ChemSusChem
10.1002/cssc.201900485
COMMUNICATION
ꢀ
ꢁ=ꢀ 1-1-'/-2+ꢀ 8,)ꢀ *92'8-32ꢀ 3*ꢀ *0%:-2ꢂ()4)2()28ꢀ
3233<=+)2%7)7ꢃꢀ%ꢀ7)6-)7ꢀ3*ꢀ'%8-32-'ꢀ*0%:-2-91ꢀ'%8%0=787ꢀ,%:)ꢀ
OH
O
1
O
HO
NHAc
n
&
3
4
))2ꢀ ():)034)(ꢃꢀ %2(ꢀ 8,)=ꢀ 23;ꢀ 3''94=ꢀ%ꢀ 92-59)ꢀ 40%')ꢀ %7ꢀ
6+%23'%8%0=787ꢀ *36ꢀ ',)137)0)'8-:)ꢀ 3<-(%8-32ꢀ 6)%'8-327ꢀ
chitin
1. SO
3
•pyridine
2
. MOH M = Na or Li
Me
Me
N
N
N
O
O
ꢅ ꢅ
)6*361)(ꢀ92()6ꢀ1-0(ꢀ'32(-8-327ꢀ97-2+ꢀꢄꢆꢃꢀ;,-',ꢀ-7ꢀ32)ꢀ3*ꢀ8,)ꢀ
1
378ꢀ -2)<4)27-:)ꢃꢀ 232ꢂ,%>%6(397ꢃꢀ %2(ꢀ 1-2-1%00=ꢀ 430098-2+ꢀ
NH
M
M
#ꢈ$
3
%
<-(%287ꢇ ꢀ!,)6)*36)ꢃꢀ8,)ꢀ*0%:-2-91ꢀ'%8%0=787ꢀ%6)ꢀ6)'3+2->)(ꢀ%7ꢀ
2ꢀ-286-+9-2+ꢀ8330ꢀ*36ꢀ'32(9'8-2+ꢀ)2:-6321)28%00=ꢀ&)2-+2ꢀ3<-(%8-:)ꢀ
OSO
O
3
OSO3
O
1
•Cl (2 equiv)
OSO
O
3
O
O
HO
HO
HO
O
y
8
6%27*361%8-327ꢀ79',ꢀ%7ꢀ ꢁ"ꢀ 3<-(%8-32 ꢀ %2(ꢀ790*3<-(%8-32ꢃ#ꢊꢋ$ꢀ
08,39+,ꢀ%2ꢀ)<%140)ꢀ3*ꢀ%ꢀ6)97%&0)ꢀ430=1)6ꢂ-113&-0->)(ꢀ*0%:-2-91ꢀ
%8%0=78ꢀ ,%7ꢀ 2):)6ꢀ &))2ꢀ ()132786%8)(ꢇꢀ ꢆ;-2+ꢀ 83ꢀ -87ꢀ )%7=ꢀ
:%-0%&-0-8=ꢀ %2(ꢀ )2:-6321)28%0ꢀ %(:%28%+)7ꢃꢀ %ꢀ ꢊꢃꢊꢋꢂ&6-(+)(ꢂ
0%:-2-91ꢀ'%8%0=78ꢀ ꢌꢁꢂꢃꢄꢍꢃꢀ;,-',ꢀ-7ꢀ()6-:)(ꢀ*631ꢀ'311)6'-%00=ꢀ
6)4%6)(ꢀ6-&3*0%:-2ꢀꢌ:-8%1-2ꢀꢁꢍꢃꢀ;%7ꢀ())1)(ꢀ83ꢀ&)ꢀ79-8%&0)ꢀ*36ꢀ
113&-0->%8-32ꢇ#ꢊꢊ$ꢀ!,)ꢀꢎꢂꢆꢂ790*%8)(ꢀ',-8-2ꢃꢀ;,-',ꢀ*92'8-32)(ꢀ%7ꢀ%ꢀ
#ꢉ$
NHAc
m
NHAc
x
NHAc
+
–
M Cl
sc-Na (M = Na) 68% yield
or
sc-Li (M = Li) 80% yield
sc-1•Na x=0.19n 87% yield
sc-1•Li x=0.29n 73% yield
%
'
%
DOWEX-1•Na
*
Me
Me
N
N
N
O
O
4
ꢅ
NH
Cl–
Me
Me
N
N
N
O
O
-
NH
SO
Na
3
SO
3
4
4
30=1)6-'ꢀ7'%**30(ꢀ*36ꢀ8,)ꢀ'%8%0=787ꢃꢀ;%7ꢀ7=28,)7->)(ꢀ&=ꢀ8,)ꢀ
6):-3970=ꢀ 6)4368)(ꢀ 7)0)'8-:)ꢀ 790*%8-32ꢀ 3*ꢀ ',-8-2ꢀ ;-8,ꢀ
1•Cl
ꢀ
ꢆ
ꢏ
@4=6-(-2)ꢃ#ꢊꢅ$ꢀ%2(ꢀ79&7)59)28ꢀ2)986%0->%8-32ꢀ;-8,ꢀꢐ%ꢆꢄꢀ36ꢀ
ꢍꢆꢎꢏꢐꢏꢀꢁꢑꢀ =28,)7-7ꢀ3*ꢀꢅꢆꢇꢁꢂꢈꢉꢀ%2(ꢀꢅꢆꢇꢁꢂꢊꢋꢀ*631ꢀ',-8-2ꢇꢀ
ꢑ-ꢆꢄꢀ%**36()(ꢀ8,)ꢀ'366)7432(-2+ꢀꢐ%ꢂꢀ36ꢀꢑ-ꢂ%77)1&0)(ꢀ790*%8)(ꢀ
'
'
,-8-2ꢀꢌꢅꢆꢇꢈꢉꢀ36ꢀꢅꢆꢇꢊꢋꢃꢀ ',)1)ꢀꢊꢍꢇꢀ!,)ꢀ()7-6)(ꢀ7946%130)'90%6ꢀ
%8%0=787ꢀ ꢌꢅꢆꢇꢁ@ꢈꢉꢀ %2(ꢀ ꢅꢆꢇꢁ@ꢊꢋꢍꢀ ;)6)ꢀ 46)4%6)(ꢀ &=ꢀ %2ꢀ -32ꢀ
C) (j) sc-Na
)
<',%2+)ꢀ6)%'8-32ꢀ3*ꢀꢁꢂꢃꢄꢀ;-8,ꢀꢅꢆꢇꢈꢉꢀ%2(ꢀꢅꢆꢇꢊꢋꢃꢀ6)74)'8-:)0=ꢃꢀ
,-',ꢀ;)6)ꢀ0=34,-0->)(ꢀ*631ꢀꢄꢆꢀ&)*36)ꢀ97)ꢇꢀ!,)ꢀ-32ꢀ)<',%2+)ꢀ
)%'8-32ꢀ;%7ꢀ'%66-)(ꢀ398ꢀ92()6ꢀ,)8)63+)2)397ꢀ'32(-8-327ꢀ&=ꢀ
3%/-2+ꢀ8,)ꢀ0=34,-0->)(ꢀꢅꢆꢇꢈꢉꢀ36ꢀꢅꢆꢇꢊꢋꢀ-2ꢀ%ꢀ1)8,%230ꢀ73098-32ꢀ3*ꢀ
ꢂꢃꢄꢀꢌꢏꢇꢒꢀ1ꢓꢃꢀꢅꢀ)59-:ꢍꢀ*36ꢀꢊꢒꢀ1-2ꢇꢀꢔ*8)6ꢀ'300)'8-32ꢀ&=ꢀ*-086%8-32ꢀ%2(ꢀ
%7,-2+ꢀ;-8,ꢀꢕ8ꢆꢃꢀ8,)ꢀ-2-8-%0ꢀ;,-8)ꢀ'3036ꢀ3*ꢀ8,)ꢀ790*%8)(ꢀ',-8-2ꢀ
962)(ꢀ=)003;ꢃꢀ-2(-'%8-2+ꢀ'3140)<%8-32ꢀ;-8,ꢀ=)003;ꢀꢁꢀꢌꢖ-+96)ꢀꢅꢔꢀ
ꢌ%ꢂ'ꢍꢍꢇꢀ!,)ꢀ3&8%-2)(ꢀ7946%130)'90)7ꢃꢀꢅꢆꢇꢁꢂꢈꢉꢀ%2(ꢀꢅꢆꢇꢁꢂꢊꢋꢃꢀ;)6)ꢀ
27309&0)ꢀ-2ꢀ'31132ꢀ36+%2-'ꢀ730:)287ꢀ79',ꢀ%7ꢀꢓ)ꢆꢄꢃꢀꢕ8ꢆꢄꢃꢀ
ꢗꢓ ꢆꢃꢀꢘꢄꢘꢐꢃꢀꢊꢃꢙꢂ(-3<%2)ꢃꢀ!ꢄꢖꢃꢀꢕ8ꢆꢔ'ꢃꢀꢕ8ꢆꢃꢀ,)<%2)ꢃꢀꢘꢄꢘ0ꢃꢀ
ꢃꢀ&98ꢀ7,3;)(ꢀ13()6%8)ꢀ7309&-0-8=ꢀ-2ꢀꢄꢆꢇꢀ!,-7ꢀ1%()ꢀ-8ꢀ
377-&0)ꢀ83ꢀ)78-1%8)ꢀ8,)ꢀ%13928ꢀ3*ꢀ-113&-0->)(ꢀꢁꢀꢌ()+6))ꢀ3*ꢀ
A)
;
ꢅ
(a) 1•Cl
(b) sc-Na
(c) sc-1•Na
6
7
ꢁ
50 μm
;
ꢅ
(d)
(e)
(k) sc-1•Na
8
-
ꢏ
ꢅ
ꢅ
ꢅ
%
4
2(ꢀꢘꢄꢘ0
ꢏ
ꢅ
50 μm
B)
(f) 1•Cl
HOD
HOD
-
113&-0->%8-32ꢃꢀꢗꢇꢚꢇꢍꢀ97-2+ꢀ8,)ꢀ73098-32ꢀꢐꢓꢛꢀ8)',2-59)ꢇꢀ!,)ꢀꢐꢓꢛꢀ
4)'8691ꢀ6):)%0)(ꢀ8,%8ꢀꢅꢆꢇꢁꢂꢈꢉꢀ%2(ꢀꢅꢆꢇꢁꢂꢊꢋꢀ,%(ꢀꢊꢉꢜꢀ%2(ꢀꢅꢉꢜꢀ
ꢗꢇꢚꢇꢃꢀ6)74)'8-:)0=ꢇꢀ!,)ꢀꢐꢓꢛꢀ74)'86%ꢀ3*ꢀꢁꢂꢃꢄꢃꢀꢅꢆꢇꢈꢉꢃꢀ%2(ꢀꢅꢆꢇꢁꢂꢈꢉꢀ
2ꢀꢗꢆꢀ6):)%0)(ꢀ8,%8ꢀ8,)ꢀ-113&-0->%8-32ꢀ,%(ꢀ3''966)(ꢀ;-8,398ꢀ%2=ꢀ
)'31437-8-32ꢀ3*ꢀ8,)ꢀ*0%:-2-91ꢀ'%8-32ꢀ%2(ꢀ790*%8)(ꢀ',-8-2ꢀꢌꢖ-+96)ꢀ
ꢅꢁꢀꢌ*ꢂ,ꢍꢍꢇꢀ!,)ꢀ ꢕꢓꢀ-1%+)7ꢀ3*ꢀꢅꢆꢇꢈꢉꢀ%2(ꢀꢅꢆꢇꢁꢂꢈꢉꢀ6):)%0)(ꢀ8,%8ꢀ
,)ꢀ36-+-2%0ꢀ8,6))ꢂ(-1)27-32%0ꢀ7432+)ꢂ0-/)ꢀ7'%**30(ꢀ3*ꢀ790*%8)(ꢀ
7
(
g) sc-Na
-
ꢅ
(
HOD
HOD
(
h) sc-1•Na
D.I. = 0.19
8
'
ꢀ
,-8-2ꢀ;%7ꢀ92',%2+)(ꢀ%*8)6ꢀ8,)ꢀ-113&-0->%8-32ꢀ3*ꢀꢁꢀꢌꢖ-+96)ꢀꢅꢘꢍꢇꢀ
(
i) recovered sc-1•Na
ꢔꢀ 1%.36ꢀ ',%00)2+)ꢀ -2ꢀ '%8%0=8-'ꢀ ꢁ"ꢀ 3<-(%8-32ꢀ -7ꢀ 8,)ꢀ
= 5a
D.I. = 0.19
(
):)0341)28ꢀ 3*ꢀ %ꢀ +6))2)6ꢀ %2(ꢀ ',)137)0)'8-:)ꢀ 1)8,3(ꢀ *36ꢀ
)832)7ꢀ'328%-2-2+ꢀ38,)6ꢀ*92'8-32%0ꢀ+63947ꢇ#ꢊꢏ$ꢀꢖ36ꢀ)<%140)ꢃꢀ-8ꢀ,%7ꢀ
))2ꢀ(-**-'908ꢀ83ꢀ%',-):)ꢀ',)137)0)'8-:)ꢀꢁ"ꢀ3<-(%8-32ꢀ3*ꢀ/)832)7ꢀ
,%8ꢀ,%:)ꢀ'%6&32ꢂ'%6&32ꢀ(39&0)ꢀ&32(7ꢀ%7ꢀ8,-7ꢀ*92'8-32%0ꢀ+6394ꢀ
)2)6%00=ꢀ92()6+3ꢀ)43<-(%8-32ꢀ92()6ꢀ8,)ꢀ3<-(%8-:)ꢀ'32(-8-327ꢇ#ꢊꢙ$
ꢆ2ꢀ8,)ꢀ38,)6ꢀ,%2(ꢃꢀꢁ%)=)6ꢂ"-00-+)6ꢀ13233<=+)2%7)7ꢀꢌꢁ"ꢓꢆ7ꢍꢃꢀ
,-',ꢀ%6)ꢀ*0%:-2ꢂ()4)2()28ꢀ)2>=1)7ꢃꢀ,%:)ꢀ&))2ꢀ;-()0=ꢀ)1403=)(ꢀ
7ꢀ &-3'%8%0=787ꢀ &)'%97)ꢀ 8,)=ꢀ 4)6*361ꢀ ',)137)0)'8-:)ꢀ ꢁ"ꢀ
<-(%8-32ꢀ3*ꢀ/)832)7ꢀ;,-0)ꢀ830)6%8-2+ꢀ8,)ꢀ%0/)2)ꢀ*92'8-32%0-8=ꢇ#ꢊꢒ$
,)6)*36)ꢃꢀ8,)ꢀ'%8%0=8-'ꢀ%'8-:-8=ꢀ3*ꢀꢅꢆꢇꢁꢂꢈꢉꢀ%2(ꢀꢅꢆꢇꢁꢂꢊꢋꢀ ;%7ꢀ
2:)78-+%8)(ꢀ*36ꢀ8,)ꢀꢁ"ꢀ3<-(%8-32ꢀ3*ꢀ79&786%8)ꢀꢌꢉꢀ&)%6-2+ꢀ%2ꢀ
0/)2)ꢀ*92'8-32%0-8=ꢃꢀ;,)6)ꢀ%ꢀ(-098)(ꢀ73098-32ꢀ3*ꢀꢌꢉꢀ-2ꢀꢓ)ꢆꢄꢀꢌꢋꢇꢊꢀ
ꢓꢍꢀ;%7ꢀ97)(ꢀ-2ꢀ8,)ꢀ46)7)2')ꢀ3*ꢀ8,)ꢀ'%8%0=78ꢀꢌꢒꢀ130ꢜꢍꢀ%2(ꢀꢄ
ꢌꢅꢀ)59-:ꢍꢀ%8ꢀꢅꢒꢀ?ꢘꢀꢌ!%&0)ꢀꢊꢍꢇꢀ!,)ꢀ-2-8-%0ꢀ6%8)7ꢀ3*ꢀ8,)ꢀꢁ"ꢀ3<-(%8-32ꢀ
-8,ꢀ8,)ꢀ'%8%0=78ꢀꢌꢀ3&7ꢍꢀ%2(ꢀ;-8,398ꢀ8,)ꢀ'%8%0=78ꢀꢌꢀ ꢍꢀ;)6)ꢀ1)%796)(ꢃꢀ
2(ꢀ8,)ꢀ)2,%2')1)28ꢀ-2ꢀ8,)ꢀ6)%'8-32ꢀ6%8)ꢀ-2ꢀ8,)ꢀ46)7)2')ꢀ3*ꢀ8,)ꢀ
%8%0=78ꢀ6)0%8-:)ꢀ83ꢀ8,%8ꢀ*36ꢀ8,)ꢀ232ꢂ'%8%0=>)(ꢀ463')77ꢀꢌꢀ3&7ꢝꢀ ꢍꢀ;%7ꢀꢀ
/
9
8
7
6
5
4
3
2
&
δ/ppm
ꢀ
8
+
ꢀ
ꢊ
ꢒꢋꢓꢔꢕꢏꢀꢌꢑꢀꢞ,383+6%4,-'ꢀ%2(ꢀ ꢕꢓꢀ-1%+)7ꢃꢀ%2(ꢀꢄꢀꢐꢓꢛꢀ74)'86%ꢀ3*ꢀ8,)ꢀ46)4%6)(ꢀ
'%8%0=787ꢇꢀꢌꢔꢍꢀꢞ,383+6%4,-'ꢀ-1%+)7ꢀ3*ꢀꢁꢂꢃꢄꢀꢌ%ꢍꢃꢀꢅꢆꢇꢈꢉꢀꢌ&ꢍꢃꢀꢅꢆꢇꢁꢂꢈꢉꢀꢌ'ꢍꢃꢀ8,)ꢀ
6
)%'8-32ꢀ1-<896)ꢀꢌ(ꢍꢃꢀ%2(ꢀ*-086%8)ꢀꢌ)ꢍꢀ3*ꢀꢅꢆꢇꢁꢂꢈꢉꢂ'%8%0=>)(ꢀꢁ"ꢀ3<-(%8-32ꢀ3*ꢀꢌꢖꢀ
;
ꢊ
ꢅ
ꢌ)286=ꢀꢙꢀ-2ꢀ!%&0)ꢀꢅꢍꢇꢀꢌꢁꢍꢀꢄꢀꢐꢓꢛꢀ74)'86%ꢀꢌꢒꢋꢋꢀꢓꢄ>ꢃꢀꢗꢆꢃꢀꢈꢋꢀ?ꢘꢍꢀ3*ꢀꢁꢂꢃꢄꢀꢌ*ꢍꢃꢀꢅꢆꢇ
%
3
ꢈꢉꢀꢌ+ꢍꢃꢀꢅꢆꢇꢁꢂꢈꢉꢀꢌ,ꢍꢃꢀ%2(ꢀꢅꢆꢇꢁꢂꢈꢉꢀ6)'3:)6)(ꢀ%*8)6ꢀ8,)ꢀ'%8%0=8-'ꢀ790*3<-(%8-32ꢀ3*ꢀ
ꢗꢉꢀꢌ)286=ꢀꢉꢀ-2ꢀ!%&0)ꢀꢅꢃꢀ-ꢍꢇꢀꢌꢘꢍꢀ ꢕꢓꢀ-1%+)7ꢀ3*ꢀꢅꢆꢇꢈꢉꢀꢌ.ꢍꢀ%2(ꢀꢅꢆꢇꢁꢂꢈꢉꢀꢌ/ꢍꢇꢀ
ꢀ
!
-
%
'
%0'90%8)(ꢀ*36ꢀ)%',ꢀ'%8%0=78ꢀ83ꢀ):%09%8)ꢀ8,)-6ꢀ4)6*361%2')ꢇꢀꢍꢆꢇ
ꢅ
ꢅ
ꢆꢀ
ꢁ
ꢂꢈꢉꢀ%2(ꢀꢅꢆꢇꢁꢂꢊꢋꢀ79'')77*900=ꢀ'%8%0=>)(ꢀ8,)ꢀ',)137)0)'8-:)ꢀꢁ"ꢀ
<-(%8-32ꢀ3*ꢀꢌꢉꢀ92()6ꢀ,)8)63+)2)397ꢀ'32(-8-327ꢀ83ꢀ+-:)ꢀ8,)ꢀ
3
;
ꢋ
'
366)7432(-2+ꢀ0%'832)7ꢀꢌꢘꢉꢐꢉꢙꢚꢕꢀ%2(ꢀꢘꢉꢐꢋꢛꢚꢕꢍꢀ;-8,398ꢀ8,)ꢀ3<-(%8-32ꢀ
*ꢀ8,)ꢀ%0/)2)ꢀ13-)8=ꢇꢀ!,)7)ꢀ7946%130)'90%6ꢀ'%8%0=787ꢀ%44%6)280=ꢀ
%
3
'
ꢋ
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Sakai, Takuya
