ChemPlusChem
10.1002/cplu.201700207
FULL PAPER
(
2.35 g, 7.25 mmol) were added to the mixture of acetonitrile (80 mL) and
concentrations ranging from 1.0 x10-6 M to 1.0 x 10-2 M in bolaamphiphile
K
2
CO
3
and refluxed overnight. The reaction was cooled down to room
Cl to precipitate the salt. The salt was
A&B. The final concentration of pyrene in each sample was 6.0 x 10-7
M
temperature and decanted into CH
2
2
and the final concentrations of the bolaamphiphiles A&B solutions were
between 2.3 ×10-9 to 2.3×10-3 M and 2.6 ×10-11 to 2.6 ×10-3 M, respectively.
filtered off and the solvent was evaporated from the filtrate to yield a crude
oil. The target compound (2) was purified from the crude oil by the
precipitation using ethyl acetate and then recrystallisation from hot ethyl
acetate. Yield: 2.4 g, 50%. M.p: 177.1-179.5 °C . 1H-NMR : (400 MHz,
Acknowledgements
CDCl
H, OCH
s, 4H, N3-CH
3
) δ 1.95 (s, 6H, C5-CH
), 3.76 (s, 6H, Ar-OCH
), 6.65 (s, 2H, Ar-CH), 7.19 (s, 2H, C6H)
3
), 2.79 (t, J = 12.1 Hz, 4H, CH
2
CO), 3.70 (s,
6
(
3
3
,) 4.00 (t, J = 12.1 Hz, 4H, N1-CH
2
), 5.15
2
Ben Boyd is the recipient of an ARC Future Fellowship. This work
was financially supported by PRESTO, JST.
Synthesis of 3,3'-(((2,5-dimethoxy-1,4-phenylene)bis(methylene))-
bis(5-methyl-2,4-dioxo-3,4-dihydropyrimidine-3,1(2H)-
diyl))dipropionic acid (3)
Keywords: Dynamic covalent bond • photo-reversible• photo-
responsive • self-assembly • thymine
1
0% NaOH (25 mL) was added to 250 mL round bottom flask which was
[
1]
a) J. M. Lehn, Angew. Chem. Int. Ed. 1990, 29, 1304-1319; b) T.
Aida, E. Meijer, S. I. Stupp, Science 2012, 335, 813-817; c) S. S.
Babu, V. K. Praveen, A. Ajayaghosh, Chem. Rev. 2014, 114, 1973-
already charged with 2 (1.5 g, 3.13 mmol) while stirring. A 100 mL of water
was added to the mixture and allowed to reflux for 4 hours. After 4 hours,
the reaction mixture was neutralised by adding HCl. The volume was
reduced until solids started to appear in the solution. The reaction mixture
was placed into an ice bath for 2 hours to obtain more solid material. After
the 2 hours, the solid was collected by filtration and washed twice with cold
2
129.
[2]
a) S. R. Bull, M. O. Guler, R. E. Bras, T. J. Meade, S. I. Stupp, Nano
Lett. 2005, 5, 1-4; b) A. Al-Shereiqi, B. Boyd, K. Saito, Chem.
Commun. 2015, 51, 5460--5462; c) S. Toledano, R. J. Williams, V.
Jayawarna, R. V. Ulijn, J. Am. Chem. Soc. 2006, 128, 1070-1071.
a) S. Mura, J. Nicolas, P. Couvreur, Nat. Mater. 2013, 12, 991-1003;
b) B. Rybtchinski, ACS Nano 2011, 5, 6791-6818; c) Y. Lu, J. Liu,
Acc. Chem. Res. 2007, 40, 315-323.
distilled
phenylene)bis(methylene))bis(5-methyl-2,4-dioxo-3,4-dihydropyrimidine-
,1(2H)-diyl))dipropionic acid (1,4-dimethoxybenzene-bis-thymine
dicarboxylic acid) (3). Yield: 1.2 g, 40%. 1Η-ΝΜR: (400 MHz, DMSO) δ
.83 (s, 6H, C5-CH ), 2.65 (t, J = 13.3 Hz, 4H, CH CO), 3.63 (s, 6H, Ar-
OCH ,), 3.93 (t, J = 13.3 Hz, 4H, N1-CH ), 4.94 (s, 4H, N3-CH ), 6.35 (s,
H, Ar CH), 7.66 (s, 2H, C6H), 10.99 (br, 2H, -COOH)
water
to
obtain
3,3'-(((2,5-dimethoxy-1,4-
3
[
3]
4]
1
3
2
3
2
2
2
[
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Synthesis of di(2,5,8,11,14,17-hexaoxanonadecan-19-yl) 3,3'-(((2,5-
dimethoxy-1,4-phenylene)bis(methylene))bis(5-methyl-2,4-dioxo-3,4-
dihydropyrimidine-3,1(2H)-diyl))dipropionate (bolaamphiphile B)
Compound 3 (0.887 g, 1.59 mmol) was dissolved in dimethylformamide
(
DMF) (20 mL) in a 250- round-bottom flask. While stirring, 4-
dimethylaminopyridine (DMAP) (0.17 g, 1.4 mmol) was added to the
mixture followed by the addition of hexaethyelene glycol monomethyl ether
(
HEG) (0.9 mL, 3.28 mmol). The flask was placed in ice bath and
dicyclohexylcarbodiimide (DCC) (0.661 g, 3.21 mmol) was then added to
the mixture while stirring. After 2 hours of stirring in the ice bath, the
reaction was allowed to commence at room temperature for 48 hours. After
4
8 hours, precipitated salt was filtered off and the filtrate was evaporated
by using rotary evaporator to remove DMF. The residue was taken up in
CHCl and filtrated again to remove further precipitated salt. The CHCl
solution was washed twice with water and then the CHCl was removed
and the residue dried in vacuo. A column chromatography was used to
separate the mixture components in the organic layer using (CHCl
methanol: acetonitrile = 5: 1: 3) and obtain a pure form of the product.
3
3
2
012, 134, 7227-7230.
3
[5]
a) T. Maeda, H. Otsuka, A. Takahara, Prog. Polym. Sci. 2009, 34,
5
81-604; b) R. J. Wojtecki, M. A. Meador, S. J. Rowan, Nat. Mater.
010, 10, 14-27; c) J.-M. Lehn, Prog. Polym. Sci. 2005, 30, 814-831.
3
:
2
Yield: 0.5 g, 45%. 1H-NMR: (400 MHz, DMSO) δ 1.92 (s, 6H, C5-CH
),
3
[6]
[7]
a) X. Yan, F. Wang, B. Zheng, F. Huang, Chem. Soc. Rev. 2012, 41,
2
.79 (t, J = 11.8 Hz, 4H, CH
CH COOCH CH ), 3.63 (m, 40H, OCH
.98 (t, J = 11.8 Hz, 4H, N1-CH ), 4.22 (m, 4H, N1-CH
s, 4H, N3-CH ), 6.61(s, 2H, Ar-CH), 7.21 (s, 2H, C6H). C-NMR (100 MHz,
): 13.0 (C5-CH ), 33.2 (N1-CH CH ), 39.4 (N3-CH ), 45.8 (N1-CH ),
), 59.0 (-OCH ), 64.0 (COOCH ), 68.8 (COOCH CH O),
CH OCH ), 70.5 (OCH CH O), 71.9 (CH -OCH ), 109.4
2
CO), 3.37 (s, 6H, O-CH
CH O), 3.73 (s, 6H, Ar-OCH
CH COOCH
3
), 3.54 (m, 4H,
6
042-6065; b) L. E. Buerkle, S. J. Rowan, Chem. Soc. Rev. 2012,
1, 6089-6102; c) H. Yang, B. Yuan, X. Zhang, O. A. Scherman,
2
2
2
2
2
3
),
4
3
(
2
2
2
2
), 5.12
Acc. Chem. Res. 2014, 47, 2106-2115; d) S. Yagai, A. Kitamura,
Chem. Soc. Rev. 2008, 37, 1520-1529.
1
3
2
CDCl
5
7
3
3
2
2
2
2
6.6 (Ar-OCH
3
3
2
2
2
a) G. Wang, C. Wang, Z. Wang, X. Zhang, Langmuir 2011, 27,
0.4 (COOCH
2
2
2
2
2
2
3
1
2375-12380; b) D. Janeliunas, P. van Rijn, J. Boekhoven, C. B.
Minkenberg, J. H. van Esch, R. Eelkema, Angew. Chem., Int. Ed.
013, 52, 1998-2001; c) C. B. Minkenberg, L. Florusse, R. Eelkema,
G. J. Koper, J. H. van Esch, J. Am. Chem. Soc. 2009, 131, 11274-
1275.
(
1
C5), 112.0 (N3-Αr), 124.8 (N3-Αr), 139.6 (C4), 151.3 (N3-Ar), 151.4 (C2),
63.8 (C6), 171.3 (COOR)
2
Critical aggregation concentration measurements
1
[
8]
9]
L. He, Y. Jiang, C. Tu, G. Li, B. Zhu, C. Jin, Q. Zhu, D. Yan, X. Zhu,
Chem. Commun. 2010, 46, 7569-7571.
Fluorescence spectroscopy was used to determine the critical aggregation
-2
concentration by using pyrene as a probe. Pyrene solution (6.0 x 10 ) was
made up by using acetone as the solvent which was then diluted by water.
The acetone in the solution mixture was evaporated to form an acetone-
free pyrene solution with a final concentration of 12.0 x 10-7 M. The pyrene
solution (2 ml) was added to each monomer solution (2 ml) whose
[
Y. Yi, H. Xu, L. Wang, W. Cao, X. Zhang, Chem.Eur. J. 2013, 19,
9
506-9510.
8
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