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Acid NaOH/air
0.04 M, 100 °C
4 h [189]
NaOH/O2
0.04 M, 95 °C
1bar, 5 min [187]
NaOH/N2
0.04 M, 95 °C
1bar, 5 min [187]
NaOH/air
18%, 25 °C
200 h [191]
NaOH/O2
0.5%, 100 °C
5 bar, 2 h [184]
Mannonic 11 18 47 15 27
Gluconic 2 5 5 2 3
Arabinonic 58 37 26 58 50
Ribonic 4 6 0 2 2
Erythronic 25 35 22 23 18
Two different pathways can form erythronic acid (11) (Scheme 7.16). The first
entails rearrangement of the glucosone to d- erythro –2,3-hexodiulose (10), followed
by an oxidative cleavage and loss of glycolic acid (12) [183]. In the second pathway,
erythronic acid (11) results from alkaline and oxidative degradation of the glucosone
(4) through arabinose (13) and arabinosone (14) as intermediates. In the
absence of dioxygen arabinose (13, Scheme 7.16) and arabinonic acid (8, Scheme
7.15), it may be formed by hydroxide ion attack at C1 and C2 respectively [185].
Minor amounts of 3-deoxy-pentonic acids (17, 18) are formed from an arabinose
intermediate (13), and the main pathway starts with a direct b-hydroxy-elimination
in the glucosone (4) followed by loss of the elements of carbon monoxide
from the intermediate 4-deoxy-d- glycero –2,3-hexodiulose (15) [187].
The yield of 3-deoxy-pentonic acids is lower in the presence of dioxygen [185],
and the formation of arabinonic and erythronic acid is particularly important.
Theander [185] stated that an attack of dioxygen to the glucosone (4, Scheme 7.17)
should give a hydroperoxide (20), which should further yield arabinonic acid (8)
and carbon dioxide. A similar attack at C3 could, via formation of a hydroperoxide
(21), result in the formation of an erythronic acid end-group (11) plus glyoxylic
acid (22).
About the same proportions of aldonic acids were produced from glucosone
and glucose treated with dioxygen and alkali [183], and cellobiose [190] and cellotriose
[192] yielded glucosyl- and cellobiosyl-arabinonic acids as the main products.
However, the presence of the substituted erythronic and mannonic acids was
also significant, especially at higher alkali concentrations. Malinen and Sjostrom
658 7Pulp Bleaching
R1 = -H for xylan
R = Polysaccharide chain
R1 = -CH2OH for cellulose and glucomannan
O
HO H
H OR
H OH
R1
O
H
+ OH-
CH2OH
O
O
H OR
H OH
R1
+
O2/OH-
COOH
H OR
H OH
R1
CH2OH
COOH
- HCOOH
+ OHH
O
H
H OR
H OH
R1
HO
O2/OH- O2/OH-
H O
O
H OR
H OH
R1
COOH
H OR
H OH
R1
H O
H
H OH
R1
OH + OH-
- ROH-
H O
H
H OH
R1
O
H
O
OH
H
H OH
R1
H O
+ OH-
- ROH
O
O
H
H OH
R1
O
H
H
HO O
H
H OH
R1
HO
H
H
HO O
H
H OH
R1
H
H
OH
HO O
H
H OH
R1
+ + H
10 D- erythro -2,3-hexodiulose
11 Erythronic acid
12 Glycolic acid
13 Arabinose
14 Arabinosone
15 4-Deoxy-D- glycero -2,3-hexodiulose
16 3-Deoxy-D- glycero -pentosulose
17 3-Deoxy-D- threo -pentonic acid
18 3-Deoxy-D- erythro -pentonic acid
19 3,4-Dihydroxybutyric acid
10 D- glycero -2,3-pentodiulose
11 Glyceric acid
13 Threose
14 Threosone
15 4-Deoxy-2,3-pentodiulose
16 3-Deoxy-Tetrosulose
17 2,4-Dihydroxybutyric acid
18 2,4-Dihydroxybutyric acid
19 2-Deoxy-glyceric acid
Scheme 7.16 Degradation pathways of the glucosone and
xylosone end-groups (adapted from Malinen [183] and
Theander [185]).
R = Cellulose chain
R1 = -CH2OH
O
HO H
H OR
H OH
R1
O
H
+
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Carbohydrate Reactions in Dioxygen-Alkali Delignification Processes | | | Peeling Reactions Starting from the Reducing End-Groups |