New Luminescent Tetraaza-tetraoxamacrobicyclic Receptors
FULL PAPER
CH), 2.20Ϫ3.10 (m, 28 H, CH
H, CH O, CH Ph and CH -Anthr.), 7.01Ϫ7.22 (m, 5 H, C
.30Ϫ7.53 (m, 8 H, H , H , H , H -Anthr.), 7.96 (d, J ϭ 8.3 Hz, 4 After cooling to room temp. the residue was taken up as a suspen-
2
N and CH
2
CH
2
), 3.30Ϫ3.80 (m, 22 3-(9-Anthryl)propionic Acid (7): A sample of 6 (1.50 g, 5.10 mmol)
was decarboxylated at 220 °C for 20 min under an inert atmosphere.
2
2
2
6 5
H
),
2
3
6
7
7
4
5
1
8
H, H , H -Anthr.), 8.25 (d, J ϭ 8.6 Hz, 4 H, H , H -Anthr.), 8.30
sion with aqueous 10% Na
2 3
CO , acidified with aqueous 10% HCl
1
0
ϩ
(
s, 2 H, H -Anthr.). Ϫ MS-FAB(ϩ); m/z: 937 [M ϩ Na ], 915 [M and the precipitate was filtered off and dried for 3 h (0.1 Torr, 40
ϩ
ϩ 1] calcd. for C60
H
74
N
4
O
4
915. Ϫ C60
H
74
N
4
O
4
(915.27): calcd.
°C) to afford 1.14 g (89%) of pure 7 as a yellow solid. Ϫ M.p.
1
C 78.72, H 8.16, N 6.12; found C 78.10, H 8.20, N 6.00.
194Ϫ195 °C. Ϫ H NMR (CDCl
3
): δ ϭ 2.81Ϫ2.84 (m, 2 H,
-Anthr.), 7.44Ϫ7.58 (m, 4 H,
CH COOH), 3.88Ϫ4.15 (m, 2 H, CH
2
2
1
,7,13,19-Tetraaza-26-benzyl-7,19-bis(naphthylmethyl)-4,10,16,22-
tetraoxabicyclo[12.12.3]heptacosane (3): Solid Na CO (0.35 g,
.30 mmol) was added to a solution of the bisamine 4 (0.32 g,
.66 mmol) and 1-chloromethylnaphthalene (0.26 g, 1.32 mmol) in
CN (30 mL), and the resulting suspension was stirred at reflux
2
3
6
7
4
5
H , H , H , H -Anthr.), 8.10 (d, J ϭ 7.8 Hz, 2 H, H , H -Anthr.),
.26 (d, J ϭ 8.8 Hz, 2 H, H , H -Anthr.), 8.38 (s, 1 H, H -Anthr.).
2
3
1
8
10
8
3
0
14 2
Ϫ C17H O
(250.30): calcd. C 81.57, H 5.65; found C 81.21, H 5.52.
CH
3
Ethyl 3-(9-Anthryl)propionate (8): solution of (1.00 g,
A
7
for six days. The reaction mixture was allowed to cool to room
temp., filtered through Celite and the solvent evaporated to afford
4.00 mmol) in absolute ethanol (50 mL) with a few drops of con-
centrated sulfuric acid was heated at reflux for 5 h. After cooling
to room temp. the solvent was evaporated, and the residue was
0
.65 g of the crude product, as a yellow viscous oil. Purification by
column chromatography (SiO , CHCl /CH OH ϭ 90:10 v/v) af-
forded 0.17 g (34%) of pure 3 as a yellow viscous oil. Ϫ H NMR
CDCl
): δ ϭ 1.80Ϫ2.00 (m, 1 H, CH), 2.25Ϫ3.05 (m, 20 H, a brown thick oil residue which was purified by crystallization with
N), 3.20Ϫ3.65 (m, 18 H, CH O and CH
Ph), 4.05 (s, 4 H, EtOH to afford 1.04 g (94%) of pure 8 as a yellow solid. Ϫ M.p.
-Napth.), 7.14Ϫ7.31 (m, 5 H, C
), 7.37Ϫ7.55 (m, 8 H, H , 64.5Ϫ65.5 °C. Ϫ H NMR (CDCl
transferred into a separating funnel with CH
2 2
Cl (50 mL) and
2
3
3
1
washed with H O (2 ϫ 15 mL). Evaporation of the solvent afforded
2
(
3
CH
CH
2
2
2
2
1
H
5
3
): δ ϭ 1.25 (t, J ϭ 7.1 Hz, 3 H,
COOH), 3.91Ϫ4.00 (m, 2 H, CH
Anthr.), 4.20 (q, J ϭ 7.1 Hz, 2 H, CH CH ), 7.43Ϫ7.56 (m, 4 H,
.39 (d, J ϭ 7.8 Hz, 1 H, -Napth.). Ϫ MS-FAB(ϩ); m/z: 781 [M H , H , H , H -Anthr.), 8.00 (d, J ϭ 8.1 Hz, 2 H, H , H -Anthr.),
2
6
3
6
7
4
3
H , H , H -Napth.), 7.76 (d, J ϭ 8.1 Hz, 2 H, H -Napth.), 7.84 (d, CH ), 2.74Ϫ2.80 (m, 2 H, CH
2
2
-
5
8
J ϭ 8.1 Hz, 2 H, H -Napth.), 8.30 (d, J ϭ 7.8, 1 H, H -Napth.),
2
3
8
2
3
6
7
4
5
8
ϩ
ϩ
1
8
10
ϩ Na] , 759 [M ϩ 1] calcd. for C48
759.04): calcd. C 75.94, H 8.25, N 7.38; found C 75.73, H 8.05, Ϫ C19
N 7.12.
6.42.
H
62
N
4
O
4
758. Ϫ C48
H
62
N O
4 4
8.27 (d, J ϭ 8.8 Hz, 2 H, H , H -Anthr.), 8.37 (s, 1 H, H -Anthr.).
(
18 2
H O
(278.35): calcd. C 81.97, H 6.53; found C 81.56, H
Diethyl 9-Anthrylmethylmalonate (5): A solution of diethyl malon-
9-(3-Hydroxypropyl)anthracene (9): A solution of 8 (0.80 g,
ate (1.42 g, 8.82 mmol) in dry THF (25 mL) was slowly added to a 2.87 mmol) in dry Et O (25 mL) was slowly added to a stirred sus-
stirred suspension of NaH (50% in mineral oil; 0.43 g, 8.82 mmol)
pension of LiAlH (0.54 g, 14.35 mmol) in dry Et O (25 mL) under
in dry THF (25 mL) at 0 °C under a nitrogen atmosphere. The an inert atmosphere. The reaction mixture was refluxed for 1 h, the
2
4
2
reaction mixture was maintained at room temperature for 1 h, in
order to promote the anion formation, then cooled to 0 °C and a
solution of 9-chloromethylanthracene (2.00 g, 8.82 mmol) in THF
excess of LiAlH
ate, H O and aqueous 20% H
with Et O (3 ϫ 20 mL). The organic phase was dried over MgSO
and the solvent evaporated in vacuo to afford 0.64 g (94%) of pure
4
was carefully destroyed by addition of ethyl acet-
2
2
SO and the product was extracted
4
2
4
(
10 mL) was quickly added. The reaction mixture was kept at room
temp. under magnetic stirring for 15 h. The solvent was evaporated
in vacuo, the residue was taken up with H O (80 mL) and CH Cl
80 mL) in a separating funnel and acidified with aqueous 10%
HCl. The organic phase was separated, and the aqueous layer was
1
9 as a yellow solid. Ϫ M.p. 97.5Ϫ98.5 °C. Ϫ H NMR (CDCl
δ ϭ 2.05Ϫ2.13 (m, 2 H, CH CH OH), 3.73 (t, J ϭ 7.8 Hz, 2H,
CH OH), 3.82 (t, J ϭ 6.2 Hz, 2 H, CH -Anthr.), 4.80 (br. s, 1 H,
OH, D O exchange), 7.42Ϫ7.53 (m, 4 H, H , H , H , H -Anthr.),
8.00 (d, J ϭ 8.7 Hz, 2 H, H , H -Anthr.), 8.30 (d, J ϭ 8.7 Hz, 2
3
):
2
2
2
2
2
(
2
2
2
3
6
7
2
4
5
extracted with CH
2
Cl
2
(2 ϫ 50 mL). The combined organic phase
1
8
10
was dried over MgSO
4
and the solvent evaporated to afford 3.00 g
H, H , H -Anthr.), 8.35 (s, 1 H, H -Anthr.). Ϫ C17H16O (236.31):
of an orange thick oil. Purification by column chromatography
SiO , CH Cl ) afforded 2.23 g (72%) of pure 5 as a yellow solid.
Ϫ M.p. 81Ϫ83 °C. Ϫ H NMR (CDCl
H, CH ), 3.87 (t, J ϭ 7.4 Hz, 1 H, CH), 3.96Ϫ4.13 (m, 4 H,
CH CH ), 4.30 (d, J ϭ 7.4 Hz, 2 H, CH CH), 7.41Ϫ7.55 (m, 4 H,
calcd. C 86.39, H 6.84; found C 86.10, H 6.68.
(
2
2
2
9
-(3-Bromopropyl)anthracene (10):
A solution of 9 (0.65 g,
1
3
): δ ϭ 1.05 (t, J ϭ 7.1 Hz,
2
.75 mmol) in toluene (40 mL) was heated at reflux and stirred with
6
3
aqueous 40% HBr (20 mL) for three days. The reaction mixture
was cooled to room temp., transferred into a separating funnel and
the organic phase separated. The aqueous phase was washed twice
with toluene (20 mL). The combined organic phase was dried over
2
3
2
2
3
6
7
4
5
H , H , H , H -Anthr.), 8.00 (d, J ϭ 8.1 Hz, 2 H, H , H -Anthr.),
1
8
10
8
.27 (d, J ϭ 8.8 Hz, 2 H, H , H -Anthr.), 8.38 (s, 1 H, H -Anthr.).
Ϫ C22
22 4
H O
(350.41): calcd. C 75.40, H 6.34; found C 75.25, H
MgSO
Purification by column chromatography (SiO
0.63 g (90%) of a green solid. Ϫ M.p. 87Ϫ88 °C. Ϫ H NMR
.02 mmol) and NaOH (0.96 g, 24.08 mmol) in 96% EtOH (50 mL) (CDCl ): δ ϭ 2.31Ϫ2.42 (m, 2 H, CH CH Br), 3.60 (t, J ϭ 6.4 Hz,
2 H, CH Br), 3.75Ϫ3.84 (m, 2 H, CH -Anthr.), 7.44Ϫ7.57 (m, 4
4
and evaporated to afford 0.9 g of dark thick oily residue.
6.28.
2
, CH Cl ) afforded
2
2
1
9-Anthrylmethylmalonic Acid (6):
A solution of 5 (2.11 g,
6
3
2
2
was stirred at room temp. for 30 min. The precipitated sodium salt
was filtered off, washed with EtOH (20 mL) and dissolved in H
10 mL) . The aqueous phase was acidified with 10% HCl, and the Anthr.), 8.30 (d, J ϭ 8.8 Hz, 2 H, H , H -Anthr.), 8.35 (s, 1 H,
2
2
2
3
6
7
4
5
O
H, H , H , H , H -Anthr.), 8.01 (d, J ϭ 8.2 Hz, 2 H, H , H -
2
1
8
(
1
0
precipitate was filtered off and dried for 3 h (0.1 Torr, 40 °C) to
H -Anthr.). Ϫ C17H15Br: calcd. C 68.23, H 5.06; found C 68.35,
afford 1.60 g (90%) of pure 6 as a yellow solid. Ϫ M.p. 209Ϫ210 H 5.18.
1
°
4
C. Ϫ H NMR ([D
6
]DMSO): δ ϭ 3.66 (t, J ϭ 7.4 Hz, 1 H, CH),
2
3
6
2
.15 (d, J ϭ 7.4 Hz, 2 H, CH ), 7.49Ϫ7.60 (m, 4 H, H , H , H ,
H -Anthr.), 8.10 (d, J ϭ 7.8 Hz, 2 H, H , H -Anthr.), 8.32 (d, J ϭ
.6 Hz, 2 H, H , H -Anthr.), 8.54 (s, 1 H, H -Anthr.), 12.8 (br. s,
H, OH, D O exchange). Ϫ C18 (294.30): calcd. C 73.45, H
.80; found C 73.60, H 4.58.
7
4
5
Acknowledgments
This work was supported by the Ministero per la Ricerca Scientif-
ica e Tecnologica (MURST, Special Program on Supramolecular
Devices) and CNR.
1
8
10
8
2
4
2
14 4
H O
Eur. J. Org. Chem. 2001, 587Ϫ594
593