The Pyrimidines, Volume 16

Chapter I. Introduction to the Pyrimidines 1

1. History 1

2. Nomenclature 3

3. The Unique Basis of Pyrimidine Chemistry 5

4. General Summary of Pyrimidine Chemistry 9

5. Physical Properties of Pyrimidines 26

Chapter II. The Principal Synthetic Method 31

1. General Scope 31

2. Use of β –Dialdehydes 32

3. Use of β-Aldehydo Ketones 34

4. Use of β Diketones 36

5. Use of β-Aldehydo Esters 38

6. Use of β-Keto Esters 48

7. Use of β-Diesters (Malonic Esters) 51

8. Use of β-Aldehydo Nitriles 59

9. Use of β -Keto Nitriles 65

10. Use of β -Ester Nitriles

11. Use of β -Dinitriles (Malononitriles)

Chapter III. Other Methods of Primary Synthesis 82

1. General Remarks 82

2. Syntheses Involving Preformed Amino-methylene Groups 82

3. Syntheses Involving an Aminomethylene Group Formed In Situ 90

4. Syntheses from Malondiamides and Malondiamidine 97

5. Other Syntheses of Pyrimidines 101

6. Formation of Pyrimidine Rmg in Fused Heterocycles 107

Chapter IV. Pyrimidine and Its C-Alkyl and C-Aryl Derivatives 116

1. Pyrimidine (Unsubstituted) 116

2. C-Alkyl- and C-Aryl-pyrimidines 119

Chapter V. Nitro-, Nitroso-, and AryIazo-pyrimidines 138

1. The Nitropyrimidines 138

2. Nitrosopyrimidines 146

3. The Arylazopyrimidines 152

Chapter VI. Halogenopyrimidines 162

1. The Preparation of 2 4. and 6-Halogenopyrimidines 162

2. The Preparation of 5-Halogenopyrimidines 168

3. The Preparation of Extranuclear Halogenopyrimidines 176

4. Properties of Halogenopyrimidines 181

5. Reactions of 2-, 4-, and 6-Halogenopyrimidines 183

6. Reactions of 5-Halogenopyrimidines 210

7. Reactions of Extranuclear Halogenopyrimidines 214

Chapter VII. Hydroxy- and Alkoxy-pyrimidines 227

1. Preparation of 2 4 and 6-Hydroxypyrimidines 227

2. Preparation of 5-Hydroxypyrimidines 237

3. Preparation of Extranuclear Hydroxypyrimidines 241

4. Preparation of Alkoxy- and Aryloxy-pyrimidines 245

5. Properties and Structure of Hydroxy- and Alkoxy-pyrimidines 249

6. Reactions of Hydroxypyrimidines 250

7. Reactions of AIkoxy- and Aryloxy-pyrimidines 254

8. Some Naturally Occurring Hydroxypyrimidines 256

9. The Alloxan Group of Pyrimidines 260

Chapter VIII. Sulphur-containing Pyrimidines 272

I. The Mercaptopyrimidines 272

2. The Thioethers: Alkylthio- and Arylthio-pyrimidines 286

3. DipyrimidinyI Disulphides and Sulphides 291

4. Pyrimidine Sulphonic Acids and Related Compounds 295

5. Alkylsulphonylpyrimidines 298

6. Thiouracil and Homologues 300

Chapter IX. The Aminopyrimidines 306

1. Preparation of 2-, 4-, and 6-Aminopyrimidines 306

2. Reparation of 5-Aminopyrimidines  313

3. Preparation of Extranuclear Aminopyrimidines 316

4. Properties of Aminopyrimidines 320

5. Reactions of Aminopyrimidines 321

6. Urethanes (Alkoxycarbonylaminopyrimidines) 336

7. Ureidopyrimidines 339

8. Other Substituted-amino-pyrimidines 341

9. Some Naturally Occurring Aminopyrimidines 345

Chapter X. The N Alylated Pyrimidines and Pyrimidine-N-Oxides 356

1. The Oxopyrimidines 357

2. The Iminopyrimidines 377

3. The N-Methylated Thiopyrirnidines 381

4. The Pyrimidine-N-Oxides 382

Chapter XI. The Pyrimidine Carboxylic Acids and Related Derivatives 389

1. The Carboxypyrimidines 389

2. Alkoxycarbonylpyrimidines (Pyrimidine Esters) 395

3. Carbamoyipyrimidines (Amidesj and Related Compounds (Hydrazidesand Azides) 397

4. Pyrimidine Nitriles 401

5. Pyrimidine Aldehydes and Their Acetals 406

6. Pyrimidine Ketones and Derivatives 415

7. The Isocyanato-. Thiocyanato-. and Isothiocyanato-pyrimidine Family 418

8. Orotic Acid: Biosynthesis of Pyrimidines 422

Chapter XII. The Reduced Pyrimidines 430

1. Preparation of Dihydropyrimidines 431

2. Preparation of Tetrahydropyrimidines 445

3. Preparation of Hexahydropyrimidines 452

4. Reactions of Reduced Pyrimidines 454

Chapter XIII The Ionization and Absorption Spectra of Pyrimidines 464

1. Ionization of Pyrimidines 464

2. The Absorption Spectra of the Pyrimidines (By S. F.Mason) 474