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Angewandte
Communications
Chemie
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Experimental Section
Synthesis of 3: A microfluidic system consisting of three T-shaped
micromixers (M1, M2, and M3), three microtube reactors (R1, R2,
and R3) and four tube pre-temperature retaining units (P1, P2, P3,
and P4; inner diameter ø = 1000 mm, length L = 50 cm) were used. A
solution of 1,4-dibromobenzene (0.10m in THF, flow rate:
6.0 mLminÀ1) and a solution of n-BuLi (0.42m in hexane, flow rate:
1.5 mLminÀ1) were introduced to M1 (ø = 250 mm) by syringe pumps.
The resulting solution was passed through R1 (ø = 250 mm, L =
3.5 cm) and was mixed with a solution of 1,4-cyclohexanedione
(0.22m in THF, flow rate: 3.0 mLminÀ1) in M2 (ø = 500 mm). The
resulting solution was passed through R2 (ø = 1000 mm, L = 50 cm)
and was mixed with a solution of bromomethyl methyl ether (2.4m in
DMF/THF, flow rate: 2.0 mLminÀ1). The resulting solution was
passed through R3 (ø = 1000 mm, L = 1 m). After a steady state was
reached, the product solution was collected and further stirred for 4 h
at 258C. The reaction mixture was quenched using a saturated NH4Cl
aqueous solution. The crude product was extracted with CH2Cl2 (3
15 mL) and was washed with brine (15 mL). The organic phase was
dried over Na2SO4 and concentrated under reduced pressure. The
crude product was purified by column chromatography (eluent: 30%
to 100% ethyl acetate in hexane) to give desired product 3 in 80%
yield.
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Synthesis of 6: A solution of 1,4-dibromobenzene (0.08m in THF,
flow rate: 3.0 mLminÀ1) and a solution of t-BuLi (0.72m in hexane,
flow rate: 1.5 mLminÀ1) were introduced to M1 (ø = 250 mm) by
syringe pumps. The resulting solution was passed through R1 (ø =
1000 mm, L = 1 m) and was mixed with a solution of functionalized 3a
(0.2m in THF/HMPA, flow rate: 3.0 mLminÀ1; HMPA = hexame-
thylphosphoramide) in M2 (ø = 500 mm). The resulting solution was
passed through R2 (ø = 1000 mm, L = 50 cm) and was mixed with
a solution of bromomethyl methyl ether (4.8m in DMF/THF, flow
rate: 2.0 mLminÀ1). The resulting solution was passed through R3
(ø = 1000 mm, L = 1 m). After a steady state was reached, the product
solution was collected and further stirred for 6 h at 258C. The crude
product was extracted with ethyl acetate (3 15 mL), dried over
Na2SO4, and concentrated under reduced pressure. The crude product
was purified by column chromatography (eluent: 20% to 50% ethyl
acetate in hexane) to give desired product 6 in 68% yield.
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Acknowledgements
This work was supported by a National Research Foundation
of Korea (NRF) grant funded by the Korean government
(MSIP; No. 2008–0061983)
[17] A. Nagaki, J. Yoshida, Lithium Compounds in Organic Syn-
thesis—From Fundamentals to Applications, Wiley-VCH, Wein-
heim, 2014, Chap. 17.
Keywords: cycloparaphenylene · flow chemistry · lithiation ·
microfluidics · microreactors
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How to cite: Angew. Chem. Int. Ed. 2016, 55, 1422–1426
Angew. Chem. 2016, 128, 1444–1448
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