Arenium Acid-Catalyzed Deuteration of Aromatic Hydrocarbons

Transcription

1 Supporting Information for Arenium Acid-Catalyzed euteration of Aromatic Hydrocarbons Simon uttwyler 1, Anna Butterfield 2, and Jay S. Siegel 2 * 1 epartment of Chemistry, Yale University, 350 Edwards Street, New Haven, Connecticut 06520, United States. 2 Organic Chemistry Institute, University of Zurich, Winterthurerstrasse 190, 8057 Zurich, Switzerland. *To whom correspondence should be addressed. jss@oci.uzh.ch GC-MS ata... S2 7 1 H and 13 C NMR spectra... S8 19 S1

2 GC-MS ata S2

3 S3

4 S4

5 S5

6 S6

7 S7

8 1H NMR, 19.4 mg in 0.9 ml C2Cl2, CHCl2 = 5.32 ppm ppm Current ata Parameters NAME sld_uzh_0032a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T SOLVENT C2Cl2 NS 16 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 Processing parameters SF MHz WW EM LB 0.10 Hz PC ppm S8 CHCl 2 H 2 O in C 2 Cl 2 1-d 14

9 ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP usec PL db PL db PL db SFO MHz F2 Processing parameters SF MHz WW EM LB 2.00 Hz PC C{1H} NMR, 19.4 mg in 0.9 ml C2Cl2, C2Cl2 = 54.0 ppm = resonances from partially deuterated product Current ata Parameters NAME sld_uzh_0032a EXPNO 3 PROBH 5 mm PABBO BB PULPROG zgpg30 T SOLVENT C2Cl2 NS 951 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec d sec ELTA sec T ppm J = 24.3 J = 24.0 J = 24.3 J = 24.1 S ppm C 2 Cl 2 1-d ppm

10 ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz F2 Processing parameters SF MHz WW EM LB 0.80 Hz PC C NMR without 1H decoupling, 19.4 mg in 0.9 ml C2Cl2, mg Cr(acac) 3 as a relaxation agent, C2Cl2 = 54.0 ppm Current ata Parameters NAME sld_uzh_0032a EXPNO 50 PROBH 5 mm PABBO BB PULPROG zg30 T SOLVENT C2Cl2 NS 3584 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec T ppm J = 24.3 J = 24.3 J = 24.0 J = 24.1 S ppm C 2 Cl 2 1-d ppm

11 1H NMR, 29.7 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm ppm Current ata Parameters NAME sld_uzh_0034a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T SOLVENT C2Cl2 NS 16 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 Processing parameters SF MHz WW no LB 0 Hz PC ppm S11 2-d 10 CHCl 2 H 2 O in C 2 Cl 2

12 F2 Processing parameters SF MHz WW EM LB 1.00 Hz PC C{1H} NMR, 29.7 mg in 0.6 ml C2Cl2, C2Cl2 = 54.0 ppm = resonances from partially deuterated product Current ata Parameters NAME sld_uzh_0034a EXPNO 2 PROBH 5 mm PABBO BB PULPROG zgpg30 T SOLVENT C2Cl2 NS 1017 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec d sec ELTA sec T ppm J = 24.3 J = 24.4 J = 24.4 J = 24.5 J = 24.5 S ppm ppm ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP usec PL db PL db PL db SFO MHz C 2 Cl 2 2-d ppm

13 1H NMR, 24.9 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm ppm Current ata Parameters NAME sld_uzh_0035a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T SOLVENT C2Cl2 NS 16 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 Processing parameters SF MHz WW no LB 0 Hz PC ppm S13 3-d 10 CHCl 2 H 2 O in C 2 Cl 2

14 F2 Processing parameters SF MHz WW EM LB 1.00 Hz PC C{1H} NMR, 24.9 mg in 0.6 ml C2Cl2, C2Cl2 = 54.0 ppm = resonances from partially deuterated product Current ata Parameters NAME sld_uzh_0035a EXPNO 2 PROBH 5 mm PABBO BB PULPROG zgpg30 T SOLVENT C2Cl2 NS 912 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec d sec ELTA sec T ppm J = 24.3 J = 24.4 J = 24.3 S ppm ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz C 2 Cl 2 ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP usec PL db PL db PL db SFO MHz 3-d ppm

15 1H NMR, 27.1 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm ppm Current ata Parameters NAME sld_uzh_0036a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T SOLVENT C2Cl2 NS 16 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P usec PL db SFO MHz F2 Processing parameters SF MHz WW no LB 0 Hz PC ppm S15 4-d 12 CHCl 2 H 2 O in C 2 Cl 2

16 Current ata Parameters NAME sld_uzh_0036a EXPNO 2 13C{1H} NMR, 27.1 mg in 0.6 ml C2Cl2, C2Cl2 = 54.0 ppm = resonances from partially deuterated product PROBH 5 mm PABBO BB PULPROG zgpg30 T SOLVENT C2Cl2 NS 1024 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec d sec ELTA sec T ppm J = 24.5 J = 24.0 S ppm ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz C 2 Cl 2 ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP usec PL db PL db PL db SFO MHz F2 Processing parameters SF MHz WW EM LB 1.00 Hz PC d ppm

17 13C NMR without 1H decoupling, 15 mg in 0.7 ml C2Cl2, mg Cr(acac) 3 as a relaxation agent, C2Cl2 = 54.0 ppm Current ata Parameters NAME sld_uzh_0036a EXPNO ppm J = 24.5 J = 24.0 S ppm PROBH 5 mm PABBO BB PULPROG zg30 T SOLVENT C2Cl2 NS 1024 S 0 SWH Hz FIRES Hz AQ sec RG W usec E 7.50 usec TE K sec T0 1 ======== CHANNEL f1 ======== NUC1 13C P usec PL db SFO MHz C 2 Cl 2 F2 Processing parameters SF MHz WW EM LB 2.00 Hz PC d ppm

18 F2 Processing parameters SI SF MHz WW no LB 0 Hz PC H NMR, 20.5 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm 7.84 Current ata Parameters NAME Anna_Cor EXPNO 2 S ppm 5-d 10 PROBH 5 mm PATXI 1H/ PULPROG zg T SOLVENT C2Cl2 NS 32 S 0 SWH Hz FIRES Hz AQ sec RG 406 W usec E usec TE K sec T0 1 CHCl 2 ======== CHANNEL f1 ======== NUC1 1H P usec PL db PL1W W SFO MHz H 2 O in C 2 Cl ppm

19 ======== CHANNEL f1 ======== NUC1 13C P usec PL db PL1W W SFO MHz ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP usec PL db PL db PL db PL2W W PL12W W PL13W W SFO MHz F2 Processing parameters SI SF MHz WW EM LB 1.00 Hz PC C{1H} NMR, 20.5 mg in 0.6 ml C2Cl2, C2Cl2 = 54.0 ppm = resonances from partially deuterated product Current ata Parameters NAME Anna_Cor EXPNO 4 PROBH 5 mm PATXI 1H/ PULPROG zgpg30 T SOLVENT C2Cl2 NS 1464 S 4 SWH Hz FIRES Hz AQ sec RG 2050 W usec E usec TE K sec sec T J = 24.4 S ppm ppm 5-d ppm