Synthesis and properties of calixarene analogs incorporating a thiophene unit in the macrocyclic ring

Article abstract of DOI:10.1002/jhet.5570380144

Calixarene analogs containing a thiophene unit in the macrocyclic ring were prepared by a stepwise method. The macrocycles adopt a cone-like form as the preferred conformation in solution. The induced chemical shift change, nOe experiment, and ¹H relaxation time (T₁) measurement supported the fact that the macrocycle forms a complex with the N-methylpyridinium salt. In contrast, O-tetramethylated macrocycles and linear phenol-formaldehyde tetramer, could not efficiently include the N-methylpyridinium salt.

Full text of DOI:10.1002/jhet.5570380144

Jan-Feb 2001
Synthesis and Properties of Calixarene Analogs Incorporating a
Thiophene Unit in the Macrocyclic Ring
293
Kazuaki Ito*, Yoshihiro Ohba, Takafumi Tamura, Tomoaki Ogata, Hajime Watanabe,
Yasumitsu Suzuki, Takayuki Hara, Yukou Morisawa and Tyo Sone
Department of Materials Science and Engineering, Faculty of Engineering, Yamagata University, Yonezawa 992-8510, Japan
Received March 8, 2000
Calixarene analogs containing a thiophene unit in the macrocyclic ring were prepared by a stepwise
method. The macrocycles adopt a cone-like form as the preferred conformation in solution. The induced
1
chemical shift change, nOe experiment, and H relaxation time (T ) measurement supported the fact that the
1
macrocycle forms a complex with the N-methylpyridinium salt. In contrast, O-tetramethylated macrocycles
and linear phenol-formaldehyde tetramer, could not efficiently include the N-methylpyridinium salt.
J. Heterocyclic Chem., 38, 293 (2001).
Introduction.
This situation inspired us to synthesize the calixarene
analogs, which were constructed by changing from the
phenol moiety to an other aromatic unit. Therefore, we
synthesized the calixarene analogs containing a thio-
phene unit in the macrocyclic ring. The use of thiophene
as a building block offers the possibility of interesting
modifications on the thiophene ring due to its high
reactivity [4]. Here we describe the syntheses of the
calixarene analogs incorporating the thiophene unit and
their complexation behavior with the N-methyl-
pyridinium ion.
Calixarenes are macrocycles available in a variety of
ring sizes and are of interest both as complexation hosts for
ion and molecules and as a skeleton for producing more
complex structures [1]. Although the chemistry of
calixarenes has been extensively studied with respect to
the modification of the frameworks at the lower (small) or
upper (large) rims of the calixarene skeleton from the
viewpoint of additional functionality, there has been
relatively little research concerning the replacement of the
phenol unit with other aromatic rings [2,3].
+
Figure 2. Chemical shift changes of the protons in N-methylpyridinium iodide (Pyr ) induced by added calixarene analog (1 or 2) or phenol-formalde-
+
-2
hyde tetramer 3 as a reference compound at 25° in deuteriochloroform:deuterioacetonitrile-d 10:1 (v/v) ([1] = [2] = [3] = [Pyr ] = 1.0 X 10 M),
3
denote the shift to higher magnetic field.

294
K. Ito, Y. Ohba, T. Tamura, T. Ogata, H. Watanabe, Y. Suzuki, T. Hara, Y. Morisawa and T. Sone
Vol. 38
-
dilution conditions (0.3-1.0 x 10 3 M) to yield 1a and 1b in 50
and 40% yields, respectively. The O-tetramethylated
macrocycles 2 were prepared from the reactions of 1 with an
excess amount of methyl iodide in the presence of sodium
hydride at 80° in 62% (2a) and 90% (2b) yields.
Results and Discussion.
Macrocycles 1 were prepared from the corresponding
acyclic oligomers in a stepwise method as shown in Scheme
1. Hydroxymethylation of the phenol-formaldehyde tetramer
3 with 35% formalin in the presence of 25% aqueous sodium
hydroxide solution led to the monohydroxymethyl tetramer 4
in 25% yield [5]. Condensation of 4 with an excess of
thiophene in the presence of p-toluenesulfonic acid without
solvent gave the linear oligomer 5 in 58% yield. Compound 5
was hydroxymethylated again, then followed by acid-
catalyzed cyclization of the resulting alcohol 6 under high
The spectroscopic properties such as nmr, ir, and FAB
mass spectra of macrocycles 1 and 2 are in agreement with
the assigned structures. Coupling constants for the protons of
the thiophene rings in 1 and 2 indicated that 1a and 2a (J =
0.0 Hz) are the 2,5-disubstituted thiophene derivative and 1b
(J = 5.3 Hz) and 2b (J = 5.0 Hz) are 2,3-disubstituted.
1
+
Figure 3. H Nmr relaxation times T [s] of calixarene analog 1a in the absence of N-methylpyridinium iodide Pyr at 25° in deuteriochloroform:-
1
+
deuterioacetonitrile-d =10:1 (v/v). The figures in the parentheses denote the changes in T in the presence of Pyr .
3
1

Jan-Feb 2001
Synthesis and Properties of Calixarene Analogs
295
5
Table 1
NOes in the Complex of 1a with Pyr at 25° in
+
Deuteriochloroform:Deuterioacetonitrile-d = 10:1 (v/v)
3
4
3
2
1
0
0.0
0.2
0.4
0.6
0.8
1.0
Molar Fraction [1a]
Observed nOe, %
N-methylpyridinium iodide (Pyr )
Figure 4. Job's plot. (δ -δ) is shift in ppm induced in the NCH proton of
Pyr , and the total concentration of 1a plus Pyr maintained at 10 mM in
deuteriochloroform:deuterioacetonitrile-d3 = 10:1 (v/v) at 20°.
f
3
+
+
+
Irradiated
phenol
N-CH
5.6
6.6
6.7
2.6
H-α
8.7
8.9
8.5
4.2
H-β
11.0
11.2
10.0
5.4
H-γ
9.5
9.8
10.9
9.4
3
H-a
H-b
H-d
H-t
thiophene
0.2
H-c proton was overlapped with the proton of cholorform.
In the ir spectra, the OH absorption of 1 was observed at
1
3357 cm-1 as a broad band in chloroform. In the H nmr
spectra of 1 in deuteriochloroform at 20°, the OH proton
signals were observed in the range of δ 6.48-9.11 ppm.
1
Comparing the ir and H nmr spectra of the phenolic OH
0.1
groups of 1 with those of calix[n]arene (ν
(n = 4), 3280 (n = 5) cm-1, δ
= 3138
OH
= 10.2 (n = 4), 8.0 (n = 5)
OH
ppm) [1a], the intramolecular hydrogen bonding in 1 is
weaker than that of the calix[n]arene due to the
introduction of the thiophene ring, which does not
contribute to intramolecular hydrogen bonding.
1
The methylene protons of 1 and 2 in the H nmr spectra
appeared as singlets at room temperature, and are not split
at -60° in deuteriochloroform, indicating that 1 is
conformationally flexible. Therefore, the conformation of
1 and 2 was evaluated using the 13C nmr chemical shift of
0.0
0
1
2
3
4
5
the ArCH Ar methylene carbon, which is used as a means
2
1
+
for assessing calixarene conformations. It is known that
the methylene carbon resonances for calixarenes appear at
ca. δ 30-33 ppm when the adjacent aryl rings are syn and at
ca. δ 36-38 ppm when they are anti [6]. Applying this to 1
and 2, the chemical shifts of the methylene carbon atoms,
which were observed in the range of δ 31.1-31.4 ppm,
suggested that all the phenol units adopt a syn orientation.
Thus, a cone-like form is the preferable conformation in
this system.
Figure 5. H Nmr titration of Pyr with 1a in deuteriochloroform:-
deuterioacetonitrile-d = 10:1 (v/v) at 20°. (δ -δ) is change in chemical
3
f
+
shift of NCH proton of Pyr as a result of added 1a.
3
+
N-methylpyridinium iodide Pyr . In the presence of 1, all
resonance peaks of the salt moved to a higher magnetic
field due to the ring current effect of the cyclophane core.
Interestingly, for the O-tetramethylated compounds 2 a
significant up-field shift due to induction was not
observed. This discrepancy suggests the importance of
intramolecular hydrogen bonding, which contributes to the
It is known that calixarenes bind quaternary ammonium
ions in solution [7]. We also investigated the host-guest
complexation behavior of marcocycles 1 and 2 with

296
K. Ito, Y. Ohba, T. Tamura, T. Ogata, H. Watanabe, Y. Suzuki, T. Hara, Y. Morisawa and T. Sone
Vol. 38
T measuremets were made by the inversion recovery method at
suppression of molecular motion. Analogously, for linear
oligomer 3 an up-field shift of the guest proton was not
observed, indicating the importance of the ring structure
during the inclusion of the cationic guest molecules.
1
25°; the deviation of the T values is within 5%. All chemicals
1
were reagent grade and were used without further purification.
Compounds 3 and 4 were prepared according to methods
reported in the literature [5].
+
Further evidence for the inclusion of Pyr in 1a was
obtained from nOe experiments [7b]. The nOe peak
intensities with respect to the protons of Pyr are shown in
Condensation Reaction of 4 with Thiophenes.
+
A mixture of 4 (8.3 g, 13 mmoles), thiophene (126 g,
1.5 moles), and p-toluenesulfonic acid (0.24 g, 1.3 mmoles) was
refluxed for 4 hours under a nitrogen atmosphere. The reaction
mixture was washed with 100 ml of water two times and dried
over anhydrous sodium sulfate. Removal of thiophene under
reduced pressure gave an oily residue that was subjected to
column chromatography on silica gel using hexane:ethyl acetate
3:1 as the eluent to give 5 (5.3 g, 58 %) as colorless crystals.
Table 1. The peak intensities are strong enough to support
+
the inclusion of Pyr into the cavity of 1a.
1
The H nmr relaxation time (T ) measurement also
1
+
supported the fact that Pyr was included in the core [8].
The T1 values for all protons of Pyr drastically decreased
when 1a was complexed with Pyr , indicating that the
+
+
formation of the complex suppressed the molecular motion
+
of both Pyr and 1a. Interestingly, a larger decrease was
4-tert-Butyl-2-((5-(tert-butyl)-3-((5-(tert-butyl)-2-hydrox-
yphenyl)methyl)-2-hydroxyphenyl)methyl-6-((5-tert-butyl)-2-
hydroxy-3-(thienymethyl)phenyl)methyl)phenol (5).
observed at the β-proton in the thiophene ring of 1a during
the formation of the complex, implying that the thiophene
ring also participated in the formation of the complex as a
π-base as well as the phenol ring.
We estimated the stoichiometry of the complex using
Job's plot method [9]. The 1:1 stoichiometry of the
complex was confirmed by a plot that contains a maximum
1
Compound 5 has mp 107-110° (ethyl acetate-hexane); H nmr
(deuteriochloroform): δ 1.24 (s, 9H, t-Bu), 1.25 (s, 18H, t-Bu x
2), 1.26 (s, 9H, t-Bu), 3.75 (s, 2H, CH ), 3.76 (s, 2H, CH ), 3.77
2
2
(s, 2H, CH ), 4.08 (s, 2H, CH ), 6.62 (d, 1H, Ar-H, 8.0 Hz), 6.78
2
2
(dd, 1H, thiophene ring proton, J = 1.5, 3.5 Hz), 6.85 (dd, 1H,
thiophene ring proton, J = 3.5, 5.5 Hz), 6.90 (d, 1H, Ar-H, J = 2.0
Hz), 6.95 (dd, 1H, Ar-H, J = 2.0, 8.0 Hz), 7.03-7.06 (m, 4H,
Ar-H x 4), 7.08 (dd, 1H, thiophene ring proton, J = 1.5, 5.5 Hz),
7.09 (d, 1H, Ar-H, J = 2.0 Hz), 7.18 (d, 1H, Ar-H, J = 2.0 Hz),
8.80 (bs, 1H, OH), 8.85 (bs, 2H, OH x 2), 8.88 (bs, 1H, OH);
at the mole ratio of 0.5 in this case. The association
+
constants (K ) of the macrocycles 1 to Pyr were
a
determined by a nonlinear least-squares fitting method of a
binding curve obtained from the 1H nmr titration (1a: K =
a
-1
104+10, 1b: 80+10 M ) [10]. This value is quite similar to
those of the calix[n]arenes (K = 52 M (n=4), K = 190
13
C nmr (deuteriochloroform): δ 31.4, 31.5, 31.8, 32.0, 32.2,
-1
a
a
33.9, 34.0, 115.1, 124.2, 124.6, 125.2, 125.6, 125.7, 125.8, 125.9,
126.2, 126.4, 126.5, 126.9, 127.0, 127.1, 127.2, 127.3, 127.6,
143.3, 143.7, 144.1, 144.2, 144.3, 147.0, 147.2, 148.6, 149.7;
-1
-1
M
(n=6), K = 132 M (n=8)) [7b]. In contrast, the
a
association constants of the O-tetramethylated
+
macrocycles 2 are very small values (2a: K =10+2, 2b:
(FAB) ms: m/z 733 (M+1) .
a
-1
6+1 M ).
Anal. Calcd. for C
H O S: C, 78.65; H, 8.25. Found: C,
48 60 4
78.82; H, 8.53.
In conclusion, we prepared the calixarene analogs
containing a thiophene ring in the macrocyclic ring. We
also elucidated that the macrocycles 1 have a binding
ability for N-methylpyridinium iodide. The formation of
Hydroxymethylation of 5.
A mixture of 5 (5.3 g, 7.2 mmoles), 23 % sodium hydroxide
aqueous solution (6.2 ml, 40 mmoles), 35 % formaldehyde
aqueous solution (25 ml, 290 mmoles), and 50 ml of methanol
was heated at 50° for 8 hours under a nitrogen atmosphere. After
cooling to room temperature, the mixture was acidified by 10 %
hydrochloride aqueous solution until pH 1, and then extracted
with 100 ml of chloroform. The extract was washed with 100 ml
of water three times and the organic layer was dried over
anhydrous sodium sulfate. Removal of solvent gave oily residue,
which was subjected to column chromatography on silica gel
using hexane:ethyl acetate 4:1 as the eluent to give 6 (3.5 g,
64 %) as crystals.
the complex was supported by the induced chemical shifts,
1
nOe experiments, and H relaxation time (T )
1
measurement. In contrast, the O-tetramethylated
compounds 2 and linear oligomer 3 could not efficiently
include the salt. This discrepancy suggests that
suppression of molecular motion and the ring structure of
the host molecule are important factors during the
inclusion of a cationic guest.
EXPERIMENTAL
4-(tert-Butyl)-2-((5-(tert-butyl)-3-((5-(tert-butyl)-2-hydroxy-3-
(hydroxy-methyl)phenyl)methyl)-2-hydroxyphenyl)methyl)-6-
((5-(tert-butyl)-2-hydroxy-3-(2-thienylmethyl)phenyl)-
methyl)phenol (6).
1
13
All melting points are uncorrected. The H and C NMR
spectra were measured with Varian Mercury 200 and Varian 500
INOVA spectrometers using tetramethylsilane as internal
standard. The IR and UV spectra were acquired on Horiba
FT-200 and Hitachi 228A spectrophotometers, respectively.
FAB-mass spectra were recorded on a JEOL JMS AX-505HA
spectrometer, using m-nitrobenzyl alcohol as the matrix. Column
chromatography was performed using silica gel (Kieselgel 60,
1
Compound 6 has mp 105-108° (ethyl acetate-hexane); H nmr
(deuteriochloroform): δ 1.17 (s, 9H, t-Bu), 1.22 (s, 9H, t-Bu),
1.25 (s, 9H, t-Bu), 1.26 (s, 9H, t-Bu), 3.85 (s, 2H, CH ), 3.86
2
(s, 4H, CH x 2), 3.88 (s, 2H, CH ), 4.59 (s, 2H, CH ), 6.83
2
2
2
(dd, 1H, thiophene ring proton, J = 0.5, 3.5 Hz), 6.83 (d, 1H,
Ar-H, J = 2.5 Hz), 6.85 (d, 1H, Ar-H, J = 2.5 Hz), 6.97 (dd, 1H,
1
63-200 mm, 70-230 mesh, Merck). The H relaxation time

Jan-Feb 2001
Synthesis and Properties of Calixarene Analogs
297
thiophene ring proton, J = 3.5, 5.0 Hz), 7.10 (d, 1H, Ar-H, J = 2.5
Hz), 7.13 (d, 1H, Ar-H, J = 2.5 Hz), 7.16 (d, 1H, Ar-H, J = 2.5
Hz), 7.17 (d, 1H, Ar-H, J = 2.5 Hz), 7.18 (dd, 1H, thiophene ring
proton, J = 0.5, 5.0 Hz), 7.19 (d, 1H, Ar-H, J = 2.5 Hz), 7.20
122.9, 125.5, 125.8, 126.0, 126.2, 126.5, 126.6, 126.7, 126.9,
127.0, 127.1, 127.2, 129.1, 143.2, 143.5, 143.7, 144.2, 144.3,
147.2, 147.7, 148.7, 148.9, 149.5, 149.8; (FAB) ms: m/z 745
+
(M+1) .
13
(d, 1H, Ar-H, J = 2.5 Hz), 9.50 (bs, 4H, OH x 4); C nmr
Anal. Calcd. for C
H O S: C, 78.99; H, 8.12. Found: C,
49 60 4
(deuteriochloroform): δ 30.7, 31.3, 31.4, 31.5, 31.7, 32.2, 33.9,
34.0, 34.1, 65.0, 121.3, 122.5, 123.5, 124.2, 125.1, 125.3, 125.7,
125.8, 125.9, 126.0, 126.1, 126.6, 126.7, 126.8, 126.9, 127.1,
127.6, 128.6, 143.1, 143.6, 143.8, 144.0, 144.2, 146.9, 147.6,
78.92; H, 8.09.
O-Tetramethylation of Macrocycles (1).
To a solution of 1 (0.40 mmole) in 6 ml of dry tetrahydrofuran
and 2 ml of dry dimethylformamide was added sodium hydride
(0.11 g, 4.6 mmoles) over 15 minutes. Methyl iodide (1.02 g,
7.2 mmole) was added and the resulting mixture was refluxed for
4 hours. After cooling to room temperature the reaction mixture
was quenched by addition of methanol and 10 % aqueous
hydrochloric acid solution. After removal of the solvent the
organic residue was extracted two times with 20 ml of
chloroform. Removal of the chloroform gave an oily residue, that
was subjected to column chromatography on silica gel using 6:1
as the eluent to give O-tetramethylated compound (2) as a
colorless oil.
+
148.4, 149.1; (FAB) ms: m/z 746 (M-OH+1) .
Anal. Calcd. for C
H O S: C, 77.13; H, 8.19. Found: C,
49 62 5
77.32; H, 8.20.
Cyclization Reaction of 6.
To a refluxing solution of dry benzene in the presence of
p-toluenesulfonic acid (1.0 g, 0.6 mmole) was slowly added
dropwised a solution of 5 ( 0.40 g, 0.54 mmole) in 100 ml of dry
benzene over 8 hours. After the addition was complete, the
mixture was further refluxed for 2 hours. After cooling to room
temperature, the mixture was washed with 100 ml of water three
times and the organic layer was dried over anhydrous sodium
sulfate. Removal of solvent gave an oily residue, which was
subjected to column chromatography on silica gel using
chloroform as the eluent to give 1a (0.20 g, 50 %) and 1b (0.16 g,
40 %) as colorless crystals.
30,32,33,34-Tetramethoxy-10,16,22,28-tetrakis(tert-butyl)-31-
thiahexacyclo[24.3.1.1 .1 .1
3(4), 5, 8(9), 10, 12(32), 14(15), 16, 18(33), 20(21), 24(34),
26(30), 27-tetradecaene (2a).
3,6 8,12 14,18 20,24
.1
]tetratriaconta-1(29),
10,16,22,28-Tetrakis(tert-butyl)-31-thiahexacyclo-
1
The yield was 62% as colorless oil; H nmr (deuterio-
3,6 8,12 14,18 20,24
[24.3.1.1 .1 .1
.1
]tetratriaconta-1(29), 3(4), 5, 8 (9),
chloroform): δ 1.16 (s, 18H, t-Bu x 2), 1.21 (s, 18H, t-Bu x 2),
2.85 (s, 6H, OMe x 2), 3.25 (s, 6H, OMe x 2), 3.80 (s, 2H, CH ),
3.85 (s, 4H, CH x 2), 6.51 (s, 2H, thiophene ring protons), 6.94
10, 12(32), 14(15), 16, 18(33), 20(21), 24(34), 26(30),
27-tetradecaene-30, 32, 33, 34-tetraol (1a).
2
2
The yield was 50
% as crystals, mp 141-144°
(d, 2H, Ar-H x 2, J = 2.6 Hz), 7.07 (d, 2H, Ar-H x 2, J = 2.4 Hz),
7.12 (d, 2H, Ar-H x 2, J = 2.6 Hz), 7.15 (d, 2H, Ar-H x 2, J = 2.4
Hz); C nmr (deuteriochloroform): δ 29.9, 30.6, 31.3, 31.4, 32.2,
1
(dichloromethane-hexane); H nmr (deuteriochloroform): δ
1.25 (s, 18H, t-Bu x 2), 1.28 (s, 18H, t-Bu x 2), 3.76 (s, 6H,
CH x 3), 4.06 (s, 4H, CH x 2), 6.60 (bs, 2H, OH x 2), 6.75
13
34.0, 34.1, 60.2, 61.2, 123.4, 125.9, 126.0, 126.5, 126.9, 132.4,
133.5, 133.8, 134.1, 143.9, 145.2, 145.7, 153.5, 154.5; (FAB) ms:
2
2
(s, 2H, thiophene ring protons), 7.00 (d, 2H, Ar-H x 2, J =
2.5 Hz), 7.19 (d, 2H, Ar-H x 2, J = 2.5 Hz), 7.21 (d, 2H, Ar-H
x 2, J = 2.5 Hz), 7.24 (d, 2H, Ar-H x 2, J = 2.5 Hz), 7.43
+
m/z 801 (M+1) .
Anal. Calcd. for C
H O S: C, 79.46; H, 8.56. Found: C,
53 68 4
13
(bs, 2H, OH); C nmr (deuteriochloroform): δ 31.2, 31.3,
79.55; H, 8.61.
31.5, 33.0, 33.9, 125.3, 125.4, 125.8, 126.1, 126.2, 126.3,
126.4, 126.8, 142.4, 143.3, 143.9, 147.9, 149.4; (FAB) ms:
m/z 745 (M+1) .
31,32,33,34-Tetramethoxy-5,11,17,19-tetrakis(tert-butyl)-24-
3,7 9,13 15,19 21,25
thiahexacyclo-[25.3.1.1 .1
.1
.0
]tetratriaconta-
+
1(31), 3(4), 5, 7(32), 9(10), 11, 13(33), 15(34), 16, 18, 21(25), 22,
27(28), 29-tetradecaene (2b).
Anal. Calcd. for C
H O S: C, 78.99; H, 8.12. Found: C,
49 60 4
78.76; H, 8.22.
1
The yield was 90% as colorless oil; H nmr (deuterio-
5,11,17,19-Tetrakis(tert-butyl)-24-thiahexacyclo-
chloroform): δ 1.11 (s, 9H, t-Bu), 1.13 (s, 9H, t-Bu), 1.22
(s, 9H, t-Bu), 1.24 (s, 9H, t-Bu), 2.54 (s, 6H, OMe x 2), 2.60
(s, 6H, OMe x 2), 3.53 (s, 2H, CH ), 3.59 (s, 2H, CH ), 3.66
3,7 9,13 15,19
21,25
[25.3.1.1 .1
.1
. 0
]tetratriaconta-1(31), 3(4), 5,
7(32), 9(10), 11, 13(33), 15(34), 16, 18, 21(25), 22, 27(28),29-
tetradecaene-31,32,33,34-tetraol (1b).
2
2
(s, 2H, CH ), 3.79 (s, 2H, CH ), 3.83 (s, 2H, CH ), 6.80
2
2
2
The yield was 40 % as crystals, mp 168-173° (dichloro-
(d, 1H, Ar-H, J = 2.5 Hz), 6.83 (d, 1H, thiophene ring proton,
J = 5.0 Hz), 6.89 (d, 1H, Ar-H, J = 2.5 Hz), 7.02 (d, 1H,
thiophene ring proton, J = 5.0 Hz), 7.04 (d, 1H, Ar-H, J = 2.5
Hz), 7.06-7.09 (m, 2H, Ar-H x 2), 7.10 (d, 1H, Ar-H, J = 2.5
Hz), 7.15 (d, 1H, J = 2.5 Hz), 7.16. (d, 1H, J = 2.5 Hz);
nmr (deuteriochloroform): δ 29.6, 30.8, 31.4, 33.9, 59.4, 59.5,
60.2, 60.3, 121.2, 124.4, 125.7, 125.8, 125.9, 126.2, 126.5,
130.6, 131.7, 132.1, 133.1, 133.2, 133.3, 133.9, 134.0, 135.7,
136.8, 144.9, 145.0, 145.3, 145.5, 154.0, 154.1; (FAB) ms:
1
methane-hexane); H nmr (deuteriochloroform): δ 1.22 (s, 9H,
t-Bu), 1.23 (s, 9H, t-Bu), 1.25 (s, 9H, t-Bu), 1.30 (s, 9H, t-Bu),
3.80 (s, 2H, CH ), 3.87 (s, 6H, CH x 3), 4.00 (s, 2H, CH ), 6.48
2
2
2
13
(bs, 1H, OH), 6.70 (d, 1H, thiophene ring proton, J = 5.3 Hz),
6.80 (bs, 1H, OH), 6.99 (d, 1H, thiophene ring proton, J =
5.3 Hz), 7.07 (d, 1H, Ar-H, J = 2.4 Hz), 7.10 (d, 1H, Ar-H, J =
2.4 Hz), 7.12 (d, 1H, Ar-H, J = 2.4 Hz), 7.13 (d, 1H, Ar-H, J =
2.4 Hz), 7.15 (d, 1H, Ar-H, J = 2.4 Hz), 7.18 (d, 1H, Ar-H, J =
2.4 Hz), 7.19 (d, 1H, Ar-H, J = 2.4 Hz), 7.20 (d, 1H, Ar-H, J =
C
+
m/z 801 (M+1) .
13
2.4 Hz, 8.99 (bs, 1H, OH), 9.11 (bs, 1H, OH); C nmr (deuterio-
Anal. Calcd. for C H O S: C, 79.46; H, 8.56. Found: C,
53 68 4
chloroform): δ 29.5, 30.0, 31.4, 31.5, 32.1, 32.4, 33.9, 34.0,
79.55; H, 8.61.

298
K. Ito, Y. Ohba, T. Tamura, T. Ogata, H. Watanabe, Y. Suzuki, T. Hara, Y. Morisawa and T. Sone
Vol. 38
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