Synthesis and structures of 1,10-phenanthroline-based extended triptycene derivatives

Article abstract of DOI:10.1055/s-0029-1219957

A series of novel 1,10-phenanthroline-based extended triptycene derivatives were conveniently synthesized in good yields, and their structures were determined by ¹H NMR, ¹²C NMR, MALDI-TOF MS spectra, and elemental analysis. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0029-1219957

LETTER
1679
Synthesis and Structures of 1,10-Phenanthroline-Based Extended Triptycene
Derivatives
S
Y
ynthesis of Exten
i
ded Triptycen
J
e
Derivat
i
ives ang,a,b Chuan-Feng Chen*a
a
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function,
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. of China
Fax +86(10)62554449; E-mail: cchen@iccas.ac.cn
b
Graduate School, Chinese Academy of Sciences, Beijing 100049, P. R. of China
Received 7 April 2010
O
N
O
N
Abstract: A series of novel 1,10-phenanthroline-based extended
triptycene derivatives were conveniently synthesized in good
1
13
H2SO4, KBr, HNO3
yields, and their structures were determined by H NMR, C NMR,
MALDI-TOF MS spectra, and elemental analysis.
N
N
Key words: triptycene, 1,10-phenanthroline, synthesis
R
R
R
R
6
6
6
6
a R = H
3a R = H, 94%
b R = Me
c R = n-Bu
d R = t-Bu
3b R = Me, 79%
3c R = n-Bu, 82%
3d R = t-Bu, 65%
1
Triptycene and its derivatives are a class of interesting
compounds with unique three-dimensional rigid frame- Scheme 1 Synthesis of 1,10-phenanthroline-5,6-quinones 3
works. They have been found wide potential applications
2
3
in synthetic molecular machines, materials science, and
that no product could be obtained when the reaction tem-
4
supramolecular chemistry. Triptycene skeleton could be
perature of 6d was above 60 °C.
extended by increasing the size of its arene blades, which
5,6
With the phenanthroline derivatives 3a–d in hand, we
then performed the condensation of 3a–d and 2,3-diami-
notriptycene 414 in refluxed methanol. The reaction took
place smoothly to give the extended triptycene derivatives
provided chances for the synthesis of higher iptycenes.
7
Recently, King reported a triphenylene-based triptycene,
which was extended both parallel and perpendicular to its
highest symmetry axis to result in large internal molecular
1
5
8
2a–d in good yields (Scheme 2). It was found that com-
free volumes (IMFV). Although the triptycenes with
pounds 2a–d have good solubility in chloroform and
large IMFV might play an important role in their practical
applications, relevant examples are still rare.
1
dichloromethane. In the H NMR spectra of 2a–d, one
singlet signal for the bridgehead proton and another sin-
In recent years, we became interested in developing new
supramolecular systems based on the triptycene-derived
glet signal for the aromatic proton H were observed.
a
13
Meanwhile, their C NMR spectra all showed one signal
9
synthetic receptors. Consequently, some of new trip-
for the bridgehead carbon and 12 signals for the aromatic
carbons. These observations were consistent with their C2
tycene derivatives with specific structures and properties
are needed. As a part of our continuing work, we herein
report the facile synthesis of a series of extended trip-
tycene derivatives by the condensation of 1,10-phenan-
throline-5,6-quinones with 2,3-diaminotriptycene or
NH2
H2N
O
N
O
2
,3,6,7,14,15-hexaaminotriptycene. These extended trip-
+
1
0
tycene derivatives containing phenanthroline moiety
N
show large IMFV, and can subsequently find wide poten-
tial applications in the development of new supramolecu-
lar systems and construction of functional materials.
According to a modified literature procedure,11 we first
prepared the 1,10-phenanthroline-5,6-quinone derivatives
R
R
3
3
a R = H
4
b R = Me
3c R = n-Bu
d R = t-Bu
3
3
a–c in good yields by the oxidation of phenanthroline de-
1
2
rivatives 6a–c (Scheme 1). Similarly, we also obtained
compound 3d in 65% yield by the oxidation of 6d at room
temperature. It was found that the temperature was im-
portant to the oxidation reaction. As a result, it was found
1
3
Ha
MeOH
reflux
N
N
2
2
2
2
a R = H, 67%
N
N
R
b R = Me, 70%
c R = n-Bu, 61%
d R = t-Bu, 68%
SYNLETT 2010, No. 11, pp 1679–1681
Advanced online publication: 04.06.2010
DOI: 10.1055/s-0029-1219957; Art ID: W05010ST
x
x
.x
x
.2
0
1
0
R
Scheme 2 Synthesis of extended triptycene derivatives 2a–d
©
Georg Thieme Verlag Stuttgart · New York

1
680
Y. Jiang, C.-F. Chen
LETTER
1
symmetry. Moreover, the structures of 2a–d were also The partial H NMR spectra of both 1c and 1d were shown
confirmed by their MALDI-TOF MS spectra and elemen- in Figure 1. One singlet (H ) for the bridgehead proton
d
tal analysis.
and three signals (H –H ) for the aromatic protons were
b d
1
3
found. Moreover, the C NMR spectra of both 1c and 1d
only showed one signal for the bridgehead carbon and
nine signals for the aromatic carbons. These results sug-
gested they all have high D symmetry. Compared with
When compound 3a or 3b was reacted with 2,3,6,7,14,
5-hexaaminotriptycene 5,14 we obtained yellow solids
1
with low solubilities. MALDI-TOF MS spectra suggested
the structures of targeted molecules 1a and 1b, but it was
difficult to further confirm them by H NMR and
NMR spectra because of their poor solubilities. However,
when 3c was reacted with 5, we found that the extended
triptycene derivative 1c could be synthesized in 28% yield
3
v
1
13
1c, the signals of protons H –H of 1d shifted obviously
b d
C
upfield while H shifted downfield, which was probably
a
due to the stronger electron-donating ability of tert-butyl
of 1d. Moreover, we also calculated the structures of 1c
and 1d by AM1 method, and the IMFV of 1c and 1d were
1
6
(
Scheme 3). Similarly, 1d was obtained in 32% yield
3
found to be about 1150 Å , which is significantly larger
from the reaction of 3d with 5. Compounds 3c and 3d
were all purified by silica gel column chromatography,
and confirmed by H NMR, C NMR, MALDI-TOF MS In summary, we have shown a facile approach to synthe-
spectra, and elemental analysis. Moreover, it was found size a series of 1,10-phenanthroline-based extended trip-
that both of 1c and 1d have good solubilities in common tycene derivatives via the condensation of 2,3-diamino-
solvents including chloroform, THF, DMF, and dichlo- triptycene or 2,3,6,7,14,15-hexaaminotriptycene with
than that reported by King.7
1
13
romethane.
1,10-phenanthroline-5,6-quinone derivatives. The useful
,10-phenanthroline blocks were induced to triptycene
skeleton to form new rigid scaffold geometry and generate
large IMFV, which might be found potential applications
in molecular assemblies and material chemistry.
1
NH2
H2N
O
N
O
N
+
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.
H2N
H2N
NH2
NH2
R
R
5
3c R = n-Bu
3d R = t-Bu
Acknowledgment
We thank the National Natural Science Foundation of China
R
(
20625206, 20772126), the National Basic Research Program
R
N
N
a
(2009ZX09501-018) and the Chinese Academy of Sciences for fi-
nancial support.
References and Notes
N
N
MeOH
reflux
(1) Bartlett, P. D.; Ryan, M. J.; Cohen, S. G. J. Am. Chem. Soc.
1942, 64, 2649.
c
(
2) (a) Iwamura, H.; Mislow, K. Acc. Chem. Res. 1988, 21, 175.
b) Kelly, T. R.; Bowyer, M. C.; Bhaskar, K. V.;
(
Bebbington, D.; Garcia, A.; Lang, F.; Kim, M. H.; Jette,
M. P. J. Am. Chem. Soc. 1994, 116, 3657. (c) Kelly, T. R.;
Silva, R. A.; Silva, H. D.; Jasmin, S.; Zhao, Y. J. Am. Chem.
Soc. 2000, 122, 6935. (d) Godinez, C. E.; Zepeda, G.;
Garcia-Garibay, M. A. J. Am. Chem. Soc. 2002, 124, 4701.
3) (a) Long, T. M.; Swager, T. M. J. Am. Chem. Soc. 2002, 124,
R
N
N
d
R
N
N
N
N
N
N
1
c R = n-Bu, 28%
1d R = t-Bu, 32%
(
R
R
3826. (b) Chong, J. H.; Ardakani, S. J.; Smith, K. J.;
Scheme 3 Synthesis of extended triptycene derivatives 1c and 1d
ManLachlan, M. J. Eur. Chem. J. 2009, 15, 11824.
4) Marc Veen, E.; Postma, P. M.; Jonkman, H. T.; Spek, A. L.;
Feringa, B. L. Chem. Commun. 1999, 1709.
5) Hart, H.; Bashir-Hashemi, A.; Luo, J.; Meador, M. A.
Tetrahedron 1986, 42, 1641.
6) Chong, J. H.; MacLachlan, M. J. J. Org. Chem. 2007, 72,
(
(
(
(
8683.
7) Hilton, C. L.; Jamison, C. R.; Zane, H. K.; King, B. T.
J. Org. Chem. 2009, 74, 405.
(
(
8) Long, T. M.; Swager, T. M. Adv. Mater. 2001, 13, 601.
9) (a) Zhu, X.-Z.; Chen, C.-F. J. Am. Chem. Soc. 2005, 127,
1
(
3158. (b) Zong, Q.-S.; Chen, C.-F. Org. Lett. 2006, 8, 211.
c) Han, T.; Chen, C.-F. Org. Lett. 2006, 8, 1069. (d) Cao,
J.; Jiang, Y.; Zhao, J.-M.; Chen, C.-F. Chem. Commun.
009, 1987. (e) Cao, J.; Lu, H.-Y.; You, X.-J.; Zheng, Q.-Y.;
1
Figure 1 Partial H NMR spectra (300Hz, CDCl ) of (1) 1c and (2)
1
3
d; resonance protons are labeled in Scheme 3
2
Synlett 2010, No. 11, 1679–1681 © Thieme Stuttgart · New York

LETTER
Synthesis of Extended Triptycene Derivatives
1681
Chen, C.-F. Org. Lett. 2009, 11, 4446. (f) Jiang, Y.; Cao, J.;
Zhao, J.-M.; Xiang, J.-F.; Chen, C.-F. J. Org. Chem. 2010,
5, 1767.
10) (a) Roelfs, G.; Feringa, B. L. Angew. Chem. Int. Ed. 2005,
4, 3230. (b) Frey, J.; Tock, C.; Collin, J.-P.; Heitz, V.;
Sauvage, J.-P. J. Am. Chem. Soc. 2008, 130, 4592.
11) Paw, W.; Eisenberg, R. Inorg. Chem. 1997, 36, 2287.
12) (a) Ishi-i, T.; Yaguma, K.; Kuwahara, R.; Taguri, Y.;
Mataka, S. Org. Lett. 2006, 8, 585. (b) Dietrich-Buchecker,
C. O.; Marnot, P. A.; Sauvage, J.-P. Tetrahedron Lett. 1982,
(50 mL) was added 3a (273 mg, 1.3 mmol). The solution was
stirred under N overnight to give a yellow solution. The
2
7
solvent was removed by rotary evaporation, and the red-
orange residue was purified by silica gel column chromatog-
raphy (eluant: MeOH–CH Cl = 1:100) to give the product
(
4
2
2
1
2a in 67% yield as yellow solid; mp >300 °C. H NMR (300
(
(
MHz, CDCl ): d = 9.45 (dd, J = 1.8, 6.3 Hz, 2 H), 9.17 (dd,
3
J = 1.8, 2.7 Hz, 2 H), 8.19 (s, 2 H), 7.63–7.59 (m, 2 H), 7.55–
1
3
7.51 (m, 4 H), 7.15–7.11 (m, 4 H), 5.74 (s, 2 H). C NMR
(75 MHz, CDCl ): d = 152.0, 147.7, 147.0, 143.6, 141.6,
3
50, 5291.
140.0, 133.2, 127.3, 126.2, 124.2, 123.8, 122.8, 53.8. MS
+
+
(
13) Preparation and Spectroscopic Data of 3d
(MALDI-TOF): m/z = 459.2 [M + H] , 481.1 [M + Na] ,
+
An ice-cold mixture of concentrated H SO (10 mL) and
497.1 [M + K] . Anal. Calcd for C H N : C, 83.82; H, 3.96;
2
4
32 18
4
HNO (5 mL) was added to 6d (438 mg, 1.5 mmol) and of
N, 12.22. Found: C, 83.71; H, 4.13; N, 12.14.
(16) Experimental Procedure and Characterizations for
Representative Compound 1c
3
KBr (1 g, 8.4 mmol). The mixture was reacted at r.t. for 8 h.
The yellow solution was poured to over 500 mL of ice,
neutralized carefully with NaOH until neutral to slightly
To a solution of compound 5 (344 mg, 1 mmol) in MeOH
(50 mL) was added 3c (1.38 g, 4.3 mmol). The solution was
acidic pH, and extracted with CHCl followed by drying
3
with Na SO and removal of solvent. The crude product was
stirred under N overnight to give a yellow solution. The
2
4
2
purified by silica gel column chromatography (eluant: PE–
solvent was removed by rotary evaporation, and the red-
orange residue was purified by silica gel column chromatog-
raphy (eluant: MeOH–CH Cl = 1:50) to give the product 1c
CH Cl = 2:3) to afford 3d in 65% yield as white solid; mp
2
2
1
1
44–146 °C. H NMR (300 MHz, CDCl ): d = 8.37 (d,
J = 8.3 Hz, 2 H), 7.58 (d, J = 8.3 Hz, 2 H), 1.52 (s, 18 H).
C NMR (75 MHz, CDCl ): d = 179.3, 177.1, 152.3, 137.1,
25.8, 121.0, 39.1, 29.8. MS (EI): m/z = 322 [M ]. Anal.
3
2
2
1
in 28% yield as yellow solid; mp >300 °C. H NMR (300
13
MHz, CDCl ): d = 9.55 (d, J = 8.3 Hz, 6 H), 8.54 (s, 6 H),
3
3
+
1
7.69 (d, J = 8.3 Hz, 6 H), 6.36 (s, 2 H), 3.35–3.29 (m, 12 H),
1.90–1.89 (m, 12 H), 1.57–1.50 (m, 12 H), 1.02 (t, J = 7.3
Calcd for C H N O : C, 74.51; H, 6.88; N, 8.69. Found: C,
2
0
22
2
2
1
3
7
4.34; H, 6.69; N, 8.57.
14) Chong, J. H.; MacLachlan, M. J. Inorg. Chem. 2006, 45,
442.
Hz, 18 H). C NMR (75 MHz, CDCl ): d = 165.9, 147.5,
3
(
(
143.5, 141.4, 140.8, 133.4, 124.9, 124.2, 123.0, 53.3, 39.0,
31.8, 22.9 14.1. MS (MALDI-TOF): m/z = 1203.6 [M + H] .
+
1
15) Experimental Procedure and Characterizations for
Representative Compound 2a
Anal. Calcd for C H N ·H O: C, 78.23; H, 6.40; N, 14.04.
Found: C, 78.34; H, 6.23; N, 13.91.
7
8
74 12
2
To a solution of compound 4 (284 mg, 1 mmol) in MeOH
Synlett 2010, No. 11, 1679–1681 © Thieme Stuttgart · New York