Zeolite catalyzed ring opening of epoxides to acetylated diols with acetic anhydride

Article abstract of DOI:10.1081/SCC-100105384

HY Zeolite is found to be a versatile catalyst for opening of epoxides to the corresponding acetylated 1,2-Diols with acetic anhydride in good yields.

Full text of DOI:10.1081/SCC-100105384

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ZEOLITE CATALYZED RING OPENING OF EPOXIDES TO
*
ACETYLATED DIOLS WITH ACETIC ANHYDRIDE
a
a
a
a
P. Ramesh , V. L. Niranjan Reddy , D. Venugopal , M. Subrahmanyam & Y.
b
Venkateswarlu
a
Organic Chemistry Division-I , Indian Institution of Chemical Technology , Hyderabad,
5
00 007, India
b
Organic Chemistry Division-I , Indian Institution of Chemical Technology , Hyderabad,
00 007, India
5
Published online: 09 Nov 2006.
To cite this article: P. Ramesh , V. L. Niranjan Reddy , D. Venugopal , M. Subrahmanyam & Y. Venkateswarlu (2001)
*
ZEOLITE CATALYZED RING OPENING OF EPOXIDES TO ACETYLATED DIOLS WITH ACETIC ANHYDRIDE , Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:17, 2599-2604,
DOI: 10.1081/SCC-100105384
To link to this article: http://dx.doi.org/10.1081/SCC-100105384
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SYNTHETIC COMMUNICATIONS, 31(17), 2599–2604 (2001)
ZEOLITE CATALYZED RING OPENING
OF EPOXIDES TO ACETYLATED DIOLS
WITH ACETIC ANHYDRIDE*
1
P. Ramesh, V. L. Niranjan Reddy, D. Venugopal,
1
2
2
M. Subrahmanyam, and Y. Venkateswarlu
1,{
1
2
Organic Chemistry Division-I and Catalysis Division,
Indian Institution of Chemical Technology,
Hyderabad 500 007, India
ABSTRACT
HY Zeolite is found to be a versatile catalyst for opening of
epoxides to the corresponding acetylated 1,2-Diols with acetic
anhydride in good yields.
The opening of epoxides to the corresponding alcohols is one of the
1
most useful reactions in organic synthesis and the acetylation of alcohols
is a fundamental process in organic chemistry and provides a cheap and
efficient means for protecting hydroxy groups during oxidation, peptide
2
coupling and glycosidation reactions. Thus, it is very important for the
epoxide to open for forming a corresponding diacetoxylated selectively
instead of a diol. In recent years, there has been a tremendous upsurge of
*
IICT Communication No. 4521.
Corresponding author. E-mail: luchem@iict.ap.nic.in
{
2
599
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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2
600
RAMESH ET AL.
interest in various chemical transformations performed in heterogeneous
3
catalysis. Moreover using inexpensive and non-corrosive catalysts, chemi-
cal transformations occur with better efficiency, high purity of the products
and easier workup, with evident economic and ecological advantages espe-
cially in industrial processes.
Zeolites as catalysts for selective organic reactions have received
considerable attention in recent decades due to their unique physical and
chemical properties such as shape selectivity, acidic and basic nature and
4
their thermal stability. Besides the general advantages associated in using
heterogeneous catalysts, like convenient to use, easy separation and being
inexpensive further more zeolites can be prepared with different porosity,
hydrophibicity, varying acid and basic strength and site distribution, which
5
makes them versatile catalysts for a variety of reactions. In this report, an
efficient ring opening of epoxides over HY zeolite as a reusable catalyst is
presented. The commercial HY zeolite obtained was from PQ Corporation.
The reaction was performed at room temperature for a fixed time and a
mixture of epoxide (10m mol) with acetic anhydride (50m mol) and the
zeolite HY (0.5 g) utilized without previous thermal or chemical treatment,
good to high yields (75–95%) were observed in all cases. Under the present
conditions chiral epoxides can be easily opened in high yields with complete
1
2
retention of optical activity (entry 7). In addition, the zeolite HY can be
reused many times with no loss in activity and it is simply by filtering the
catalyst, washing with acetone, drying and immediately reusing.
Here zeolite HY shows considerable catalytic activity. As expected the
bulkiness of the reagent represents a crucial factor in this process. It limits or
completely inhibits its diffusion through the pores of the catalyst and the
reaction probably occurs only on the external surface or on the external
acidic sites.
EXPERIMENTAL
In a typical procedure the epoxide (10mmol) and acetic anhydride
50mmol) were placed in a flask with stirring. After 5 min zeolite HY
0.5 g) was added and the mixture was stirred at room temperature for the
(
(
appropriate time (see Table). After completion of reaction, the mixture was
poured into an ice cold water and extracted with ethyl acetate and the
catalyst filtered off. After evaporation of the solvent, the diacetate could
be purified by column chromatography by eluting with Hexane : EtOAc
1
2
(
was taken in a 5 ml round bottom flask contain 0.5 ml of acetic anhydride
8 : 2). In case of 9a,15-epoxy africanane (entry 7), 10mg of the epoxide

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Table. Ring Opening of Epoxides to Acetylated Diols with Acetic
Anhydride over Zeolite HY
Yield
(%)
Time
(hrs)
Entry
Substrate
Product
after stirring for 5 min zeolite HY (20mg) was added and the reaction
mixture was stirred for 18 h then after usual work up the corresponding
diacetate obtained 85% yield.
In conclusion, we have described a mild, highly efficient and conveni-
ent method for the opening of epoxides with acetic anhydride and are pro-
moted by zeolite HY. All the diacetate obtained are in high yields under
same experimental conditions studied. The catalyst can be reused without
any loss of activity.

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RAMESH ET AL.
,2-Diacetoxy-cyclohexane 1a: Bp 116–118 C, IR (neat) v(max): 1735,
6
ꢀ
1
–
1 1
1
730, 1239, and 1095 cm . H NMR (200 MHz, CDCl ): d 4.75 (d, 2H,
3
þ
J ¼ 16 Hz), 2.02 (br s, 6H), 1.23–1.75 (m, 8H). EIMS: m/z (%) 200 [M ]
3), 142 (87), 141 (5), 99 (45), 81 (80), 70 (8), and 43 (100). Anal. Calcd
for C H O : C, 59.98; H, 8.05. Found: C, 59.86; H, 8.08.
(
1
0
16
4
7
ꢀ
1
,2-Diacetoxy-1-phenyl-ethane 2a: Bp: 119–120 C, IR (neat) v(max):
–
1 1
3
010, 1738, 1730, and 1360 cm . H NMR (200 MHz, CDCl ): d 7.3 (br
3
s, 5H), 6.0(dd, 1H, J ¼ 7.2, 5.1 Hz), 4.3 (2H, m), 2.08 (br s, 3H), 2.11 (s,
þ
3
1
H). EIMS: m/z (%) 222 [M ] (3), 195 (4), 164 (31), 150(11), 122 (15),
07 (35), 105 (100), 91 (93), 77 (46), 57 (9), and 43 (93). Anal. Calcd for
7
b
C H O : C, 68.85; H, 6.35. Found: C, 64.82; H, 6.41.
1
2
14
4
8
,2-Diacetoxy-hexane 3a: Bp 107–108 C, IR (neat) v(max): 2940, 1736,
ꢀ
1
–
1 1
1
3
732, 1262, and 1130cm . H NMR (200 MHz, CDCl ): d 5.01 (m, 1H),
3
.96 (dd, 1H, J ¼ 8.1, 6.2 Hz), 4.2 (dd, 1H, J ¼ 5.1, 3.2 Hz), 2.05 (d, 6H,
þ
J ¼ 16 Hz), 1.6 (br s, 6H), 0.89 (t, 3H). EIMS: m/z (%) 202 [M ] (2),
1
71 (51), 158 (4), 142 (3), 129 (8), 127 (10), 111 (25), 97 (12), 69 (75), 57
(
Found: C, 59.28; H, 8.95.
18), 55 (41), and 43 (100). Anal. Calcd for C H O : C, 59.39; H, 8.97.
1
0
18
4
9
,2-Diacetoxy-3-chloro-propane 4a: Bp 95–96 C, IR (neat) v(max):
ꢀ
1
736, 1730, 1240, 1080, and 720 cm . H NMR (200 MHz, CDCl3):
–
1
1
1
d 5.18 (m, 1H), 4.19 (dd, 1H, J ¼ 10, 8.1 Hz), 4.36 (dd, 1H, J ¼ 8.2, 4.5 Hz),
þ
3
.65 (t, 2H), 2.08 (s, 3H), 2.12 (s, 3H). EIMS: m/z (%) 135 [M -AcOH]
(
C H ClO : C, 43.20; H, 5.70; Cl, 18.22. Found: C, 43.41; H, 5.92; Cl,
10), 119 (22), 76 (14), 60 (6), 57 (70), and 43 (97). Anal. Calcd for
9
a
7
11
4
1
8.25.
1
,2,3-Triacetoxy-propane 5a: Bp 258–259 C, IR (neat) v(max): 1746,
0
ꢀ
1
734, 1728, 1330, 1242, and 1165 cm . H NMR (200 MHz, CDCl3):
–
1
1
1
d 5.2 (m, 1H), 4.12 (dd, 2H, J ¼ 10, 6.1 Hz), 4.4 (dd, 2H, J ¼ 6.1, 4.2 Hz),
2
1
6
.1 (br s, 9H). EIMS: m/z (%) 218 (28), 176 (27), 148 (8), 129 (12), 120(9),
02 (20), 85 (47), 72 (27), and 60 (24). Anal. Calcd for C H O : C, 49.54; H,
9
14
6
.47. Found: C, 49.47; H, 6.50.
-(4-Methylphenoxyl)-1,2-diacetoxy-propane 6a: Bp 163–165 C, IR
1
1
ꢀ
3
neat) v(max): 3030, 1742, 1733, and 1280 cm . H NMR (200 MHz,
–
1
1
(
CDCl ): d 7.05 (d, 2H, J ¼ 12 Hz), 7.78 (d, 2H, J ¼ 10Hz), 5.31 (m, 1H),
3
4.42 (dd, 1H, J ¼ 7.5, 5.1 Hz), 4.23 (dd, 1H, J ¼ 10, 7.5 Hz), 4.18 (t, 2H),
2.3 (s, 3H), 2.1 (s, 3H), 2.08 (s, 3H). EIMS: m/z (%) 266 (3), 154 (8), 159 (62),
147 (8), 121 (15), 108 (35), 91 (15), 57 (8), and 43 (100). Anal. Calcd for
C H O : C, 63.15; H, 6.81. Found: C, 63.10; H, 6.84.
1
4
18
5
1
,15-Diacetoxyafricanane 7a: IR (neat) v(max): 1735, 1740, 1260, and
2
9
–
1 1
1
1
0
095 cm , H NMR (200 MHz, CDCl ): d 4.62 (d, 1H, J ¼ 13 Hz), 4.12 (d,
3
H, J ¼ 13 Hz), 2.04 (s, 3H), 2.02 (s, 3H), 1.5–1.9 (m, 7H), 0.95 (s, 3H),
.90 (s, 3H), 0.88 (s, 3H), 0.52 (m, 2H), 0.18 (m, 1H). EIMS: m/z (%) 262

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2603
þ
[
M -AcOH] (4), 220 (6), 207 (12), 202 (36), 187 (20), 159 (30), 133 (10),
107 (20), 95 (40), and 55 (100). Anal. Calcd for C H O : C, 70.77; H, 9.38.
Found: C, 70.80; H, 9.35.
19 30 4
ACKNOWLEDGMENTS
We are thankful to the Director IICT, and Dr. J. S. Yadav for their
encouragement. P. R and VLNR thankful for UGC, New Delhi and
Ministry of Health, New Delhi for providing fellowship.
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Received in the UK May 30, 2000

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