Aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) as a highly efficient and reusable catalyst for alcoholysis, hydrolysis, and acetolysis of epoxides

Article abstract of DOI:10.1080/00397911.2016.1223309

Alcoholysis, hydrolysis, and acetolysis of epoxides were carried out in the presence of a catalytic amount of aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) to give the corresponding β-substituted alcohols in good yields. Alcoholysis and hydrolysis of epoxides catalyzed by ATRT proceeded faster than those by pyridinium p-toluenesulfonate (PPTS).

Full text of DOI:10.1080/00397911.2016.1223309

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Aniline-terephthalaldehyde resin p-
toluenesulfonate (ATRT) as a highly efficient and
reusable catalyst for alcoholysis, hydrolysis, and
acetolysis of epoxides
Kiyoshi Tanemura & Tsuneo Suzuki
To cite this article: Kiyoshi Tanemura & Tsuneo Suzuki (2016): Aniline-terephthalaldehyde resin
p-toluenesulfonate (ATRT) as a highly efficient and reusable catalyst for alcoholysis, hydrolysis,
and acetolysis of epoxides, Synthetic Communications, DOI: 10.1080/00397911.2016.1223309
To link to this article: http://dx.doi.org/10.1080/00397911.2016.1223309
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Date: 14 October 2016, At: 14:14

SYNTHETIC COMMUNICATIONS®
http://dx.doi.org/10.1080/00397911.2016.1223309
Aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) as
a highly efficient and reusable catalyst for alcoholysis,
hydrolysis, and acetolysis of epoxides
Kiyoshi Tanemura and Tsuneo Suzuki
Chemical Laboratory, School of Life Dentistry at Niigata, Nippon Dental University, Hamaura-cho,
Niigata, Japan
ABSTRACT
ARTICLE HISTORY
Received 2 June 2016
Alcoholysis, hydrolysis, and acetolysis of epoxides were carried out in
the presence of a catalytic amount of aniline-terephthalaldehyde resin
p-toluenesulfonate (ATRT) to give the corresponding β-substituted
alcohols in good yields. Alcoholysis and hydrolysis of epoxides
catalyzed by ATRT proceeded faster than those by pyridinium
p-toluenesulfonate (PPTS).
KEYWORDS
Acetolysis; alcoholysis;
aniline resins; epoxides;
hydrolysis; solid acids
GRAPHICAL ABSTRACT
Introduction
Ring-opening reactions of epoxides with numerous nucleophiles are of great importance in
synthetic organic chemistry because of the usefulness in the preparation of various
synthetic intermediates. Treatments of epoxides with alcohols,[1–8] water,[9–15] and acetic
acid[9–15] afford β-alkoxy alcohols, diols, and β-acetoxy alcohols, respectively. These trans-
formations are very frequently carried out by using Lewis acids,[16–18] Brønsted acids,[19–21]
and basic reagents. However, the use of some acidic catalysts often encounters serious
problems such as polymerization of substrates, low activity, and inconvenient handling
of catalysts. Therefore, the development of highly active and mildly acidic catalysts for ring
CONTACT K. Tanemura
tanemura@ngt.ndu.ac.jp
Chemical Laboratory, School of Life Dentistry at Niigata, Nippon
Dental University, Hamaura-cho, Niigata 951-8580, Japan.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsyc.
Supplemental data (Full experimental detail, IR spectra, and H and 13C NMR spectra) can be accessed on the publisher’s
1
website.
© 2016 Taylor & Francis

2
K. TANEMURA AND T. SUZUKI
Figure 1. Plausible structure of ATRT.
opening of epoxides is still required. Among them, mildly acidic solid acids provide the
convenient workup procedure and the reuse of the catalyts.[22–24] As for commercially
available polymers, a few examples such as poly(4-vinylpyridinium p-toluenesulfonate)
[polyPPTS][25] and poly(4-vinylpyridinium chloride) [polyPCL][26] are known. However,
these polymers are expensive.
We have recently reported that aniline-terephthalaldehyde resin p-toluenesulfonate
(ATRT)[27] (Fig. 1) and more active diphenylamine-terephthalaldehyde resin p-toluenesul-
fonate [DTRT (H)][28] with high sulfonate group contents are useful acidic polymer cata-
lysts for tetrahydropyranylation of alcohols, deprotection of tetrahydropyranyl (THP)
ethers and tert-butyldimethylsilyl (TBDMS) ethers, and acetalization of carbonyl
compounds.[8–10] ATRT possessed higher activities than pyridinium p-toluenesulfonate
(PPTS) for the deprotection of THP ethers and TBDMS ethers and the dimethylacetaliza-
tion of carbonyl compounds.[27,29] In this article, we report that ATRT can act as a highly
efficient catalyst for alcoholysis, hydrolysis, and acetolysis of epoxides under mild con-
ditions. Furthermore, the activities of ATRT for ring opening reactions of epoxides are
compared with those of PPTS.
Results and discussion
First, we examined the catalytic activity of various mildly acidic polymers for ethanolysis of
styrene oxide (1). The results are shown in Table 1. We also prepared ATRT (H) with high
sulfonate group content by the treatment of ATRT with p-toluenesulfonic acid (TsOH) at
90 °C for 8 h in water, but the increase in the yield of 2-ethoxy-2-phenylethanol (10) was
not observed (entries 1 and 2). When DTRT (H) was employed, the yield of 10 was quite
low (2%) (entry 3). Elemental analysis indicated that nominal composition of the recovered
DTRT (H) was C19.32H16.58N1.00O2.87 0.28 [DTRT (H): C17.38H15.43N1.00O2.02S0.34], suggest-
S
ing the decomposition of the catalyst. The proportion of the p-toluenesulfonate salt per
aniline unit decreased from 34% to 28%. Furthermore, the increase in the proportion of
carbon, hydrogen, and oxygen atoms was observed. However, the structure of decomposed
DTRT (H) is not clear at the present time. Activity of polyPPTS was comparable to that of
ATRT (entries 1 and 4).

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Table 1. Ethanolysis of 1 catalyzed by mildly acidic polymers.a
Entry
Catalyst
Acid density (mmol gÀ 1
)
Yield (%)b
1
2
3
4
5
ATRT
1.01
1.55
1.17
3.5
60
55
2
56
17
ATRT (H)
DTRT (H)
PolyPPTS
PolyPCL
6.5
aEpoxide 1 (5.0 mmol), catalyst (1 mol%), EtOH (10 mL), room temp, 45 min.
bIsolated yield.
As shown in Table 2, various epoxides 1–8 reacted with several alcohols catalyzed by
ATRT to give the corresponding β-alkoxy alcohols 9–30 in good yields. Only 1 mol% of
the catalyst was sufficient to complete the reactions except the reaction of cyclohexene
oxide (2) with allyl alcohol (entry 9). Alcoholysis of 1 with MeOH proceeded very quickly
at room temperature within 7 min to give 9 in 99% yield with the exclusive attack at the
benzylic position. The reactions of 1 with the other alcohols such as EtOH, nPrOH, iPrOH,
Table 2. Alcoholysis of epoxides catalyzed by ATRT.a
Entry
Epoxide
ROH
Time (h)
Product (Yieldb)
1
MeOH
EtOH
7 min
1.5 h
15 h
8 h
9 (99%)
10 (97%)
11 (92%)
12 (80%)
13 (96%)
14 (99%)
15 (86%)
16 (80%)
17 (80%)
18 (82%)
2
3
nPrOH
iPrOH
4c
5
=
H2C CHCH2OH
HC�CCH2OH
MeOH
3 h
6
1 h
7
10 min
96 h
137 h
96 h
8
EtOH
9c,d
10
H2C CHCH2OH
=
HC�CCH2OH
11
MeOH
4 h
19 (51%)
20 (41%)
12
MeOH
12 h
21 (69%)
22 (16%)
(Continued)

4
K. TANEMURA AND T. SUZUKI
Table 2. Continued.
Entry
Epoxide
ROH
Time (h)
Product (Yieldb)
13
14
MeOH
MeOH
32 h
24 h
23 (95%)
24 (69%)
25 (16%)
15
MeOH
48 h
26 (90%)
16
17
18
19
MeOH
EtOH
1.5 h
15 h
15 h
2 h
27 (98%)
28 (99%)
29 (96%)
30 (90%)
=
H2C CHCH2OH
H2C�CCH2OH
aEpoxide (5.0 mmol), ATRT (50 mg, 1 mol%), alcohol (10 mL), room temp.
bIsolated yield.
cThe reaction was conducted at 40 °C.
d2 mol% of ATRT was used.
allyl alcohol, and 2-propyn-1-ol proceeded more slowly (entries 2–6). Treatment of 2 with
MeOH proceeded very quickly at room temperature within 10 min to afford 15 in 86%
yield. Alcoholysis of 2 with EtOH, allyl alcohol, and 2-propyn-1-ol proceeded much more
slowly compared with those of 1 (entries 2, 5, 6, and 8–10). Only trans isomers were
obtained in the reactions of 2. The reactions of 4–7, which contain deactivating groups
such as an ethereal linkage and an ester function, proceeded more slowly than that of 3
Table 3. Competitive alcoholysis of epoxides catalyzed by ATRT.a
Entry
1
Epoxides
Time
Products (yieldb)
1 þ 3
7 min
9 (98%)
19 (11%) 20 (12%)
9 (99%)
23 (0%)
9 (99%)
24 (5%) 25 (1%)
9 (99%)
26 (0%)
15 (84%)
19 (4%) 20 (4%)
15 (86%)
23 (0%)
15 (81%)
2
3
1 þ 5
1 þ 6
1 þ 7
2 þ 3
2 þ 5
2 þ 6
2 þ 7
1 þ 2
7 min
7 min
7 min
10 min
10 min
10 min
10 min
1 h
4
5
6
7
24 (3%) 25 (trace)
15 (86%)
8
26 (0%)
9c
14 (91%)
18 (9%)
aEpoxides (5.0 mmol), ATRT (50 mg, 1 mol%), MeOH (10 mL), room temp.
bIsolated yield.
c2-Propyn-1-ol was used instead of MeOH.

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Table 4. Hydrolysisa and acetolysisb of epoxides catalyzed by ATRT.
Entry
1a
Epoxide
Time (h)
1
Product (yieldc)
2a
1
3a,d,e
24
4a
5a
6a
36
97
48
7a,d,e,f
87
8b
9b
0.5
1
10b
60
92
11b,d
12b,d
13b
163
48
aEpoxide (2.0 mmol), ATRT (100 mg, 5 mol%), MeCN-H2O (1:1) (4 mL), room temp.
bEpoxide (2.0 mmol), ATRT (100 mg, 5 mol%), acetic acid (4 mL), room temp.
cIsolated yield.
d10 mol% of ATRT was used.
eMeCN-H2O (2:1) was used.
fThe reaction was conducted at 40 °C.

6
K. TANEMURA AND T. SUZUKI
Table 5. Recycle experiments for the reactions of epoxide 1.
Yields (%)a
Entry
1st
2nd
3rd
4th
5th
1b
2c
3d
92
87
85
90
87
88
92
84
90
89
82
87
88
83
87
aIsolated yields.
bEpoxide 1 (5.0 mmol), ATRT (50 mg, 1 mol%), EtOH (10 mL), room temp, 1.5 h.
cEpoxide 1 (2.0 mmol), ATRT (100 mg, 5 mol%), MeCN-H2O (1:1) (4 mL), room temp, 1 h.
dEpoxide 1 (2.0 mmol), ATRT (100 mg, 5 mol%), acetic acid (4 mL), room temp, 0.5 h.
possessing an alkyl chain. Ring-opening reactions of 3, 4, and 6 provided regioisomers. The
reactions of 4–6 possessing ethereal linkage with MeOH underwent with the preferential
attack of MeOH at the terminal positions. Various substituents such as an isopropoxy
group, a phenoxy group, a double bond, and an ester function were tolerated during the
reactions (entries 12–15).
Table 3 summarizes the results for the competitive alcoholysis of epoxides. Selective ring
opening of epoxide 1 in the presence of epoxide 3 possessing an alkyl chain, epoxide 5 or 6
Table 6. Reactions of epoxides catalyzed by ATRT and PPTS.
(a) Alcoholysis of epoxides.a
ATRT
PPTS
Entry
Epoxide
Time product (yield)
Time product (yield)
1b
2c
3d
1
1
6
1.5 h 10 (97%)
1.5 h 14 (99%)
21 h 24 (68%)
25 (19%)
4 h 10 (95%)
4.5 h 14 (97%)
157 h 24 (66%)
25 (16%)
4
8
1.5 h 27 (98%)
7 h 27 (91%)
aEpoxide (5.0 mmol), catalyst (1 mol%), MeOH (10 mL), room temp.
bEtOH was used instead of MeOH.
c2-Propyn-1-ol was used instead of MeOH.
d2 mol% of catalyst was used.
(b) Hydrolysis of epoxides.a
ATRT
PPTS
Entry
Epoxide
Time product (yield)
Time product (yield)
1
1
2
3
6
1 h 31 (86%)
1 h 32 (98%)
24 h 33 (89%)
24 h 36 (90%)
3 h 31 (84%)
3 h 32 (91%)
240 h 33 (83%)
96 h 36 (87%)
2
3b,c
4b
aEpoxide (2.0 mmol), catalyst (5 mol%), MeCN-H2O (1:1) (4 mL), room temp.
b10 mol% of catalyst was used.
cMeCN-H2O (2:1) was used.
(c) Acetolysis of epoxides.a
ATRT
PPTS
Entry
Epoxide
Time product (yield)
Time product (yield)
1
1
2
4
6
2 h 38 (87%)d
5 h 39 (80%)
92 h 42 (83%)
48 h 44 (83%)
2 h 38 (88%)
5 h 39 (80%)
76 h 42 (85%)
40 h 44 (84%)
2
3b
4c
aEpoxide (2.0 mmol), catalyst (1 mol%), acetic acid (4 mL), room temp.
b10 mol% of catalyst was used.
c5 mol% of catalyst was used.
dCompound 38 was obtained in 48% yield in the absence of ATRT.

SYNTHETIC COMMUNICATIONS®
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possessing an alkoxy group, or epoxide 7 possessing an ester function was observed to give 9
in good yield (entries 1–4). Similarly, epoxide 2 reacted preferentially in the presence of
epoxide 3, 5, 6, or 7 to give 15, respectively (entries 5–8). Selective ring opening of 1 with 2-
propyn-1-ol in the presence of 2 led to the production of 14 in good yield (entry 9). These results
were similar to those observed in the other acid catalysts such as electrogenarated acid.[4,10]
Table 4 shows the results for hydrolysis and acetolysis of various epoxides using 5–10 mol%
of ATRT. ATRT works efficiently to give the corresponding diols 31–37 in good yields by the
reactions of 1–7 in MeCN-H2O. Treatments of 1–6 in acetic acid catalyzed by 5–10 mol% of
ATRT resulted in the formation of β-acetoxy alcohols 38–44 in good yields. Regioselective
formation of β-acetoxy alcohols was observed in every case except epoxide 3. The other regioi-
somers were not detected for the acetolysis of epoxides 1, 2, and 4–6.
In order to check the reusability of the catalyst, ATRT was removed by filtration and
employed for the next experiment. ATRT was recycled five times without the loss of
activity for alcoholysis, hydrolysis, and acetolysis of 1 (Table 5).
It is interesting to note that alcoholysis and hydrolysis of various epoxides promoted by
ATRT proceeded faster than those by PPTS (Tables 6a and 6b). The higher activity of
ATRT might be attributed to the hydrophobic effect of polymers.[30–33] Acetolysis of
epoxides catalyzed by ATRT proceeded with almost the same rate or somewhat slower
than those by PPTS (Table 6c). In these cases, the reactions were partially catalyzed by
acetic acid because the acetolysis of 1 in the absence of ATRT afforded 38 in 44% yield
(entry 1). PPTS is widely used as a mild reagent for many transformations such as tetra-
hydropyranylation of alcohols,[34] deprotection of THP ethers[34] and silyl ethers,[35] and
alcoholysis of epoxides.[36,37] However, it is somewhat difficult to handle in air because
PPTS is hygroscopic. ATRT will be useful for these transformations because of its reusable
and nonhygroscopic properties.
Conclusion
We have demonstrated that ATRT is an efficient solid acid catalyst for ring opening
reactions of epoxides with alcohols, water, and acetic acid. Alcoholysis and hydrolysis of
epoxides catalyzed by ATRT were faster than those by PPTS. It is worth pointing out that
(1) ATRT can be synthesized by only one step (heating a mixture of aniline, terephthalal-
dehyde, and TsOH in EtOH followed by grinding; see the Supporting Information), (2) the
workup procedure is remarkably simple, and (3) ATRT is nonhygroscopic and easy to
handle.
Experimental
General procedure for alcoholysis of epoxides catalyzed by ATRT
ATRT (50 mg, 1.0 mol%) was added to a solution of 1 (600 mg, 5.0 mmol) in dry EtOH
(10 mL). The mixture was stirred at room temperature for 1.5 h. The catalyst was collected
and washed with EtOH. Evaporation of the filtrate gave a residue, which was purified by
column chromatography on silica gel using hexane–acetone (3:1) as eluent to afford 10[38]
(803 mg, 97%).

8
K. TANEMURA AND T. SUZUKI
General procedure for hydrolysis of epoxides catalyzed by ATRT
ATRT (100 mg, 5.0 mol%) was added to a solution of 1 (240 mg, 2.0 mmol) in MeCN-H2O
(1:1) (4 mL). The mixture was stirred at room temperature for 1 h. The catalyst was
collected and washed with MeCN. Evaporation of the filtrate gave a residue, which was
purified by column chromatography on silica gel using hexane–acetone (2:1) as eluent
to afford 31[38] (237 mg, 86%).
General procedure for acetolysis of epoxides catalyzed by ATRT
ATRT (100 mg, 5.0 mol%) was added to a solution of 1 (240 mg, 2.0 mmol) in acetic acid
(4 mL). The mixture was stirred at room temperature for 0.5 h. The catalyst was collected
and washed with Et2O. Evaporation of the filtrate gave a residue which was purified by
column chromatography on silica gel using hexane–acetone (2:1) as eluent to afford 38[38]
(313 mg, 87%).
Acknowledgments
We thank the Center for Instrumental Analysis, Institute for Research Promotion, Niigata University
for 1H and 13C NMR measurements. We thank the Division of Chemical Analysis, Systems
Engineering, for the elemental analyses. We thank JEOL Ltd. for the high-resolution mass analysis.
Funding
We thank Nippon Dental University for the Research Promotion Grant (NDU Grants N-16010).
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