Graphite oxide catalyzed synthesis of β-amino alcohols by ring-opening of epoxides

Article abstract of DOI:10.3906/kim-1604-45

Graphite oxide as a heterogeneous and recyclable solid acid catalyzed a simple and efficient method for the synthesis of β-amino alcohols by ring opening of epoxides with amines. This method is effective with various aromatic and aliphatic amines under solvent-free conditions. The corresponding β-amino alcohols are obtained in high yields (56%-95%) and short reaction times (15-30 min) with high regio- and chemoselectivity under metal-free conditions.

Full text of DOI:10.3906/kim-1604-45

Turk J Chem
Turkish Journal of Chemistry
(2017) 41: 70 – 79
¨
http://journals.tubitak.gov.tr/chem/
˙
c
⃝ TUBITAK
doi:10.3906/kim-1604-45
Research Article
Graphite oxide catalyzed synthesis of β-amino alcohols by ring-opening of
epoxides
Maryam MIRZA-AGHAYAN1,∗, Farzaneh ALVANDI1, Mahdieh MOLAEE TAVANA1,
Rabah BOUKHERROUB2
1Chemistry and Chemical Engineering Research Center of Iran (CCERCI), Tehran, Iran
2University of Lille, CNRS, Centrale Lille, ISEN, UMR 8520 - IEMN, F-59000 Lille, France
Received: 16.04.2016
•
Accepted/Published Online: 18.06.2016
•
Final Version: 22.02.2017
Abstract: Graphite oxide as a heterogeneous and recyclable solid acid catalyzed a simple and efficient method for the
synthesis of β -amino alcohols by ring opening of epoxides with amines. This method is effective with various aromatic
and aliphatic amines under solvent-free conditions. The corresponding β -amino alcohols are obtained in high yields
(56%–95%) and short reaction times (15–30 min) with high regio- and chemoselectivity under metal-free conditions.
Key words: Ring opening, epoxides, amines, β -amino alcohols, graphite oxide, metal-free conditions
1. Introduction
The ring opening of epoxides with amines is an important and elegant route for the synthesis of β -amino alcohols,
which are versatile intermediates for the synthesis of a wide range of natural and synthetic pharmacological
products.1,2 Therefore, a large number of methods have been developed for this chemical transformation.3−5
The conventional synthesis of β -amino alcohols consists of heating epoxides with an excess of amines at elevated
temperatures.6 There are some limitations to this classical approach such as the requirement of elevated reaction
temperatures in the case of less reactive amines, lower reactivity of the sterically hindered amines/epoxides,
and poor regioselectivity of the epoxide ring opening. Thus, several promoters/activators such as Lewis acids
(Er(OTf)3 ,7 Yb(OTf)3 ,8 LiClO4 ,9 Al2 O3 ,10 Zn(BF4)121), heterogeneous catalysts (mesoporous activated
carbon,12 magnetic nano Fe3 O4 ,13 nanoporous aluminosilicates,14 sulfated tungstate15), and metal halides
(ZrCl SbCl137) have been employed for the ring opening of epoxides with amines. The ring-opening reaction
16
4,
of epoxides with amines under solvent-free conditions has also been investigated in several reports.11,18,19
Nevertheless, many of these methodologies suffer from one or more disadvantages such as elevated temperatures,
long reaction times, high pressure, moderate yields, requirement of stoichiometric amounts of catalyst, use of
air and moisture sensitive catalysts, and hazardous organic solvents. The various catalysts and experimental
conditions used are summarized in Table 1.13,14,20−27 Therefore, further efforts are required for aminolysis of
epoxides with amines.
Graphite oxide (GO), an available and inexpensive material,28 and graphene oxide and its functionalized
derivatives have been utilized as heterogeneous catalysts for several organic transformations.29−37 The surface
of GO comprises several oxygen-containing groups such as epoxy, hydroxyl, and carbonyl, which provide an
∗Correspondence: m.mirzaaghayan@ccerci.ac.ir
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MIRZA-AGHAYAN et al./Turk J Chem
acidic character to the material. Recently, we have applied GO as a solid acid catalyst for the alcoholysis
of epoxides,38 conversion of oxiranes into thiiranes,39 and esterification of organic acids with alcohols.40 In
continuation of our investigation on the use of GO as a heterogeneous solid acid catalyst, we report herein a
simple and efficient method for the ring opening of epoxides by various amines under solvent-free conditions
(Scheme 1). To the best of our knowledge, the ring-opening reaction of epoxide with amines catalyzed by GO
has not been reported before.
Table 1. Various catalysts and conditions for aminolysis of epoxides with amines.
Entry Catalyst and conditions
Time
Yield (%)
60–93
1
Organobismuth triflate complex [O(CH2C6H4)2Bi(OH2)]+[OSO2 CF3]− 2.5–8 h
(5 mol%), H2O, rt.20
2
3
Mesoporous aluminosilicate (120 mg/mmol), CH2Cl2, rt.21
Nanoporous aluminosilicate materials (120 mg/mmol epoxide), CH2Cl2, 2–24 h
6–24 h
58–79
10–80
rt.14
4
Schiff bases supported on poly(vinyl chloride) (5 mol%), 1,4-dioxane, 50 6–8 h
◦C.22
80–93
32–99
◦
5
6
Magnetic nano Fe3O4 (10 mol%), rt to 80 C.13
6–24 h
Fe(III) substituted Wells–Dawson type polyoxometalate, α2-[(n- 40–350 min 60–98
C4H9)4N]7P2W17FeO61.3H2O (3 mol%), CH3CN, rt.23
7
8
Y(NO3)3.6H2O (1 mol%), rt.24
1–7 h
72–92
36–94
Zirconium sulfophenyl phosphonate (50 mg/mmol epoxide), 40 ◦C under 2–48 h
N2.25
9
10
Metallocene (Cp2MCl2, M = Ti, Zr, V) (10 mol%), rt.26
◦
Sn(OTf)2 (10 mol%), CH3CN or CH2Cl2, rt to 80 C.27
1.5–70 h
6–105 h
32–99
11–99
Scheme 1. Aminolysis of epoxides catalyzed by GO.
2. Results and discussion
Initially, we screened the ring-opening reaction of styrene oxide (1 mmol) with aniline (1 mmol) at room
temperature in the absence of GO. The resulting mixture was stirred for the time indicated in Table 2 prior to
GC/MS analysis. Only traces of the corresponding β -amino alcohol were obtained; the starting materials were
recovered even after 24 h stirring at room temperature (entry 1, Table 2). In the next step, we investigated
the ring-opening reaction of styrene oxide (1 mmol) with aniline (1 mmol) in the presence of 10 mg of GO.
The reaction proceeded smoothly to produce 2-phenyl-2-(phenylamino)ethanol in 86% after 15 min. The result
indicates that the aminolysis is regioselective. It should be noted that increasing the reaction time had low or no
impact on the reaction yield; indeed, 2-phenyl-2-(phenylamino)ethanol was obtained in 87% and 90% yield after
2 and 3 h, respectively (entry 2, Table 2). We further evaluated the catalytic activity of GO in different solvents.
When the aminolysis reaction of styrene oxide with aniline was performed in neat dichloromethane, acetonitrile,
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MIRZA-AGHAYAN et al./Turk J Chem
or water at room temperature for 2 or 4 h in the presence of 10 mg of GO, the ring opening took place but the
yields were low (entries 3–5, Table 2). The comparison of entries 2 and 3–5 clearly indicates that the tested
solvents do not improve the reaction yield and solvent-free conditions are better. The obtained results under
our experimental conditions showed that the reaction is faster under solvent-free conditions. It is thought that
the diffusion path between molecules is small under solvent-free conditions due to the high concentrations of
reactants and thus the reaction is rapid.41,42 Finally, we examined the effect of GO concentration for aminolysis
of styrene oxide with aniline (entries 6 and 7, Table 2). Notably larger amounts of GO catalyst did not improve
the reaction yield. A comparison of entries 2, 6, and 7 suggests that 10 mg of GO is sufficient for this reaction.
Table 2. Different conditions for the ring opening of styrene oxide with aniline at room temperature.
Entry GO
Solvent Time
Yielda (%)
2
1
2
3
4
5
6
7
-
10 mg
-
-
24 h
15 min, 2 h, 3 h 86, 87, 90
10 mg CH2Cl2 2 h, 4 h
10 mg CH3CN 2 h, 4 h
10 mg H2O
5 mg
15 mg
2, 14
27, 57
10, 15
71
2 h, 4 h
15 min
15 min
-
-
89
aGC/MS yield.
Under the above optimized reaction conditions, aminolysis of a wide range of epoxides (1 mmol) such as
styrene oxide, 2-ethyloxirane, 2-(phenoxymethyl)oxirane, 2-(butoxymethyl)oxirane, and 7-oxabicyclo[4.1.0]heptane
with aromatic amines (1 mmol) such as aniline; 4-methoxy, hydroxy, chloro, nitro, methyl, and 2,5-dimethylaniline;
diphenyl, benzyl, and dibenzylamine; aliphatic amines such as n-propylamine; and cyclic amines such as mor-
pholine was investigated for the synthesis of the corresponding β -amino alcohols in the presence of GO (10 mg).
As indicated in Table 3, aminolysis of styrene oxide with aromatic amines such as aniline, 4-methoxy, hydroxyl,
nitro, and diphenylamine in the presence of 10 mg of GO gave the corresponding β -amino alcohols in 77%–93%
yield after 15 min at room temperature (entries 1–5). The results showed that the aminolysis of styrene oxide
proceeds nicely with aromatic amines with electron-releasing or withdrawing groups even though the presence
of withdrawing groups on the aromatic ring tends to decrease the reaction yield and prolong the reaction time
(entry 4, Table 3). In contrast to aromatic amines, aliphatic amines such as n-propylamine require higher
temperature (60 ◦ C) (entry 6, Table 3).
Next, we performed the ring opening of 2-ethyloxirane with aromatic and cyclic aliphatic amines such as
aniline and morpholine; 2-(phenylamino)butan-1-ol and 2-morpholinobutan-1-ol were isolated in 83% and 90%
yield, respectively, after 15 min (entries 7 and 8, Table 3). It should be noted that aminolysis of styrene oxide
and 2-ethyloxirane is regioselective and the corresponding β -amino alcohols resulted from nucleophilic attack
at the more hindered carbon atom of the epoxide ring.
Furthermore, aminolysis of 2-(phenoxymethyl)oxirane with aniline, 4-methoxy, 2,5-dimethylaniline, ben-
zylamine, and morpholine afforded the corresponding β -amino alcohols in 88%, 94%, 90%, 87%, and 84%
yield, respectively (entries 9–13, Table 3). The reaction is regioselective with preferential nucleophilic attack
at the less hindered carbon atom of the epoxide ring; steric effects dominate over electronic effects. Simi-
larly, the ring-opening reaction of 2-(butoxymethyl)oxirane with aniline, 4-chloroaniline, and dibenzyl amine
gave 1-butoxy-3-(phenylamino)propan-2-ol, 1-butoxy-3-((4-chlorophenyl)amino)propan-2-ol, and 1-butoxy-3-
(dibenzylamino)propan-2-ol in 81%, 56%, and 70%, respectively, after 15 min at room temperature (entries
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MIRZA-AGHAYAN et al./Turk J Chem
Table 3. Aminolysis of epoxides with amines catalyzed by GO.a
Time
(min)
Yieldb
(%)
Entry
1
Epoxide
Amine
aniline
Product
15
15
15
30
8643
9343
9144
7743
2
3
4
4-methoxyaniline
4-hydroxyaniline
4-nitroaniline
5
diphenylamine
15
8145
6
7
n-propylamine
20c
15
9146
aniline
8347
8
morpholine
15
9047
9
aniline
15
15
8843
9443
10
4-methoxyaniline
11
12
2,5-dimethylaniline
benzylamine
15
15
90
8747
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MIRZA-AGHAYAN et al./Turk J Chem
Table 3. Continued.
Time
(min)
Yield
(%)
Entry
13
Epoxide
Amine
Product
morpholine
15
8448
8149
56
14
15
aniline
15
4-chloroaniline
120d
16
dibenzylamine
15
70
17
18
aniline
15
15
8044
4-chloroaniline
7350
19
20
4-methylaniline
morpholine
15
15
8051
9548
a Conditions: a mixture of epoxide (1 mmol), amine (1 mmol), and GO (10 mg) was reacted at room temperature for
the time indicated in Table 3.
b Refer to GC/MS yield.
c The reaction was performed at 60 ◦ C.
d The reaction was performed at 80 ◦ C.
14–16, Table 3). However, aminolysis yield of 2-(butoxymethyl)oxirane with 4-chloroaniline is moderate even
at higher temperature (80 ◦ C) and longer reaction time (120 min) (entries 15, Table 3).
Finally, we investigated the preparation of amino alcohols from a cyclic epoxide, 7-oxabicyclo[4.1.0]heptane,
and aromatic amines such as aniline, 4-chloro, and 4-methylaniline and a cyclic amine such as morpholine; the
corresponding amino alcohols were obtained in 80%, 73%, 80%, and 95%, respectively, after 15 min (entries
17–20, Table 3).
74

MIRZA-AGHAYAN et al./Turk J Chem
From the results in Table 3, GO allowed the synthesis of β -amino alcohols from epoxides in relatively
short reaction times as compared to the methods described in the literature.7−27 For example, when magnetic
nano Fe3 O4 (10 mol%) was used as a catalyst for aminolysis of styrene oxide with aniline, the corresponding
β -amino alcohol was obtained in 83% yield after 20 h13 compared to 86% using GO after only 15 min (entry 1,
Table 3). 2-((4-Nitrophenyl)amino)-2-phenylethanol was synthesized through aminolysis of styrene oxide with
4-nitroaniline in 38%, 68%, and 58% yield, respectively, after 48, 1.5, and 48 h using metallocene (Cp2 MCl2 ,
M = Ti, Zr, V, 10 mol%) as catalysts;26 the yields were lower than 77% for the same chemical transformation
using GO as catalyst after only 15 min (entry 4, Table 3). In another report, Curini and co-workers25 prepared
1-butoxy-3-(phenylamino)propan-2-ol in 94% yield by the aminolysis of 2-(butoxymethyl)oxirane with aniline
using zirconium sulfophenyl phosphonate as a catalyst at 40 ◦ C under nitrogen after 19 h. The yield was
slightly higher than 81% obtained using GO, although the reaction proceeded much faster using GO (15 min)
(entry 14, Table 3).
To evaluate the reusability of GO after the ring opening of styrene oxide with aniline, ethyl acetate was
added and the mixture was filtered through a sintered funnel to recover the catalyst. The recovered catalyst
was dried in an oven at 80 ◦ C for 30 min. The ring opening of styrene oxide with aniline in the presence of
10 mg of the recovered GO was performed for seven consecutive cycles for 15 min at room temperature. The
recycled GO was efficient for aminolysis of styrene oxide to the corresponding 2-amino alcohol even after seven
consecutive times without loss of activity; the yield was about 82% (Table 4).
Table 4. Reusability of GO catalyst for the ring opening of styrene oxide with aniline.
Run 1st 2nd 3rd 4th 5th 6th 7th
Yield (%) 86 89 83 83 80 81 82
The graphite oxide surface comprises various oxygen-containing groups such as hydroxyl and carbonyl
groups, which confer an acidic character to the material.52 This property has recently been exploited for the con-
version of oxiranes into thiiranes,39 esterification of organic acids,40 and preparation of 1,4-dihydropyridines.53
The possible mechanism of the reaction involved activation of the epoxide ring by GO (Scheme 2). Hydroxyl
and carboxylic groups of GO can activate the epoxide ring through interaction with the oxygen atom of epoxide
to increase the susceptibility of the epoxide ring to nucleophilic attack by the nitrogen atom of amine. As
shown in Table 3, the nucleophilic attack was remarkably regioselective. For styrene oxide, the nucleophilic
attack occurred at the more highly substituted carbon atom of the epoxide ring. The nucleophilic attack on the
sterically more hindered position of the epoxide suggests that the reaction is controlled by electronic effects (SN1
mechanism). Indeed, electronic effects dominate over steric effects; the intermediate carbocation is stabilized
through resonance with the phenyl ring, leading to a nucleophilic attack at a more hindered position. The simi-
lar nucleophilic attack of amine at more hindered position was observed for ring opening of 2-ethyloxirane. The
results obtained for other epoxides (2-(phenoxymethyl)oxirane and 2-(butoxymethyl)oxirane) indicated that the
nucleophilic attack occurs at the less hindered carbon atom of the epoxide ring (SN2 mechanism). The SN2
mechanism is preferred in these cases due to the electron-withdrawing effect of the oxygen atom on the epoxide
ring.
75

MIRZA-AGHAYAN et al./Turk J Chem
Scheme 2. A plausible mechanism for aminolysis of epoxide catalyzed by GO.
Next, we evaluated the efficiency of this methodology for selective aminolysis of epoxide rings during
intermolecular competitive reactions. To demonstrate the selectivity of aminolysis, aniline (1 mmol) was added
to a mixture of styrene epoxide (1 mmol) and 2-(phenoxymethyl)oxirane (1 mmol) in the presence of 10 mg
of GO. The formation of the corresponding products in 3:97 ratio, respectively, after 15 min clearly indicates
the high selectivity of this process (Scheme 3). The selective aminolysis of 2-(phenoxymethyl)oxirane can be
explained by the chelating ability of the oxygen atoms of the phenoxy group and the epoxide oxygen atom of
2-(phenoxymethyl)oxirane with GO, which increases the susceptibility of the epoxide ring to nucleophilic attack
by aniline (Scheme 4).
Scheme 3. Selectivity of aminolysis of epoxide during intermolecular competition catalyzed by GO.
Scheme 4. The possible chelating ability of 2-(phenoxymethyl)oxirane with GO.
To demonstrate the chemoselectivity of this method, cyclohexene oxide (1 mmol) was added to a mixture
of aniline (1 mmol) and morpholine (1 mmol) in the presence of 10 mg of GO. After 15 min reaction, only
the product of morpholine with cyclohexene oxide was formed, indicating the very high chemoselectivity of this
process (Scheme 5).
Scheme 5. Chemoselective aminolysis of cyclohexene oxide with aromatic and aliphatic amines catalyzed by GO.
76

MIRZA-AGHAYAN et al./Turk J Chem
3. Conclusion
In summary, GO was used as a solid acid catalyst for the aminolysis of a wide range of epoxides with various
amines. The aminolysis of epoxides in the presence of GO provided the corresponding β -amino alcohol
derivatives in good to high yields. Moreover, the catalyst was reused several times without any loss of activity.
This protocol offers simplicity of operation and short reaction times under metal-free conditions with high regio-
and chemo-selectivity.
4. Experimental
1 H NMR spectra were recorded on a Bruker 500 MHz in CDCl3 using tetramethylsilane as internal standard.
13 C NMR spectra were recorded on a Bruker 125 MHz in CDCl3 . Mass spectra were obtained on a FISONS
GC 8000/TRIO 1000 under 70 eV. Infrared (IR) spectra were recorded from KBr disks with a Bruker Vector
22 Fourier transform infrared (FTIR) spectrometer.
4.1. General procedure for aminolysis of epoxides
To a solution of epoxide (1 mmol) and amine (1 mmol) was added 10 mg of graphite oxide (GO) at room
temperature and the mixture was stirred for the time indicated in Table 3 prior to GC/MS analysis. The
resulting mixture was filtered and washed with ethyl acetate for catalyst separation, and extracted with
ethyl acetate. The organic layer was dried over Na2 SO4 , filtered, and evaporated under reduced pressure.
Purification was achieved by column chromatography using ethyl acetate/n-hexane as eluent. Spectroscopic
data for unknown products:
1-(2,5-Dimethylphenylamino)-3-phenoxypropan-2-ol (entry 11, Table 3): Colorless oil, TLC Rf = 0.30
(ethyl acetate/n-hexane, 1:5); 1 H NMR (DMSO-d6 , 500 MHz): δ = 2.22 (s, 3H, CH3), 2.31 (s, 3H, CH3), 2.81
(dd, J = 2.9 Hz, J = 4.9 Hz, 1H, CH2 NH), 2.96 (dd, J = 4.1 Hz, J = 4.8 Hz, 1H, CH2 NH), 3.52 (m, 1H,
CHOH), 4.02 (dd, J = 5.6 Hz, J = 11.0 Hz, 3H, CH2 CHOH), 6.65 (s, 1H, Ar), 6.99 (m, 5H, Ar), 7.35 (m, 2H,
Ar); 13 C NMR (DMSO-d6 , 125 MHz): δ = 14.56, 17.38, 45.16, 50.60, 69.12, 115.08, 116.99, 120.70, 120.88,
121.67, 129.95, 130.84, 137.12, 143.26, 158.93; MS (EI) (70 eV), m/z (%): 271 (12) [M]+ , 254 (9) [M-OH]+ ,
177 (7) [M-H-OPh]+ , 166 (3) [M-2,5-dimethylphenyl]+ , 163 (12) [M-H-CH2 OPh]+ , 134 (37), 118 (65), 107
(7), 105 (25), 90 (35), 89 (37), 77 (95), 50 (60), 40 (100); IR (KBr): ν = 3436, 3061, 3004, 2924, 1624, 1495,
1242, 1039, 753 cm−1
.
1-Butoxy-3-((4-chlorophenyl)amino)propan-2-ol (entry 15, Table 3): Pale yellow oil, TLC Rf = 0.37)
dichloromethane); 1 H NMR (DMSO-d6 , 500 MHz): δ = 0.83 (t, J = 7.4 Hz, 3H, CH3), 1.15 (m, 2H, CH2 CH3),
1.36 (m, 2H, CH2 CH2 CH3), 2.87 (dd, J = 6.5 Hz, J = 11.0 Hz, 1H, CH2 NH), 3.05 (dd, J = 4.9 Hz, J =
11.2 Hz, 1H, CH2 NH), 3.31 (m, 2H, OCH2 CH2), 3.32 (m, 2H, CH2 CHOH), 3.68 (m, 1H, CHOH), 3.98 (m,
1H, CH2 NH), 5.82 (s, 1H, CHOH), 6.7 (m, 4H, Ar); 13 C NMR (DMSO-d6 , 125 MHz): δ = 14.78, 19.71, 31.84,
47.33, 68.82, 71.16, 73.82, 114.18, 119.56, 129.33, 148.75; MS (EI) (70 eV), m/z (%): 257 (12) [M]+ , 240 (3)
[M-OH]+ , 222 (2) [M-Cl]+ , 184 (2) [M-OBu]+ , 167 (5) [M-OH-OBu]+ , 140 (100), 126 (5), 117 (5), 111 (57),
87 (10), 75 (20), 57 (40), 43 (8); IR (KBr): ν = 3390, 2963, 1622, 1495, 1261, 1091, 800, 637 cm−1
.
1-Butoxy-3-(dibenzylamino)propan-2-ol (entry 16, Table 3): Colorless oil, TLC Rf = 0.42 (ethyl acetate/n-
hexane, 1:5); 1 H NMR (DMSO-d6 , 500 MHz): δ = 0.97 (t, J = 7.4 Hz, 3H, CH3), 1.43 (m, 2H, CH3 CH2),
1.62 (m, 2H, CH3 CH2 CH2 CH2 O), 2.64 (dd, J = 6.5 Hz, J = 2.7 Hz, 1H, CH2 N), 2.82 (dd, J = 4.2 Hz, J =
77

MIRZA-AGHAYAN et al./Turk J Chem
2.7 Hz, 1H, CH2 N), 3.21 (m, 1H, CHOH), 3.41 (m, 2H, CH3 CH2 CH2 CH2 O), 3.72 (m, 3H, OCH2 CHOH), 3.8
(s, 4H, NCH2 Ar), 7.36 (m, 10H, Ar); 13 C NMR (DMSO-d6 , 125 MHz): δ = 14.42, 16.68, 32.19, 44.71, 51.39,
53.41, 77.25, 77.26, 77.77, 127.45, 128.66, 128.83, 140.34; MS (EI) (70 eV), m/z (%): 328 (37) [MH]+ , 327 (10)
[M]+ , 326 (30) [M-H]+ , 310 (5) [M-OH]+ , 254 (3) [M-OBu]+ , 248 (20) [M-H2 -Ph]+ , 236 (3) [M-CH2 Ph]+ ,
210 (100), 194 (3), 174 (3), 134 (10), 118 (7), 106 (10); IR (KBr): ν = 3459, 3062, 2931, 2870, 1645, 1495,
1251, 1115, 1028, 746 cm−1
.
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