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Ⅰ．Introduction1

Ⅱ．The Evolution of Lignin Chemistry5

Ⅲ．The Definition and Distribution of Lignin14

Ⅳ．Color Reaction of Lignified Materials24

A．Introduction24

B．Preparation of the Material24

C．Color Reactions with Aliphatic Compounds25

D．Color Reactions with Phenolic Compounds26

E．Color Reactions with Aromatic Amines29

F．Color Reactions with Heterocyclic Compounds30

G．Color Reactions with Inorganic Reagents40

1．The M？ule Test41

2．Other Color Reactions Involving Chlorination42

3．Color Reactions with Inorganic Acids43

4．Other Inorganic Color Reagents44

H．Color Reactions with Dyestuffs45

Ⅴ．The Isolation of Lignin49

A．Preparation of the Plant Material49

B．Native Lignin51

C．Insoluble Lignins54

1．Acid Lignins54

a．Sulfuric Acid or Klason Lignin55

ⅰ．Preparation of Sulfuric Acid Lignin56

b．Hydrochloric Acid or Willst？tter Lignin56

ⅰ．Preparation of Hydrochloric Acid Lignin58

ⅱ．Modified Methods59

c．Hydrofluoric Acid Lignin60

2．Cuoxam or Freudenberg Lignin61

a．Preparation of Cuoxam Lignin62

3．Periodate or Purves Lignin63

D．Organosolv Lignins65

1．Alcohol Lignins65

a．Methanol Lignin66

b．Ethanol Lignin69

c．Butanol and Amyl Alcohol Lignins69

d．Cyclohexanol Lignin70

e．Benzyl Alcohol Lignin70

f．Glycol Lignins70

g．Glycol Monomethyl Ether Lignin74

h．Chlorohydrin Lignins74

2．Aldehyde Lignins76

a．Formaldehyde Lignin76

b．Chloral Lignin77

3．Ethyl Acetoacetate Lignin77

4．Dioxane Lignins78

5．Phenol Lignins82

a．Unsubstituted Phenol Lignins82

ⅰ．Preparation of Phenol Spruce Lignin83

b．Substituted Phenol Lignins85

6．Mercapto Lignins85

a．Butylmercapto Lignin86

b．Benzylmereapto Lignin86

c．Thioglycolie Acid Lignin87

ⅰ．Preparation of Thioglycolic Acid Lignin87

7．Organic Acid Lignins88

a．Formic Acid Lignin88

b．Acetic Acid Lignin89

ⅰ．Preparation of Acetic Acid Lignin90

c．Chloroacetic Acid Lignins93

d．Other Organic Acid Lignins94

8．Organic Amine Lignins94

E．Lignins Extracted with Inorganic Reagents96

1．Introduction96

2．Lignins Isolated by Alkaline Reagents96

a．Ammonia Lignin96

b．Hydrazino Lignin97

c．Alkali or Soda Lignins98

ⅰ．Isolated with Aqueous Alkaline Solutions98

ⅱ．Commercial Alkali Lignins105

ⅲ．Isolated with Alcoholic Alkaline Solutions107

d．Thiolignin108

3．Lignin Isolated by Bisulfites111

a．Lignosulfonic Acid111

ⅰ．Isolation as Basic Lignosulfonate112

ⅱ．Isolation by the Salting Out Method115

ⅲ．Isolation by Dialysis123

F．Lignin Isolated by Hydrotropic Solvents125

G．Lignin Isolated by a Mild Hydrogenation126

Ⅵ．The Determination of Lignin133

A．Introduction133

B．Interfering Substances134

1．Polysaccharides134

2．Pectins137

3．Proteins137

4．Fats,Waxes,and Resins138

5．Tannins and Phlobaphenes138

6．Coloring Matters139

7．Other Organic Substances139

8．Inorganic Matters139

C．The Effect of Pretreatments on the Lignin Determination140

1．Organic Solvents140

2．Water140

3．Dilute Alkali142

4．Dilute Acid(Prehydrolysis)145

5．Summary148

D．Preparation of the Sample149

E．Lignin Determination Methods151

1．Direct Methods151

a．Determination with Strong Mineral Acids151

ⅰ．Sulfuric Acid Method151

ⅱ．Hydrochloric Acid Method159

ⅲ．Hydrofluoric Acid Method162

ⅳ．Mixed Acids162

b．Determination as Alkali Lignin164

2．Indirect Methods164

a．By Removing the Lignin and Weighing the Carbo-hydrate Residue164

b．By Reaction with Halogens166

c．By Reduction of Nitric Acid168

d．By Determining the Methoxyl Content169

e．By the Reaction with Phloroglucinol170

f．Mehta＇s Colorimetric Method170

g．By Extraction with Phenol171

3．Determination of Lignin in Spent Liquors171

a．Lignin in Soda and Sulfate Spent Liquor172

b．Lignin in Sulfite Spent Liquor172

F．Comparison of Lignin Determination Methods173

Ⅶ．The Physical Properties of Lignin182

A．Introduction182

B．Solubility183

C．Melting Point184

D．Heat of Combustion185

E．Color185

F．Density185

G．Viscosity186

H．Molecular Weight188

1．Determination of the Unit Molecular Weight by Chemical Means189

2．Determination of the Molecular Weight by Physical Means191

3．Molecular Weight of Lignosulfonic Acids195

I．Spreading Experiments197

J．The Colloidal Nature of Lignin199

K．The Conductivity of Lignosulfonic Acid208

L．X-Ray Investigations of Lignin211

M．Refractive Index215

N．Optical Activity215

O．The Fluorescence of Lignin216

P．Ultraviolet Absorption Spectra217

Q．Infrared Absorption Spectra230

Ⅷ．The Elementary Composition and Constituent Groups of Lignin236

A．Elementary Composition236

B．The Phenylpropane Carbon Structure242

C．Methoxyl Groups243

D．Methylenedioxy Group246

E．Hydroxyl Groups246

F．Aromatic Hydrogen Atoms254

G．The Carbonyl Group255

H．Terminal CH3C-Groups259

I．Double Bonds260

Ⅸ．The Acylation and Acylysis of Lignin270

A．Acylation270

1．Introduction270

2．Protolignin271

3．Isolated Lignins271

a．Insoluble Lignins271

b．Organosolv Lignins274

e．Alkali Lignin276

d．The Xanthation of Lignin278

e．Lignosulfonic Acid279

B．Acylysis280

1．Formolysis280

a．Protolignin280

2．Acetolysis281

a．Protolignin281

ⅰ．With Acetic Acid in the Presence of Catalysts281

ⅱ．With Acetic Anhydride in the Presence of a Catalyst284

ⅲ．With Acetyl Bromide286

b．Isolated Lignin287

Ⅹ．The Alkylation of Lignin291

A．Introduction291

B．Protolignin292

1．Diazomethane292

2．Dimethyl Sulfate292

C．Isolated Lignins295

1．Isolated Native Spruce Lignin295

2．Acid Lignins297

3．Organosolv Lignins298

4．Lignosulfonic Acid303

D．The Stability of the Methoxyl Groups in Methylated Lignin305

Ⅺ．The Halogenation of Lignin309

A．Fluorination309

B．Chlorination309

1．Protolignin309

a．In an Aqueous Medium309

b．In Methanol316

2．Isolated Lignin318

a．In an Aqueous Medium with Chlorine Gas318

b．In Organic Solvents with Chlorine Gas319

c．With Other Chlorinating Agents324

3．Lignosulfonic Acid326

C．Bromination327

1．Protolignin327

2．Isolated Lignin328

3．Lignosulfonic Acid332

D．Iodination333

1．Protolignin333

2．Isolated Lignin334

3．Lignosulfonic Acid336

E．Thiocyanogenation336

Ⅻ．The Nitration of Lignin339

A．The Action of Nitric Acid on Protolignin339

B．Nitrolignins from Isolated Lignins347

C．The Nitration of Lignosulfonic Acid353

D．Theoretical Aspects of the Nitration of Lignin355

ⅩⅢ．The Sulfonation of Lignin359

A．Introduction359

B．Protolignin361

1．With Sulfurous Acid361

2．With Bisulfites362

3．Sulfonation by Sulfolysis366

4．The Effect of Pretreatment of Protolignin on its Sulfonation367

C．Isolated Lignin372

D．Reactive Groups in Lignosulfonic Acid373

E．Theories on the Sulfonation of Lignin and the Sulfonation of Model Substances377

F．Conclusions389

ⅩⅣ．The Hydrolysis of Lignin394

A．In an Aqueous Neutral Solution394

B．In an Alkaline Medium397

1．Protolignin397

2．Isolated Lignins400

3．Lignosulfonates405

4．Alkali Lignin416

a．Introduction416

b．From Protolignin416

c．From Isolated Lignin422

5．Thiolignin422

a．From Protolignin422

b．From Isolated Lignin428

c．The Reaction Mechanism between Lignin and Sodium Sulfides428

C．Acid Hydrolysis431

1．Demethylation of Lignin432

ⅩⅤ．The Alcoholysis of Lignin453

A．Introduction453

B．Alcohol Lignins453

1．Protolignin453

a．The Action of Alcohols and Mineral Acids453

b．Methanolysis454

c．Ethanolysis456

d．Alcoholysis with Other Alcohols457

2．Isolated Lignins458

3．Theories on the Formation of Alcohol Lignin460

C．Polyalcohol Lignins461

1．Protolignin461

2．Isolated Lignins463

D．Alcobolysis to Monomolecular Lignin Building Stones465

ⅩⅥ．The Mercaptolysis of Lignin483

A．Introduction483

B．Protolignin483

1．With Mercaptans483

2．With Thioglycolic Acid484

3．With Other Mercapto Fatty Acids491

C．Isolated Lignins491

D．The Reaction Mechanism494

ⅩⅦ．The Phenolysis of Lignin497

A．Protolignin497

B．Isolated Lignins(Secondary Phenol Lignins)502

C．The Reaction Mechanism of Phenol Lignin Formation507

ⅩⅧ．Reduction,Hydrogenation,and Hydrogenolysis of Lignin511

A．Reduction511

1．Introduction511

2．Reduction with Hydriodie Acid and Red Phosphorus511

3．Reduction by the Wolff-Kishner Method514

B．Hydrogenation and Hydrogenolysis514

1．Introduction514

2．Hydrogenation at Low Temperatures(below 300°C．)516

a．In Neutral Solution516

b．In Alkaline Solution521

3．Pressure Hydrogenation at High Temperatures(over 300°C．)526

a．In Neutral Solution,without Catalysts526

b．In Neutral Solution,with Catalysts528

c．In Alkaline Solution529

d．With Primary Alcohols in the Presence of Alkali531

ⅩⅨ．The Oxidation of Lignin536

A．Introduction536

B．Oxidation in a Neutral Solution536

1．Protolignin536

2．Isolated Lignin538

3．Lignosulfonates541

C．Oxidation in an Acid Medium543

1．Protolignin543

2．Isolated Lignin544

D．Oxidation in an Alkaline Medium546

1．Protolignin546

2．Isolated Lignin547

3．Vanillin Formation552

ⅩⅩ．The Alkali Fusion of Lignin563

A．Introduction563

B．Protolignin and Isolated Lignins563

C．Lignosulfonic Acids571

ⅩⅪ．Special Reactions with Lignin574

A．The Action of Benzaldehyde on Lignin574

B．The Effect of Grignard Reagent on Lignin Preparations574

C．The Action of Diazobenzenesulfonic Acid on Lignin576

D．The Action of Potassium in Liquid Ammonia on Lignin576

E．Condensation of Lignin with Nitrodimethylaniline578

F．The Dehydrogenation of Lignin578

G．Sulfuric Acid Lignin Ester579

ⅩⅫ．The Thermal Decomposition of Lignin581

A．Dry Distillation in the Absence of Catalysts581

B．Dry Distillation in the Presence of Zinc Dust(Zinc Dust Distillation)589

C．Destructive Distillation in the Presence of Silver591

D．Thermal Decomposition in the Presence of Nickel592

E．Destructive Distillation in the Presence of Hydrogenation Catalysts594

F．Thermal Decomposition with Lime in the Presence of Alcohol596

ⅩⅩⅢ．The Biological Decomposition of Lignin599

A．By Digestive Microorganism(Metabolism of Lignin)599

B．By Soil Microorganisms603

C．By Wood-destroying Fungi607

D．The Biological Decomposition of Lignosulfonates614

E．Coal Formation615

ⅩⅩⅣ．Theories on the Structure of Lignin621

A．Introduction621

B．Lignin Formulas without Basic Building Stones621

1．Cross and Bevan＇s Formula621

2．Dorée and Barton-Wright＇s Formula624

3．Fuchs＇ Formulas625

C．Lignin Formulas with Basic Building Stones628

1．Klason＇s Theory628

2．Kürschner＇s Lignin Formula638

3．Pavolini＇s Formula642

4．Rassow and Gabriel＇s Formula643

5．Chambovet＇s Formula643

6．Freudenberg＇s Theory644

7．Hibbert＇s Theory651

8．Erdtman＇s Theory665

D．Conclusions669

ⅩⅩⅤ．The Linkage of Lignin in the Plant675

A．Introduction675

B．Lignin in a Physical Mixture with Other Plant Constituents675

C．Lignin in Chemical Combination with Other Plant Constituents678

D．Conclusions687

ⅩⅩⅥ．Theories on the Formation of Lignin694

A．Introduction694

B．Lignin,a Reaction Product Formed during its Isolation695

C．The Formation of Lignin in the Growing Plant707

D．Formation of Lignin by Direct Assimilation Synthesis710

E．Cellulose as the Precursor of Lignin710

F．Pentosans or Pentoses as Precursors of Lignin712

G．Pectins as Precursors of Lignin715

H．Water-soluble Sugars as Lignin Precursors716

1．Wislicenus＇ Theory716

2．The Jonas-Schrauth Theory719

3．Phillips＇ Theory728

4．Vanzetti＇s Theory730

ⅩⅩⅦ．Synthetic Lignins733

Appendix742

A．Purification of Lignin Derivatives742

B．Methoxyl Determinations in Lignin and Lignin Derivatives744

C．Purification of Dioxane745

D．Preparation of Cuprammonium Hydroxide Solution(Schweizer Reagent)746

1．Analysis for Copper746

2．Analysis for Ammonia747

E．Preparation of Ethylenediamine Copper Hydroxide Solution747

F．Preparation of Hydrogenation Catalysts747

1．Nickel-Kieselguhr Catalyst747

2．Raney Nickel Catalyst747

3．Copper-Chromium Oxide Catalyst748

G．Preparation of a Saturated Aqueous Chlorine Dioxide Solution748

H．Preparation of Periodic Acid749

Author Index750

Subject Index766