The synthesis of novel crown ethers, part IX, 3-phenyl chromenone-crown ethers

Article abstract of DOI:10.1002/jhet.5570380608

3-Phenyl- and 3-(p-methoxyphenyl)-7,8-dihydroxy and -6,7-dihydroxychromenones were prepared from ethyl 3-oxo-2-phenylpropanoate, ethyl 3-oxo-2-(4-methoxyphenyl)-propanoate and the trihydroxy benzenes in H₂SO₄. 3-Aryl-7,8- and 3-aryl-

Full text of DOI:10.1002/jhet.5570380608

Nov-Dec 2001
The Synthesis of Novel Crown Ethers,
1291
Part IX, 3-Phenyl Chromenone-Crown Ethers
M. Bulut [a] and Ç. Erk [b]*
.
[a] University of Marmara, Department of Chemistry, Kadıköy, 81040, Istanbul, Turkey
.
[b] Technical University of Istanbul, Department of Chemistry, Maslak, 80626, Istanbul, Turkey
Received June 29, 2001
3-Phenyl- and 3-(p-methoxyphenyl)-7,8-dihydroxy and -6,7-dihydroxychromenones were prepared from
ethyl 3-oxo-2-phenylpropanoate, ethyl 3-oxo-2-(4-methoxyphenyl)-propanoate and the trihydroxy benzenes
in H SO . 3-Aryl-7,8- and 3-aryl-6,7-dihydroxy-2H-chromenones reacted with the bis-dihalides of poly-
2
4
glycols in DMF/MeCO to afford 12-Crown-4, 15-Crown-4 and 18-Crown-6-chromenones. The products
3
were identified with IR, 1H NMR, low and high resolution mass spectroscopy and elemental analysis. Some
+
+
+
+
1:1 cation association constants, K , of the 3-phenyl chromenone crown ethers with Li , Na , K and Rb
b
cations were studied by steady state emission fluorescence spectroscopy; K chromenone-crown complexes
b
displayed crown ether-cation binding selectivity rules properly in acetonitrile.
J. Heterocyclic Chem., 38, 1291 (2001).
Introduction.
(4-methoxyphenyl) acetate via Claisen condensation. The
6,7-dydroxychromenones, 2a and 2b were prepared from
1a reacting with 1f and 1g. 7,8-Dihydroxychromenones,
2c and 2d were prepared from 1b reacting with 1f and 1g
Macrocyclic ethers have been used to estimate cationic
recognition and selective cation binding with different
physical methods [1-3]. The effect of the cation on the
chromophore crown ethers utilised fluorescence
spectroscopy since the binding of cations mostly induce
changes in triplet energy relative to excited singlet,
in concentrated H SO , Scheme 1. The chromenone-
2
4
crown ethers were obtained by cyclic condensation of the
o-dihydroxy-chromenones with the bisdihalides and
bisditosylates of polyglycols.
Namely, 2a reacted with 1c, 1d and 1e to afford the
crown ethers, 3a, 3b and 3c. Compound 2c reacted with
1c, 1d and 1e to afford the crown ethers, 4b, 4c and 4d.
Accordingly, 2d reacted with 1c, 1d and 1e to afford the
crown ethers, 4d, 4e and 4f, in the presence of
S
→ T and ground state T → S energies of the
1
1 1 0
chromophore moieties [4-7].
We have recently synthesised various crown ethers
with different chromophore moieties and reported their
cationic interactions using steady state fluorescence
spectroscopy in acetonitrile [8-10]. The crown ether
derivatives of the 4-H and 4-methyl-6,7-dihydroxy- and
-7,8-dihydroxycoumarins displayed the binding effect
of alkali cations on the fluorescence emission spectra.
They exhibited good agreements on the cation radii and
the macrocyclic molecule size as reported [8-10]. The
chromophore ethers were mostly capable of displaying
the effect of the cation via UV-VIS spectra due to the
restriction on the π-electron flow [11]. The reports of
Sammes et al [12], and Rodriguez-Ubis et al [13], on
such structures have shown the importance of the
synthesis and cation recognition role of chromo-
fluorogenic compounds. Detailed information, on the
literature was also given in our recent report [14].
Na CO /DMF, Scheme 1. The full spectral data of the
2
3
original products are given in the experimental part while
the known compounds are presented with just NMR data.
Cationic Fluorescence Measurements.
The cation binding constants, K of chromenone-crowns
b
+
+
+
+
with Li , Na , K , and Rb perchlorates obtained
according to Equations 1-3 were found to be rather
interesting. 3-Phenylchromenones exhibit strong fluores-
cence emission intensities due to their high quantum
yields.
+ →
+
L + M
M L
(1)
(2)
(3)
←
+
+
K = [M L]/[L] [M ]
b
The present work deals with the preparation of the novel
crown ethers bearing 3-phenylcromenone moieties, which
were studied with fluorescence spectroscopy to investigate
cation complex formation with Li , Na , K , and Rb
perchlorates [8-11].
(I - I )/(I
- I ) = K [M ]
x b o
x
o
max
The association constants K , estimated from the
b
+
+
+
+
emission fluorescence spectra of the chromenone-crown
complexes displayed ether-cation binding selectivity rules
in acetonitrile (AN), Table 1. However, 7,8-dioxa
derivatives have exhibited CEFS upon cation complexing
while the 6,7-dioxa-chromenones gave CEQFS as they are
complexed in AN. Similar behaviours were also observed
from other derivatives of such chromophore structures in
our earlier studies [8-10].
Results and Discussion.
Organic Synthesis.
Starting products of ethyl phenyl acetate, 1f and ethyl
(4-methoxyphenyl) acetate 1g, were prepared from ethyl
format reacting with ethyl phenyl acetate and ethyl

1292
M. Bulut and Ç. Erk
Vol. 38
Table 1
The Fluorescence Properties and 1:1 Association, lnK of Crown Ethers at 25 °C in AN
b
ex
em
Compound
λ
λ
I
I
Cat.
lnK
b
∆G (kJ/mol)
o
max
+
3a
3b
3c
381
381
370
370
350
350
350
367
367
367
367
367
444
444
443
443
440
443
443
425
425
425
425
425
550
550
870
865
888
930
896
270
295
88
50
50
500
50
700
690
770
90
Li
3.75
4.39
6.55
5.65
6.95
7.64
8.36
6.25
6.28
6.27
7.92
7.51
9.2
+
Na
Na
10.8
16.2
13.9
15.7
18.8
20.6
15.4
15.5
15.5
19.5
18.5
+
+
K
+
Na
+
K
+
Rb
+
4a
4b
Li
+
90
Na
+
266
280
180
Li
+
101
110
Na
+
K

Nov-Dec 2001
The Synthesis of Novel Crown Ethers
1293
EXPERIMANTAL
-1 1
(OH), 1700 (C=O), 1450 (CH), 1190 (CO) cm ; H NMR
(acetone-d , 400 MHz): δ 6.78 (s, H, ArH), 6.89 (s, H, ArH), 7.42
6
The starting chemicals were from MERCK or FLUKA unless
otherwise cited. Initial compounds, 1c - 1d were available from
our earlier studies [8-11]. IR spectra were taken as KBr pellets
with a JASCO FT-IR spectrometer, model-5300. High resolution
EI Mass spectra were obtained with FISONS instrument, model
(m, 3H, ArH), 7.67 (d, 2H, ArH), 7.69 (s, H, cumH): ms: m/z 254
+
+
+
+
(M ), 226 (M -28), 152 (M -102), 141 (M -113), 113.
Anal. Calcd for C
H
O : C, 70.86; H, 3.96. Found C, 70.81;
4
15 10
H, 4.01
6,7-Dihydroxy-3-(4-methoxyphenyl)-2H-chromen-2-one (2b).
1
VG-ZABSPEC. H NMR spectra were obtained with a
BRUKER spectrometer, model AVANCE-400CPX and TMS was
the internal standard. All mp reported are uncorrected.
Combustion analyses were acquired with a LECO-932 CHN
analyser. The steady state fluorescence emission spectra were
recorded with a JEOL spectrofluorometer, model FP-750 using
the standard software at 25 °C.
1,2,4-Triacetoxybenzene, 1a (4.2 g, 25 mmol), 1g (5.5 g,
25 mmol) and H SO (10 mL, 85 %) were heated for 2 hours to
2
4
afford (2b), 4.26 g (60 %), mp 256 °C (pink powder, methanol);
-1 1
IR (KBr) 3400 (OH), 1700 (CO), 1500 (CH), 1180 (CO) cm ; H
NMR (acetone-d , 400 MHz): δ 3.60 (s, 3H, OCH ), 6.91 (d, 2H,
6
3
ArH), 7.18 (d, H, ArH), 7.60 (d, 2H, ArH), 7.68 (s, H, cumH):
+
+
The 1:1 binding constants, K , were estimated according to the
ms: m/z 284 (M ), 256 (M - 28), 155.
Anal. Calcd for C O : C, 67.60; H, 4.25. Found C, 67.55;
b
method of de Silva et al, [7] using the equation, K [M ] =
b
o
H
16 12
5
[I - I ]/[I
- I ] from the data of steady state fluorescence
x
o
max
x
H, 4.19
emission spectroscopy. The intensity of the free (uncomplexed)
macrocycle is I and the I , is the fluorescence peak intensity of a
7,8-Dihydroxy-3-phenyl-2H-chromen-2-one (2c).
o
x
crown ether in the presence of any cation concentration, [M ].
0
A mixture of pyrogallol, 1b (5.25 g, 42 mmol), ethyl α-formyl
I
is obtained in the presence of excess of a cation concentra-
max
acetate, 1f (8.0 g, 42 mmol) and H SO (20 mL, 95 %) were
2
4
-3
tion. The solutions of the cations in dry CH CN, (5.0.10 mol/L)
3
heated at 85 °C for one hour to afford (2c), 9.0 g (87 %), mp 186
were added stepwise to a stirred 2.00 mL solution of the macro-
°C (acetone); IR (KBr) 3300 (OH), 1680 (C=O), 1280 (C-H),
-4
cyclic ether, (2.5.10 mol/L) in dry CH CN in a 10-mm quartz
-1
1
3
1160 (CO) cm ; H NMR (acetone-d , 400 MHz): δ 6.89 (s, H,
6
cell placed in the spectrophotometer cell compartment. The
Ar), 7.12 (s, H, ArH), 7.18 (m, 3H, Ph), 7.69 (d, 2H, Ph), 7.71
[I - I ] / [I
- I ] values are plotted versus [M ] from the
+
+
x
o
max
x
o
(s, H, cumH), 8.00 (s, 2H, OH): ms: m/z 254 (M ), 226 (M -28),
recorded intensity data. The slope of the least squared line gives
+
+
152 (M -102), 141 (M -113), 113.
Anal. Calcd for C O : C, 70.86; H, 3.96. Found C, 70.80;
the binding constant, K , (±0.08). However, only the behaviour
b
H
15 10
4
of compounds 3a-3c and 4a, 4b have been reported due to the
limited solubility of others in AN.
H, 3.98
7,8-Dihydroxy-3-(4-methoxyphenyl)-2H-chromen-2-one (2d).
A mixture of pyrogallol, 1a (1.7 g, 14 mmol), 1g (2.8 g, 14
Ethyl 3-Oxo-2-phenylpropanoate (1f).
A solution of dry ether (200 ml) methylformat (24.5 g,
410 mmol), ethyl phenyl acetate (76.8 g, 400 mmol) and Na
(9.45 g, 410 mmol) were mixed and heated for 24 hours. The
mmol) and H SO (10 mL, % 85) was heated at 85 °C for one
2
4
hour then poured into the ice-water. It was filtered, dried and
dissolved in boiling methanol with charcoal then filtered and
dried to give (2d), 2.0 g (50 %), mp 176 °C (acetone); IR (KBr)
mixture was washed with water, dried (Al O ) and distilled to
2
3
give (1f), 58.0 g (30 %), bp 80 °C/0.05 torr-; IR (KBr) 3020 (Ph),
-1
1
3491 (OH), 2872 (CH), 1722 (C=O), 1120 (C-O) cm ; H NMR
(acetone-d , 400 MHz): δ 3.53 (s, 3H, OCH ), 6.85 (d, 2H, ArH),
-1
1
1720 (C=0) cm ; H NMR (CDCl , 400 MHz): δ 1.31 (t, 3H,
3
6
3
OCH ), 4.25 (d, H, CH), 4.31 (q, 2H, OCH ), 7.38 (m, 3H, Ar),
3
2
6.97 (d, 2H, ArH), 7.10 (d, 2H, ArH), 7.95 (s, 2H, OH): ms: m/z
7.49 (d, 2H, Ph), 12.1 (d, 1H, CHO).
+
+
284 (M ), 256 (M - 28), 155.
Anal. Calcd for C O : C, 67.60; H, 4.25. Found C, 67.65;
Ethyl 2-(4-Methoxyphenyl)-3-oxopropanoate (1g).
H
16 12
5
H, 4.20
A solution of dry ether (200 mL) methylformat (12.2 g,
205 mmol), ethyl (4-methoxyphenyl) acetate (44.4 g, 200 mmol)
and Na (4.75 g, 205 mmol) were refluxed for 24 hours. The
14-Phenyl-2,3,5,6,8,9-hexahydro-13H-[1,4,7,10]tetraoxacyclo-
dodecino[2,3-g]chromen-13-one (3a).
solution was washed with water, dried (Al O ) and the ether was
2
3
Compound 1c (3.80 g, 20 mmol), Na CO (4.25 g, 40 mmol),
DMF (45 mL) and 2a (5.1 g, 20 mmol) were heated at 80-90 °C
for 36 hours while stirring, then acidified with HCl (2 %, 45 mL)
and filtered, dried then dissolved in CHCl filtered and dried on
2
3
evaporated. The distilled residue yielded (1g), 17.0 g (38 %), bp
120 °C/0.05 torr-; IR (KBr) 3030 (Ph), 2890 (CH ), 1735 (C=0),
3
-1
1
1150 (CO) cm ; H NMR (CDCl , 400 MHz): δ 1.31 (t, 3H,
3
CH ), 3.77 (s, 3H, OCH ), 4.31 (q, 2H, OCH ), 4.26 (d, H, CH),
3
3
3
2
Al O . The residue was purified by column chromatography
6.86 (d, 2H, ArH), 7.20 (d, 2H, ArH), 11.90 (d, 1H, CHO).
2
3
(Al O /CH Cl ) to give (3a), 1.40 g (19 %), mp 148 °C
2
3
2
2
6,7-Dihydroxy-3-phenyl-2H-chromen-2-one (2a).
(methanol); IR (KBr) 2990 (CH ), 1720 (C=O), 1280 (CH), 1110
(C-O) cm
2
-1
1
; H NMR (CDCl , 400 MHz): δ 3.81 (s, 4H,
1,2,4-Triacetoxybenzene, 1a (10.5 g, 62.5 mmol), 1f (12 g,
3
2OCH ), 3.86 (t, 2H, OCH ), 3.96 (t, 2H, OCH ), 4.24 (m, 4H,
62.5 mmol) and H SO (40 mL, 85 %) were heated for 3 hours
2
2
2
2
4
2OCH ), 6.91 (s, H, ArH), 7.15 (s, H, ArH), 7.18 (m, 3H, Ph),
and cooled then poured into a water-ice mixture. The filtered raw
product was dried and dissolved in hot methanol (100 mL) and
boiled with the added charcoal then filtered to give (2a), 11.7 g
(73 %), mp 258 °C (yellowish crystals, acetone)-; IR (KBr) 3280
2
+
7.69 (d, 2H, Ph), 7.71 (s, H, cumH): ms: m/z 368 (M ), 280
+
(M -C H O ), 196, 168; For C
H O HRMAS Calcd.
4
8
2
21 20 6
368.125989; Found. 368.125643.

1294
M. Bulut and Ç. Erk
Vol. 38
17-Phenyl-2,3,5,6,8,9,11,12-octahydro-15H-[1,4,7,10,13]-
pentaoxacyclopentadecino[2,3-g]chromen-15-one (3b).
NMR (CDCl , 400 MHz): δ 3.79 (m, 12H, 6OCH ), 4.00 (m, 4H,
3 2
2OCH ), 4.26 (t, 2H, OCH ), 4.41 (t, 2H, OCH ), 6.89 (d, H,
2
2
2
ArH), 7.22 (d, H, ArH), 7.44 (m, 3H, Ph), 7.71 (d, 2H, Ph), 7.75
Compound 1d (4.60 g, 20 mmol), Na CO (4.25 g, 40 mmol),
2
3
+
+
(s, H, cumH) ms: m/z 456 (M ), 280 (M -C H O ), 196, 140;
8
16 4
DMF (45 mL) and 2a (5.1 g, 20 mmol) treated as outlined above
to afford (3b), 1.23 g (15 %), mp 203 °C (acetonitril); IR (KBr)
For C
H O HRMAS Calcd. 456.178418; Found. 456.178598.
25 28 8
-1
1
2870 (CH ), 1714 (C=O), 1278 (C-H), 1130 (C-O) cm ;
H
14-(4-Methoxyphenyl)-2,3,5,6,8,9-hexahydro-13H-[1,4,7,10]-
tetraoxacyclododecino[2,3-h]chromen-13-one (4d).
2
NMR (CDCl , 400 MHz): δ 3.78 (s, 8H, 4CH ), 3.96 (t, 4H,
3
2
2CH ), 4.20 (m, 4H, 2OCH ), 6.84 (s, H, ArH), 6.95 (s, H, ArH),
2
2
Compound 1c (3.80 g, 20 mmol), Na CO (4.25 g, 40 mmol),
2
3
7.43 (m, 3H, Ph), 7.70 (d, 2H, Ph), 7.72 (s, H, cumH): ms: m/z
DMF (45 mL) and 2d (5.1 g, 20 mmol) reacted as described
above to afford (4d), 2.14 g (27 %), mp 182 °C (THF); IR (KBr)
+
+
412 (M ), 280 (M -C H O ), 225, 199, 140; For C
H O
6
12
3
23 24 7
HRMAS Calcd. 412.152203; Found. 412.149698.
-1
1
2825 (CH ), 1710 (C=O), 1210 (C-H), 1140 (C-O) cm
H
2
;
20-Phenyl-2,3,5,6,8,9,11,12,14,15-nonahydro-18H-[1,4,7,10,-
13,16]hexaoxacyclooctadecino[2,3-g]chromen-18-one (3c).
NMR (CDCl , 400 MHz): δ 3.85 (m, 4H, 2OCH ), 3.87 (s, 3H,
3
2
OCH ), 4.00 (t, 2H, OCH ), 4.26 (t, 2H, OCH ), 4.44 (t, 2H,
3
2
2
OCH ), 6.89 (d, 1H, ArH), 6.99 (d, 2H, ArH), 7.22 (d, 1H, ArH),
2
Compound 1e (2.74 g 10 mmol), K CO (2.76 g, 20 mmol),
2
3
+
7.66 (d, 2H, ArH), 7.68 (s, 1H, cumH): ms: m/z 398 (M ), 310
DMF (30 mL) and 2a (2.55 g, 10 mmol) treated as described
above to afford (3c), 0.49 g (10 %), mp 162 °C (ether); IR (KBr)
+
(M -C H O ), 226, 155; For C
H O HRMAS Calcd.
4
8
2
22 22 7
398.136553; Found. 398.140785.
-1
1
2890 (CH ), 1720 (C=O), 1280 (C-H), 1120 (C-O) cm
H
2
;
NMR (CDCl , 400 MHz): δ 3.68 (s, 4H, 2OCH ), 3.72 (m, 4H,
17-(4-Methoxyphenyl)-2,3,5,6,8,9,11,12-octahydro-15H-
[1,4,7,10,13]pentaoxacyclopentadecino [2,3-h]chromen-15-one
(4e).
3
2
2OCH ), 3.77 (m, 4H, 2OCH ), 3.95 (m, 4H, OCH ), 4.20
2
2
2
(m, 4H, ArH) 6.83 (s, H, ArH), 6.93 (s, H, ArH), 7.40 (m, 3H,
+
Ph), 7.69 (d, 2H, Ph), 7.71 (s, H, cumH): ms: m/z 456 (M ), 280
Compound 1d (4.60 g, 20 mmol), Na CO (4.25 g, 40 mmol),
+
2
3
(M -C H O ), 196, 140; For C
H O HRMAS Calcd.
8
16
4
25 28 8
DMF (45 mL) and 2d (5.1 g, 20 mmol) reacted as described
above to afford (4e), 1.85 g (21 %), mp 134 °C (acetonitrile); IR
456.178418; Found. 412.176691
-1
14-Phenyl-2,3,5,6,8,9-hexahydro-13H-[1,4,7,10]tetraoxacy-
clododecino[2,3-h]chromen-13-one (4a).
(KBr) 2810 (CH ), 1720 (C=O), 1225 (C-H), 1140 (C-O) cm
2
;
1
H NMR (CDCl , 400 MHz): δ 3.76 (m, 4H, 2OCH ), 3.86
3
2
(m, 3H, OCH ), 3.98 (m, 4H, 2OCH ), 4.00 (t, 2H, OCH ), 4.39
3
2
2
Compound 1c (3.80 g, 20 mmol), Na CO (4.25 g, 40 mmol),
2
3
(t, 2H, OCH ), 6.86 (d, 2H, ArH), 6.98 (d, 2H, ArH), 7.19 (d, 1H,
2
DMF (45 mL) and 2c (5.1 g, 20 mmol) treated as described above
to afford (4a), 1.61 g (22 %), mp 177 °C (acetonitril); IR (KBr)
+
ArH), 7.66 (d, 2H, ArH), 7.68 (s, 1H, cumH): ms: m/z 442 (M )
+
310 (M - C H O ), 284, 226, 155; For C
H O HRMAS
-1
1
6
12
3
24 26 8
2825 (CH ), 1710 (C=O), 1290 (C-H), 1118 (C-O) cm
H
2
;
Calcd. 442.162768; Found. 442.163086.
NMR (CDCl , 400 MHz): δ 3.85 (m, 4H, OCH ), 3.88 (t, 2H,
3
2
OCH ), 3.95 (t, 2H, 2OCH ), 4.27 (t, 2H, OCH ), 4.38 (t, 2H,
20-(4-Methoxyphenyl)-2,3,5,6,8,9,11,12,14,15-nonahydro-18H-
[1,4,7,10,13,16]hexaoxacyclooctadecino[2,3-h]chromen-18-one
(4f).
2
2
2
OCH ), 6.87 (d, 1H, ArH), 7.20 (d, 1H, ArH), 7.43 (m, 3H, Ph),
2
+
+
7.68 (d, 2H, Ph), 7.72 (s, H, cumH): ms: m/z 368 (M ), 280 (M -
C H O ), 196, 168, 140; For C HRMAS Calcd.
H
O
6
4
8
2
21 20
Compound 1e (2.74 g 10 mmol), K CO (2.76 g, 20 mmol),
2
3
368.125989; Found. 368.127181.
DMF (30 mL) and 2d (5.1 g, 20 mmol) reacted as described
above to afford (4f), 0.44 g (9 %), mp 112 °C (ether); IR (KBr)
17-Phenyl-2,3,5,6,8,9,11,12-octahydro-15H-[1,4,7,10,13]pen-
taoxacyclopentadecino[2,3-h]chromen-15-one (4b).
-1
1
2825 (CH ), 1715 (C=O), 1215 (C-H), 1150 (C-O) cm
H
2
;
NMR (CDCl , 400 Hz): δ 3.70 (m, 4H, 2OCH ), 3.78 (m, 8H,
3
2
Compound 1d (4.60 g, 20 mmol), Na CO (4.25 g, 40 mmol),
2
3
4OCH ), 3.86 (s, 3H, OCH ), 3.96 (t, 2H, OCH ), 4.02 (t, 2H,
2
3
2
DMF (45 mL) and 2c (5.1 g, 20 mmol) treated as described above
to afford (4b), 1.73 g (21 %), mp 138 °C (acetonitril); IR (KBr)
OCH ), 4.27 (t, 2H, OCH ), 4.38 (t, 2H, OCH ), 6.88 (d, 2H,
2
2
2
ArH), 6.98 (d, 2H, ArH), 7.21 (d, 1H, ArH), 7.66 (d, 2H, ArH),
-1
1
2830 (CH ), 1720 (C=O), 1290 (C-H), 1120 (C-O) cm
H
2
;
+
+
7.69 (s, 1H, cumH): ms: m/z 486 (M ), 310 (M - C H O ),
8
16 4
NMR (CDCl , 400 MHz): δ 3.83 (m, 8H, 4OCH ), 3.87 (t, 2H,
3
2
284, 226, 155; For C
Found 486.187198.
H O HRMAS Calcd. 486.188983;
26 30 9
OCH ), 3.99 (t, 2H, OCH ), 4.25 (t, 2H, OCH ), 4.40 (t, 2H,
2
2
2
OCH ), 6.89 (d, H, ArH), 7.21 (d, H, ArH), 7.42 (m, 3H, Ph),
2
+
7.70 (d, 2H, Ph), 7.75 (s, H, cumH): ms: m/z 412 (M ), 280
(M -C H O ), 225, 196, 140; For C
Acknowledgements.
+
H O HRMAS Calcd.
6
12
3
23 24 7
The support of this work with ITU / DPT-126 project to purchase
the JEOL-FP750 spectrofluorometer was heartily acknowledged.
412.152203; Found. 412.153009.
20-Phenyl-2,3,5,6,8,9,11,12,14,15-nonahydro-18H-
[1,4,7,10,13,16]hexaoxacyclooctadecino[2,3-h]chromen-18-one
(4c).
REFERENCES AND NOTES
Compound 1e (2.74 g 10 mmol), K CO (2.76 g, 20 mmol),
2
3
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(1997).
DMF (30 mL) and 2c (25.5 g, 10 mmol) treated as described
above to afford (4c), 0.78 g (17 %), mp, 75 °C (THF); IR (KBr)
-1
1
2815 (CH ), 1715 (C=O), 1260 (C-H), 1120 (C-O) cm
H
;
2

Nov-Dec 2001
The Synthesis of Novel Crown Ethers
1295
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