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1 INDEX Downloaded via on November 17, 2018 at 20:16:32 (UTC). See for options on how to legitimately share published articles. Absorption curve of kraft lignin 77 Acetal lignins 118 Acetals in isolating lignin 111 Acid-catalyzed condensation reactions Acidolysis of Bjôrkman spruce lignin..24, 26 Acidolvsis of dihydrodehydrodiconiferyl alcohol 22,23 Acidolysis of guaiacylglycerol β- 2-methoxyphenyl) ether 24 Additivity, principle of 39 Aldol condensation 84 Aliphatic oxidation products of wood Alkali fusion 149 Alkali lignin. 145 Alkaline hydrogénation of lignin 249 Alkaline pulping 85, 90 and CH 20 formation Alkoxvl groups, determination of 113 Aniline Aromatic oxidation products of wood Aromatic sites in lignin, reactivity of 47 Aromatic units in lignin Artificial lignin 3 Arvlglycerol β-aryl ether systems in ' lignin 24, 28-9 Β Barium dioxide 149 Base-catalyzed displacement reactions...48 Beech lignin 18 Benzaldehyde, extraction of wood with Biphenyl structures 157 l,2-bisguaiacyl-l,3-propanediol 31 1,2-Bisguaiacylpropanone 31 Bis-3,5-di-0-methylpyrogallylmethane Bis-4-hydroxy-3,5-dimethoxvphenvlmethane ' 93, 98, 107 Bisyringyl from maplewood 251 Bivanillyl from maplewood 251 Bjôrkman lignin..29, 76, 92, 226 Bjôrkman spruce lignin, acidolysis of..24, 26 Bleaching of pulps 71, 91 Calcium lignosulfonate 210 Cambial sap 2 Cannizzaro reaction 132 Carbohydrate p-hydroxybenzyl ether 16 /3,7-Carbon-carbon cleavage reaction Carbon-oxygen linkage Carbonyl content of lignin 65, 71 Carbonyl groups in lignin 128 α-carbonyls in kraft lignin 80 α-carbonyl syringols, phenoxy radicals from 55 Catalytic hydrogénation 206 Catalysts for hydrogénation 207 of lignin 239 Catechols, metal complexes with 86, 88 Cellulose, solvolytic degradation of 120 Chalcones 85, 88 Chlorination of guaiacylpropane unit 48 CHoO formation in alkaline pulping Chromatograms of hydrol lignin Chromatography, vapor phase 250 Chromophore 7 in kraft lignin 75, 83, 85 in lignin 70 Color formation in pulps 90 role of oxygen in 91 Condensation 214, 231 aldol. 84 reactions 234 acid-catalyzed 48 of lignin 84 Coniferaldehyde 3, 29 Coniferyl alcohol 2, 4 Constitutional scheme for lignin 59 Constitutional scheme for spruce lignin..1,3 Core structure in lignin 247 />-Coumaryl alcohol 2, 4 Coupling reactions 162 Creosol 68, 158 w-cresol 209, 212, 216, Cresol 208 />-Cresol , 209, 212, 216, 218 Critical oxidation potentials 170, 172 Cross-linking of the lignin polymer 214 Cupric oxide 148 2,5-Cyclohexadienone structure 33 D Decarbinolation 39 Degradation of diphenols 163 Degradation mechanism 167 Dehydrogenation, oxidative 85 Demethylation 168 Desugared spent liquor 215 Desulfonated lignin 208, 213, 217 Deuterated model compounds 42 Deuterated phenol derivatives 41 Deuteration, selective 48

2 264 LIGNIN S T R U C T U R E A N D REACTIONS Diaryl ethers in lignin 8 5,5'-Diethyl-2,2'-dihydroxy-3,3'- dimethoxybiphenyl Differential infrared spectra of lignins in wood Diguaiacylmethane... 67, 103 Dihydrodehydrodiconiferyl alcohol, acidolysis of 22, 23 0,0'-Dihydroxybiphenyls 163, 165 l,2-(4,4'-dihydroxy-3,3'-dimethoxydiphenyl)-ethane 254 2,4'-Dihydroxy-3,3'-dimethoxy-5- ethylbi benzyl 254 2',4-Dihydroxy-5'-methyl-3,3',5- trimethoxydiphenylmethane 254 3',4-Dihydroxy-6'-methyl-3,4',5- trimethoxydiphenylmethane 254 ^//-Dihydroxydiphenylmethanes 67, 70 4,4'-Dihydroxy-3,3'-dimethoxystilbene 31 4,4'-Dihydroxy-3,3'-5,5'-tetramethoxystilbene 98, 100 l,2-(4,4'-dihydroxy-3,3',5,5'-tetramethoxydiphenyl)-ethane 254 4,4'-Dihydroxy-3,5,3'-tetra-ter/-butyldiphenylmethane 105 Dilignols 4, 5, 8, 11 Dimeric lignin acidolysis products 27 Dimerization 163 Dimers, structure of 249 2,6-Dimethoxyphenol 98, 100 2,2-Dimethoxypropane, extraction of wood with 117 2,6-Dimethoxyquinone 98, 99 Dimethyl sulfide 206 Diphenylmethanes 85 Diphenols, degradation of 163 Displacement reactions, base-catalyzed ,4-Divanillyltetrahydrofuran 29 Ε Electrophilic displacement reactions 38 lignin reactivity in 38 EPR spectrum of syringoxyl... 58, 59, 60, 62 Es terifi dation of wood oxidation products 185 Etching Ether groups in lignin 66 Ether linkage 241 p-ethylphenol 218 Eugenol 218 Extraction of periodate lignin with acetals 120 Extraction of wood with benzaldehyde 117 with 2,2-dimethoxypropane 117 F Formaldehyde formation in alkaline pulping Formation of quinones 91 Free radical content 88 of lignin 70 vs. fungal decay of woods 51, 53, 56 Free semiquinone radical 68 Fungal decay of woods, free radical content US 51, 53, 56 G Gas chromatography 211, 230 Gas-liquid chromatography 240 of wood oxidation products 183, 202 Gel filtration 36 Guaiacol. 211, 218 derivatives 146 Guaiacylglycerol /S-(2-methoxyphenyl) ether Guaiacylpropane unit, chlorination of Guaiacylpropane unit, nitration of 48 Guaiacyl units in lignin 228, 235, 236 H Half-life of the quinonemethides.. 7 Half-life of radicals 5 Hardwood lignins, syringoxyl as a model for.. 58 Hemilignin 36 Homologous lignosulfonates 36 Hydrochloric acid spruce lignins 206 Hydrocracking 206 Hydrogénation, alkaline 249 Hydrogénation, catalytic 206 Hydrogénation catalysts 207 Hydrogénation of coal 207 Hydrogénation of lignin 205, 238 catalysts for 239 mechanism of 255 Hydrogenolysis of aspenwood meal 242 Hydrogenolysis, ph vs 242 Hydrogenolysis of lignin 206, 226, 238 Hydrogenolysis of sprucewood meal Hydrol lignins 227, 228 chromatograms of proton distribution in 231 Hydrolysis of lignin 115 Hydroreforming 206 Hydroxyl group determination 142 ω-hydroxyguaiacylacetone 24, 27 from lignin 25, 28 ρ-hydroxy phenyls-hydroxy ace tone 29 Hydroxymethylation of lignins 131 Infrared spectroscopy 216 of lignin 110, 121 Ionization Δβ curves 82, 92, 100 Isolation of dilignols 17 Isolation of lignin 240 by continuous extraction 114, 117 by ethanolysis 112 by solvolysis 110 Isolation of monolignols 17 Isolation of trilignols 17

3 I N D E X 265 β-keto groups in lignin 112 Klason lignin 240 Kraft lignin 77, 131, 158, 215 absorption curve of 77 <*-carbonyls in 78 chromophores in 75, 83, 85 condensed positions in 131 reduced 81 uncondensed positions in 131 Laccase 3 Lignin accessible side-chain portion of 247 alkali 145 alkaline degradation 255 alkaline hydrogénation of 249 aromatic units in artificial 3 arylglycerol-fl-aryl ether systems in 24, beech 18 biphenyl structure in 257 Bjôrkman 76, 92 -building stones 3 -carbohydrate bonds 119 acetyl groups as benzyl ether groups as glycoside bonds as 119 snake-cage resin as 120 carbonyl content of 65, 71 carbonyl groups in 128 α-carbonyls in 78 chromophores in 70, 75, 83, 85 condensation with formaldehyde 141 condensation reactions of 84 constitutional scheme for 59 core structure in 247 degradation of 227 degradation products 239 desulfonated. 208, 217 diaryl ethers in 8 ether groups in 66 free radical content of 70 guaiacyl units in 228, 235, 236 hydrogénation of 205, 238 hydrogénation, dimers from 249 hydrogenolysis of 206, 226, 238 hydrolysis 115 ω-hydroxyguaiacyl ace tone from....25, 28 isolation of 240 by continuous extraction 114, 117 by ethanolysis 112 β-keto groups in 112 Klason 240 kraft 75, 77, 78, 83, 85, 131, 158, 215 models 68, 92,96, 108, 158 reaction with formaldehyde , 142 native 215 natural 3 oxidation of 157 alkali 145 Lignin {Continued) oxidation products, stable free radicals in 51 phenylcoumarone systems in 24, 31 polymer, cross-linking of 214 polyphenylpropanoid structure in 247 quinhydrone species in 51 rate of extraction of.115, 119 reaction of formaldehyde with , 141 reactive sites in 126 reactivity of aromatic sites in 47 reactivity of electrophilic displacement reactions 38 salts, paramagnetism of 51 spruce milled wood 66, 71 stable free radicals in 51 structures in 128 structure and reactivity 22 sulfonic acid. 206 syringyl units in 228, 235, 236 Lignins acetyl 118 hydroxymethylation of 131 infrared spectra 110, 121 isolation by solvolysis 110 periodate extraction with acetals 120 softwood 77 in wood, differential infrared spectra of. 111 Lignocellulose 178 Lignosulfonates, homologous.36 Lignosulfonic acids 36 Liquor, desugared spent 215 M Maple lignin 251 Metal complexes with catechols 86, 88 Methanol lignin.207, 227 Methoxylated benzenecarboxylic acids 3 Methoxyquinone 103 α-methylvanillyl alcohol 92, 97 reactions of 92 Mild hydrolysis of spruce lignin 11, 12 Model compounds 227, 238, 244, 251 Models, lignin.92, 96, 108, 158 Monomeric lignin, acidolysis products Monolignols 4, 5 Monophenols 207, 208, 210, 212, 217 Monophenol yield 211, 217 Ν Native lignin 215 Nitration of guaiacylpropane units 48 Nitric acid oxidation of wood 178, 182 Nitrobenzene oxidation of wood , 182 NMR spectroscopy 226, 230 NMR spectrum of dimers 251 of model compounds 251 of monomers 251 Noguchi catalyst 209 Noguchi process 205, 207, 209, 224

4 266 LIGNIN S T R U C T U R E A N D REACTIONS Ο Oligolignols.. 4, 8, 14 Ortho-para director 218 Oxalic acid 147, 155 Oxidation of alkali lignin 145 of lignin 157 of phenols 157, 160 products of white fir wood. 188, 195, of wood 177, 193 Oxidative coupling 160 degradation of wood 177 dehydrogenation 85 reactions of phenols 105 Oxygen in color formation 91 effect on the reaction of syringl alcohol with alkali 94, 96 Oxygen oxidation of wood 178, 183 Palladium catalyst Paramagnetism of lignin salts 51 Partial rate factors for protododeuteration 42 Paste oil recoveries 213 Pasting oil 211, 212 Peroxydase 3 Phenol 208, 210,239, 250 o-phenol alcohols and color reaction with FeCl Phenylcoumaran system 78 in lignin 24, 31 models for 78 Phenol oxidation 157, 160 Phenolic lignin degradation products Phenylpropanoid structure in lignin 247 Phenols from coal and petroleum 209 Phenols, oxidative reactions of 105 Phenoxyl radical 160 Phenoxy radicals from α-carbonyl syringols 55 Phthalic acid 147, 154 ph vs. hydrogenolysis 242 Pinoresinol 6, 29, 236 Polycarboxybenzenes from wood oxidation 181, 199, 203 Polylignols 4 Preferential liberation of phenylpropanoid units 244 Principle of additivity 39 Products from reaction of vanillyl alcohol with alkali 102 Protododeuteration 40 partial rate factors for 42 Protolignin Proton distribution in hydrol lignin 231 Pulping alkaline 85, 90 sulfite 84 Pulps bleaching of.. 71,91 color formation in 90 Quinhydrone species in lignin 51 Quinonoid structures 85 ο,ρ-qui nones 95 Quinones, formation of 91 Quinonemethides 6, 7, 8, 14, 65, 70, 84, 92, 257 half-life of 7 R Radical half-life 5 Raney nickle catalyst 227, 238, 240, 245 Raschig analysis 212 Reaction medium, ph of 242 Reaction of formaldehyde with lignin...125, 141 Reaction of model compounds in formaldehyde. 142 Reaction of syringyl alcohol 92, 107 with alkali 98 effect of oxygen on 94, 96 Reaction of vanillyl alcohol with alkali, products from 102 Reaction of white birchwood meal with alkali 96 Reactions acid-catalyzed condensation 48 base-catalyzed displacement 48 condensation 234 coupling 162 electrophilic displacement 38 of lignin, condensation 84 of α-methylvanillyl alcohol 92 of vanillyl alcohol 92 Reactive sites in lignin 126 Reactivity of aromatic sites in lignin 47 Red phosphorus 206 Reduced kraft lignin 81 Repeating units in spruce lignin 36 Ring fission 163 Sap, cambial 2 Selective deuteration 48 Sequential methylation 184 Sinapyl alcohol 3, 4 Sodium hydroxide 96 Softwood lignins 77 Spruce lignin constitutional scheme for 1, 3 mild hydrolysis of 11,12 repeating units in 36 Spruce milled wood lignin 66, 71 Stilbenes 78, 92 Structure and reactivity of lignin 22 Sulfite pulping 84 Sulfite-spent liquor 208 Synthesis of syringoxyl 58, 62 Syringaldehyde 98, 100 Syringaresinol 18 Syringoxyl EPR spectrum of 58, 59, 60, 62

5 I N D E X 267 Syringoxyl {Continued) as a model for hardwood lignins 58 synthesis of 58, 62 Syringyl alcohol 67, 68 with alkali, reaction of 98 methyl ester of 93, 97 reaction of 92, 98 Syringylcresol 68 Syringyl units in lignin 228, 235, 236 Τ 3,3',5,5'-Tetramethoxy-4,5'- diphenoquinone 100 Timberline 3 Toluene 219 Trilignols 11,12 Trimeric sequence in lignin 31 3,4,5-Trime thoxy benzyl alcohol 96 U Uncondensed lignin 9 V Vanillic acid 105, 146 Vanillin 104, 146, 206 Vanillyl alcohol 67,68 methyl ester of 93, 97 reactions of 92, 107 Vanillylcresol 68 Vapor phase chromatography 250 W White birchwood meal with alkali, reaction of 96 White fir wood 182 oxidation products of 188, 195, Wood aliphatic oxidation products of aromatic oxidation products of with benzaldehyde, extraction of 117 with 2,2-dimethoxypropane, extraction of 117 nitric acid oxidation of 178, 182 nitrobenzene oxidation of 178, 182 oxidation of. 177, 193 oxidative degradation of 177 oxygen oxidation of 178, 183 white fir 182 Wood oxidation, polycarboxybenzenes from , 199, 203 Wood oxidation products esterification of 185 gas-liquid chromatography of , 202 Wood saccharification 207