Page 7 of 9
Journal of Materials Chemistry C
Please do not adjust margins
Journal Name
ARTICLE
starting materials has been converted to the products. Then the 27.2, 23.0, 17.9, 14.5, 14.1, 14.0. HRMS(APCI): calcd for C36H44O4S2,
DOI: 10.1039/C8TC00895G
reaction was stopped by addition of water and extracted with CHCl3 m/z 604.2681; found, m/z 604.2943.
(15 ml x 3). The organic layers were combined and washed with
NaHCO3 solution, 30 ml water (three times) and dried over
magnesium sulfate. After filtration, the volatile CHCl3 was removed
through rotary evaporator. The crude product was chromatographed
4-Dodecyl-2-(2-(thiophen-2-yl)azulen-6-yl)thiophene (TAT-3). To a 1-
necked 50 ml RBF was added diethyl 6-(4-dodecylthiophen-2-yl)-2-
(thiophen-2-yl)azulene-1,3-dicarboxylate (TAT-2, 500 mg, 0.8 mmol),
20 ml ethanol and 14 ml 2M KOH solution. The mixture was refluxed
on silica gel using hexane/ethyl acetate (2/1, v/v) as eluant. This was
overnight. Upon cooling, the 20 ml 1M HCl solution was added to
1
obtained as bright yellow solid (80%). H-NMR (δ, CDCl3): 9.48 (d, 2
acidify the mixture. The precipitated crystals were collected by
filtration, washed with water, and dried in vacuo.
H, J =11.44 Hz), 7.58 (d, 2 H, J = 11.16 Hz), 7.48 (d, 2 H, J= 4.12 Hz),
7.10 (m, 2 H), 4.23 (m, 4 H), 1.09 (t, 6 H, J = 7.08 Hz). 13C NMR: δ
A mixture of above product (438 mg, 0.8 mmol) and freshly prepared
164.9, 155.7, 148.2, 140.3, 136.8, 136.5, 128.2, 126.7, 126.3, 123.5,
100% phosphoric acid, which was obtained by dissolving phosphorus
122.7, 60.6, 13.7. HRMS(APCI): calcd for C21H17F3O7S2, m/z 502.0368;
pentaoxide (1.28 g) in 85% phosphoric acid (3.2 g), was heated at 130
found, m/z 502.0674.
°C for 10 min with occasional stirring with a glass rod. After the
reaction mixture was cooled, the mixture was poured into ice-water
1,3-Bis[2-(3-n-dodecylthienyl)]azulene (TAT-1). To a round bottom
flask added magnesium turning (37.5 mmol) and anhydrous THF (30
and extracted with CHCl3. The organic layer was washed with water,
ml). Under argon protection,
a
solution of 2-bromo-3-
dried over MgSO4, and concentrated via rotary evaporator. The
crude product was chromatographed on silica gel using hexane/
dodecylthiophene in anhydrous THF (10 ml) was added dropwise
with stirring. After finishing the addition, the resulting mixture was
stirred at room temperature for 1 hour and then reflux for 4 hours
until all magnesium turnings were disappeared. The formed Grignard
reagent was then transferred to mixture of 1,3-dibromoazulene (6
mmol) and Ni(dppp)Cl2 (0.22 g) in anhydrous THF that has been
cooed in ice-water bath. After all Grignard reagent was transferred,
the reaction mixture was then warm to room temperature and reflux
overnight. The mixture was cooled down to room temperature and
then dilute HCl solution (200 ml) was added under stirring. The
organic layer was separated and the aqueous layer was extract with
ether for 3 times. Combined the organic layers and washed with
sodium bicarbonate solution, water, and brine successively. It was
dried over magnesium sulfate and purified by chromatography on
silica gel using hexane as eluant. The product was dark green oil
(60%). 1H-NMR (δ, CDCl3): 8.36 (d, 2H, J = 9.64 Hz), 7.92 (s, 1H), 7.61
(t, 1H, J = 9.76 Hz), 7.34 (d, 2H, J = 5.24 Hz), 7.16 (t, 2H, J = 9.84 Hz),
7.09 (d, 2H, J = 5.16 Hz), 2.56 (t, 4H, J = 7.56 Hz), 1.52 (m, 4H), 1.22
(m, 36H), 0.87 (t, 6H, J = 5.32 Hz).
1
CHCl3 (1/2, v/v) as eluent to afford green solid (46%). H-NMR (δ,
CDCl3): 8.16 (d, 2 H, J = 10.68 Hz), 7.57-7.50 (m, 5 H), 7.34 (m, 2 H),
7.12 (m, 1 H), 7.00 (s, 1 H), 2.64 (t, 2 H, J = 7.72 Hz), 1.68-1.26 (m, 20
H), 0.87 (m, 3 H). 13C NMR: δ 145.3, 142.3, 140.3, 134.8, 128.8, 127.5,
126.8, 125.9, 122.8, 122.5, 115.1, 32.3, 32.0, 31.1, 30.9, 30.1, 29.9,
29.7, 27.8, 23.1, 14.5, 14.1, 9.2. HRMS(APCI): calcd for C30H36S2, m/z
460.2258; found, m/z 460.2297.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We acknowledge financial support of this work from the Science
and Engineering Research Council (Grant 1527200019) of
Agency for Science, Technology and Research of Singapore. DFT
calculation was supported by the A*STAR Computational
Resource Centre through the use of its high performance
computing facilities.
Diethyl
6-(4-dodecylthiophen-2-yl)-2-(thiophen-2-yl)azulene-1,3-
dicarboxylate (TAT-2). To a 3-necked 100 ml RBF was added LiCl (84
mg, 1.98 mmol), AsPh3 (0.202 g, 0.66 mmol), Pd(PPh3)4 (76.2 mg,
.
0.066
mmol)
and
diethyl
2-(thiophen-2-yl)-6-
(((trifluoromethyl)sulfonyl)oxy)azulene-1,3-dicarboxylate (7, 0.33g,
0.66 mmol). The RBF was connected to a vacuum pump and then
flashed with Ar. After repeating 3 times, 15 ml degassed 1,4-dioxane
was added under Ar. Tributyl(4-dodecylthiophen-2-yl)stannane (0.36
g, 0.66 mmol) was added via syringe and the mixture then reacted at
80 °C for 8 hours. Upon the check with TLC, the reaction mixture was
first diluted with ethyl acetate and then 8 ml of saturated KF aqueous
solution was added to precipitate the excess tin reagents. The
organic volatile was removed through rotary evaporator. The crude
product was chromatographed on silica gel using hexane/ethyl
acetate (4/1, v/v) as eluent to afford brown solid (62%). 1H-NMR (δ,
CDCl3): 9.46 (d, 2 H, J = 11.08 Hz), 7.81 (d, 2 H, J = 11.12 Hz), 7.43 (m,
1 H), 7.40 (m, 1 H), 7.11-7.05 (m, 3 H), 4.21 (m, 4 H), 2.72 (t, 2 H, J =
7.84 Hz), 1.63 (m, 4 H), 1.33 (m, 16 H), 1.04 - 0.87 (m, 9 H). 13C NMR:
δ 146.9, 146.1, 141.0, 139.0, 138.3, 138.0, 129.5, 128.1, 127.8, 127.5,
126.5, 126.2, 125.0, 119.3, 60.5, 32.1, 31.0, 30.8, 30.1, 29.4, 28.2,
References
1
2
3
4
P. Foggi, F. V. R. Neuwahl, L. Moroni and P. R. Salvi, J. Phys.
Chem. A, 2003, 107, 1689.
S. V. Shevyakov, H. Li, R. Muthyala, A. E. Asato, J. C. Croney, D.
M. Jameson and R. S. H. Liu, J. Phys. Chem. A, 2003, 107, 3295.
F. X. Redl, O. Köthe, K. Röckl, W. Bauer and J. Daub, J.
Macromol. Chem. Phys., 2000, 201, 2091.
R. S. H. Liu and A. E. Asato, Journal of Photochemistry and
Photobiology C: Photochemistry Reviews, 2003, 4, 179-194.
5
6
R. S. H. Liu, J. Chem. Educ., 2002, 79, 183.
M. J. Bearpark, F. Bernardi, S. Clifford, M. Olivucci, M. A. Robb,
B. R. Smith and T. Vreven, J. Am. Chem. Soc., 1996, 118, 169.
F. Wang, Y.-H. Lai, N. M. Kocherginsky and Y. Y. Kosteski, Org.
7
8
9
Lett., 2003,
H. Xin, C. Ge, X. Yang, H. Gao, X. Yang and X. Gao, Chem. Sci.,
2016, , 6701.
H. Xin and X. Gao, ChemPlusChem, 2017, 82, 945-956.
5, 995.
7
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins