Preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in aqueous media with β-cyclodextrin-SO3H as a recyclable catalyst

Article abstract of DOI:10.1039/c3gc42400f

A new β-cyclodextrin-SO₃H-assisted, convenient and efficient strategy for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in aqueous media is described. The catalyst can be readily recovered and reused for the next reaction for at least three runs without any significant impact on the yields of the products. The main advantages of this protocol include short reaction times, practical simplicity, high yields, recyclable catalysts, safety, and cheapness of benign solvents. This journal is the Partner Organisations 2014.

Full text of DOI:10.1039/c3gc42400f

Green Chemistry
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Preparation of 2,3-dihydroquinazolin-4(1H)-one
derivatives in aqueous media with β-cyclodextrin-
SO3H as a recyclable catalyst†
Cite this: Green Chem., 2014, 16,
3210
Jian Wu,*a,b Xianli Du,a,b Juan Ma,a,b Yuping Zhang,a,b Qingcai Shi,a,b Lijun Luo,a,b
Baoan Song,*a,b Song Yanga,b and Deyu Hua,b
A new β-cyclodextrin-SO3H-assisted, convenient and efficient strategy for the preparation of 2,3-dihydro-
quinazolin-4(1H)-one derivatives in aqueous media is described. The catalyst can be readily recovered
and reused for the next reaction for at least three runs without any significant impact on the yields of the
products. The main advantages of this protocol include short reaction times, practical simplicity, high
yields, recyclable catalysts, safety, and cheapness of benign solvents.
Received 22nd November 2013,
Accepted 3rd March 2014
DOI: 10.1039/c3gc42400f
www.rsc.org/greenchem
Aqueous media have received high priority as green media
in organic synthesis due to them being safe, cheap, environ-
Introduction
2,3-Dihydroquinazolinone derivatives are an important class mentally friendly, and non-toxic.27 An increasing number of
of fused heterocycles due to their broad range of potential bio- publications28 are indicative of the potential of aqueous media
logical pharmacological activities,1–6 as well as their impor- as ‘designer solvents’ for various chemical reactions, such as
tance in preparation of drug molecules and natural the Knoevenagel condensation reaction,29 Reformatsky reac-
products.7–10 In recent years, a large number of protocols tion,30 Diels–Alder reaction,31 Suzuki coupling,32 Michael
for preparation of 2,3-dihydroquinazolin-4(1H)-ones have been addition,33 Claisen rearrangement,34 Stille coupling reaction,35
developed in different ways using gallium(III) triflate,11 etc. In the reported strategies for preparation of 2,3-dihydro-
iodine,12 silica sulfuric acid,13 montmorillonite K-10,14 [Zn- quinazolin-4(1H)-ones, several protocols were also carried out
(PFO)2],15 KAl(SO4)2·12H2O,16 MCM-41-SO3H,17 Al(H2PO4)3,18 in aqueous media and showed good results.15,16,20,21,26
[bmim]BF4,19 sulfamic acid,20 β-cyclodextrin,21 cellulose-
SO3H,22 chloride,23
ammonium low-valent titanium synthesis of 2,3-dihydroquinazolin-4(1H)-ones by ring closure
In the current work, we disclosed a novel methodology for
reagents,24 Cu-CNTs25 and MNP-PSA (N-propylsulfamic acid of substituted 2-aminobenzamides with aldehydes (or ketone),
supported onto magnetic Fe3O4 nanoparticles)26 as catalysts. and one-pot three-component condensation of substituted
These reported methodologies produce good results in many isatoic anhydrides, a primary amine (or ammonium acetate)
instances. However, some of the synthetic strategies suffer and a carbonyl derivative in the presence of β-cyclodextrin-
from certain limitations such as expensive catalysts, low yields SO3H in aqueous media, respectively. To the best of our knowl-
of products, long reaction times, high reaction temperature, edge, this is the first reported synthesis of this important class
tedious procedures for preparation of catalysts and tedious of fused heterocycles from cheap and easily available starting
work-up conditions. Hence, the development of an efficient, materials by employing cheap, recyclable and easily available
simple, easy work-up and environmentally benign protocol β-cyclodextrin-SO3H as an efficient catalyst in a green medium.
using a recyclable catalyst and a green solvent for the synthesis
of quinazolinone derivatives is still desirable and in demand.
Results and discussion
aResearch and Development Center for Fine Chemicals, Guizhou University, Guiyang,
Initially, β-cyclodextrin-SO3H was simply synthesized according
550025, People’s Republic of China. E-mail: wujian2691@126.com,
to the method reported recently.36 The –SO3H content
basong@gzu.edu.cn; http://fcc.gzu.edu.cn; Fax: +86-851-8292090
bState Key Laboratory Breeding Base of Green Pesticide and Agricultural
obtained was in agreement with the proposed method, the
value was 0.52 mequiv. g−1, and it matched that reported in
Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering,
Ministry of Education, Guizhou University, Guiyang, 550025, People’s Republic of
the literature.36 Subsequently, to investigate the effects of
China
solvent, reaction time, and the amount of catalyst on the yield,
we carried out the reaction of 2-aminobenzamide with benz-
†Electronic supplementary information (ESI) available: Detailed experimental
procedures and full compound characterization. See DOI: 10.1039/c3gc42400f
3210 | Green Chem., 2014, 16, 3210–3217
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reaction. As reported in ref. 21, the yield was low (Table 1,
entry 18) under catalyst free conditions, which may be due to
the poor solubility of benzaldehyde in water at elevated temp-
eratures resulting in the formation of undesired products, but
5% of catalyst can give a moderate yield (74%, Table 1, entry
17) for this reaction. An increase in the amount of catalyst can
enhance the yield, and the reaction proceeds smoothly to give
higher yield (95%) by the addition of >10% of catalyst. Never-
theless, the yields were not enhanced obviously by further
increasing the amount of catalyst (Table 1, entry 16). Moreover,
p-TSA (Table 1, entry 19) and sulfamic acid (Table 1, entry 20)
were also employed as catalysts, but the yields were lower than
that of β-cyclodextrin-SO3H. After the completion of the reac-
tion, the product was precipitated and was completely isolated
by filtration from the aquatic phase. However, the catalyst
β-cyclodextrin-SO3H still remained in the filter liquor that
could be used directly as a catalyst medium for the next reac-
tion, and the yield was still around 90% after the catalyst
system was recycled for four runs (Table 1, entry 11).
Encouraged by the initial success, we applied the optimal
protocol to a variety of substituted 2-aminobenzamide and
different aldehydes. Generally, the reactions were performed
using 10 mol% of β-cyclodextrin-SO3H in H2O under room
temperature for 25 min to give the desired products in good to
excellent yields; the results are summarized in Table 2. It was
observed that most of the reactions of substituted 2-amino-
benzamide with aldehydes proceeded smoothly. However, the
yields were slightly lower at room temperature for part of the
reaction (Table 2, entries 17–31), which may be due to the poor
solubility of aldehydes in water, but when the reaction temp-
erature was sited around 50 °C, the yields of the products can
be enhanced (Table 2, entries 17–31) and the reactions pro-
ceeded smoothly. In addition, the substituent on the aromatic
aldehydes showed slightly different effects on the yields, reac-
tions of aromatic aldehydes with electron-donating groups
afforded little better yields of products than those with the
electron-withdrawing groups (Table 2, entries 17–31). More-
over, the reactions of heterocyclic aldehydes with furan
(Table 2, entries 1, 3, 4, 7–9, 11, 13, and 15), pyridine (Table 2,
entry 30), thiophene (Table 2, entry 31), and thiazole (Table 2,
entry 32) also give excellent yields. Furthermore, the reusability
of the catalyst should also be checked randomly via several
reactions using filter liquor with β-cyclodextrin-SO3H in it as a
catalytic system for new runs (Table 2, entries 1, 6, 7, 15, 16);
these results indicated that the aqueous media containing
β-cyclodextrin-SO3H could be reused several times but with
slight decrease in the product yield.
Scheme 1 Synthesis of 2-phenyl-2,3-dihydroquinazolin-4(1H)-one.
Table 1 Optimization for synthesis of 2-phenyl-2,3-dihydroquinazolin-
4(1H)-one (model reaction)a
Amount of
catalyst
Time
Entry Solvent
(min) Temperature (mol%)
Yieldb
1
2
3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
EtOH
MeCN
CH2Cl2
Benzene 60
Toluene 60
60
60
60
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50
10c
10c
10c
10c
10c
10c
10c
10c
10c
10c
10c
10c
10c
10c
15c
5c
80
75
76
58
55
70
78
96
THF
MeOH
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
60
60
60
30
25
15
5
25
25
25
25
25
25
25
95
95, 93, 90, 88d
91
70
96
96
80
r.t.
r.t.
r.t.
r.t.
r.t.
95
74
0
56, 5521
80
10e
10f
76
a All the reactions were carried out with 2-aminobenzamide (1 mmol),
benzaldehyde (1 mmol), and water (10 mL). b Isolated yields. c Catalyst
was β-cyclodextrin-SO3H. d Catalyst system was recycled four runs.
e Catalyst was p-TSA. f Catalyst system was sulfamic acid.
aldehyde as a model reaction (Scheme 1) in different solvents
under different conditions. The results are summarized in
Table 1.
After screening several solvents, it can be noted that the
non-polar solvents such as benzene and toluene gave only
moderate yields of the products (58% and 55%, respectively),
and the polar solvents (EtOH, MeCN, CH2Cl2 and MeOH) give
much better yields than benzene and toluene; THF also gave a
good yield for the reaction (Table 1, entry 7). However, water
can give an excellent yield (96%) for this reaction (Table 1,
entry 9). Then, the reaction was conducted at room tempera-
ture for screening the suitable reaction time; the results
showed that a moderate yield (70%) could be obtained after
reaction for 5 min (Table 1, entry 13); it was observed that the
yield (91%) increased after reaction for 15 min (Table 1, entry
12); however, the yield was not enhanced after 25 min. Based
on these studies, the reaction temperature was further investi-
gated; the results indicated that the yields were not enhanced
obviously by raising the temperature (Table 1, entries 14 and
15). We next examined the effect of the amount of catalyst on
this reaction, and the results (Table 1, entries 16–18) indicated
that the amount of catalyst played an essential role in this
The scope of the reaction was further investigated by using
several ketones instead of aldehydes. The results listed in
Table 3 show that the reactions also can be conducted
smoothly, most of the reactions showed excellent yields. It is
noteworthy that substituted 2,3-dihydroquinazolin-4(1H)-one
derivatives with a spiro centre could be prepared in excellent yields
(Table 3, entries 5–15). The reusability of the catalyst was also
investigated via the reaction of 2-aminobenzamide with cyclo-
hexanone (Table 3, entry 5). We also found that the catalytic
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Table 2 β-Cyclodextrin-SO3H catalyzed synthesis of 2,3-dihydroquinazolin-4(1H)-one derivativesa
Entry
1
Rb
H
R1
H
Ar
Yield (%)
Mp (°C)
96, 94, 91, 89c
166–168 (165–167)14
2
3
8-Me
H
Et
Et
80, 95d
92
214–215
119–120 (120–121)37
4
5
6
7
8-Me
8-Me
8-Me
8-Me
Me
Me
Et
92
182–183
135–136
152–153
106–107
94
96, 93, 89, 85c
96, 95, 91, 88c
Et
8
9
8-Me-6-Cl
8-Me-6-Cl
Me
Et
96, 94d
95, 92d
155–156
168–170
10
11
8-Me-6-Cl
8-Me-6-Cl
Et
H
97
95
228–230
179–180
12
13
7-Cl
7-Cl
Me
Me
92
95
211–213
176–178
14
15
7-Cl
7-Cl
H
H
93.5
186–187
203–204
96, 94, 90, 88c
16
H
H
92, 91, 88, 88c
191–192 (189–193)12b
17
18
H
H
H
H
83, 90 d
82, 91d
205–207 (204–206)38
182–183
19
20
8-Me
8-Me
Me
Et
85, 94d
86, 94d
122–124
111–112
21
22
H
H
87, 94d
147–149 (148–150)39
270–271
7-Cl
Me
81, 90.2d
23
24
7-Cl
7-Cl
Me
Me
80, 90.5d
88, 97.1d
207–209
203–205
3212 | Green Chem., 2014, 16, 3210–3217
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Table 2 (Contd.)
Entry
Rb
R1
Ar
Yield (%)
Mp (°C)
25
26
7-Cl
7-Cl
Me
Me
86, 94.7d
83, 91.3d
189–190
248–250
27
7-Cl
H
87, 94.5d
235–237
28
29
7-Cl
7-Cl
H
85, 95d
85, 94d
210–213
171–172
Me
30
31
32
H
H
80, 92d
82, 93.3d
94
191–193 (190–192)24
193–195
7-Cl
7-Cl
Me
Me
251–253
a All the reactions were conducted with substituted 2-aminobenzamide (1 mmol), aldehydes (1 mmol), β-cyclodextrin-SO3H (0.1 mmol), and
water (10 mL). b The position of the R is referring to the structure of 2,3-dihydroquinazolin-4(1H)-one derivatives. c Catalyst system was recycled
four runs. d The second yields were obtained at 50 °C.
system can be reused several times without significantly The reaction was then performed at different temperatures
decreasing the yields of the products.
(Table 4, entries 7–10), and the results show that good yield
After we obtained excellent yields by reaction of substituted could be obtained at 80 °C (85%, Table 4, entry 8). Based on
2-aminobenzamide with aldehydes (or ketone), we noted these studies, the reaction time and the amount of catalyst
that the substituted 2-aminobenzamide can be prepared from were further investigated; the results indicated that the best
isatoic anhydride with amines.40 And in recent years, several amount of catalyst was 15%, and the time was 30 min (Table 4,
methods for preparation of 2,3-disubstituted quinazolin-4(3H)- entry 10), the yields were not enhanced by increasing the
ones via multi-component (isatoic anhydride, amines amount of catalyst (Table 4, entry 11) and reaction time
and aldehydes) reactions have been reported by using silica (Table 4, entry 12). And it can be seen from entry 15 (Table 4)
sulfuric acid,13 zinc(II) perfluorooctanoate [Zn(PFO)2],15 that the yield decreased sharply (58%) when the amount of
KAl(SO4)2·12H2O,16 ionic liquid,19 and cellulose-SO3H22 as catalyst was 0. Moreover, the yield was slightly affected by
reusable catalysts. From this point of view, we sought to investi- decreasing the reaction time (Table 4, entries 10, 12 and 13).
gate multi-component reactions to prepare the 2,3-disubsti- Same as the reaction of substituted 2-aminobenzamide with
tuted quinazolin-4(3H)-ones by using β-cyclodextrin-SO3H as aldehydes, the product was conveniently isolated by filtration,
a catalyst, which may result in good catalytic effect. Hence, and the filter liquor containing the catalyst was used directly as a
we firstly carried out the reaction of isatoic anhydride catalyst system medium for the next reaction; the result shown
with NH4OAc and furaldehyde as a model reaction under in entry 10 suggested that the catalyst system can be recycled
different conditions (Scheme 2). The results are summarized more than three times.
in Table 4.
Encouraged by the initial success in the production of
From the table, it is observed that the multi-component 2-(furan-2-yl)-2,3-dihydroquinazolin-4(1H)-one via the multi-
reaction proceeded poorly in benzene and toluene (the yields component reaction strategy to investigate the general scope
were less than 50%, Table 4, entries 1 and 2). Nevertheless, the and versatility of this strategy in the preparation of substi-
yields can be enhanced in solvents of ethanol (Table 4, entry tuted 2,3-dihydroquinazolin-4(1H)-one, different substituted
3), acetonitrile (Table 4, entry 4), dichloromethane (Table 4, isatoic anhydrides, amines, aldehydes (or ketone) were
entry 5) and H2O (Table 4, entries 6–14). Especially, water is examined under optimized conditions, respectively. Excitingly,
much more suitable for such a reaction (Table 4, entry 6). the corresponding substituted 2,3-dihydroquinazolin-4(1H)-
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Table 3 β-Cyclodextrin-SO3H catalyzed synthesis of 2,3-dihydroquinazolin-4(1H)-one derivativesa
Entry
1
Rb
H
R1
H
Temperature (°C)
r.t.
Yield (%)
92.3
Mp (°C)
182–183 (184–185)12c
2
3
4
5
8-Me
8-Me
7-Cl
H
Me
Me
Me
H
r.t.
r.t.
r.t.
50
92
161–162
94
205–207
92
161–163
94, 94, 91, 90c
220–221 (217–219)24
6
8-Me
Me
Et
50
50
50
50
50
95.2
92
180–181
142–143
166–168
201–202
198–199
7
8-Me
8
8-Me-6-Cl
8-Me-6-Cl
8-Me-6-Cl
Me
H
90
9
96
10
H
93
11
H
H
50
92
258–259 (257–260)23
12
13
7-Cl
7-Cl
Me
Me
50
50
93
94
277–278
213–215
14
15
7-Cl
7-Cl
H
H
50
50
92
95
223–224
209–210
a All the reactions were conducted with substituted 2-aminobenzamide (1 mmol), ketones (1 mmol), β-cyclodextrin-SO3H (0.1 mmol), and water
(10 mL). b The position of the R is referring to the structure of 2,3-dihydroquinazolin-4(1H)-one derivatives. c Catalyst system was recycled four
runs.
the isatoic anhydride was substituted or not, the amines were
NH4OAc (Table 5, entries 1, 4, 5, 15, 16, 18, 21, 24, and 25) or
MeNH2 (or EtNH2), or the carbonyl compounds were aldehydes
(entries 1–17) or ketones (Table 5, entries 18–25). These find-
Scheme 2 Synthesis of 2-(furan-2-yl)-2,3-dihydroquinazolin-4(1H)-
one.
ings indicate that the multi-component reactions proceed
smoothly using β-cyclodextrin-SO3H as a catalyst in aqueous
media. In addition, several reactions (Table 5, entries 2, 8, and
21) were selected randomly to examine the recyclability of the
catalyst system; the results indicate that the catalyst system can
be recycled several times.
Some possible mechanisms for preparation of 2,3-dihydro-
quinazolin-4(1H)-ones from substituted-1H-benzo[d][1,3]oxazine-
one derivatives were successfully and smoothly obtained, and
the results are listed in Table 5. From the table, it can be
observed that most of the substituted 2,3-dihydroquinazolin-4-
(1H)-ones were obtained in good yields irrespective of whether
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Table 4 Optimization for β-cyclodextrin-SO3H catalyzed synthesis of
2-(furan-2-yl)-2,3-dihydroquinazolin-4(1H)-onea
Table 5 β-Cyclodextrin-SO3H catalyzed synthesis of 2,3-dihydroquin-
azolin-4(1H)-onea
Amount of
catalyst
(mol%)
Time
(min)
Entry
Solvent
Temperature
Yieldb
1
2
3
4
5
6
7
8
Benzene
Toluene
EtOH
MeCN
CH2Cl2
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
30
30
30
30
30
30
30
30
30
30
30
40
20
30
30
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50
10
40
45
69
65
68
72
78
85
R1 or
NH4OAc
10
10
10
10
10
10
10
10
15
20
15
15
15
0
Entry
Rb
R2
R3
Yieldc (%)
1
2
3
4
5
6
7
8
H
NH4OAc
Et
Me
NH4OAc
NH4OAc
Et
Me
Et
Me
Et
Me
Me
Me
Me
NH4OAc
NH4OAc
Me
NH4OAc
Me
Me
NH4OAc
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
–C6H5
–C6H5
–C6H5
90
8-Me
7-Cl
7-Cl
7-Cl
H
8-Me
8-Me
8-Me-6-Cl
8-Me-6-Cl
7-Cl
7-Cl
8-Me
7-Cl
7-Cl
7-Cl
7-Cl
H
88, 87, 84, 84d
86
89
90
89
–C6H5
80
Furan-2-yl
Furan-2-yl
Furan-2-yl
Furan-2-yl
Furan-2-yl
Furan-2-yl
Furan-2-yl
2-Cl-6-F-C6H3
3-MeO-C6H4
4-F3O-C6H4
3-MeO-C6H4
4-F3O-C6H4
3-MeO-C6H4
Et
9
Refluxing
80
80
80
80
70
80
86
10
11
12
13
14
15
91, 90, 88c
84
91
92
81
87
58
85, 84, 83, 81d
9
86
87
88
90
85
86
89
89
10
11
12
13
14
15
16
17
18
19
20
21
H2O
a All the reactions were carried out with isatoic anhydride (1 mmol),
furaldehyde (1 mmol), NH4OAc (1.2 mmol), and water (10 mL).
b Isolated yields. c Catalyst system was recycled three runs.
H
85
88
87
Me
Me
Me
2,4-dione (three component one-pot reaction) or substituted-
2-aminobenzamide have been reported before.15,18,22 According
to experimental observations and also other mechanisms
reported in the literature,15 a plausible mechanism of the reac-
tion is proposed as shown in Scheme 3. Firstly, the substituted-
1H-benzo[d][1,3]oxazine-2,4-dione (1) was activated by β-cyclo-
dextrin-SO3H (2) to give an intermediate 4, then the carbonyl
unit of the intermediate 3 was attacked by N-nucleophilic amine
(5) to produce an intermediate 6, which in turn affords an inter-
mediate 7. Then intermediate 8 was formed in the presence of
β-cyclodextrin-SO3H, and substituted-2-aminobenzamide (9) was
formed through decarboxylation of 8. Simultaneously, aldehydes
(or ketones) (10) were activated by β-cyclodextrin-SO3H to give
intermediate 11. Subsequently, the reaction of intermediate 11
with 9 proceeds to result in the formation of intermediate 12.
Then proton transfer of 12 leads to intermediate 13. Finally,
intermediate 14 was formed by a ring closure via dehydration,
which in turn affords the target product 15.
8-Me
7-Cl
H
Et
Et
89
–CH2CH2
CH2CH2CH2–
–CH2CH2CH2
CH2CH2–
–CH2CH2CH2
CH2CH2–
86, 86, 83, 84d
22
23
8-Me
8-Me
Me
Et
85
85
24
25
H
7-Cl
NH4OAc
NH4OAc
–CH2CH2CH2CH2–
–CH2CH2CH2CH2–
89
88
a All the reactions were carried out with isatoic anhydride (1 mmol),
furaldehyde (1 mmol), amine (1.2 mmol), and water (10 mL). b The
position of the R is referring to the structure of 2,3-dihydroquinazolin-
4(1H)-one derivatives. c Isolated yields. d Catalyst system was recycled
three runs.
Conclusions
In this work, we have described a successful strategy for the
efficient and convenient preparation of substituted 2,3-di-
hydroquinazolin-4(1H)-ones using β-cyclodextrin-SO3H as a cata-
lyst in water by ring closure of substituted 2-aminobenzamide
with aldehydes (or ketone) and the multi-component one-pot
condensation of isatoic anhydride with amines and aldehydes
(or ketone). It was suggested that β-cyclodextrin-SO3H shows
high catalytic activity. Moreover, the catalyst can be readily
recovered and reused for at least three runs without any signifi-
cant impact on the yield of the products, most important of
all, the catalyst could be reused directly by using the filtrate as
Scheme 3 A possible mechanism for the formation of 2,3-dihydroquin-
the next reaction without any treatment. The current strategy azolin-4(1H)-one derivatives.
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offers several advantages such as high yields and purity of pro- in filter liquor could be used directly as a catalyst medium for
ducts, low amount of catalyst, safe, cheap and environmentally the next runs.
benign solvent and an easy experimental workup procedure.
Furthermore, we are trying our best to develop more reaction
by using β-cyclodextrin-SO3H as a catalyst in an environmental
way, and the related work is underway in our laboratory.
Acknowledgements
Financial support from the National Natural Science Foun-
dation of China (21302025), the Special Foundation of Gover-
nor for Outstanding Talents in Guizhou (no. 2011-38), and the
Introduction of Talent Research Projects of Guizhou University
(no. 2011-24) is gratefully acknowledged.
Experimental section
General methods
Unless otherwise stated, all the reagents and reactants were
purchased from commercial suppliers; melting points were
uncorrected and determined on a XT-4 binocular microscope
(Beijing Tech Instrument Co., China). The 1H-NMR and Notes and references
13C-NMR spectra were recorded on a JEOL ECX 500 NMR
1 (a) J. F. Wolfe, T. L. Rathman, M. C. Sleevi, J. A. Campbell
spectrometer (JEOL Ltd, Japan) at room temperature operating
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Preparation of β-cyclodextrin-SO3H.36 To
a well stirred
mixture of β-cyclodextrin (10.0 g, 4.5 mmol) in CH2Cl2
(50 mL), chlorosulfonic acid (2.00 g, 10 mmol) was added
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.
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3216 | Green Chem., 2014, 16, 3210–3217
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