Supporting Information 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions Iwona Bownik, Peter Šebej,, Jaromír Literák*,, Dominik Heger,, Zdeněk Šimek, Richard S. Givens, Petr Klán*,, Department of Chemistry, Masaryk University, Kamenice 5, 625 00, Brno, Czech Republic. RECETOX, Faculty of Science, Masaryk University, Kamenice 5, 625 00, Brno, Czech Republic. Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Malott Hall, Lawrence, Kansas 66045, United States * E-mail: literak@chemi.muni.cz; Phone: +420-54949-5580; Fax: +420-54949-2443; E-mail: klan@sci.muni.cz; Phone: +420-54949-4856; Fax: +420-54949-2443 Contents Titration Data Preparative Irradiation Data NMR Spectra UV Spectrum of 1f Output spectrum of a medium-pressure Hg lamp S2 S3 S4 S5 S6 S26 S27 S28 S1
Figure S1. The ph Dependence of the Absorption Spectra of 1a in Aqueous Buffers (see the main text for details) Table S1. The molar absorption coefficients of the A and B forms in 1a c a compound ε (A form) ε (B form) 1a 3400 12130 1b 4820 18020 1c 1760 12540 a Molar absorption coefficients (mol dm 3 cm 1 ) were obtained using a UV titration method from the deconvoluted spectra (see Figure 1 and the Experimental Part in the main text). S2
Figure S2. Titration of 1a using NMR: the ph dependence of 1 H NMR chemical shifts measured for the OH group. The buffered (phosphate, c = 62.4 mmol dm 3 ) aqueous solution of 1a (~7 10 3 mol dm 3 ) was titrated in the ph range of 3.07 12.31 with the solution of NaOD in D 2 O. Figure S3. Titration of 1a using NMR: the ph dependence of 1 H NMR chemical shifts measured for the NH group. The buffered (phosphate, c = 62.4 mmol dm 3 ) aqueous solution of 1a (~7 10 3 mol dm 3 ) was titrated in the ph range of 3.07 12.31 with the solution of NaOD in D 2 O. S3
Figure S4. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The formate buffer composition: HCOONa (c = 8.6 10 2 mol dm 3 ) was titrated with a DCl solution in D 2 O. The yields were determined by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). Figure S5. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The acetate buffer composition: CH 3 COONa (c = 4.3 10 2 mol dm 3 ) titrated with a DCl solution in D 2 O. The yields were determined by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). S4
Figure S6. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The phosphate buffer composition: Na 3 PO 4 (c = 5.6 10 2 mol dm 3 ) titrated with a DCl solution in D 2 O. The yields were obtained by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). Figure S7. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The acetate buffer composition: CH 3 COONa (c = 4.3 10 2 mol dm 3 ) titrated with a DCl solution in D 2 O. The yields were obtained by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). S5
Figure S8. 1 H NMR (CD 3 OD, 500 MHz): 2-(Diethylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1a) 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 f1 (ppm) 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 S6
Figure S9. 13 C { 1 H} NMR (CD 3 OD, 126 MHz): 2-(Diethylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1a) 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 S7
Figure S10. 1 H NMR (CD3OD, 500 MHz): 1-(4-Hydroxyphenyl)-2-(piperidin-1-yl)ethanone hydrobromide (1b). 2.01 1.81 2.07 2.06 2.02 5.85 8.0036 8.0211 6.9972 7.0147 4.9078 3.6710 3.2310 1.9376 2.0370 S8
Figure S11. 13 C { 1 H} NMR (CD 3 OD, 126 MHz): 1-(4-Hydroxyphenyl)-2-(piperidin-1-yl)ethanone hydrobromide (1b). 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 S9
Figure S12. 1 H NMR (CD 3 OD, 500 MHz): 2-Amino-1-(4-hydroxyphenyl)ethanone hydrochloride (1c). 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 f1 (ppm) 4.0 3.5 3.0 2.5 2.0 1.5 1.0 S10
Figure S13. 13 C { 1 H} NMR (CD 3 OD, 126 MHz): 2-Amino-1-(4-hydroxyphenyl)ethanone hydrochloride (1c). 191.37 165.21 132.10 126.94 116.89 45.78 S11
Figure S14. 1 H NMR (CD 3 OD, 500 MHz): Methyl ester of N-[2-(4-hydroxyphenyl)-2-oxoethyl]glycine hydrochloride (1d). 2.00 1.61 2.14 2.22 2.73 8.06 8.04 7.09 7.07 4.89 4.26 4.00 S12
Figure S15. 13 C { 1 H} NMR (CD 3 OD, 126 MHz): Methyl ester of N-[2-(4-hydroxyphenyl)-2-oxoethyl]glycine hydrochloride (1d). 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 S13
Figure S16. 1 H NMR (DMSO-d 6, 500 MHz): Methyl ester of N-[2-(4-hydroxyphenacyl)-2-oxoethyl]phenylalanine hydrochloride (1e). S14
Figure S17. 13 C { 1 H} NMR (DMSO-d 6, 126 MHz): Methyl ester of N-[2-(4-hydroxyphenacyl)-2-oxoethyl]phenylalanine hydrochloride (1e). S15
Figure S18. 1 H NMR (CDCl 3, 500 MHz): 1-(4-(benzyloxy)phenyl)-2-bromoethanone (4) S16
Figure S19. 13 C { 1 H} NMR (DMSO-d 6, 126 MHz): 1-(4-(benzyloxy)phenyl)-2-bromoethanone (4) S17
Figure S20. 1 H NMR (DMSO-d 6, 500 MHz): 2-(4-benzyloxyphenyl)-N,N,N-triethyl-2-oxoethanaminium bromide (5) S18
Figure S21. 13 C { 1 H} NMR (DMSO-d 6, 126 MHz): 2-(4-benzyloxyphenyl)-N,N,N-triethyl-2-oxoethanaminium bromide (5) S19
9.22 Figure S22. 1 H NMR (DMSO-d6, 500 MHz): triethyl[2-(4-hydroxyphenyl)-2-oxoethyl]amonium bromide (1f) 0.85 2.00 2.02 1.94 6.04 10.71 7.93 7.95 6.91 6.93 5.02 3.57 3.59 3.60 3.62 2.50 1.20 1.22 1.23 S20
Figure S23. 13 C { 1 H} NMR (DMSO-d 6, 126 MHz): triethyl[2-(4-hydroxyphenyl)-2-oxoethyl]amonium bromide (1f) 189.47 163.55 131.01 125.64 115.49 58.22 53.94 39.52 7.52 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0-10 S21
Figure S24. 1 H 15 N HMBC NMR (DMSO-d 6, 500 MHz): triethyl[2-(4-hydroxyphenyl)-2-oxoethyl]amonium bromide (1f) f1 (ppm) CH 3 CN S22
Figure S25. 1 H NMR (DMSO-d 6 /dry HCl, 500 MHz): 2-(Methylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1g) 12.5 12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 f1 (ppm) 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0-0.5 S23
Figure S26. 13 C { 1 H} NMR (DMSO-d 6 /dry HCl, 126 MHz): 2-(Methylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1g) S24
Figure S27. 1 H NMR (DMSO-d 6 /dry HCl, 50 0 MHz): 2-(Butylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1h) 12.5 12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 f1 (ppm) 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0-0.5 S25
Figure S28. 13 C { 1 H} NMR (DMSO-d 6 /dry HCl, 126 MHz): 2-(Butylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1h) S26
Figure S29. UV-vis absorption in a) acetate buffer (ph = 4.02, c = 5.0 10 2 mol dm 3 ), c (1f) = 4.17 10 5 mol dm 3 ) (black solid line) and in b) phosphate buffer (ph = 8.37, c = 5.0 10 2 mol dm 3 ), c (1f) = 3.67 10 5 mol dm 3 ) (red solid line): triethyl[2-(4-hydroxyphenyl)-2- oxoethyl]amonium bromide (1f) 5 4 3 5 4 / 10 4 mol 1 dm 3 cm 1 ~ / 10 4 cm 1 3 2 1 / nm 0 200 250 300 350 400 450 S27
Figure S30. Output spectrum of 40 W medium-pressure Hg discharge lamp equipped with a 313-nm-band-pass filter: λ em = 313.5 ± 1.5 nm (bandwidth at half-height). 5 4 3 2 1.0 0.8 I / a.u. ~ / 10 4 cm 1 0.6 0.4 0.2 0.0 / nm 200 250 300 350 400 450 500 S28