Rational Design of Fluorescent Phosgene Sensors

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1 Supporting Information Rational Design of Fluorescent Phosgene Sensors Pradip Kundu, and Kuo Chu Hwang* Department of Chemistry, National Tsing Hua University, Hsinchu 30043, Taiwan R.O.C. Spectral data of 7-hydroxy coumarin (1p), yield: 25% (m.p. 230 C ); 1 H NMR (Acetone-d 6, 500 MHz) δ (ppm): 9.53 (brs, 1H) 7.85 (d, J = 10.0 Hz, 1H), 7.50 (d, J = 8.5 Hz, 1H), 6.83 (dd, J = 2.5, 9.0 Hz, 1H), 6.74 (d, J = 2.5 Hz, 1H), 6.15 (d, J = 9.5 Hz, 1H); 13 C NMR (Acetone-d 6, 125 MHz) δ (ppm): , , , , , , , , ; HRMS `Calcd for [C 9 H 6 O 3 + H + ] , found Both 1 H and 13 C NMR spectra match well with those provided by Sigma-Aldrich company. Spectral data of coumarin (2p) S1, yield: 30% (m.p. 70 C ); 1 H NMR (CDCl 3, 400 MHz) δ (ppm): 7.71 (d, J = 9.6 Hz, 1H), 7.54 (dt, J = 1.2, 7.2 Hz, 1H), 7.49 (dd, J = 1.6, 8.0 Hz, 1H), 7.34 (d, J = 8.0 Hz, 1H), 7.28 (dt, J = 1.2, 7.6 Hz, 1H), 6.43 (d, J = 9.2 Hz, 1H); 13 C NMR (CDCl 3, 100 MHz) δ (ppm): , , , , , , , , ; HRMS Calcd for [C 9 H 6 O 2 + H + ] , found Spectral data of 6H-benzo[c]chromen-6-one (3p) S2 : HRMS `Calcd for [C 13 H 8 O 2 +H + ] , found Spectral data of 3-(naphthalen-1-yl)quinolin-2(1H)-one (4p): 1 H NMR (Acetone-d 6, 400 MHz) δ (ppm): 8.82 (brs, 1H), (m, 6H), (m, 6H); 13 C NMR (Acetone-d 6, 125 MHz) δ (ppm): , , , , , , , , , , , , , , , , , , ; HRMS `Calcd for [C 19 H 13 NO + H + ] , found Spectral data of quinolin-2(1h)-one (5p):2 (m.p C ); 1 H NMR (CDCl 3, 400 MHz) δ (ppm): 8.56 (brs, 1H) 7.87 (d, J = 9.2 Hz, 1H), (m, 2H), 7.40 (d, J = 8.3 Hz, 1H), 7.25 (m, 1H), 6.75 (d, J = 9.0 Hz, 1H); HRMS `Calcd for [C9H7NO + H + ] , found Spectral data of naphtho[2,3-b]azet-2(1h)-one (6p): After completion of the reaction (0.5 mmol starting material was taken; monitored by TLC), it was quenched with water and extracted with CHCl 3 (3 x 20 ml). The organic layer was washed with water (2x 10 ml) and dried (Na 2 SO 4 ). The solvent was removed under reduced pressure and the crude residue obtained was sent for analysis. IR (KBr), ν max : an intense characteristic band at 1778 cm -1 for strained amide bond; S3 1 H NMR (Acetone-d6, 400 MHz) δ (ppm): (brs, 1H) 8.70 (s, 1H), (m, 1H), (m, 2H), (m, 2H); 13 C NMR (Acetone-d6, 125 MHz) δ (ppm): , , , , , , , , , , ; HRMS `Calcd for [C 11 H 7 NO + H + ] , found S1

2 Scheme SI. Experimental setup for in-situ generation of phosgene from triphosgene. The cool trap A contains Aliquat 336 in hexane; the cool trap B contains a phosgene sensing molecule (such as, 2,4-dihydroxy cinnamic acid) and pyridine in chloroform; cool traps C, D & E contain methanol; Injector F contains triphosgene in hexane. F N 2 A B C D E S2

3 Figure S1. (a) Fluorescence emission spectra from a chloroform solution containing 1 μm of o-hydroxycinnamic acid (2) in the absence (black line) and the presence of different phosgene concentrations. The concentrations of phosgene are labeled in the figure. The excitation wavelength is 315 nm. The chemical structure of the coupling product, courmarin (2p), is shown in the figure. (b) The increase in the fluorescence intensity at 378 nm is plotted as a function of the phosgene concentration. The Inset optical images of the blue fluorescence are from the excited 2p at different phosgene concentrations as labeled on top of each image. The inset plot shows linear fitting of the experimental data. S3

4 S4

5 Figure S2. 1 H and 13 C NMR spectra of phosgene reaction products: (a) and (b) are 1 H and 13 C NMR spectra for 7-hdydroxy courmarin (1p), respectively, whereas spectra (c) and (d) are for 1 H and 13 C NMR spectra of courmarin (2p), respectively. S5

6 Figure S3. (a) Fluorescence emission spectra from a chloroform solution containing 1 µm of 2'-hydroxy-2-biphenylcarboxylic acid (3) in the absence (black line) and the presence of different phosgene concentrations. The concentrations of phosgene are labeled in the figure. The excitation wavelength is 330 nm. The chemical structure of the coupling product, 6H-benzo[c]chromen-6-one (3p), is shown in the figure. (b) The increase in the fluorescence intensity at 395 nm is plotted as a function of the phosgene concentration. The Inset optical images of the blue fluorescence are from the excited 3p at different phosgene concentrations as labeled on top of each image. The inset plot shows linear fitting of the experimental data. S6

7 Figure S4. (a) Fluorescence emission spectra from a chloroform solution containing 1 μm of (E)-3-(2-aminophenyl)-2-(naphthalen-1-yl) acrylic acid (4) in the absence (black line) and the presence of different phosgene concentrations. The concentrations of phosgene are labeled in the figure. The excitation wavelength is 380 nm. The chemical structure of the coupling product, 3-(naphthalen-1-yl) quinolin-2(1h))-one (4p), is shown in the figure. (b) The increase in the fluorescence intensity at 428 nm is plotted as a function of the phosgene concentration. The Inset optical images of the blue fluorescence are from the excited 4p at different phosgene concentrations as labeled on top of each image. The inset plot shows linear fitting of the experimental data. S7

8 Figure S5. (a) Fluorescence emission spectra from a chloroform solution containing 1 µm of 2-aminocinnamic acid (5) in the absence (black line) and the presence of different phosgene concentrations. The concentrations of phosgene are labeled in the figure. The excitation wavelength is 380 nm. The chemical structure of the coupling product, quinolin-2(1h)-one (5p), is shown in the figure. (b) The increase in the fluorescence intensity at 452 nm is plotted as a function of the phosgene concentration. The Inset optical images of the blue fluorescence are from the excited 5p at different phosgene concentrations as labeled on top of each image. The inset plot shows linear fitting of the experimental data. S8

9 Supplementary References S1. Tanemura, K., Suzuki, T. J. Heterocyclic Chem. 2002, 39, S2. Kemperman, G.-J., Horst, B. T., Goor, D. V., Roeters, T., Bergwerff, J., Eem, R. V., Basten, J. Eur. J. Org. Chem. 2006, S3. Wentrup C., Bender H., Gross G., J. Org. Chem. 1987, 52, S9