Wood Sci. Technol.

19:289-312 (1985)
Wood Science
and ~zdmok~y
9 Springer-Verlag 1985

Chemistry of delignification *
Part 1: General concept and reactions during pulping
J. Gierer, Stockholm, Sweden

Smnmary. Delignificafion processes comprising various pulping and bleaching reactions are
reviewed in the light of a general concept dividing these reactions into nucleophilic and
electrophilic categories. It is shown by numerous examples that pulping is due to the action of
external nucleophilic species attacking electron-deficient centres in carbonyl and conjugated
carbonyl (=enone) structures and to the presence of neighbouring nucleophilic groups
attacking the fl-c_arbon atom of side chains. On the other hand, bleaching is initiated by
electrophilic species attacking electron-rich centres in aromatic nuclei and unsaturated, ring-
conjugated side chains. These initial bleaching reactions are followed by nucleophilic
reactions taking place during the same or during subsequent bleaching steps.
The efficiency of a particular delignification procedure is determined by the extent of
cooperation between nucleophilic and electrophilic reactions.
During delignification processes carbohydrate constituents of wood are subject to
reactions which follow mechanisms analogous to those of lignins. This provides an explana-
tion for the fact that the selectivity of pulping and bleaching processes is limited.

Introduction

Chemical delignification in the broadest sense includes all processes resulting in

partial or total removal of lignin from wood or hgnin-containing ( = unbleached)
pulps by the action of appropriate reagents. In addition to purely chemical events,
these processes comprise a n u m b e r of morphological and physical p h e n o m e n a
(W~flder, Daleski 1964). However, it has been shown that these p h e n o m e n a do not
affect the chemical course of delisnification , at least not to any decisive extent
(Procter et al. 1967; Fergus, Goring 1969).
In earlier decades, results from studies of the delignification reactions have
essentially contributed to the concepts of lignin structure proposed at that time.
More recently, the trend has been in the opposite direction. The great advances in
the elucidation of the structural features of lignin achieved by biosynthetic and

Academy Lecture presented at the Ninth Cellulose Conference, Syracuse, USA, May
24-27, 1982. Extended Version of a survey article published in Holzforschung 36 (1982):
43-51 and 55-64
Part 2: Reactions of lignins during bleaching, will be published in No. 1/86 and contains
all literature references
290 J. Gierer

H2COHI H27OH
HC-- CO
I

HzCOH CO 0 ' ?H HC
-- 0
-~ mco~ ~o .. ~c- ,~'~

r II '~y "y HC -- / /o~

I l + ~ I I I
H9. ,0 9~ ~ HCOH He. rtCOH
M e O ~ . _ . ~ O M e H 2 COH zL zL~ ~L
~co~',~o.,~o o>e 6 c~ ~~176
~~( ~ ~ o ~ ' ~ ~loMo
I t C "/ "~-I I I I I
H? O H21 I tHC O OH O-
H C O (C6HmO~)nH HC- CE

H27OH HC~.o/CH2 MeO OH Ha?OHcH

0 CH
I H~?OH OMe H~COH II
__OMe H=pH CH

HCOH C OMe

u----~OMe OMe OMe

--0 --0

HC-O[CHzOH
] CH2OH CH-OH []~ ['OCH3
;~ .~-o- -d." o.
~ + ~o~ ,~o_
CH2OH 1-12COH 0CH3
• ~I+Ho' ,~L
-o ,+~o~
HC~.~(~CH 2
3 {]~OCH 3

0(:i 3 "

oH -4~ r+,

Fig. 1. Schematic model of the conslimtion of spruce lJgnin according to Freudenberg, Neish
(t 968) (upper part) and Adler (1977) (lower part)
Chemistry ofdelignification, Part 1 291

Kraft (sulfate) pulping Chlorine bleaching

Soda (alkali) pulping
Neutral sulfite pulping
Acidic sulfite pulping
Chlorine dioxide bleaching
Oxygen bleaching
Ozone bleaching
Alkali-treatment
Hydrogen peroxide bleaching
Hypochlofite bleaching

Fig. 2. Pulping processes Fig. 3. Bleaching processes

analytical studies (for summaries, see Freudenberg, Neish 1968; AdIer 1977) have
initiated extensive efforts aimed at clarifying mechanisms involved in delignilica-
tion processes. At this stage it is probably appropriate to summarize the results of
these mechanistic studies.
Since it will not be possible to cover all important contributions to this area of
research, the reader is referred to the comprehensive books "Pulping processes" by
S. Rydholm (1965 a) and "Lignius" edited by K. V. Sarkanen and C. H. Ludwig
(1971). Both books contain chapters describing the most important delignification
processes in chemical terms. In addition, some survey articles have appeared during
the past 15 years which summarize the chemistry of particular pulping (Gierer
1970, 1980; Gellerstedt 1976) and bleaching (Singh 1979) methods.
The main purpose of this review is to define a common basis for the chemical
reactions underlying the delignification processes currently used in the production
of chemical pulp. These reactions will be interpreted in conventional terms, i.e. via
mechanisms well established in organic chemistry. Features common to different
processes will be emphasized and a general concept coveting the main deli~ifica-
tion reactions will be presented.
Delignification is brought about by two types of structural change in lignin
which may be connected to each other. The first involves degradation by cleavage
of certain interunit linkages and the second entails introduction of hydrophilic
groups into the polymer and its fragments.
In view of the complexity of lignin structure, comprising various types of ether
and carbon-carbon bonds (for schematic illustrations, see Fig. 1), a large number of
possible degradation reactions may be envisaged. This number is increased still
further, taking into account the fact that delignification is achieved by different
pulping (Fig. 2) and bleaching (Fig. 3) processes and sequences under a great
variety of conditions.
Therefore, two simplifications have to be made if the description of the
delignification processes in chemical terms is to be rationalized.
The first is to reduce the complex lignin structure to a single arylpropane unit
(Fig. 4) in which R may refer to H, aryl or alkyl and R 1 may represent an aroxyl,
aryl or alkyl group. The unit may be phenolic (R a =H) or non-phenolic (R 2-=
adjacent unit). The 5-position may be unsubstituted, substituted by a methoxyl
group or linked to an adjacent lignin unit. By varying the substituents R, R 1 and
R 2, all prominent lignin structures, such as phenolic and non-phenolic/~-aryl ether-,
a,/~-diarylether-, 1,2-diarylpropane-, arylcoumaran- and lignane structures (Fig. 5),
are represented.
292 J. Gierer

H2COH
I
HC-R I
I
HC-OR

. - ~ ] ] ' - OCH3
IOR 2

R=H, ory[ or alky[

R I = aroxyl, ctryl or alkyl
R 2= H, aIkyt or ary[ Fig. 4. Arylpropane unit, general formula

R1
oroxyt aryt aLkyL

HCOH HCOH

+o-C
R ory[
o-c HC~O

alkyl I i
H -C, t
HC - -
I
I
CH
I
HC-O-CH HC-O --CH ,,,.~O/CH2

Fig. 5. Prominent liEnin structures

General c o n c e p t

The second simplification requires the introduction of the general concept whereby
the reactions are divided into two categories, i.e. nucleophilic reactions, in which the
delignifying reagent supplies an electron pair for the generation of a temporary or
permanent chemical bond to lignin, and electrophilic reactions in which the deligni-
fying reagent accepts an electron pair or an unpaired electron for the generation of
such a bond.
An inspection of the delignification reactions reveals that pulping is due
exclusively to nucleophilic reactions (Gierer 1970), whereas lignin-degrading bleach-
ing is initiated by electrophilic reactions which are followed by nucleophilic (and
eventually further electrophilic) processes (cf. e.g. oxygen bleaching, Gierer and
Imsgard 1977). Lisnin-retaining bleaching is primarily, if not exclusively, due to
nucleophilic reactions.
Chemistry ofdefignificafio~Pa~ 1 293

Sites of electrophilic and nucleophilic attack in lignins and lignin degradation

products

The generalized arylpropane trait (Fig. 4) contains a free (R 2 =H) or ethefified

(R 2= adjacent unit) hydroxyl group inpara-position to the propane side chain. This
group carries lone pairs of electrons on the oxygen atom, capable of overlap with
the ~-electron system of the aromatic ring. Centres of high electron density in the
ortho- and para-positions (6- in Scheme 1, left-hand part) are thereby generated. In
lignin structures, containing an aliphatic double bond conjugated to the aromatic
ring, high electron density is also encountered at the t-carbon atom (Scheme 2, left-
hand part). These centres, located at every second carbon atom of the arylpropane
skeleton, constitute the sites of attack by electrophiles. Thus, the electrophilic
reactions follow the general rules of aromatic electrophilic substitution (Fleming
1976).
Conversely, elimination of the a-substituent, or, in ring-conjugated structures,
the y-substituent (R1), results in the formation of enone intermediates of the
quinone methide type (right-hand parts of Schemes 1 and 2). This conversion
involves the loss of a neutral molecule in acidic media (after protonation), and of
an anion in alkaline media, from the arylpropane unit, creating centres of low
electron density (6+) at the carbonyl carbon and at carbon atoms in vinylogous
positions to the carbonyl carbon (Wagner, Gompper 1974). The centres of electron
deficiency (6+ in Schemes 1 and 2 fight-hand parts) constitute the sites for attack
by nucleophiles. Schemes 1 and 2 show that these centres are also located at every
second carbon atom and alternate with the sites open to attack by electrophiles.
An analogous relationship between centres of high and low electron density can
be observed with enols from a-carbonyl structures, as shown in Scheme 3.
In acidic media (upper parts of Schemes 1 and 2), this distribution of high and
low electron densities, i.e. of sites for electrophilic and nucleophilic attack respec-

acidic media

a.ack by
=etectrophites
I
HC-R
6~
1

- - ~
H~_R 1

=
.H~-R1H
= '
. ~
I
HCS*

" [
7l +
!
attack by
nucteophiles
CH 3 "''-~'OCH 3 -'"~'OCH3|
R/0 R/O R/O J
R = H , Alk or Ar RI=OH, OArorOAIk

alkatine media

I I I
HC-R } HC-R 1 HE6+
=- ~ + attack by
electrophiles 6- 6- - - -- nucleophile~
-" OCH3 - OCH3 -" -,~.-OCH3
O O- O
R 1 = OH, OAr or OAIk

Scheme 1. Sites of electrophilic (6--) and nucleophilic (6+) attack in arylalkane units
294 J.Gierer

acidic media
H2~ -RI H2C-RII H2C6*
HC6- HC HC
l II I
CH CH CH6*
a t t a c k by attack by
etectrophites nucleophites
/ ~ "OCH3 -- -,,11/6+-0CH,.
R .-O R--O R.--0

R = H, AIk or Ar R1-OH,OArorOAIk

aikatine media
H2~ - R I H2C-RI
I H2~I6*
HC6- HC HC
~I II I
CH CH CH6*
a t t a c k by " 6- ~ --R1 .K~ attack by
electrophites 6- 6- - - ~ " '§' ~ ~Lv nucIeophiIes
/ : OCH3 / OCH3
0 O-
R I =OH, OAr or OAlk

Scheme 2. Sites of electrophilic (6-) and nucleophilic (6 + ) attack in arylpropene units

acidic media

R--C.6- R-C -
I '...5- II |5+ |
C-OH C-OH . H+,-RIH C=OH
J attack by
electrophites . OCH3 . OCH3 . OCH3 nuc[eophiles
/0 /0 /0

alkaline media
H2C-R1 H2C--R 1 H2C 6*
I I II
R--C.~- R--C R--C
I "-.-, 0- II 15+
C-O C--O- --R 1 C=O
attack by
-etectrophites / OCH3 . OCH3 / OCH3 nucleophlles
/0 /0 /0

R =OAr, Ar or AIk R1 =OH, OAr or OAlk

Selaeme 3. Sites of electrophilic (6-) and nucleophilic (6+) attack in traits containing an a-
carbonyl group
Chemistry ofdelignification, Part 1 295

tively, applies to both phenolic (R= H) and non-phenolic (R= alkyl or aryl) units.
However, in alkaline media (lower parts of Schemes 1 and 2) it is encountered only
in phenolic structures.
Assigning the sites of attack by electrophiles and nucleophiles to alternate
carbon atoms (Schemes 1 and 2) does not account for two important facts:
1) In acidic media, the lone pairs of electrons on the oxygen of the aromatic
methoxyl group(s) may contribute to the total distribution of electron density on
the aromatic ring creating sites of high electron density also in the para- and ortho-
positions to this group (or groups) (cf. e.g. acidic chlorination reactions, Dence 1971,
and acidic condensation reactions, Nimz 1966).
2) Nucleophilic reactions with participation of neighbouring groups, e.g.
cleavage offl-aryl ether bonds involving an ionized a- or ),-suls or hydroxyl
group, take place at the t-carbon atom of the side chain, usually constituting a site
of attack for electrophiles. The explanation for this exception is given in the
following section.

Reactions of lignins during pulping

General remarks

As mentioned in the preceding section, the reactions of lignin during conventional

pulping processes are nucleophilic in nature, negativley charged ions or neutral
molecules constituting the active species. Since phenolic and non-phenolic variants
of the general arylpropane type of unit (Fig. 4) behave differently, particularly in
alkaline media, it is appropriate at this point to differentiate between pulping
reactions involving phenolic, and those involving non-phenolic units.

A Reactions of phenolic units

Formation and reactions of quinone methide intermediates

During the initial stage of pulping processes, phenolic units are readily converted
into quinone methides or, in acidic media, into the corresponding conjugate acids
(Schemes 1 and 2, R--- H, right-hand parts).
ff R' in Scheme 1 refers to an aroxy (-OAr) residue of the adjacent arylpropane
unit, the transition into the quinone methide structure involves cleavage of the
benzyl ether linkage and represents the first important mode of lignin fragmenta-
tion.
Quinone methides may be viewed as carbonyl compounds in which the
electronic characteristics of the functional group are transferred to a vinylogous
carbon atom by conjugation. These intermediates may undergo two types of
reaction, both involving rearomatization as driving force (Scheme 4). The first is
attack by a nucleophile (N) from the pulping liquor (N= O, S, SOs) or from lignin
(N--internal nucleophile) resulting in the introduction of a polaric group or in
condensation (right-hand part). The second type of reaction is enolization by
296 J.Gierer
H2COH H2COH
HC-R HC-R HC-R
I 1 I
CH -H § HC +H2N HC-NH § H+
acidic

I~OCH ' 'CH20 JI~OCH3 ~ I"@OCH3

..o [OH] J[O'H] .~o [OH]

H2COH H2COH
I I
pH HC-R HC-R HC-R
II I I
CH HC § H2N HC-NH
neutral

,~OCH3 'CH20 ..Jl~OCH3 ~ ~"~ OCH3

OH O OH

H2COH H2COH
HC-R HC-R HC-R
II I I
alkaline CH "
-H* HC * HN--H* HC-N-
-CH20 =

/ OCH3 / OCH3 -" OCH3

O- O O-

N = O, S, SO3 or internal nucleophile

R = OAr~Ar or Ark

Scheme 4. Competition between addition of nucleophile to, and abstraction of proton (with
formaldehyde elimination) from, quinone raethide intermediates in acidic, neutral and
alkaline solutions

proton abstraction, elimination of the terminal hydroxymethyl group (as formal-

dehyde) and formation of unsaturated ring-conjugated structures (styrenes and
stilbenes, left-hand part). Nucleophilic addition and enolization compete with
each other, the result of this competition being determined by the nucleophilicity
and basicity of the internal and external reagents present.

Neighbouring group participation reactions

When a strongly nucleophilic species is present in the pulping liquor, addition to
quinone methide intermediates will dominate over enolization. In alkaline media,
the introduced a-substituent may ionize and in this form attack the fl-carbon atom
in fl-aryl ether structures in a second nucleophilic process (Scheme 5). This
neighbouring group participation (NGP) type of reaction proceeds via three-
membered intermediates and brings about cleavage of the fl-aryl ether bond. It
constitutes the second important mode oflignin fragmentation during pulping.
NGP-reactions are strongly favoured. The attacking nucteophilic group is
permanently held in the immediate vicinity of the reaction centre and the entropy
change (AS ~ on passing to the transition state is thus more favourable than for the
corresponding intermolecular reaction (Page, Jencks 1971; Page 1973; Frost,
Chemistry of delignification, Part 1 297

H2COH OCH3 H2COH

oc.,
N--CH - =

.- Loc.a .- oc.3
..o [o-] ..o [o-]
N - = neighbouring group
Scheme 5. fl-Aryl ether cleavage by internal displacement (neighbouring group participation)

Pearson 1961). In solution, this entropy effect more than offsets the unfavourable
AH ~ values caused by the formation of highly strained three-membered transition
states (Capon, McManus 1976).

B Reactions of non-phenolic units

Conjugate acids ofquinone methides as intermediates
Conversion of non-phenolic units into quinone methide intermediates (in the
conjugate acid form) with elimination of the a-substituent can only be achieved by
acidic pulping. Under such conditions, a-hydroxy, a-alkoxy and a-aroxy groups are
protonated which enhances their ability to depart as neutral molecules, water,
alcohols and phenols, respectively (Scheme 6, left-hand part). In alkaline media
such a conversion is precluded, since it would require the departure of hydroxide,
alkoxide or aroxide ions, i.e. poor leaving groups (Breslow 1966; Pine et al. 1980)
from (positively charged) conjugate acids ofquinone methides.

Neighbouring group participation reactions

Conversely, fragmentation of non-phenolic units through cleavage of fl-aryl ether
linkages, involving participation of an adjacent hydroxyl group, is limited to
alkaline pulping, the reaction requiring predissociation of the participating group
(cf. section A).
Analogous to the cleavage of the same type of bond in phenolic units, this
fragmentation mode proceeds v/a formation of the corresponding three-membered
cyclic intermediate (NGP-reaction, Scheme 5).
A similar cleavage of fl-aryl ether bonds in non-phenolic units via a NGP
reaction is observed also with structures containing an a-carbonyl group and
forming a double bond in conjugation to the latter (enone structure). Such inter-
mediates add nucleophiles to the 7 carbon atom (Scheme 3) and the resulting
addition products then undergo fragmentation, in analogous manner to those
formed from quinone methides (Scheme 5).
In the following sections, these general features of the chemistry of pulping will
be illustrated by a brief description of the processes currently in use. The main
reactions involved, their sites of nucleophilic attack and the initial intermediate(s)
and products are summarized in Table 1.
Table 1. Pulping
OO

Reagent Type(s) of reaction Sites of attack Initial intermediate(s) Outlined in

(nucleophile) or product(s) reaction
scheme nr

HO- Proton abstraction phenolic and aliphatic OH groups phenolates and alcoholates
Nucleophilic addition C 6+ in quinone methide benzyl and cinnamyl alcohols 4 (N = O)
intermediates
other enone intermediates hydroxy-enols

HS- Nucleophilic addition C o+ in quinone methide benzyl and cinnamyl thiols 4 (N = S)

intermediates 7
other enone intermediates mercapto-enols 10
Nucleophilic displacement methoxyl-C atom methyl mercaptan 11

R-O-' Nucleophilic displacement fl-C atom in fl-aryl ether structures oxiranes 5 (N = O)

(NGP-reaction) 9

R-S-" Nucleophilic displacement fl-C atom in fl-aryl ether structures thiiranes 5 (N = S)

(NGP-reaction)

R-Aft)- ' Nucleophilic displacement fl-C atom in fl-aryl ether structures spiro cyclohexadienones 15
(NGP-reaction) aryl coumarans 15

HSO~- Nucleophilic addition C ~+ in quinone methide benzyl and cinnamyl 4 0q = SO3)

intermediates sulfonic acids 17, 18
other enone intermediates enol sulfonJc acids

9
Table 1 (continued)

Reagent Type(s) of reaction Sites of attack Initial intermediate(s) Outlined m

(nucleophile) or product(s) reaction
scheme nr

SOs Nucleophilic addition
Nucleophilic displacement
C o+ in quinone methide benzyl and cinnamyl sulfonic acids 4 (N = SOs)
intermediates
other enone intermediates enol suffonic acids
0
fl-earbon at.om in fl-aryl a,fl-disulfonic acids
ether-a-sulfonic acid structures 19
methoxyl-C atom methanesulfonic acid 2O

I Conjugate addition C 6+ in quinone methide arylpropyl-substituted 13, 14

- C- (Michael reaction) and other enone intermediates cyclohexadienones 21, 22
I
(carbanion) formaldehyde hydroxym ethyl-cyclo-hexadienones 14

SOn 9H20 Nucleophilic addition C 6+ in quinone methide a-and y-sulfonic acids 4 (N = SOs)
intermediates of the 21
oxonium ~ benzylium ion type

9 R represents a fl-aryl ether structure, attached to O-, S- or a phenolate residue, ArO-, in the a- (or y-)position
yHa C -
I
HC- O-~
I
a HC-
&
~g
300 J. Gierer

Pulping in alkaline media (Soda and kraft pulping)

Fragmentations
Cleavage of ether bonds
The main fragmentation reactions of lignin in alkaline media are the cleavages of
a-aryl ether bonds in phenolic units (Scheme 1, lower fight-hand part, R 1= OAr)
and of fl-aryl ether bonds (Scheme 5) in phenolic (N= S) and non-phenolic (N = O)
units (Gierer, Smedman 1965; Gierer, Nortn 1962).
Cleavage of fl-aryl ether bonds in phenolic units presupposes the introduction
of hydrosulfide ions by nucleophilic addition to quinone methide intermediates
(kraft pulping, Scheme 7, cf. also Scheme 4, lower fight-hand part, N=S) and
proceeds via thiiranes (scheme 8). These intermediates lose their sulfur in ele-
mental form to give conjugated structures of the coniferyl alcohol type (Brunow
et al. 1972; Gierer et al. 1973; Mortimer 1982). In the absence of hydrosulfide ions
(soda pulping), the quinone methide intermediates are preferentially converted into
ring-conjugated structures of the styrene-, stilbene- and 1,4-diarylbuta-l,3-diene
types (scheme 4, left-hand part) (Gierer 1970).
The different behaviour of quinone methide intermediates towards hydroxide
and hydrosulfide ions (see General remarks) explains the beneficial effect of the
latter on the rate and extent of delignification.
Cleavage of a-aryl ether linkages involving conversion of phenolate units into
quinone methide intermediates and cleavage of fl-aryl ether linkages in phenolic
units via participation of introduced sulfhydryl groups both proceed with relative
ease. Therefore, these two fragmentation modes have been tentatively ascribed to
the initial phase of kraft pulping (Gierer 1980).
The remaining main fragmentation reaction of alkaline pulping, i.e. cleavage of
fl-aryl ether bonds in non-phenolic units, also involves the participation of a
neighbouring ionized group, a hydroxyl group in the a-(or ~)position, and leads to
the formation of oxirane intermediates (Scheme 9, cf. also Scheme 5, N = O).
The oxirane ring is readily opened by the action of nucleophiles present in the
cooking liquor (hydrosulfide and hydroxide ions) to give the corresponding 1,2-
monothioglycols (Gierer, Wallin 1965) and 1,2-glycols (Gierer, Nortn 1962),
respectively (Scheme 9).
Cleavage of fl-aryl ether bonds in non-phenolic units during kraft pulping also
occurs in structures containing an a-carbonyl group (Scheme 3). This sulfidolytic
fragmentation is outlined in Scheme 10 (Gierer et al. 1980).
The cleavage of fl-aryl ether bonds in non-phenolic units via oxirane inter-
mediates is the dominant process in alkaline lignin fragmentation. It requires
relatively drastic conditions with respect to alkalinity and temperature. Conse-
quently, it takes place mainly during the bulk (= main) phase of alkaline pulping
processes, where it appears to determine the rate oflignin dissolution (Gierer 1980).
As with the cleavage of a- and fl-aryl ether bonds in phenolic units (see above), the
cleavage of fl-aryl ether bonds in non-phenolic units generates new phenolic
moieties which, in their turn, may undergo the same type of fragmentation as
described for phenolic units originally present (see above) provided they are of the
a- or fl-aryl ether type (alkaline "llgnin peeling").
Chemistry ofdelignification, Part 1 301

IH I I
HCO+R ~ H§ HCOR HO-.._ HCOR

-" OCH3 -" OCH3 - ocH3

/ o [oH] ..o [oH] o-

ltRoH IRo-
HC HC+ HC

..J]~OCH 3 ""---" .~}}..OCH 3 /~]LOCH3

/O§ [O+H] /O [OH] O
R = H, Alk or Ar
Scheme 6. Conversion of a lignin unit into quinone methide intermediate in acidic media
(left-hand part), in alkaline media (fight-hand part)
m

H2~I H2CI--S
C- R1 HC - R1
I I
CH +2 HS--H + -S-CH

H2COH
I
-Y/ --;; OOCH
HC-R 1 0 O-
I

CH
H2COH
1
"'OOCH3 +HS- HC-R 1
O I
-S--CH

-'~OCH 3
R1=aroxyl, aryl or aIkyl O-
Scheme 7. Nucleophilic addition ofhydrosulfide ions to quinone methide intermediates

H2COH] " H2~OH H2COH]

H~ --O - ~ %--
OCH, HI(: HC
S , _S ~ II
-S--CH OCH3 --0"~__. "~CH ~ CH

.~OCH3 "P-- - .~OCH 3 J~OCH 3

O- O- O-
Scheme8. Sulfidolytic fl-aryl ether cleavage by neighbouring group participation and
elimination of elemental sulfur from thiirane intermediate
302 J. Gierer

H2COH H2COH H2COH

I ')7-- I I
HC--O--~ HC HC-O-
I ocH3 o~1 + HO- I
-O-CH OCH3 -'0 ..~ "c H ~ HO-CH

-" OCH3 / OCH3 / OCH3

/O /O /O
Scheme 9. Alkaline /3-aryl ether cleavage by neighbouring group participation and alkaline
cleavage ofoxirane intermediate

H2COH H2C TS-CH2

I
HC-R -H2~
,,
C-R §HS--H" \.el
I I I
CO C=O C=O

-'~]]"OCH 3 /~OCH 3 -'~]LOCH3

/O /O ,.,0
R = OAr,Ar or Ark
JR=OAr]I -R-

CH2 S,~lH2
sutphidollon HS- II
CH -S O "CH
ond -,, I ~ I
condensation HO- CO CO
products
.-OCH, -'OCH,
/O /O
Scheme 10. Sulfidolytic fl-aryl ether cleavage in units containing an a-carbonyl group

J%JLoc.3 9 Hs- 9 HO- ---,-- .~L. o- * CH3S- 9 H20

I ,. /

~o [o-] ~o [o-]

/ OCH3 + CH3S- ~ / ~ O [qOi + CH3SCH3

/ 0 [0~ O-

2CH3S- § 1/202 +H20 -~-- CH3S-SCH3 § 2HO-

Scheme 11. Methyl-aryl ether cleavage by hydrosulfide- and methyl mereaptide ions
Chemistry ofdeligifification, Part 1 303

I 1 I

- CII - H +''- --C--@" ' -H

'~'-" -C=O
I I I

I _ -C=O
-C

."%-'"OCHa - ' - ~ - -oc% -" "-y -OCH,~

0 "0 O-

Scheme 12. Alkaline cleavage of carbon-carbon bonds by retrograde aldol reactions

Thus, the alkaline (Scheme 9) and sulfidolytic (Scheme 10) cleavage of fl-aryl
ether bonds in non-phenolic units, the alkaline cleavage of a-aryl ether bonds
(Scheme 1, R 1 =OAr) and the sulfidolytic cleavage of fl-aryl ether bonds in
phenolic units (Scheme 8) cooperate and complement each other in the overall
fragmentation of lignin during sulfate pulping.
Due to their strongly nucteophitic character, hydrosulfide ions also bring about
a limited cleavage of methyl aryl ether bonds (Scheme 11), a reaction which is not
anchimerically assisted. Methyl mercaptan and the corresponding catechol struc-
ture are formed as cleavage products. Methyl mercaptide ions may subsequently
cleave a further methyl aryl ether bond to give dimethyl sulfide or may be oxidized
to yield dimethyl disulfide. Hydroxide ions, being much weaker nucleophiles, react
with methyl aryl ether structures only to a negligible extent.

Cleavage of carbon-carbon bonds

A minor portion of lignin fragmentation during alkaline pulping processes may be
ascribed to the cleavage of carbon-carbon bonds in side chains and between side
chains and aromatic nuclei. This fragmentation mode is due to alkali-promoted
retrograde aldol reactions (Shemyakin; Shuchikina 1956; House 1965, 1972) and
results in the formation of carbonyl-containing and other fragments (Scheme 12).
Certain types ofhydroxylated side-chains, originally present in lignins or generated
by addition of water to intermediary conjugated structures, undergo this fragmen-
tation to varying extents (Enkvist, Turunen 1964; Gierer et al. 1972, 1973). Since
the fi-carbon atom is the main point of attachment in side-chains for the adjacent
lignin unit, fragmentation by scission of a carbon-carbon bond takes place
primarily if the bond between C a and C# or between Ca and the aromatic nucleus
is cleaved. It is clear that cleavage of the C y - C r bond with elimination of
formaldehyde from quinone methide intermediates (Scheme 4, left part) does not
result in fragmentation but gives rise to conjugated structures. These may then
undergo cleavage at the olefmic double bond in the manner generally described in
Scheme 12, upper part. Liberated formaldehyde may enter condensation reactions
304 J. Oierer

with phenolic nuclei to yield products of the diarylmethane type (scheme 14,
following paragraph).

Condensations
As indicated above (Scheme 4), external nucleophiles, present in the cooking liquor
and responsible for the rate and extent of delignification, have to compete with
internal nucleophiles, in particular carbanions from phenolic and enolic structures,
for quinone methide intermediates (Scheme 13). Due to the reversibility of the
addition step, the final result of this competition is dependent not only on the
nucleophilicity of the species involved, but also on the ability of the addition
products to undergo fast, irreversible subsequent reactions. Thus, in structures con-
taining a ~substituent which can be eliminated (e.g. the aroxy substituent in fi-aryl
ether structures, R=OAr), fragmentation by neighbouring group participation
(scheme 13, upper part) ~ outweigh condensation by virtue of the greater
nucleophilicity of the external nucleophile (NH-, N = S) compared to the internal
"competitors" (carbanions). However, in structures lacking a &substituent which
can be eliminated (e.g. R = Ar or Alk), only the reversible addition of an internal
nucleophile, e.g. a cyclohexadienone anion, is followed by a fast, irreversible
reaction step, i.e. abstraction of a proton from the primary addition product with
re-aromatization (Scheme 13, lower part). Tnerefore, the external nucleophile,
although stronger than the internal counterparts, does not prevent, but possibly
retards, condensation (Gierer, Ljunggren 1979).

I I
HC-R HC...
I
HC-N- - R- _ HCI / N

HC-R
HC
I
I 9 0- 0-

/'[~OCH 3
0 z/ I I
HC--R
I H _H +
HC -- H

~ 0 0CH3 ~0- 0CH3

/ - . ~ "OCH3 ." ~ "OCH3
NH-= external O- O-
nucleophile
[e.g.N =O or S)
R = OAr, Ar, AI.k
Scheme 13. Competitive addition of external (upper part) and internal (lower part) nucleo-
philes to quinone methide intermediates. In case of fl-aryl ether structures JR=OAr], the
reversible addition of the external nucleophile is followed by fl-aryl ether cleavage involving
neighbouring group participation
Chemistryofdelignifieafion,Part 1 305

HCO#
I
HOCH~+
.
I pCH 3
,'==(
C=~=OI
I
c o-
I OCH3
.c o-
I OCH3

H3CO "- H3CO "- H3CO~o "" ~ H3CO~'" '

O
I I I I
HC- HC - HC- HC-
-H +

H3CO H3CO O + ~j~ H3CO H3CO

..",..IT..-~OCH3 .- ~ "OCH 3 -"~ - O C H 3

O O- O-
I I I i
HC- HC- HC- HC-
+ CH20 .~
-- H
H3CO CH20- H3CO~._CH20 H
O- O O-
~-HO-
i I
i
HC- HC- HC-
H3CO~_H
H3CO~ CH2~oCH3 H3CO@CH2
O
I
HC- I-H* I
HC-

H3CO_ ~ C H 2 -~_ OCH3

O O
Scheme14. Alkali-promotedcondensationreactionsof phenolicunits

Condensation reactions may be viewed as conjugate additions (Michael reac-

tions) in which quinone methides, extended quinone methides or side chain enone
structures function as acceptors, and carbanions from phenolic or enolic units serve
as adding nucleophiles (Scheme 14, upper half, also Scheme 13, lower part).
Formaldehyde, liberated from quinone methide intermediates as outlined in
Scheme 4 (left part), constitutes another important acceptor for carbanions from
phenolic structures. The primary addition product, a hydroxybenzyl alcohol, is
converted into the corresponding o-quinone methide which adds a further
carbanion of the same or of a different type affording the corresponding
diarylmethane structure (Scheme 14, lower part).

Condensations followed by fragmentations

In general condensation reactions, generating new carbon-carbon bonds, counter-
act lignin degradation (Scheme 13). However, in certain structures, the initial
306 J.Gierer
H2COH OCH3
i%--~ H2COH
I ;'
H - OCH3 H"' i ' ~ "--' '= O
-H%-CH20
CH OCH3
= H3

/ -,~-OCH3 .- ~ "OCH3 /~OCH 3

O-

H2COH OCH3

/~]~OCH 3 " = /~OCH3

O- O-
Scheme15. fl-Arylether cleavagewith participation of condensedphenolicmoieties

condensation may be followed by a fragmentation step which, in part at least,

compensates for the increase in molecular weight caused by condensation.
Thus, primary condensation products from phenolic structures of the benzyl
alcohol type (Scheme 14, upmost line) undergo fragmentation by elimination of the
benzyl alcohol side chain as aldehyde (cleavage of the Ca-aryl bond).
Other fragmentations following condensation reactions have been observed
with condensation products from fl-aryl ether structures (Scheme 15) (Gierer,
Pettersson 1977; Gierer, Nelson 1978; Gierer, Ljunggren 1983). In these products,
the condensed (or the original) phenolic moiety, in its ionized form, attacks the t-
carbon atom and eliminates the fl-aroxy substituent. As a result these aryl (upper
part) and phenolate ion (lower part) participation reactions give rise to stilbene and
arylcoumaran type structures, respectively. The fragmentation reactions given by
condensation products from the fl-aryl ether type of structure suggest addition of an
appropriate phenol to the alkaline pulping liquor in order to protect lignin from
self-c,ondensation and enhance li,~-nin degradation by neighbouring group par-
ticipation reactions of the types outlined in Scheme 15.
Condensation with a phenolic compound followed by fragmentation of the
condensation product through fl-aryl ether cleavage also constitutes the basis of a
recent modification of delignification, i.e. alkaline pulping in the presence of
anthraquinone (AQ). This additive stabilizes the wood polysaceharides by
oxidizing their reducing end groups to aldonic acid groups, thereby being reduced
to anthrahydroquinone (AHQ) (L6wendahl, Samuelson 1977, 1978a, 1978b). The
latter reagent (AHQ) was found to be mainly, if not exclusively, responsible for the
beneficial effect of the additive (AQ) on the rate of alkaline delignification. ]2fis
effect was interpreted by proposing the following reaction course (Scheme 16)
(Gierer et al. 1979; cf. also Landucci 1980):
Chemistry ofdelisnification , Part 1 307

H3CO I H3CO H3Cq I

-.o-

H3CO.~ " H3CO ]~ ""

O- O O-
_H+

H3CO~o_---.

HC CHOH
\ -H~
H3CO'~'- H3CO'~ j''-
O- O- AQ

AQ anthmqulnone
AHQ anthmhydroquinone
Scheme 16. Alkaline fl-aryl ether cleavage in phenolic units with participation of condensed
anthrahydroquinone

1) Nucleophilic addition of the monoanion of AHQ (AHQ-, in the oxanthrone

form) to quinone methide intermediates of the fl-aryl ether type, followed by
2) Heterolytic fragmentation (Grob, Schiess 1967; Grob 1969) of the addition
products resulting in cleavage of the fl-aryl ether bond, formation of structures of
styrene type and regeneration of AQ.
This mechanism of alkaline fl-aryl ether cleavage, involving participation of an
additive temporarily incorporated into lignin, is reminiscent of the mechanism of
alkaline lignin fragmentation during kraft pulping which is enhanced by the
presence of hydrosulfide ions (Schemes 7 and 8) (Gierer 1980); Both ionic species,
AHQ- and HS-, add to quinone methide intermediates and facilitate lignin
degradation by subsequent fl-aryl ether cleavage. The analogy extends even to the
regeneration of the oxidized forms (AQ and S ~ by intramolecular disproportiona-
tion of the addition products (Schemes 8 and 16) and to the oxidation of reducing
end groups in the carbohydrate constituents (stabilization) by the oxidized forms.
Thus, in contrast to other phenols which condense with lignin and subsequently
promote lignin fragmentation (Scheme 15), AHQ and its oxidized form may
308 J. Gierer

function as an accelerator of lignin degradation many times before irreversibly

condensing with partners other than ~aryl ether structures (Fullerton, Ahem 1979;
Algar et al. 1979; Fullerton, Fleming 1980; Cassidy et al. 1981).
Prerequisites of any additive with potential activity in alkaline lignin degrada-
tion, by facilitating fl-aryl ether cleavage, are
1) Formation ofa monoanion which adds to quinone methide (Schemes 4, 7, 13
and 16) or other enone (Scheme 10) intermediates and
2) ionization of the added moiety to yield a further monoanion, able to attack
the t-carbon" atom in a NGP-reaction (Schemes 5, 8, 10, 13 and 15) or to undergo
intramolecular disproportionation (Scheme 16). The efficiency with which a partic-
ular additive fulfils these requirements depends in part on the ease of regeneration
during or after the fl-aryl ether cleavage.

Pulping in neutral media (Neutral sulfite pulping)

Fragmentations
In neutral media, fragmentation reactions are essentially limited to the cleavage of
a- and fl-aryl ether bonds in phenolic units. The behaviour of phenolic a-aryl ether
structures during neutral sulfite pulping is analogous to that during sulfate pulping
(Gierer 1970). In both processes, these structures convert readily into quinone

R R

~co-"--~ c H 3 C O ' ~ ?H
OH CH .2HSO~ OH CH-SO~-

-'J~ocH3 - - -"~OCH3
0 OH
R R R
/ " HSO3

H3c~?H H3CO"~1~'~" ? H H3CO1"~"- ?H

o--cH OH CH *HSO~ OH C.H-SOs

-" OCH3 / OCH3 - OCH3

OH 0 OH
-cH~ [ ~ R

H3CO'~'-I~/"- CH H3CO'~ CH2

R = side chain oH HC .._HS03~_ OH cH-so~
-~' ocHa J~LIocH3
OH OH
Sr 17. Nucleophilic addition of hydrosulfite ions to quinone methide intermediates
from aryleoumnran structures
Chemistry ofdelignificafion, Part 1 309

methide intermediates (Scheme l, R 1= O A r ) which then add the nucleophile (N,

Scheme 4) present in the pulping liquor to give the corresponding addition product,
i.e. a-mercaptide (N = S) or a-sulfonic acid (N= SO3) structures.
The sulfonation reactions in neutral media by nucleophilic addition of hydro-
sulfite ions to quinone methide intermediates are exemplified by the behaviour of
arylcoumaran (Scheme 17) (Gellerstedt, Gierer 1968) and 1,2-diaryl-propane-l,3-
diol (Scheme 18) structures (Gellerstedt et al. 1976). Analogies to the sulfidation
reactions (Scheme 7) are clear.
In phenolic fl-aryl ether structures, the initial sulfonation in the a-position may
be followed by sulfitolytic cleavage of the fl-aryl ether bond in a SN2 type of
reaction with formation of the corresponding a,fl-disulfonic acid structures
(scheme 19) (Gellerstedt, Gierer 1970). Elimination of the sulfonic acid group from
the a-position via rearrangement to a quinone methide intermediate, followed by
proton and formaldehyde elimination from the latter, affords the corresponding
styrene-fl-suffonic acid structure. The extent of this sulfitolytic fl-aryl ether cleavage
and of the subsequent conversion into styrene-fl-sulfonic acid structures increases
with increasing pH.
As is true for hydrosulfide ions (Scheme 11), hydrosulfite (and sulfite) ions are
able to cleave methyl aryl ether bonds to a considerable extent. In this reaction,
methanesulfonic acid and the corresponding catechol structure are formed as
aliphatic and as aromatic cleavage product, respectively (Scheme 20) (Gierer,
Koutek 1969).

H2~ ,,q_~OCH3 H2C-SO3 9CH3

HC \ HC-SO~ '

-Hy 9
O
OCH 3 -
OH
OCH3

H2(~OH OCH3 H2~IOH,.~CH3 H2(~OH OCH3

c-O-o HC~-OH
i ,=~,
HCOH ' HC \

OH 0 OH
OCH3
ff•CH3 H2C~--OH
, =
CH +HSO~ HC-SO~ '

-" OCH3 -" OCH3

OH OH
Scheme 18. Nucleophilic addition of hydrosulfite ions to quinone methide intermediates
from 1,2-diarylpropane-1,3-diol structures
310 J. Gierer

H2COH OCH3 H2COH H2COH

I
H -0 HC- SO3- HC-S03"-
I I
HC-S03 * S03" HC- S03"- - so3"
P
HC

..~]~OCH 3 - - O ~ H3 "" , . ~ O C H 3 ~'~OCH 3

O-- O-- 0

- H+I -CH20

HC-SO3-
II
CH

-"~OCH 3
O-
Scheme 19. Sulfitolytic/3-aryl ether cleavage in phenolic a-sulfonic acid structures, followed
by elimination of the a-suKonic acid group

~,. * S03-- ~ ~ + CH3SO3-

.- OCH3 .- O[OH]
1o [oH] [HSOs .~O[OH]
Scheme 20. Methyl-aryl ether cleavage by sulfite- and hydrosulfite ions

Non-phenolic units of the fl-aryl ether type behave differently during neutral
sulfite pulping as compared to kraft pulping. In neutral media, the side-chain
hydroxyl groups are not ionized and thus are unable to participate in fl-aryl ether
cleavage. Consequently, this abundant type of interunit linkage (in non-phenolic
units) is virtually stable towards neutral sulfite under pulping conditions.
Cleavage of carbon-carbon bonds does not appear to take place either to any
noticeable extent. This fragmentation mode would also require alkaline conditions.

Condensations
In spite of the facile formation of quinone methide intermediates (Schemes 17 and
18), condensation reactions have not been reported to take place to any appreciable
extent under the conditions of neutral sulfite pulping. This may be explained by the
absence in neutral pulping liquors of the other required reaction partner, i.e.
appropriate carbanions.

Pulping in acidic media (Acidic sulfite pulping)

Fragmentations
In acidic media, both phenolic and non-phenolic units can be converted into
conjugate acids of the corresponding quinone methide intermediates (Scheme 1,
Chemistry ofdelignification, Part 1 311

upper half). If this transformation involves elimination of the aroxy group of an

adjacent unit ( R 1 ~ O A r ) , fragmentation will again take place.
Conjugate acids ofquinone methides constitute more reactive electrophiles than
their neutral counterparts. This is revealed by the finding that even nucleophiles of
low inherent reactivity, such as aqueous sulfur dioxide (SO2"H20), can add to
these intermediates and that even weak bases, such as water, can bring about
enohzation (Scheme 4, topmost line). In the absence of nucleophiles, e.g. under the
conditions of "acidolysis" (Adler 1968, 1977), enolization of quinone methide
intermediates of the fl-aryl ether type (R=OAr) (in the conjugate acid form)
followed by acidic hydrolysis of the resulting styrene-fl-aryl ether bond leads to

I
HC-R
I
HC-SO3H + H+

-'J~OCH 3
HC-R
I
/0 ~H]
HC

.-J~OCH 3
I0+~+H~
] ~ I
HC-R
I
HC-R

~ '[}.O*H OCH 3
.--"-.~""OCH3
~"I~ OH OCH3
-'-"-i~""OCH3
/O ~H] ~O [OH]

R = OAr, Ar, AIk

Scheme21. Competitive addition of aqueous sulfur dioxide (sulfonation) and internal
nucleophile (condensation)

H&'~H OCH3 ocH3

' ' -.co
HC + HC-O-H =

-- OCH3 -- OCH3 -'"-y"'OCH 3 .--.,~-OCH3

~o [OH] 9"['o~ ~o [o~ .o [ou]

I H I

• 0.3 A.
+ -L "~ ~ ~" ]] ...C)[OH] H3COF..
II~ ...O[OH]
-" OCH~ "~y"'O*CH3 "'y"OCH3
..o [OH] ..0 [OH] ..0 [OH] ..0 [OH]
Scheme 22. Acid-promoted condensation reactions of phenolic and non-phenolic units
312 J. Gierer

extensive lignin degradation. However, in the presence of nucleophiles, such as

S Q " H20 present in acidic sulfite pulping liquors, nucleophilic addition is the
predominating process affording phenolic and non-phenolic a-sulphonic acid struc-
tures (scheme 21, upper part).
As is true for neutral sulfite pulping, acidic sulfite pulping does not result in any
appreciable cleavage of fl-aryl ether bonds in non-phenolic units. Under acidic
conditions, aliphatic hydroxyl groups are undissociated and thus unable to
participate in t-ether cleavage. Even sulfitolytic cleavage of fl-aryl ether bonds in
a-sulfonated structures (cf. reactions during neutral sulfite pulping, Scheme 19) is
precluded, aqueous sulfur dioxide being too weak a nucleophile to accomplish this
reaction.
The poorer nucleophilicity of SOa 9HaO, as compared to that of hydrosulfite
and sulfite ions, is also reflected by the behaviour of methyl aryl ether bonds. In
contrast to the partial cleavage during neutral sulfite pulping (Scheme 20), these
bonds are essentially stable towards acidic sulfite solutions.

Condensations
As is observed in alkaline media (Scheme 13), the external nucleophile from the
pulping liquor (SOa -HaO) has to compete with internal nucleophilic species for
quinone methide intermediates, here in the form of their conjugate acids (Scheme
21). These acidic condensations (Schemes 21 and 22) are analogous in format to
the condensations in alkaline media (Scheme 14) and lead also to the formation of
1,1-diarylpropane structures. Moreover, the alkali-promoted fragmentation of
certain condensation products involving aryl participation (Scheme 15, upper part)
has its parallel in the acidic fragmentation of condensation products, involving
phenonium rearrangement (Kratzl, Oburger 1980; Gierer, Nor6n, unpublished
results).
Thus, as described in the general remarks, alkaline and acidic pulping processes
exhibit both common and differing features: In both types of processes quinone
methide intermediates are readily formed (Schemes 1 and 2) which in a-aryl ether
structures results in the first main mode of lignin fragmentation. In both types of
processes these intermediates undergo enolization or add either external nucleo-
philes (Scheme 4) resulting in further lignin degradation or internal nucleophiles
leading to lignin condensation.
However, the reactions of lignin in alkaline pulping differ from those in acidic
pulping insofar as the conversion into quinone methide structures, i.e. the first main
mode of fragmentation, is restricted to phenolic units. Moreover, alkaline pulping,
in contrast to acidic pulping, brings about cleavage offl-aryl ether bonds by NGP-
reactions which constitute the second main mode of fragmentation.

(Received March 30, 1984)

Prof. Dr. Josef Gierer

Royal Institute of Technology
Dept. of Organic Chemistry/Wood Chemistry
S-100 44 Stockholm, Sweden