide104

(ⅶ)Functional derivatives of formic acid,109

(ⅷ)Derivatives of orthoformic acid112

b．Saturated fatty acids114

(ⅰ)Formation and preparation of primary and secondary fatty acids115

(ⅱ)Synthesis of acids with tertiary groups123

(ⅲ)Physical properties of fatty acids124

(ⅳ)Chemical properties and reactions of fatty acids126

(ⅴ)Individual fatty acids130

3．Functional derivatives of the fatty acids139

a．Esters139

(ⅰ)Methods of formation139

(ⅱ)Properties144

(ⅲ)Reactions144

(ⅳ)Individual esters146

b．Acid or acyl halides150

(ⅰ)Formation150

(ⅱ)Properties and reactions of acyl halides152

(ⅲ)Individual acyl halides154

c．Mixed anhydrides with inorganic oxy-acids155

d．Carboxylic acid anhydrides156

(ⅰ)Formation of simple anhydrides156

(ⅱ)Formation of mixed anhy-drides158

(ⅲ)Properties and reactions of acid anhydrides158

(ⅳ)Individual anhydrides159

e．Peroxy-acids(per-acids)and acyl peroxides16

(ⅰ)Formation of peroxy-acids160

(ⅱ)Properties of peroxy-acids162

(ⅲ)Reactions of peroxy-acids162

(ⅳ)Peroxy-esters163

(ⅴ)Diacyl peroxides164

f．Amides165

(ⅰ)General methods of preparation166

(ⅱ)Properties and reactions of amides171

(ⅲ)Individual carboxamides173

g．Carbohydrazides173

(ⅰ)Preparation173

(ⅱ)Properties and reactions174

(ⅲ)Individual carbohydrazides174

h．Acyl azides175

(ⅰ)Preparation175

(ⅱ)Properties175

(ⅲ)Reactions175

i．Nitriles or alkyl cyanides177

(ⅰ)General methods of preparation177

(ⅱ)Properties and reactions179

(ⅲ)Individual nitriles182

j．Carboxamide chlorides and imidoyl chlorides182

k．Alkyl imidates183

l．Amidines185

m．Hydroxamic acids and hydroximoyl chlorides189

(ⅰ)Hydroxamic acids189

(ⅱ)Hydroximoyl chlorides190

n．Amidoximes191

o．Hydroxamic acid-oximes(oxyamidoximes)and nitroso-oximes191

p．Hydrazidines,amidrazones and 1,2-dihydroformazans192

4．Thiocarboxylic acids193

a．Monothiocarboxylic acids and esters194

(ⅰ)Preparation of thiocarboxylic acids194

(ⅱ)Preparation of thiol-or S-alkyl thio-esters195

(ⅲ)Preparation of thion-esters or O-alkyl thio-esters195

(ⅳ)Reactions of monothiocarboxylic acids196

(ⅴ)Indivi-dual monothiocarboxylic acids196

b．Dithiocarboxylic acids and their derivatives196

(ⅰ)Preparation196

(ⅱ)Reactions196

(ⅲ)Individual dithiocarboxylic acids197

c．Nitrogen derivatives of thiocarboxylic acids197

(ⅰ)Thionamides;thioamides197

(ⅱ)Thiolimidates(isothioamides,iminothioethers,thiolimidic esters,S-alkyl thioimidates)200

5．Halogen substitution products of the fatty acids201

a．Halogenated acetic acids207

b．Halogenated propionic acids212

c．Halogen derivatives of higher fatty acids214

6．Derivatives of ortho-fatty acids215

a．Ortho-esters215

(ⅰ)Preparation215

(ⅱ)Reactions216

(ⅲ)Individual ortho-esters217

b．Other ortho-compounds218

7．Unsaturated aliphatic monocarboxylic acids218

a．Introduction218

(ⅰ)Methods of isolation and analysis of unsaturated acids218

(ⅱ)Biolo-gical significance of unsaturated acids219

(ⅲ)General references220

b．Synthesis of unsaturated acids220

(ⅰ)αβ-Ethylenic acids220

(ⅱ)βγ-andγδ-Ethylenic acids221

(ⅲ)Ethylenic acids with isolated double bonds222

(ⅳ)αβ-Acetylenic acids222

(ⅴ)Acetylenic acids with isolated triple bonds223

(ⅵ)Allenic acids223

c．Properties and reactions224

(ⅰ)Hydrogenation and reduction224

(ⅱ)Polymerisation225

(ⅲ)Oxi-dation225

(ⅳ)Action of alkalis226

(ⅴ)Action of sulphuric acid226

(ⅵ)Addition of halogens227

(ⅶ)Addition of mercuric acetate227

(ⅷ)Characteristic reactions of αβ-unsaturated acids227

d．Unsaturated acids with three carbon atoms228

e．Unsaturated acids with four carbon atoms230

f．Unsaturated acids with 5-10 carbon atoms233

(ⅰ)C5-acids223

(ⅱ)C6-acids234

(ⅲ)C7-acids237

(ⅳ)C8-acids238

(ⅴ)C9-acids239

(ⅵ)C10-acids239

g．Unsaturated acids with 11-17 carbon atoms240

(ⅰ)C11-acids240

(ⅱ)C12-acids241

(ⅲ)C13-acids242

(ⅳ)C14-acids242

(ⅴ)C15-acids243

(ⅵ)C16-acids243

h．Unsaturated acids with 18 carbon atoms244

(ⅰ)-Enoic and -ynoic acids244

(ⅱ)-Dienoic and -enynoic acids246

(ⅲ)-Trienoic and -enediynoic acids247

(ⅳ)-Tetraenoic acids249

i．Unsaturated with more than 18 carbon atoms249

(ⅰ)C20-acids249

(ⅱ)C22-acids251

(ⅲ)C23-acids252

(ⅳ)C24-acids252

(ⅴ)C26-acids252

(ⅵ)C27-acids252

Chapter 10．Carbon Monoxide,Isocyanides and Fulminic Acid＆by M．F．ANSELL253

1．Introduction253

2．Carbon monoxide254

a．Metal carbonyls255

(ⅰ)Formation and preparation255

(ⅱ)Structure256

b．Carbonyl hydrides or hydrocarbonyls257

c．Synthetic uses of carbon monoxide258

3．Isocyanides,isonitriles or carbylamines262

4．Fulminic acid264

Chapter 11．Carbonic Acid and its Derivatives＆by R．HOWE268

1．Metacarbonic acid and its esters268

a．Esters of carbonic acid271

(ⅰ)Primary esters of carbonic acid;alkyl hydrogen carbonates271

(ⅱ)Neutral estets,dialkyl carbonates,alkoxycarbonyloxyalkanes272

(ⅲ)Percarbonates274

b．Anhydrides of primary esters of carbonic acid274

(ⅰ)Esters of dicarbonic acid274

(ⅱ)Mixed anhydrides of primary carbo-nates and monocarboxylic acids;alkoxycarbonyl esters275

2．Halides of carbonic acid276

a．Monohalide esters277

(ⅰ)Chloroformic esters,alkyl chloroformates,chlorocarbonates or alkoxy-carbonyl chlorides277

(ⅱ)Alkyl fluoroformates278

b．Carbonyl halides279

3．Sulphur analogues of carbonic acid and their derivatives281

a．Carbon oxysulphide and carbon disulphide282

b．Thiocarbonic acids284

(ⅰ)Monothiocarbonic acids284

(ⅱ)Dithiocarbonic acids285

(ⅲ)Trithiocarbonic acid287

c．Halides of the thiocarbonic acids289

4．Amides and related derivatives of carbonic acid and the thiocarbonic acids290

a．Carbamic acid derivatives290

(ⅰ)Alkyl carbamates,urethanes291

(ⅱ)Carbamic acid derivatives of the amino-carboxylic acids297

(ⅲ)N-Halogeno-,nitroso- and nitro-urethanes299

(ⅳ)Carbamoyl chlorides,＂urea chlorides＂,301

(ⅴ)Carbamoyl phosphates302

b．Urea and its derivatives303

Constitution of urea304

Formation of urea305

Manulacture of urea306

Reactions of urea307

Urea clathrate compounds308

Determi-nation of urea310

(ⅰ)Alkylureas311

(ⅱ)Diureas314

(ⅲ)Halogenoureas314

(ⅳ)Nitroso-and nitro-ureas314

(ⅴ)Ureides315

c．Derivatives of iminodicarboxylic acid and nitrilotricarboxylic acid316

(ⅰ)Derivatives of iminodicarboxylic acid316

(ⅱ)Derivatives of nitrilo-tricarboxylic acid320

d．Derivatives of iminocarbonic acid and isourea320

(ⅰ)Derivatives of iminocarbonic acid320

Derivatives of isourea321

e．Hydrazino,hydrazo,azo,azido and hydroxyamino derivatives of carbonic acid322

(ⅰ)Hydrazinecarboxylic acids and their derivatives322

(ⅱ)Azodicarb-oxylic acid and its derivatives326

(ⅲ)Azides of derivatives of carb-onic acid327

(ⅳ)Hydroxyamino derivatives of carbonic acid327

f．Sulphur analogues of carbamic acid and urea328

(ⅰ)Sulphur analogues of carbonic acid and its derivatives328

(ⅱ)Thiourea,isothiourea and their derivatives334

(ⅲ)Hydrazino,azo and azido derivatives of thiocarbonic acid339

5．Guanidine and its derivatives341

6．Nitriles and imides of carbonic and thiocarbonic acids354

a．Cyanic acid and its derivatives354

(ⅰ)Esters of cyanic acid356

(ⅱ)Cyanogen halides361

b．Sulphur compounds of cyanogen363

(ⅰ)Thiocyanic acid363

(ⅱ)Thiocyanogen halides366

(ⅲ)Alkyl thio-cyanates,esters of thiocyanic acid367

(ⅳ)Alkyl isothiocyanates,esters ofisothiocyanic acid369

c．Cyanamide and its derivatives373

d．Derivatives of carbodi-imide376

7．Derivatives of orthocarbonic acid379

a．Esters,tetra-alkoxymethanes379

b．Amino-derivatives of orthocarbonic acid379

c．Sulphur derivatives of orthocarbonic acid380

(ⅰ)Esters380

(ⅱ)Sulphenyl halides and sulphonic acids381

INDEX383