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. E-mail: jss@oci.uzh.ch GC-MS ata... S2 7 1 H and 13 C NMR spectra... S8 19 S1
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1H NMR, 19.4 mg in 0.9 ml C2Cl2, CHCl2 = 5.32 ppm 7.80 7.75 7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 ppm Current ata Parameters NAME sld_uzh_0032a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T 61980 SOLVENT C2Cl2 NS 16 S 0 SWH 10330.578 Hz FIRES 0.166676 Hz AQ 2.9998820 sec RG 574.7 W 48.400 usec E 7.50 usec TE 298.2 K 1 3.00000000 sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P1 10.28 usec PL1 1.00 db SFO1 499.9530874 MHz F2 Processing parameters SF 499.9499952 MHz WW EM LB 0.10 Hz PC 1.00 10 9 8 7 6 5 4 3 2 1 ppm 4.17 4.01 7.18 2.00 4.17 4.01 7.18 2.00 7.71 7.68 7.48 7.38 S8 CHCl 2 H 2 O in C 2 Cl 2 1-d 14
======== CHANNEL f1 ======== NUC1 13C P1 7.25 usec PL1 2.00 db SFO1 125.7250987 MHz ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP2 80.00 usec PL2 1.00 db PL12 16.82 db PL13 17.00 db SFO2 499.9519998 MHz F2 Processing parameters SF 125.7124482 MHz WW EM LB 2.00 Hz PC 1.40 13C{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 600596 SOLVENT C2Cl2 NS 951 S 0 SWH 30030.029 Hz FIRES 0.050000 Hz AQ 9.9999733 sec RG 13004 W 16.650 usec E 7.50 usec TE 298.2 K 1 30.00000000 sec d11 0.03000000 sec ELTA 29.89999962 sec T0 1 140.89 140.36 128.90 127.54 127.44 127.03 129.5 129.0 128.5 128.0 127.5 127.0 126.5 ppm 54.00 140.89 140.36 128.90 127.54 127.44 127.03 J = 24.3 J = 24.0 J = 24.3 J = 24.1 S9 142 141 140 ppm C 2 Cl 2 1-d 14 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
======== CHANNEL f1 ======== NUC1 13C P1 7.25 usec PL1 2.00 db SFO1 125.7250987 MHz F2 Processing parameters SF 125.7124551 MHz WW EM LB 0.80 Hz PC 1.40 13C NMR without 1H decoupling, 19.4 mg in 0.9 ml C2Cl2, + 1.5 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 54050 SOLVENT C2Cl2 NS 3584 S 0 SWH 30030.029 Hz FIRES 0.555597 Hz AQ 0.8999825 sec RG 10321.3 W 16.650 usec E 7.50 usec TE 297.1 K 1 1.00000000 sec T0 1 129.5 129.0 128.5 128.0 127.5 127.0 126.5 ppm 140.82 140.29 128.86 127.49 127.40 126.99 140.82 140.29 128.86 127.49 127.40 126.99 J = 24.3 J = 24.3 J = 24.0 J = 24.1 S10 142 141 140 ppm 54.00 C 2 Cl 2 1-d 14 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
1H NMR, 29.7 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm 8.0 7.9 7.8 7.7 7.6 7.5 7.4 ppm Current ata Parameters NAME sld_uzh_0034a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T 103302 SOLVENT C2Cl2 NS 16 S 0 SWH 10330.578 Hz FIRES 0.100004 Hz AQ 4.9998670 sec RG 456.1 W 48.400 usec E 7.50 usec TE 297.2 K 1 30.00000000 sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P1 10.28 usec PL1 1.00 db SFO1 499.9530874 MHz F2 Processing parameters SF 499.9499952 MHz WW no LB 0 Hz PC 1.00 10 9 8 7 6 5 4 3 2 1 ppm 2.10 1.93 2.18 1.96 1.96 2.10 1.93 2.18 1.96 1.96 7.99 7.98 7.98 7.96 7.89 7.89 7.88 7.69 7.67 7.66 7.43 7.42 7.41 S11 2-d 10 CHCl 2 H 2 O in C 2 Cl 2
F2 Processing parameters SF 125.7124522 MHz WW EM LB 1.00 Hz PC 1.40 13C{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 600596 SOLVENT C2Cl2 NS 1017 S 0 SWH 30030.029 Hz FIRES 0.050000 Hz AQ 9.9999733 sec RG 13004 W 16.650 usec E 7.50 usec TE 297.5 K 1 30.00000000 sec d11 0.03000000 sec ELTA 29.89999962 sec T0 1 139.87 137.31 132.85 130.43 128.07 127.64 126.74 121.73 120.31 128.5 128.0 127.5 127.0 ppm 54.00 139.87 137.31 132.85 130.43 128.07 127.64 126.74 121.73 120.31 J = 24.3 J = 24.4 J = 24.4 J = 24.5 J = 24.5 S12 140 138 136 134 132 ppm 122.0 121.5 121.0 120.5 ppm ======== CHANNEL f1 ======== NUC1 13C P1 7.25 usec PL1 2.00 db SFO1 125.7250987 MHz ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP2 80.00 usec PL2 1.00 db PL12 16.82 db PL13 17.00 db SFO2 499.9519998 MHz C 2 Cl 2 2-d 10 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
1H NMR, 24.9 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm 8.30 8.25 8.20 8.15 8.10 8.05 8.00 ppm Current ata Parameters NAME sld_uzh_0035a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T 61980 SOLVENT C2Cl2 NS 16 S 0 SWH 10330.578 Hz FIRES 0.166676 Hz AQ 2.9998820 sec RG 456.1 W 48.400 usec E 7.50 usec TE 297.2 K 1 3.00000000 sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P1 10.28 usec PL1 1.00 db SFO1 499.9530874 MHz F2 Processing parameters SF 499.9499952 MHz WW no LB 0 Hz PC 1.00 10 9 8 7 6 5 4 3 2 1 ppm 4.04 4.00 2.10 4.04 4.00 2.10 8.22 8.11 8.04 S13 3-d 10 CHCl 2 H 2 O in C 2 Cl 2
F2 Processing parameters SF 125.7124522 MHz WW EM LB 1.00 Hz PC 1.40 13C{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 600596 SOLVENT C2Cl2 NS 912 S 0 SWH 30030.029 Hz FIRES 0.050000 Hz AQ 9.9999733 sec RG 10321.3 W 16.650 usec E 7.50 usec TE 297.4 K 1 30.00000000 sec d11 0.03000000 sec ELTA 29.89999962 sec T0 1 128.0 127.5 127.0 126.5 126.0 125.5 125.0 ppm 131.55 127.40 125.96 125.10 125.00 54.00 131.55 120.31 127.40 125.96 125.10 125.00 J = 24.3 J = 24.4 J = 24.3 S14 132.0 131.5 ppm ======== CHANNEL f1 ======== NUC1 13C P1 7.25 usec PL1 2.00 db SFO1 125.7250987 MHz C 2 Cl 2 ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP2 80.00 usec PL2 1.00 db PL12 16.82 db PL13 17.00 db SFO2 499.9519998 MHz 3-d 10 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
1H NMR, 27.1 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 ppm Current ata Parameters NAME sld_uzh_0036a EXPNO 1 PROBH 5 mm PABBO BB PULPROG zg30 T 61980 SOLVENT C2Cl2 NS 16 S 0 SWH 10330.578 Hz FIRES 0.166676 Hz AQ 2.9998820 sec RG 456.1 W 48.400 usec E 7.50 usec TE 297.5 K 1 3.00000000 sec T0 1 ======== CHANNEL f1 ======== NUC1 1H P1 10.28 usec PL1 1.00 db SFO1 499.9530874 MHz F2 Processing parameters SF 499.9499952 MHz WW no LB 0 Hz PC 1.00 10 9 8 7 6 5 4 3 2 1 ppm 6.12 5.92 6.12 5.92 8.67 7.69 S15 4-d 12 CHCl 2 H 2 O in C 2 Cl 2
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 600596 SOLVENT C2Cl2 NS 1024 S 0 SWH 30030.029 Hz FIRES 0.050000 Hz AQ 9.9999733 sec RG 10321.3 W 16.650 usec E 7.50 usec TE 297.9 K 1 30.00000000 sec d11 0.03000000 sec ELTA 29.89999962 sec T0 1 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0 ppm 130.19 127.33 123.45 54.00 130.19 127.33 123.45 J = 24.5 J = 24.0 S16 130 ppm ======== CHANNEL f1 ======== NUC1 13C P1 7.25 usec PL1 2.00 db SFO1 125.7250987 MHz C 2 Cl 2 ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP2 80.00 usec PL2 1.00 db PL12 16.82 db PL13 17.00 db SFO2 499.9519998 MHz F2 Processing parameters SF 125.7124522 MHz WW EM LB 1.00 Hz PC 1.40 4-d 12 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13C NMR without 1H decoupling, 15 mg in 0.7 ml C2Cl2, + 1.0 mg Cr(acac) 3 as a relaxation agent, C2Cl2 = 54.0 ppm Current ata Parameters NAME sld_uzh_0036a EXPNO 60 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 ppm 130.14 127.30 123.42 54.00 130.14 127.30 123.42 J = 24.5 J = 24.0 S17 130 ppm PROBH 5 mm PABBO BB PULPROG zg30 T 54050 SOLVENT C2Cl2 NS 1024 S 0 SWH 30030.029 Hz FIRES 0.555597 Hz AQ 0.8999825 sec RG 10321.3 W 16.650 usec E 7.50 usec TE 297.2 K 1 1.00000000 sec T0 1 ======== CHANNEL f1 ======== NUC1 13C P1 7.25 usec PL1 2.00 db SFO1 125.7250987 MHz C 2 Cl 2 F2 Processing parameters SF 125.7124563 MHz WW EM LB 2.00 Hz PC 1.40 4-d 12 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
F2 Processing parameters SI 65536 SF 500.1300204 MHz WW no LB 0 Hz PC 1.40 1H NMR, 20.5 mg in 0.6 ml C2Cl2, CHCl2 = 5.32 ppm 7.84 Current ata Parameters NAME Anna_Cor EXPNO 2 S18 7.90 7.85 7.80 ppm 5-d 10 PROBH 5 mm PATXI 1H/ PULPROG zg T 61982 SOLVENT C2Cl2 NS 32 S 0 SWH 10330.578 Hz FIRES 0.166671 Hz AQ 2.9999788 sec RG 406 W 48.400 usec E 20.00 usec TE 300.0 K 1 3.00000000 sec T0 1 CHCl 2 ======== CHANNEL f1 ======== NUC1 1H P1 7.70 usec PL1 1.50 db PL1W 15.41768265 W SFO1 500.1330885 MHz H 2 O in C 2 Cl 2 10 9 8 7 6 5 4 3 2 1 ppm
======== CHANNEL f1 ======== NUC1 13C P1 11.55 usec PL1 4.00 db PL1W 167.83465576 W SFO1 125.7703052 MHz ======== CHANNEL f2 ======== CPPRG2 waltz16 NUC2 1H PCP2 80.00 usec PL2 1.50 db PL12 21.83 db PL13 25.00 db PL2W 15.41768265 W PL12W 0.14289568 W PL13W 0.06886826 W SFO2 500.1320005 MHz F2 Processing parameters SI 65536 SF 125.7577160 MHz WW EM LB 1.00 Hz PC 1.40 13C{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 781246 SOLVENT C2Cl2 NS 1464 S 4 SWH 39062.500 Hz FIRES 0.050000 Hz AQ 9.9999990 sec RG 2050 W 12.800 usec E 20.00 usec TE 300.0 K 1 30.00000000 sec 11 0.03000000 sec T0 1 136.29 131.37 127.17 54.00 136.29 131.37 127.17 J = 24.4 S19 136 135 134 133 132 ppm 127.5 127.0 ppm 5-d 10 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm