Silica sulfuric acid; an efficient and reusable catalyst for regioselective ring opening of epoxides by alcohols and water

Article abstract of DOI:10.1080/10426500490459722

The nucleophilic ring opening reactions of epoxides by aliphatic alcohols and water are achieved efficiently in the presence of catalytic amounts of silica sulfuric acid with high degree of regioselectivity. The catalyst is reusable and can be applied several times without any decrease in the yield of reactions.

Full text of DOI:10.1080/10426500490459722

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Phosphorus, Sulfur, and Silicon and the Related
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SILICA SULFURIC ACID; AN EFFICIENT AND REUSABLE
CATALYST FOR REGIOSELECTIVE RING OPENING OF
EPOXIDES BY ALCOHOLS AND WATER
Peyman Salehi a , Minoo Dabiri a , Ali Zolfigol b & Ali Bodaghi Fard a
a Shahid Beheshti University , Tehran, Iran
b Bu-Ali Sina University , Hamadan, Iran
Published online: 16 Aug 2010.
To cite this article: Peyman Salehi , Minoo Dabiri , Ali Zolfigol & Ali Bodaghi Fard (2004) SILICA SULFURIC ACID; AN EFFICIENT
AND REUSABLE CATALYST FOR REGIOSELECTIVE RING OPENING OF EPOXIDES BY ALCOHOLS AND WATER, Phosphorus, Sulfur, and
Silicon and the Related Elements, 179:6, 1113-1121, DOI: 10.1080/10426500490459722
To link to this article: http://dx.doi.org/10.1080/10426500490459722
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Phosphorus, Sulfur, and Silicon, 179:1113–1121, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490459722
SILICA SULFURIC ACID; AN EFFICIENT
AND REUSABLE CATALYST FOR REGIOSELECTIVE
RING OPENING OF EPOXIDES BY
ALCOHOLS AND WATER
Peyman Salehi,a Minoo Dabiri,a Mohammad Ali Zolfigol,b and
Mohammad Ali Bodaghi Farda
Shahid Beheshti University, Tehran, Irana and Bu-Ali Sina
University, Hamadan, Iranb
(Received August 5, 2003; in final form August 21, 2003)
The nucleophilic ring opening reactions of epoxides by aliphatic al-
cohols and water are achieved efficiently in the presence of catalytic
amounts of silica sulfuric acid with high degree of regioselectivity. The
catalyst is reusable and can be applied several times without any de-
crease in the yield of reactions.
Keywords: β-Alkoxy alcohols; alcoholysis; epoxides; hydrolysis; silica
sulfuric acid; vicinal-diols
Epoxides are valuable intermediates in organic synthesis because their
nucleophilic ring opening is a powerful tool to access at many important
1,2-difunctionalized compounds.1,2
β-Alkoxy alcohols constitute an important class of organic com-
pounds both because this type of functionality is often present in nat-
urally occurring compounds and because their oxidation is the easiest
way to the synthesis of α-alkoxy aldehydes and ketones or α-alkoxy
acids.3 The more common protocol for the synthesis of β-alkoxy alco-
hols is the alcoholysis of epoxides under acidic conditions.4−15 However
the yields are not always satisfactory and in some cases a mixture of
regioisomers are obtained.
We recently have reported the preparation of silica sulfuric acid and
some of its applications in synthetic methodology.16−19 In this article
we report on a very efficient method for regioselective ring opening of
We are grateful to Shahid Beheshti University Research Council for partial support
of this work.
Address correspondence to Peyman Salehi, Department of Photochemistry, Medicinal
Plants Research Institute, Shahid Beheshti University, Evin, Tehran, PO Box 19835 389,
Iran. E-mail: p-salehi@cc.sbu.ac.ir
1113

1114
P. Salehi et al.
epoxides by alcohols and water in the presence of catalytic amounts of
silica sulfuric acid.
RESULTS AND DISCUSSION
The reaction of epoxides with primary, secondary, and tertiary alcohols
in the presence of 0.01–0.2 molar equivalents of silica sulfuric acid was
investigated and the corresponding β-alkoxy alcohols were obtained in
good to excellent yields with high degree of regio- and chemoselectivity
(Scheme 1, Table I).
SCHEME 1
In the case of styrene oxide the attack of nucleophile to the more
hindered carbon showed that electronic effect controlled the course
of the reactions. Methanolysis of optically active styrene oxide in the
presence of the catalyst ended up with the formation of the corre-
sponding β-methoxy alcohol with nearly 93% inversion of configuration
(Scheme 2).
This showed that attack of nucleophile and ring opening of epoxide
almost occurred simultaneously. Similar behavior was also observed in
the case of cyclohexene oxide which was transformed only to the trans
vicinal alkoxy alcohols (Table I, entries 5–8).

Ring Opening of Epoxides
1115
TABLE I The Reaction of Epoxides with Aliphatic Alcohols in the Presence
of Silica Sulfuric Acid at Room Temperature
Cat./Sub.
(mole ratio)
Time
(min)[hr]
Yield
(%)
Entry
R1
R2
Product
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1a
1a
1a
1a
1b
1b
1b
1b
1c
1c
1c
1c
1c
1d
1d
1d
1d
1d
1d
1e
1e
1e
1e
1e
1e
1f
0.02
0.02
0.05
0.05
0.05
0.05
0.05
0.05
0.1
(1)
(3)
(5)
(3)
(2)
(25)
[1]
(10)
(20)
(45)
[1.5]
[3]
(50)
(30)
[1]
[1.2]
[1]
[1.5]
(45)
[1.5]
[2]
98
97
97
96
96
87
86
90
96
95
96
88
94
96
94
92
92
90
94
96
97
94
94
92
95
92
92
90
88
92
Me
2a
2a
2a
2a
n-Pr
i-Pr
Allyl
Me
n-Pr
i-Pr
Allyl
Me
n-Pr
i-Pr
t-Bu
Allyl
Me
n-Pr
n-Bu
i-Pr
t-Bu
Allyl
Me
n-Pr
n-Bu
i-Pr
t-Bu
Allyl
Me
n-Pr
i-Pr
t-Bu
Allyl
3c
3c
3c
3c
3c
3d
3d
3d
3d
3d
3d
3e
3e
3e
3e
3e
3e
3f
0.1
0.15
0.15
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.2
0.2
0.2
0.2
[2]
[2]
[5.5]
[3]
[2]
[1.3]
[5]
[9]
0.2
0.15
0.15
0.15
0.15
0.15
1f
1f
1f
1f
3f
3f
3f
3f
[3.5]
SCHEME 2

1116
P. Salehi et al.
In other model compounds that electron withdrawing groups were
attached to the epoxide ring, the electronic and steric effects acted in
the same direction and the products of the attack of nucleophiles to the
less hindered carbon atoms were obtained (Table I, entries 9–30). The
reactions were chemoselective and cleavage of other carbon-oxygen and
carbon-halogen bonds was not observed in any case. Also the dou-
ble bond in allyl glycidyl ether remained intact under the reaction
conditions.
In some representative reactions, after isolation of the products, the
solid catalyst was washed and reloaded with fresh reagents for fur-
ther runs. No decrease in the yield was observed after several runs,
demonstrating that silica sulfuric acid can be reused in these reactions
with no discharge to the environment.
The products in entries 16 and 22 (Table I) are known as choleretic
drugs with international names Dibuprol and Febuprol respectively.20
We also have investigated the hydrolysis reactions of epoxides in the
presence of catalytic amounts of silica sulfuric acid (Scheme 3, Table II).
SCHEME 3
The reactions were carried out in acetone-water (2/1: v/v) as solvent
and the corresponding vicinal diols were obtained in excellent yields. In
the case of cyclohexene oxide the trans-1,2-dihydroxy cyclohexane was
obtained in 94% yield (Table II, entry 2).
TABLE II Hydrolysis of Epoxides in the Presence of Silica Sulfuric Acid
Cat./Sub.
(mole ratio)
Time/Temp.
(min)/[◦C]
Yield
(%)
Entry
R1
Product
1
2
1a
1b
0.01
0.01
(3)[rt]
(5)[rt]
98
94
4a
Trans-1,2-
cyclohexandiol
3
4
5
6
1c
1d
1e
1f
0.05
0.05
0.1
(100)[reflux]
(35)[reflux]
(150)[reflux]
(120)[reflux]
95
96
94
92
4c
4d
4e
4f
0.1

Ring Opening of Epoxides
1117
Catalytic nature of the reactions, high degree of regio- and chemos-
electivity, cheapness and stability of the reagent and ease of work up
procedure are among the outstanding features of this method which
makes it an attractive addition to the previous reported procedures.
The catalyst is recyclable and can be used for minimum four more runs
in most of the reactions.
EXPERIMENTAL
General
All of the products are known compounds and were characterized by
comparison of their spectral data (1HNMR, IR) and physical properties
with those reported in the literature.4,6,11 1HNMR spectra were run on
a Bruker Avance 500 MHz spectrometer. IR spectra were obtained by a
Shimadzu 470 spectrophotometer. The reaction monitoring was accom-
plished by TLC on SIL G/UV 254 sheets. Optical purity determination
was accomplished by HPLC on a Shimadzu SPD-6 AV instrument using
a Vancomycin chiral column. Silica sulfuric acid was prepared accord-
ing to our previously reported procedure.16 All yields refer to isolated
products.
General Procedure for the Alcoholysis of Epoxides
Silica sulfuric acid (equal to 0.04–0.4 mmol of H+) was added to a so-
lution of epoxide (2 mmol) in alcohol (7 ml). The mixture was stirred
magnetically at room temperature for the appropriate period of time
(Table I). The progress of the reaction was followed by TLC. After com-
pletion of the reaction, the mixture was filtered through a silica gel pad
and washed with chloroform (20 ml). Evaporation of the solvent fol-
lowed by purification on a silica gel column gave the desired β-alkoxy
alcohols in 86–98% yields.
General Procedure for the Hydrolysis of Epoxides
To a solution of epoxide (2 mmol) in acetone-water (2/1:v/v, 7 ml), sil-
ica sulfuric acid (equal to 0.02–0.2 mmol of H+) was added. The re-
action mixture was stirred magnetically at the optimum temperature
(Table II). The mixture was passed through a silica gel pad followed
by washing the pad with diethyl ether. Ethereal solution was dried
(Na2SO4) and concentrated to afford the corresponding vicinal diols in
92–98% yields.

1118
P. Salehi et al.
REFERENCES
[1] J. C. Smith, Synthesis, 624 (1984).
[2] C. Bonini and G. Righi, Synthesis, 225 (1994).
[3] T. Kino, H. Hatanaka, M. Hashimato, et al., J. Antibiot., 40, 1249 (1987).
[4] G. H. Posner and D. I. Rogers, J. Am. Chem. Soc., 99, 8208 (1977).
[5] G. A. Olah, A. P. Fung, and D. Meidar, Synthesis, 280 (1981).
[6] N. Iranpoor and I. Mohammadpour Baltork, Tetrahedron Lett., 31, 735 (1990).
[7] N. Iranpoor and I. Mohammadpour Baltork, Synth. Commun., 20, 2789
(1990).
[8] N. Iranpoor, B. Tamami, and K. Niknam, Can. J. Chem., 75, 1913 (1997).
[9] N. Iranpoor, M. Shekarriz, and F. Shiriny, Synth. Commun., 28, 347 (1998).
[10] M. Chini, P. Crotti, C. Gardelli, and F. Macchia, Synlett, 673 (1992).
[11] N. Iranpoor and P. Salehi, Synthesis, 1152 (1994).
[12] P. Salehi, B. Seddighi, M. Irandoost, and F. K. Behbahani, Synth. Commun., 30,
2967 (2000).
[13] N. Iranpoor and F. Shiriny Zardaloo, Synth. Commun., 24, 1959 (1994).
[14] Y. J. Liu, T. Y. Chu, and R. Engel, Synth. Commun., 22, 2367 (1992).
[15] C. Moberg, L. Rakos, and L. Tottie, Tetrahedron Lett., 33, 2191 (1992).
[16] M. A. Zolfigol, Tetrahedron, 57, 9509 (2001).
[17] M. A. Zolfigol, F. Shirini, A. Ghorbani Choghamarani, and I. Mohammadpoor-
Baltork, Green Chemistry, 4, 562 (2002).
[18] P. Salehi, M. Dabiri, M. A. Zolfigol, and M. A. Bodaghi Fard, Tetrahedron Lett., 44,
2889 (2003).
[19] M. A. Zolfigol and A. Bamoniri, Synlett, 1621 (2001).
[20] M. Negwar and H. G. Scharnow, Organic-Chemical Drugs and Their Synonyms
(Wiley-VCH, Weinheim, 2001), pp. 644 and 874.
SUPPLEMENTARY INFORMATION
Spectral Data of the Products
2a (R2 = Me): 1HNMR (CDCl3), δ(ppm): 3.3(3H, s), 3.6(1H, dd), 3.7(1H,
dd), 3.8(1H, s), 4.3(1H, dd), 7.3(5H, m). IR(neat), υ(cm−1): 3405(s),
3050(m), 3015(m), 2950(s), 2860(s), 2840(s), 1445(s), 1100(s), 1037(s).
1
2a (R2 = n-Pr): HNMR (CDCl3), δ(ppm): 1.0(3H, t), 1.7(2H, sex),
3.4(2H, m), 3.65(1H, dd), 3.73(1H, dd), 4.0 (1H, s), 4.5 (1H, dd), 7.4(5H,
m). IR(neat), υ(cm−1): 3410(s), 3045(m), 3015(m), 2960(s), 2855(s),
1447(s), 1098(s), 1060(s), 1037(s).
1
2a (R2 = i-Pr): HNMR (CDCl3), δ(ppm): 1.17(3H, d), 1.24(3H, d),
3.6(4H, m), 4.6(1H, dd), 7.3(5H, m). IR(neat), υ(cm−1): 3425(s), 3015(m),
2930(s), 2865(s), 1435(s), 1375(s), 1085(s), 967(s).
2a (R2 = allyl): 1HNMR (CDCl3), δ(ppm): 3.66(1H, dd), 3.75(1H, dd),
3.9(1H, dd), 4.0(1H, dd), 4.3(1H, s), 4.5(1H, dd), 5.3(2H, dd), 6.0(1H,
m), 7.3(5H, m). IR(neat), υ(cm−1): 3415(s), 3055(s), 3044(m), 2905(s),
1482(m), 1443(s), 1092(s), 1055(s).

Ring Opening of Epoxides
1119
Trans-2-methoxycyclohexanol: 1HNMR (CDCl3), δ(ppm): 0.8–
2.7(10H, m), 3.2(3H, s), 4.0(1H, s). IR(neat), υ(cm−1): 3415(s), 2915(s),
2900(s), 1453(s), 1188(s), 1097(s).
Trans-2-n-propoxycyclohexanol: 1HNMR (CDCl3), δ(ppm):
0.9(3H, t), 1–2.3(10H, m), 3.4(1H, s), 2.9–3.8(4H, m). IR(neat), υ(cm−1):
3415(s), 2920(s), 2850(s), 1462(s), 1390(s), 1265(s), 1077(s).
Trans-2-allyloxycyclohexanol: 1HNMR (CDCl3), δ(ppm): 1–
2.1(8H, m), 2.9–3.4(2H, m), 3.8(1H, s), 3.9(1H, dd), 4.1(1H, dd), 5.1(2H,
dd), 5.9(1H, m). IR(neat), υ(cm−1): 3410(s), 3065(m), 2920(s), 2830(s),
1450(s), 1073(s), 980(s).
3c (R2 = Me): 1HNMR (CDCl3), δ(ppm): 3.27(3H, s), 3.3–3.9(5H,
m), 3.91(2H, d), 4.3(1H, s), 5.1(2H, dd), 5.8(1H, m). IR(neat), υ(cm−1):
3410(s), 3065(m), 2880(s), 1640(w), 1450(m), 1190(s), 1098(s), 920(s).
1
3c (R2 = n-Pr): HNMR (CDCl3), δ(ppm): 0.8(3H, t), 1.5(2H, quin),
3.3–3.9(7H, m), 3.9(2H, d), 4.1(1H, s), 5.2(2H, dd), 5.8(1H, m). IR(neat),
υ(cm−1): 3420(s), 3065(m), 2965(s), 2925(s), 1640(w), 1465(m), 1188(m),
1100(s).
3c (R2 = i-Pr): 1HNMR (CDCl3), δ(ppm): 1.1(6H, d), 3.3–3.8(6H,
m), 3.87(1H, s), 3.92(2H, d), 5.1(2H, dd), 5.8(1H, m). IR(neat), υ(cm−1):
3400(s), 3080(w), 2980(s), 2920(s), 2840(s), 1650(w), 1460(m), 1370(s),
1120(s), 1080(s).
1
3c (R2 = t-Bu): HNMR (CDCl3), δ(ppm): 1.1(9H, s), 3.2–3.8(5H,
m), 3.9(2H, d), 5.1(1H, s), 5.2(2H, dd), 5.8(1H, m). IR(neat), υ(cm−1):
3400(s), 3080(w), 2980(s), 2930(s), 1650(w), 1470(m), 1360(s), 1195(s),
1085(s).
1
3c (R2 = allyl): HNMR (CDCl3), δ(ppm): 3.3–3.8(6H, m), 4.0(4H,
d), 5.2(4H, dd), 5.9(2H, m). IR(neat), υ(cm−1): 3420(s), 3080(w), 2960(s),
2910(s), 1635(s), 1450(s), 1375(m), 1090(s).
1
3d (R2 = Me): HNMR (CDCl3), δ(ppm): 0.8(3H, t), 1.2(2H, sex),
1.4(2H, quin), 3.3(3H, s), 3.3–3.9(7H, m), 4.0(1H, s). IR(neat, υ(cm−1):
3420(s), 3410(s), 2920(s), 2870(s), 1465(m), 1370(s), 1190(m), 1020(s),
1075(s).
1
3d (R2 = n-Pr): HNMR (CDCl3), δ(ppm): 0.8(6H, t), 1.3(2H, sex),
1.5(4H, m), 3.3–3.9(9H, m), 4.0(1H, s). IR(neat, υ(cm−1): 3420(s),
3065(w), 2915(s), 1450(m), 1230(m), 1190(m), 1105(s).
1
3d (R2 = n-Bu): HNMR (CDCl3), δ(ppm): 0.8(6H, t), 1.3(4H, sex),
1.5(4H, quin), 3.3–4.0(9H, m), 4.4(1H, s). IR(neat), υ(cm−1): 3415(s),
2915(s), 1450(m), 1230(m), 1190(m), 1020(s).
3d (R2 = i-Pr): 1HNMR (CDCl3), δ(ppm): 0.8(3H, t), 1.0(6H, d),
1.3(2H, sex), 1.4(2H, quin), 3.2–4.0(9H, m). IR(neat), υ(cm−1): 3420(s),
2955(s), 2855(s), 1465(s), 1399(s), 1250(m), 1193(s), 1110(s).
3d (R2 = t-Bu): 1HNMR (CDCl3), δ(ppm): 0.9(3H, t), 1.2(9H, s),
1.3(2H, sex), 1.5(2H, quin), 3.2–4.1(8H, m). IR(neat), υ(cm−1): 3415(s),

1120
P. Salehi et al.
2960(s), 2855(s), 1465(s), 1400(s), 1360(s), 1230(m), 1193(s), 1110(s),
1085(s).
1
3d (R2 = allyl): HNMR (CDCl3), δ(ppm): 0.8(3H, t), 1.3(2H, sex),
1.5(2H, quin), 3.2–3.9(7H, m), 4.0(2H, d), 4.1(1H, s), 5.1(2H, dd), 5.8(1H,
m). IR(neat), υ(cm−1): 3380(s), 2970(s), 1635(w), 1445(m), 1395(s),
1360(s), 1230(m), 1195(s), 1083(s).
3e (R2 = Me): 1HNMR (CDCl3), δ(ppm): 3.4(3H, s), 3.5–4.3(5H, m),
4.5(1H, s), 6.9–7.4(5H, m). IR(neat), υ(cm−1): 3405(s), 3065(w), 2920(s),
2850(s), 1485(s), 1245(s), 1030(s).
1
3e (R2 = n-Pr): HNMR (CDCl3), δ(ppm): 1.0(3H, t), 1.7(2H, sex),
3.5(2H, t), 3.5–4.3(5H, m), 4.5(1H, s), 6.9–7.4(5H, m). IR(neat), υ(cm−1):
3410(s), 3065(w), 2960(s), 2930(s), 2890(s), 1480(s), 1240(s), 1050(s).
1
3e (R2 = n-Bu): HNMR (CDCl3), δ(ppm): 0.9(3H, t), 1.4(2H, sex),
1.6(2H, quin). 3.5–4.3(7H, m), 5.5(1H, s), 6.9–7.4(5H, m). IR(neat),
υ(cm−1): 3415(s), 3070(w), 2970(s), 2935(s), 2880(s), 1490(s), 1250(s),
1060(s).
3e (R2 = i-Pr): 1HNMR (CDCl3), δ(ppm): 1.2(6H, d), 3.6–4.4(6H, m),
5.1(1H, s), 6.9–7.4(5H, m). IR(neat), υ(cm−1): 3420(s), 3065(w), 2970(s),
2920(s), 1590(s), 1490(s), 1245(s), 1070(s).
3e (R2 = t-Bu): 1HNMR (CDCl3), δ(ppm): 1.3(9H, s), 3.5–4.4(6H, m),
6.9–7.4(5H, m). IR(neat), υ(cm−1): 3390(s), 3040(w), 2980(s), 2920(s),
1600(s), 1495(s), 1450(s), 1390(s), 1250(s), 1190(s), 1075(s), 1040(s).
1
3e (R2 = allyl): HNMR (CDCl3), δ(ppm): 3.6–4.3(7H, m),5.3(2H,
dd), 6.0(1H, m), 6.3(1H, s), 6.9–7.4(5H, m). IR(neat), υ(cm−1): 3405 (s),
3055(w), 2920(s), 2910(s), 1595(s), 1495(s), 1450(s), 1236(s), 1075(s),
1037(s).
3f (R2 = Me): 1HNMR (CDCl3), δ(ppm): 3.36(3H, s), 3.4–4.0(5H, m),
6.5(1H, s). IR(neat), υ(cm−1): 3405(s), 2960(s), 2920(s), 2850(s), 1450(s),
1150(s), 1075(s).
1
3f (R2 = n-Pr): HNMR (CDCl3), δ(ppm): 0.9(3H, t), 1.6(2H, sex),
3.4(2H, t), 3.45–4.0(5H, m), 5.0(1H, s). IR(neat), υ(cm−1): 3405(s),
2960(s), 2920(s), 2860(s), 1460(s), 1110(s), 1075(s).
3f (R2 = i-Pr): 1HNMR (CDCl3), δ(ppm): 1.1(6H, d), 3.4–4.4(6H,
m), 4.5(1H, s). IR(neat), υ(cm−1): 3385(s), 2965(s), 2920(s), 1585(m),
1450(m), 1395(s), 1193(s), 1080(s).
3f (R2 = t-Bu): 1HNMR (CDCl3), δ(ppm): 1.2(9H, s), 3.4–4.5(6H, m).
IR(neat), υ(cm−1): 3370(s), 2960(s), 2920(s), 1395(s), 1193(s), 1070(s).
3f (R2 = allyl): 1HNMR (CDCl3), δ(ppm): 3.4–3.9(5H, m), 4.0(2H, d),
4.5(1H, s), 5.2(2H, dd), 5.9(1H, m). IR(neat), υ(cm−1): 3380(s), 3070(w),
2910(s), 2895(s), 1640(m), 1190(s), 1100(s), 1065(s).
4a: 1HNMR (CDCl3), δ(ppm): 3.2(2H, s), 3.7(2H, m), 4.8(1H,
dd), 7.35(5H, m). IR(KBr), υ(cm−1): 3300(s), 3200(s), 2920(s),2910(s),
1442(s), 1335(s), 1095(s), 1045(s), 1019(s).

Ring Opening of Epoxides
1121
Trans-1,2-dihydroxy cyclohexane: 1HNMR (CDCl3), δ(ppm):
1.2(4H, m), 1.7(2H, m), 2.0(2H, m), 3.3(2H, m), 4.0(2H, s). IR(KBr),
υ(cm−1): 3365(s), 2915(s), 2850(s), 1457(s), 1357(s), 1195(s), 1067(s),
1032(s).
1
4c: HNMR (CDCl3), δ(ppm): 3.4(2H, s), 3.5(2H, m), 3.58(1H, dd),
3.68(1H, dd), 3.9(1H, m), 4.0(2H, d), 5.2(2H, dd), 5.9(1H, m). IR(KBr),
υ(cm−1): 3435(s), 3070(m), 2950(s), 2910(s), 1640(w), 1415(m), 1105(s),
1071(s), 1050(s).
4d: 1HNMR (CDCl3), δ(ppm): 0.9(3H, t), 1.2(2H, sex), 1.5(2H, quin),
3.3–3.7(7H, m), 3.8(2H, s). IR(neat), υ(cm−1): 3340(s), 3330(s), 2950(s),
2910(s), 1445(s), 1335(m), 1220(m), 1188(m), 1092(s), 1045(s), 1020(s).
1
4e: HNMR (CDCl3), δ(ppm): 3.2(2H, s), 3.7(1H, dd), 3.8(1H, dd),
4.0(2H, d), 4.1(1H, m), 6.9–7.4(5H, m). IR(KBr), υ(cm−1): 3435(s),
3205(s), 3095(s), 2905(s), 1590(s), 1490(s), 1450(s), 1245(s), 1165(s),
1110(s), 1060(s).