Lignin Structure and Reactions

and C H 2 0 formation. 140-1 ... α-Carbonyl syringols, phenoxy radicals from. 55 ..... 67, 68 with alkali, reaction of. 98 methyl ester of. 93, 97 re...
0 downloads 0 Views 466KB Size
Download PDF
Downloaded by 192.169.140.100 on May 23, 2018 | https://pubs.acs.org Publication Date: January 1, 1966 | doi: 10.1021/ba-1966-0059.ix001

INDEX

Absorption curve of kraft lignin 77 Acetal lignins 118 Acetals in isolating lignin 111 A c i d - c a t a l y z e d c o n d e n s a t i o n r e a c t i o n s . . . .48 A c i d o l y s i s o f B j ô r k m a n s p r u c e l i g n i n . . 2 4 , 26 Acidolvsis of dihydrodehydrodiconiferyl alcohol 22,23 A c i d o l y s i s o f g u a i a c y l g l y c e r o l β2-methoxyphenyl) ether 24 A d d i t i v i t y , principle of 39 A l d o l condensation 84 A l i p h a t i c oxidation products of w o o d . . 178-9 A l k a l i fusion 149 Alkali lignin . 145 Alkaline h y d r o g é n a t i o n of lignin 249 Alkaline pulping 85, 90 and C H 0 formation 140-1 A l k o x v l groups, determination of 113 Aniline. . . . . . . 219 A r o m a t i c o x i d a t i o n products o f w o o d . . 180-1 A r o m a t i c sites i n l i g n i n , r e a c t i v i t y o f 47 A r o m a t i c units in lignin 234-5 Artificial lignin 3 A r v l g l y c e r o l β-aryl ether systems i n ' lignin 24, 2 8 - 9 2

Β B a r i u m dioxide 149 B a s e - c a t a l y z e d d i s p l a c e m e n t r e a c t i o n s . . .48 Beech lignin 18 B e n z a l d e h y d e , e x t r a c t i o n o f w o o d w i t h . . 117 B i p h e n y l structures 157 l,2-Bisguaiacyl-l,3-propanediol 31 1,2-Bisguaiacylpropanone 31 B i s - 3 , 5 - d i - 0 - m e t h y l p y r o g a l l y l m e t h a n e . . . .67 Bis-4-hydroxy-3,5-dimethoxvphenvlmethane ' 9 3 , 9 8 , 107 B i s y r i n g y l from maplewood 251 B i v a n i l l y l from maplewood 251 B j ô r k m a n lignin . . 2 9 , 7 6 , 9 2 , 226 B j ô r k m a n s p r u c e l i g n i n , a c i d o l y s i s o f . . 2 4 , 26 Bleaching of pulps 7 1 , 91

C a l c i u m lignosulfonate 210 C a m b i a l sap 2 Cannizzaro reaction 132 C a r b o h y d r a t e p - h y d r o x y b e n z y l ether 16 / 3 , 7 - C a r b o n - c a r b o n c l e a v a g e r e a c t i o n . . . .241 Carbon-oxygen linkage 241

C a r b o n y l content of lignin 6 5 , 71 C a r b o n y l groups i n lignin 128 α - C a r b o n y l s in kraft lignin 80 α - C a r b o n y l syringols, phenoxy radicals from 55 Catalytic hydrogénation 206 C a t a l y s t s for h y d r o g é n a t i o n 207 of lignin 239 Catechols, metal complexes w i t h 86, 88 Cellulose, solvolytic degradation of 120 Chalcones 8 5 , 88 Chlorination of guaiacylpropane unit 48 C H o O f o r m a t i o n i n a l k a l i n e p u l p i n g . . . 140-1 Chromatograms of hydrol lignin 232-33 C h r o m a t o g r a p h y , v a p o r phase 250 Chromophore 7 in kraft lignin 7 5 , 8 3 , 85 in lignin 70 Color formation in pulps 90 role o f o x y g e n i n 91 Condensation 2 1 4 , 231 aldol. 84 reactions 234 acid-catalyzed 48 of lignin 84 Coniferaldehyde 3, 2 9 Coniferyl alcohol 2, 4 C o n s t i t u t i o n a l s c h e m e for l i g n i n 59 C o n s t i t u t i o n a l s c h e m e for s p r u c e l i g n i n . . 1 , 3 Core structure in lignin 247 />-Coumaryl alcohol 2, 4 C o u p l i n g reactions 162 Creosol 6 8 , 158 w-Cresol 2 0 9 , 2 1 2 , 2 1 6 , 218 0-Cresol 208 />-Cresol. . . . . 2 0 8 , 2 0 9 , 2 1 2 , 2 1 6 , 218 Critical oxidation potentials 170, 172 C r o s s - l i n k i n g o f the l i g n i n p o l y m e r 214 C u p r i c oxide 148 2,5-Cyclohexadienone structure 33

D Decarbinolation Degradation of diphenols Degradation mechanism Dehydrogenation, oxidative Demethylation Desugared spent liquor Desulfonated lignin Deuterated model compounds Deuterated phenol derivatives D e u t e r a t i o n , selective

39 163 167 85 168 215 2 0 8 , 2 1 3 , 217 42 41 48

263 Marton; Lignin Structure and Reactions Advances in Chemistry; American Chemical Society: Washington, DC, 1966.

Downloaded by 192.169.140.100 on May 23, 2018 | https://pubs.acs.org Publication Date: January 1, 1966 | doi: 10.1021/ba-1966-0059.ix001

264

L I G N I N

Diaryl ethers in lignin 8 5,5'-Diethyl-2,2'-dihydroxy-3,3'dimethoxybiphenyl . · · · . · • -254 Differential infrared spectra of lignins in wood Ill Diguaiacylmethane... 67, 103 Dihydrodehydrodiconiferyl alcohol, aci­ dolysis of 22, 23 0,0'-Dihydroxybiphenyls 163, 165 l,2-(4,4'-Dihydroxy-3,3'-dimethoxydiphenyl)-ethane 254 2,4'-Dihydroxy-3,3'-dimethoxy-5ethylbi benzyl 254 2',4-Dihydroxy-5'-methyl-3,3',5trimethoxydiphenylmethane 254 3',4-Dihydroxy-6'-methyl-3,4',5trimethoxydiphenylmethane 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 isolation of 17 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.. .48 3,4-Divanillyltetrahydrofuran 29

Ε Electrophilic displacement reactions 38 lignin reactivity in 38 E P R spectrum of syringoxyl... 58, 59, 60, 62 Es terifi dation of wood oxidation prod­ ucts 185 Etching .···.··. 151 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 pulping Formation of quinones Free radical content of lignin vs. fungal decay of woods

alkaline 140-1 91 88 70 51, 53, 56

S T R U C T U R E

A N D

R E A C T I O N S

Free semiquinone radical 68 Fungal decay of woods, free radical con­ tent 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 .. .. 24 Guaiacylpropane unit, chlorination of. . . .48 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, p H vs 242 Hydrogenolysis of lignin 206, 226, 238 Hydrogenolysis of sprucewood meal. .244-45 Hydrol lignins 227, 228 chromatograms of 232-33 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 of lignin Ionization Δβ curves Isolation of dilignols Isolation of lignin by continuous extraction by ethanolysis by solvolysis Isolation of monolignols Isolation of trilignols

Marton; Lignin Structure and Reactions Advances in Chemistry; American Chemical Society: Washington, DC, 1966.

216 110, 121 82, 92, 100 17 240 114, 117 112 110 17 17

265

I N D E X

Lignin {Continued)

Downloaded by 192.169.140.100 on May 23, 2018 | https://pubs.acs.org Publication Date: January 1, 1966 | doi: 10.1021/ba-1966-0059.ix001

β-Keto groups in lignin 112 Klason lignin 240 Kraft lignin 77, 131, 158, 215 absorption curve of 77