《CHEMISTRY OF CARBON COMPOUNDS VOLUME IV PART A HETEROCYCLIC COMPOUNDS》

Chapter Ⅰ．Compounds with Three-and Four-Membered Heterocyclic Rings＆by T．S．STEVENS10

1．Ethylene Oxides(Oxirans)11

2．Ethylene Sulphides(Thiirans)11

3．Ethyleneimines(Aziridines)14

4．Three Membered Rings with Two Hetero Atoms20

5．Trimethylene Oxides(Oxetans)20

6．Trimethylene Sulphides(Thietans)22

7．Trimethyleneimines(Azetidines)22

8．Other Four Membered Rings25

a．Silicon Compounds25

b．Rings Containing Two Oxygen or Sulphur Atoms25

c．Rings Containing Two Nitrogen Atoms26

d．Rings Containing One Nitrogen and One Oxygen or Sulphur Atom27

Chapter Ⅱ．Compounds Containing a Five Membered Ring with One Hetero Atom,Nitrogen＆by T．S．STEVENS28

1．Pyrroles and Hydropyrroles28

Synthetic Methods28

General Properties34

a．Pyrrole and its Substitution Products40

(ⅰ)Pyrrole40

N-Derivatives of Pyrrole41

(ⅱ)C-Alkyl-and C-Aryl-pyrroles43

(ⅲ)Halogenopyrroles45

(ⅳ)Nitro-,Nitroso-and Amino-pyrroles47

(ⅴ)Hydroxypyrroles49

(ⅵ)Sulphur Derivatives of Pyrroles51

(ⅶ)Alcohols and Related Compounds51

(ⅷ)Aldehydes and Ketones52

(ⅸ)Carboxylic Acids55

b．Dihydropyrroles(Pyrrolines)59

c．Tetrahydropyrroles(Pyrrolidines)61

d．Compounds Having Two or More Unfused Pyrrole Rings68

2．Indoles and Hydroindoles71

Synthetic Methods71

General Properties and Reactions77

a．Indole and its Substitution Products81

(ⅰ)Indole81

N-Derivatives81

(ⅱ)C-Alkyl-,C-Aryl-and Related Indoles82

(ⅲ)Halogenoindoles85

(ⅳ)Sulphur Compounds85

(ⅴ)Nitro-,Amino-and Related Indoles86

(ⅵ)Hydroxyindoles87

(ⅶ)Metal and Metalloid Derivatives91

(ⅷ)Indolyl Carbinols and Related Amines92

Aminoalkylindoles92

(ⅸ)Aldehydes and Ketones95

(ⅹ)Carboxylic Acids96

b．Dihydroindoles(Indolines)100

Oxoindolines(Indolinones)102

c．Tetra-,Hexa-and Octa-Hydroindoles109

d．Compounds Having More than One Indole Nucleus109

3．isoIndoles and isoIndolines112

4．Other Bicyclic Pyrrole Systems115

a．Spirocyclic Systems115

b．Cycloalkenopyrroles116

c．Fused Systems of Two Heterocyclic Rings117

5．Benzoindoles(Except Carbazole)119

6．Carbazole120

Synthetic Methods121

General Properties and Reactions122

(ⅰ)Carbazole and its N-Substituted Derivatives123

(ⅱ)C-Alkylcarbazoles125

(ⅲ)Halogenocarbazoles125

(ⅳ)Nitro-and Amino-carbazoles125

(ⅴ)Hydroxycarbazoles127

(ⅵ)Sulphonic Acids and Related Compounds128

(ⅶ)Organometallic Derivatives128

(ⅷ)Alcohols,Aldehydes and Ketones128

(ⅸ)Carboxylic Acids129

(ⅹ)Tetrahydro-carbazoles130

(ⅹⅰ)Other Reduced Carbazoles133

(ⅹⅱ)Compounds Having More Than One Carbazole Nucleus134

(ⅹⅲ)Benzocarbazoles134

7．Other Tricyclic Pyrrole Systems136

Chapter Ⅲ．Compounds Containing a Five Membered Ring with One Hetero Atom,Oxygen or Sulphur＆by T．S．STEVENS138

The Furan Group138

1．Monocyclic Furans and Hydrofurans138

a．Furan and its Substitution Products138

Synthetic Methods138

General Properties and Reactions141

Ring Fission143

(ⅰ)Furan144

(ⅱ)Alkyl-and Aryl-furans146

(ⅲ)Halogenofurans147

(ⅳ)Sulphonic Acids148

(ⅴ)Nitrofurans148

(ⅵ)Aminofurans149

(ⅶ)Hydroxyfurans149

(ⅷ)Furfuryl Alcohol and Related Compounds151

(ⅸ)Aldehydes and Ketones152

(ⅹ)Carboxylic Acids155

b．Dihydrofurans159

c．Tetrahydrofurans162

d．Compounds with Two or More Unfused Furan Nuclei166

e．Polyene Derivatives of Furan167

2．2:3(4:5)-Benzofuran(Coumarone)and its Hydrogenated Products168

Synthetic Methods169

General Properties and Reactions171

a．Benzofuran and its Substitution Products172

(ⅰ)Benzofuran172

(ⅱ)Alkyl-and Aryl-benzofurans173

(ⅲ)Halogeno-benzofurans173

(ⅳ)Nitro-and Amino-benzofurans174

(ⅴ)Hydroxy-benzofurans175

(ⅵ)Alcohols,Aldehydes and Ketones175

(ⅶ)Carb-oxylic Acids178

b．2:3-Dihydrobenzofurans(Coumarans)179

c．Other Reduced Benzofurans185

3．3:4-Benzofuran(isoBenzofuran)186

4．Other Bicyclic Systems with a Furan Ring190

5．Dibenzofuran or Diphenylene Oxide and its Hydrogenated Products192

Synthetic Methods192

Properties and Reactions193

a．Dibenzofuran and Derivatives195

b．Reduced Dibenzofurans195

c．Natural Products Related to Dibenzofuran197

6．Other Tri-and Poly-cyclic Systems with a Furan Ring199

a．Condensed Systems of Benzene Rings with One Furan Nucleus199

b．Systems of Benzene Rings and More Than One Furan Nucleus201

c．Other Tri-and Poly-cyclic Furans202

The Thiophen Group203

7．Monocyclic Thiophens and Hydrothiophens203

a．Thiophen and its Substitution Products203

Synthetic Methods203

General Properties205

(ⅰ)Thiophen207

Metal and Metalloid Derivatives of Thiophens208

(ⅱ)Alkyl-and Aryl-thiophens210

(ⅲ)Halogenothiophens212

(ⅳ)Nitro-and Amino-thiophens214

(ⅴ)Hydroxythiophens215

(ⅵ)Sulphonic Acids,Mercaptans and Related Compounds216

(ⅶ)Thiophen Alcohols and Related Compounds216

(ⅷ)Aldehydes and Ketones217

(ⅸ)Thiophencarboxylic Acids219

Acids Having the Carboxyl Group in the Side-Chain220

b．Dihydrothiophens221

c．Tetrahydrothiophens222

d．Compounds Having Two or More Unfused Thiophen Rings224

8．Thionaphthens225

Synthetic Methods225

General Properties228

a．Thionaphthen and its Substitution Products229

b．Reduced Thionaphthens232

9．Other Bicyclic Thiophens235

a．3:4-Benzothiophens(isoBenzothiophens)235

b．Other Cycloalkenothiophens236

c．Systems of Two Fused Thiophen Rings237

10．Dibenzothiophens238

11．Other Tri-and Poly-cyclic Systems Containing the Thiophen Ring240

12．Selenophens and Tellurophens242

Chapter Ⅳ．Compounds Containing a Five Membered Ring with Two Hetero Atoms:Pyrazole and Iminazole Groups＆by J．D．LOUDON244

Nomenclature244

1．Pyrazole Group245

a．Pyrazoles245

Syntheses245

Properties249

(ⅰ)Halogeno-,Nitroso-,Nitro-and Sulphonic Derivatives253

(ⅱ)Amino-and Azo-pyrazoles254

(ⅲ)Hydroxypyrazoles255

(ⅳ)Alcohols,Aldehy-des,Ketones257

(ⅴ)Carboxylic Acids258

(ⅵ)Pyrazolenines260

b．Pyrazolines261

Syntheses261

Properties263

(ⅰ)Alkyl-and Aryl-pyrazolines264

(ⅱ)Substituted Pyrazolines265

(ⅲ)Pyrazolones268

c．Pyrazolidines276

d．Indazoles or Benzopyrazoles278

Synthetic Methods of Formation279

Properties281

(ⅰ)Halogeno-,Nitro-and Amino-indazoles282

(ⅱ)Ketones and Car-boxylic Acids284

(ⅲ)Reduced indazoles284

e．Condensed Polycyclic Pyrazoles285

2．Iminazole Group286

Syntheses286

Properties290

a．Iminazole,its Homologues and Derivatives292

(ⅰ)Halogeno-,Nitro-and Amino-iminazoles294

(ⅱ)Sulphur-Containing Derivatives295

(ⅲ)Alcohols and Related Compounds296

(ⅳ)Alde-hydes and Ketones298

(ⅴ)Iminazole Carboxylic Acids298

b．Iminazolines301

(ⅰ)2-Iminazolines301

(ⅱ)2:5-Dihydroiminazoles or 3-Iminazolines306

(ⅲ)2:3-Dihydroiminazoles or 4-Iminazolines306

c．Iminazolidines308

(ⅰ)Ketoiminazolidines309

(ⅱ)Diketoiminazolidines312

(ⅲ)Triketo-iminazolidines320

d．Benziminazoles321

Methods of Synthesis322

Properties325

Benziminazole,its Homo-logues and Substitution Products326

(ⅰ)Halogeno-,Nitro-,Sulpho-and Amino-Derivatives327

(ⅱ)Alcohols etc．,Aldehydes and Ketones328

(ⅲ)Carboxylic Acids329

(ⅳ)Reduced Benziminazoles329

e．Condensed Polycyclic Iminazoles331

Chapter Ⅴ．Compounds Containing a Five Membered Ring with Two Hetero Atoms:Dioxole and Oxazole Groups and Their Thia Analogues＆by J．D．LOUDON332

1．Compounds Containing a Five Membered Ring with Oxygen and/or Sulphur as the Two Hetero Atoms332

2．isoOxazole Group334

a．isoOxazole,its Homologues and Substitution Products334

Syntheses334

Properties336

(ⅰ)Halogeno-,Nitro-and Sulphonic Derivatives338

(ⅱ)Amino Deriva-tives339

(ⅲ)Alcohols etc．,Aldehydes and Ketones340

(ⅳ)isoOxazole Carboxylic Acids341

b．isoOxazolines and Their Derivatives343

Synthetic Methods343

(ⅰ)isoOxazolines344

(ⅱ)isoOxazolones345

c．isoOxazolidines348

d．Benzisooxazoles and Related Compounds348

(ⅰ)Benzisooxazoles(Indoxazenes)349

(ⅱ)Anthranils351

3．Oxazole Group353

a．Oxazole,its Homologues etc353

Syntheses353

Properties357

Aldehydes,Ketones and Carboxylic Acids359

b．Oxazolines361

(ⅰ)4:5-Dihydrooxazoles or 2-Oxazolines361

Syntheses361

4-Oxazolones(4-Keto-2-Oxazolines)365

5-Oxazolones(5-Keto-2-oxazolines)365

(ⅱ)2:5-Dihydrooxazoles or 3-Oxazolines370

(ⅲ)2:3-Dihydrooxazoles or 4-Oxazolines371

c．Oxazolidines372

d．Benzoxazoles and Condensed Polycyclic Oxazoles375

4．isoThiazole Group379

a．Benzisothiazoles380

b．Benzisoselenazoles385

5．Thiazole Group385

a．Thiazoles385

Syntheses386

Properties388

(ⅰ)Halogeno-,Nitro-and Sulpho-thiazoles391

(ⅱ)Amino-and Hydroxy-thiazoles392

(ⅲ)Alcohols and Related Compounds397

(ⅳ)Thiazole Aldehydes and Ketones399

(ⅴ)Thiazole Carboxylic Acids400

b．Thiazolines403

(ⅰ)4:5-Dihydrothiazoles(2-Thiazolines)403

(ⅱ)2:5-Dihydrothiazoles(3-Thiazolines)407

(ⅲ)2:3-Dihydrothiazoles(4-Thiazolines)407

c．Thiazolidines407

d．The Penicillins414

Structure of Degradation Products417

Penicillamine,Penilloaldehydes,Penaldic and Penicilloic Acids417

Penilloic Acids419

Penillic Acids,Penillamines and isoPenillic Acids419

Penicillenates421

Benzyl-penillonic Acid421

Structure of Penicillin423

e．Benzothiazoles425

Syntheses425

Properties426

(ⅰ)Halogeno-,Nitro-and Sulpho-benzothiazoles428

(ⅱ)Amino-and Hydroxy-benzothiazoles429

(ⅲ)Aldehydes,Ketones and Carboxylic Acids433

(ⅳ)Reduced Benzothiazoles433

(ⅴ)Condensed Polycyclic Thiazoles435

f．Selenazoles435

Chapter Ⅵ．Compounds Containing a Five Membered Ring with More Than Two Hetero Atoms＆by E．HOGGARTH439

Five Membered Rings with Three Hetero Atoms439

1．Triazoles439

a．1:2:3-Triazoles439

Methods of Preparation439

Properties443

Structure of 1:2:3-Triazoles444

(ⅰ)Halogen Derivatives of 1:2:3-Triazole445

(ⅱ)C-Hydroxy-1:2:3-Triazoles445

(ⅲ)C-Amino-1:2:3-triazoles446

(ⅳ)1:2:3-Triazole Aldehydes447

(ⅴ)1:2:3-Triazolecarboxylic Acids448

b．Benzotriazoles449

Methods of Preparation449

Properties450

Structure of the Benzo-triazoles451

c．1:2:4-Triazoles452

Methods of Preparation452

Properties458

Structure of 1:2:4-Triazoles458

(ⅰ)Halogen Derivatives of 1:2:4-Triazole460

(ⅱ)Hydroxy-and Amino-Derivatives of 1:2:4-Triazole460

(ⅲ)1:2:4-Triazolecarboxylic Acids463

2．Oxadiazoles464

a．1:2:3-Oxadiazoles464

b．1:2:5-Oxadiazoles(Furazans)466

c．Benzo-1:2:5-oxadiazoles469

d．1:2:4-Oxadiazoles(Azoximes)469

e．1:3:4-Oxadiazoles471

3．Thiadiazoles473

a．1:2:3-Thiadiazoles(Diazosulphides)473

b．Benzo-1:2:3-thiadiazoles474

c．1:2:5-Thiadiazoles474

d．1:2:4-Thiadiazoles(Azosulphimes)475

e．1:3:4-Thiadiazoles476

4．Dioxazoles,Dithiazoles and Oxathiazoles479

Five Membered Rings with Four Hetero Atoms481

5．Tetrazoles481

6．Thiatriazoles and Dithiadiazoles486

Chapter Ⅶ．Compounds Containing a Six Membered Ring with One Hetero Atom,Nitrogen＆by N．CAMPBELL488

1．Pyridine and its Derivatives488

Structure of Pyridine489

Fine Structure of the Pyridine Molecule490

Methods of Synthesis492

Separation,Purification and Identification of Pyridine Bases499

Properties and Reactions of the Pyridine Bases;Comparison with Benzene and Nitrobenzene500

Reactions with Metal Compounds501

Diene Addition501

Pyridinium Compounds504

Pyridinium Betaines507

Properties of the Pyridinium Betaines509

Pyridinium Salts and Betaines as Synthetic Reagents510

Fission of the Pyridine Ring512

a．Pyridine,its Homologues and Substitution Products514

(ⅰ)Pyridine514

Pyridine-N-Oxides516

(ⅱ)Pyridine Homologues518

Reactivity of the 2-and 4-Picolines519

(ⅲ)Phenylpyridines526

(ⅳ)Pyridone Methides528

(ⅴ)Halogenopyridines530

(ⅵ)Nitro-pyridines536

(ⅶ)Pyridinesulphouic Acids537

(ⅷ)Aminopyridines538

Properties and Structure539

Azopyridines and Related Com-pounds542

(ⅸ)Hydroxypyridines544

(ⅹ)Pyridthiols or Pyrid-thiones548

(ⅹⅰ)Alcohols of the Pyridine Series549

Vitamin B6551

(ⅹⅱ)Pyridine Aldehydes552

(ⅹⅲ)Pyridine Ketones554

(ⅹⅳ)Pyridine-carboxylic Acids556

Pyridine Polycarboxylic Acids562

(ⅹⅴ)Pyridine Arsenicals564

(ⅹⅵ)Dipyridyls564

b．Dihydropyridines566

c．Tetrahydropyridines．Piperideines567

d．Hexahydropyridine．Piperidine569

(ⅰ)Piperidine and its Homologues570

(ⅱ)N-Alkyl-and N-Aryl-Piper-idines572

Fission of the Piperidine Ring574

(ⅲ)Piperidine Deriva-tives576

(ⅳ)Hydrogenated Pyridinecarboxylic Acids578

(ⅴ)Piper-idones581

e．Dipiperidyls583

2．Quinoline and its Derivatives584

Structure of Quinoline585

Fine Structure of Quinoline586

Methods of Synthesis586

Separation,Purification and Identification of the Quinoline Bases594

Properties of the Quinoline Bases．Comparison with Naphthalene594

Quinolinium Compounds597

Ring-Fission601

a．Quinoline,its Homologues and Substitution Products602

(ⅰ)Quinoline602

(ⅱ)Quinoline Homologues603

(ⅲ)Phenylquinolines604

(ⅳ)Quinolone Methides604

(ⅴ)Halogenoquinolines607

(ⅵ)Nitroquinolines610

(ⅶ)Quinolinesulphonic Acids612

(ⅷ)Amino-quinolines and Related Compounds613

Properties614

Amino-quinoline Derivatives as Chemotherapeutic Drugs617

Quiuolylhydra-zines and Related Compounds618

(ⅸ)Hydroxyquinolines or Quino-linols620

Aminohydroxyquinolines626

Quinoline Quinones627

(ⅹ)Quinolinethiols627

(ⅹⅰ)Quinoline-aldehydes628

(ⅹⅱ)Quinolyl Ketones630

(ⅹⅲ)Quinolinecarboxylic Acids631

(ⅹⅳ)Hydroxy-quinolinecarboxylic Acids635

(ⅹⅴ)Diquinolyls637

(ⅹⅵ)Quinoline Dyes637

Quinophthalones638

Dyes Derived from Naphtho-[2′:3′-5:6]-quinoline640

b．Hydrogenated Quinolines641

3．isoQuinoline and its Derivatives645

Constitution645

Synthetic Methods646

Fission of the isoQuinoline Ring649

General Properties651

isoQuinolinium Compounds653

a．isoQuinoline and its Substitution Products654

(ⅰ)isoQuinoline,its Alkyl and Aryl Derivatives654

(ⅱ)Halogenoiso-quinolines656

(ⅲ)Nitration and Sulphonation of iso Quinoline657

(ⅳ)Aminoisoquinolines658

(ⅴ)Hydroxyisoquinolines or iso Quinolinols659

(ⅵ)iso Quinoline-aldehydes and Ketones660

(ⅶ)iso Quinoline-carboxylic Acids662

(ⅷ)Diisoquinolyls663

b．Hydrogenated iso Quinolines663

4．Cyclopolymethylenepyridines666

5．Acridine and its Derivatives667

Synthetic Methods668

Acridinium Compounds671

a．Acridine and its Substitution Products673

(ⅰ)Acridine and Homologues673

(ⅱ)Halogenoacridines674

(ⅲ)Nitroacridines676

(ⅳ)Aminoacridines677

Acridine Compounds of Therapeutic Importance679

Acridine Dyes681

(ⅴ)Hydroxyacridines or Acridols684

Acridone and its Derivatives685

(ⅵ)Diacridyl Com-pounds688

b．Hydrogenated Acridines689

6．Phenanthridine and its Derivatives691

Methods of Synthesis692

a．Phenanthridine and its Substitution Products694

(ⅰ)Phenanthridine and its Homologues694

(ⅱ)Halogeno-,Nitro-and Amino-phenanthridines695

(ⅲ)Phenanthridinium Compounds697

(ⅳ)Hydroxyphenanthridines．Phenanthridones698

b．Hydrophenanthridines701

7．Benzoquinolines702

8．Benzoisoquinolines705

9．Naphthoquinolines and Naphthoisoquinolines706

a．Benzacridines(Naphthacridines)709

b．Dibenzacridines710

c．Benzophenanthridines712

INDEX715