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SUPPORTING INFORMATION Solvents for Solid-Phase Synthesis

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SUPPORTING INFORMATION Solvents for Solid-Phase Synthesis Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2016 SUPPORTING INFORMATION Solvents for solid-phase synthesis Stefan Lawrenson, Michael North*, Fanny Peigneguy and Anne Routledge* Department of chemistry, University of York, York, UK, Y10 5DD. Contents Reproducibility of resin swelling S2 Allocation of training set solvents to groups S5 3D plots of HSPiP predictions S14 Predictions of solvents to swell each resin S23 Swelling of resins in dimethyl isosorbide S40 Swelling of resins in cyclopentyl methyl ether S41 Swelling of resins in butan-2-one S42 Swelling of resins in 4-methylpentan-2-one S43 Swelling of resins in isopropyl acetate S44 Solvent list and parameters used for mixed solvent study S45 NMR spectra of compounds 28 and 29 S46 S1 Reproducibility of resin swelling Merrifield resin Average Swelling Solvent Run 1 Run 2 Run3 Run 4 Run 5 Error (mL g-1) 2 1.80 1.90 1.70 1.80 1.80 1.80 0.10 4 2.80 3.10 3.00 2.80 3.00 2.94 0.16 8 4.30 4.00 4.30 4.20 4.40 4.24 0.24 12 5.10 5.30 5.50 5.80 5.40 5.42 0.38 17 3.80 3.60 3.90 3.70 4.30 3.86 0.44 20 1.80 1.80 1.80 1.80 1.80 1.80 0.00 24 1.80 1.80 1.80 1.80 1.30 1.70 0.40 CH2Cl2 5.90 5.80 6.20 6.10 6.30 6.06 0.26 7.0 6.0 ) 1 - g 5.0 L 4.0 m ( g 3.0 n i l l e 2.0 w s 1.0 0.0 S2 ChemMatrix resin Average Swelling Solvent Run 1 Run 2 Run3 Run 4 Run 5 Error (mL g-1) 2 5.80 5.80 5.80 6.00 6.00 5.88 0.12 4 4.90 4.60 4.80 4.80 4.80 4.78 0.18 8 4.60 4.70 4.80 4.90 5.00 4.80 0.20 12 4.60 4.30 4.80 4.30 4.60 4.52 0.28 17 3.80 3.60 3.80 4.00 3.90 3.82 0.22 20 6.00 5.80 6.30 5.90 6.00 6.00 0.30 24 6.80 6.80 6.80 6.70 6.80 6.78 0.08 CH2Cl2 9.30 9.10 9.10 9.00 9.30 9.16 0.16 10.0 ) 8.0 1 - g L 6.0 m ( g 4.0 n i l l e 2.0 w s 0.0 S3 ArgoGel resin Average Swelling Solvent Run 1 Run 2 Run3 Run 4 Run 5 Error (mL g-1) 2 4.80 4.60 4.80 4.90 4.80 4.78 0.18 4 4.50 4.30 3.90 4.00 3.80 4.10 0.40 8 4.80 4.80 4.30 4.60 4.80 4.66 0.36 12 4.30 4.40 4.50 4.30 4.80 4.46 0.34 17 4.30 4.60 4.10 4.40 4.30 4.34 0.26 20 3.80 3.80 3.80 3.80 3.80 3.80 0.00 24 3.30 3.10 3.10 3.30 3.40 3.24 0.16 CH2Cl2 7.70 7.80 7.30 7.80 8.00 7.72 0.42 9.0 8.0 ) 1 7.0 - g 6.0 L m 5.0 ( 4.0 g n i l 3.0 l e 2.0 w s 1.0 0.0 S4 Allocation of training set solvents to groups Merrifield resin Maximum swelling 6.3 mL g-1; minimum swelling 1.8 mL g-1 6 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 2.55 acetone (4), D-limonene (18), p-cymene (19), 6 MeOH (20), EtOH (21), isopropanol (22) -valerolactone (11), dimethyl carbonate (16), 2.55 3.30 5 diethyl carbonate (17) 3.30 4.05 EtOAc (8) 4 4.05 4.80 3 4.80 5.55 DMF 2 5.55 6.30 cyclopentanone (7), 2-MeTHF (12), NMP, CH2Cl2 1 5 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 2.70 acetone (4), D-limonene (18), p-cymene (19), 5 MeOH (20), EtOH (21), isopropanol (22) -valerolactone (11), dimethyl carbonate (16), 2.70 3.60 4 diethyl carbonate (17) 3.60 4.50 EtOAc (8) 3 4.50 5.40 DMF 2 5.40 6.30 cyclopentanone (7), 2-MeTHF (12), NMP, CH2Cl2 1 4 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 2.93 acetone (4), dimethyl carbonate (16), D-limonene (18), 4 p-cymene (19), MeOH (20), EtOH (21), isopropanol (22) 2.93 4.05 EtOAc (8), -valerolactone (11), diethyl carbonate (17) 3 4.05 5.18 DMF 2 5.18 6.30 cyclopentanone (7), 2-MeTHF (12), NMP, CH2Cl2 1 S5 ParaMax resin Maximum swelling 7.8 mL g-1; minimum swelling 1.8 mL g-1 6 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 2.80 D-limonene (18), p-cymene (19), 6 MeOH (20), EtOH (21), isopropanol (22) 2.80 3.80 5 3.80 4.80 dimethyl carbonate (16) 4 acetone (4), EtOAc (8), -valerolactone (11), 4.80 5.80 3 diethyl carbonate (17) 5.80 6.80 2 6.80 7.80 cyclopentanone (7), 2-MeTHF (12), NMP, DMF, CH2Cl2 1 5 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 3.00 D-limonene (18), p-cymene (19), 5 MeOH (20), EtOH (21), isopropanol (22) 3.00 4.20 4 acetone (4), EtOAc (8), -valerolactone (11), 4.20 5.40 3 dimethyl carbonate (16), diethyl carbonate (17) 5.40 6.60 2 6.60 7.80 cyclopentanone (7), 2-MeTHF (12), NMP, DMF, CH2Cl2 1 4 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 3.30 D-limonene (18), p-cymene (19), 4 MeOH (20), EtOH (21), isopropanol (22) 3.30 4.80 dimethyl carbonate (16), 3 acetone (4), EtOAc (8), -valerolactone (11), 4.80 6.30 2 diethyl carbonate (17) 6.30 7.80 cyclopentanone (7), 2-MeTHF (12), NMP, DMF, CH2Cl2 1 S6 JandaJel resin Maximum swelling 8.8 mL g-1; minimum swelling 1.8 mL g-1 6 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 2.97 acetone (4), diethyl carbonate (17), MeOH (20), EtOH (21), 6 isopropanol (22) 2.97 4.13 dimethyl carbonate (16) 5 4.13 5.30 D-limonene (18) 4 5.30 6.47 EtOAc (8), p-cymene (19), DMF 3 6.47 7.63 2 cyclopentanone (7), -valerolactone (11), 2-MeTHF (12), 7.63 8.80 1 NMP, CH2Cl2 5 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 3.20 acetone (4), diethyl carbonate (17), MeOH (20), EtOH (21), 5 isopropanol (22) 3.20 4.60 dimethyl carbonate (16) 4 4.60 6.00 EtOAc (8), D-limonene (18), p-cymene (19) 3 6.00 7.40 DMF 2 cyclopentanone (7), -valerolactone (11), 2-MeTHF (12), 7.40 8.80 1 NMP, CH2Cl2 4 groups Swelling range Solvents Rank ethylene carbonate (1), propylene carbonate (2), cyrene (3), 1.80 3.55 acetone (4), diethyl carbonate (17), MeOH (20), EtOH (21), 4 isopropanol (22) 3.55 5.30 dimethyl carbonate (16), D-limonene (18) 3 5.30 7.05 EtOAc (8), p-cymene (19), DMF 2 cyclopentanone (7), -valerolactone (11), 2-MeTHF (12), 7.05 8.80 1 NMP, CH2Cl2 S7 TentaGel resin Maximum swelling 5.5 mL g-1; minimum swelling 1.8 mL g-1 6 groups Swelling range Solvents Rank 1.80 2.42 p-cymene (19), EtOH (21), isopropanol (22) 6 2.42 3.03 diethyl carbonate (17), D-limonene (18), MeOH (20) 5 3.03 3.65 propylene carbonate (2), acetone (4), 2-MeTHF (12) 4 ethylene carbonate (1), cyrene (3), EtOAc (8), -valerolactone 3.65 4.27 3 (11), dimethyl carbonate (16), NMP, DMF 4.27 4.88 cyclopentanone (7) 2 4.88 5.50 CH2Cl2 (Note only one solvent in group 1) 1 5 groups Swelling range Solvents Rank 1.80 2.54 p-cymene (19), EtOH (21), isopropanol (22) 5 2.54 3.28 diethyl carbonate (17), D-limonene (18), MeOH (20) 4 ethylene carbonate (1), propylene carbonate (2), cyrene (3), 3.28 4.02 acetone (4), EtOAc (8), -valerolactone (11), 2-MeTHF (12), 3 dimethyl carbonate (16), NMP, DMF 4.02 4.76 2 4.76 5.50 cyclopentanone (7), CH2Cl2 1 4 groups Swelling range Solvents Rank diethyl carbonate (17), D-limonene (18), p-cymene (19), EtOH 1.80 2.73 4 (21), isopropanol (22) propylene carbonate (2), acetone (4), 2-MeTHF (12), MeOH 2.73 3.65 3 (20) ethylene carbonate (1), cyrene (3), EtOAc (8), -valerolactone 3.65 4.58 2 (11), dimethyl carbonate (16), NMP, DMF 4.58 5.50 cyclopentanone (7), CH2Cl2 1 S8 ArgoGel resin Maximum swelling 7.7 mL g-1; minimum swelling 1.8 mL g-1 6 groups Swelling range Solvents Rank 1.80 2.78 p-cymene (19), EtOH (21), isopropanol (22) 6 2.78 3.77 5 ethylene carbonate (1), propylene carbonate (2), acetone (4), 3.77 4.75 2-MeTHF (12), diethyl carbonate (17), D-limonene (18), 4 MeOH (20) cyrene (3), EtOAc (8), -valerolactone (11), dimethyl 4.75 5.73 3 carbonate (16), NMP, DMF 5.73 6.72 cyclopentanone (7) 2 6.72 7.70 CH2Cl2 (Note only one solvent in group 1) 1 5 groups Swelling range Solvents Rank 1.80 2.98 p-cymene (19), EtOH (21), isopropanol (22) 5 2.98 4.16 ethylene carbonate (1), acetone (4), MeOH (20) 4 propylene carbonate (2), cyrene (3), EtOAc (8), - 4.16 5.34 valerolactone (11), 2-MeTHF (12), dimethyl carbonate (16), 3 diethyl carbonate (17), D-limonene (18), NMP, DMF 5.34 6.52 cyclopentanone (7) 2 6.52 7.70 CH2Cl2 (Note only one solvent in group 1) 1 4 groups Swelling range Solvents Rank 1.80 3.28 p-cymene (19), EtOH (21), isopropanol (22) 4 ethylene carbonate (1), propylene carbonate (2), acetone (4), 3.28 4.75 2-MeTHF (12), diethyl carbonate (17), D-limonene (18), 3 MeOH (20) cyrene (3), cyclopentanone (7), EtOAc (8), -valerolactone 4.75 6.23 2 (11), dimethyl carbonate (16), NMP, DMF 6.23 7.70 CH2Cl2 (Note only one solvent in group 1) 1 S9 HypoGel resin Maximum swelling 4.8 mL g-1; minimum swelling 1.8 mL g-1 6 groups Swelling range Solvents Rank 1.80 2.30 p-cymene (19), MeOH (20), EtOH (21), isopropanol (22) 6 2.30 2.80 propylene carbonate (2), diethyl carbonate (17), D-limonene (18) 5 ethylene carbonate (1), acetone (4), EtOAc (8), dimethyl 2.80 3.30 4 carbonate (16) 3.30 3.80 cyrene (3),-valerolactone (11) 3 3.80 4.30 2-MeTHF (12) 2 4.30 4.80 cyclopentanone (7), NMP, CH2Cl2, DMF 1 5 groups Swelling range Solvents Rank propylene carbonate (2), D-limonene (18), p-cymene (19), 1.80 2.40 5 MeOH (20), EtOH (21), isopropanol (22) ethylene carbonate (1), acetone (4), EtOAc (8), 2.40 3.00 4 dimethyl carbonate (16), diethyl carbonate (17) 3.00 3.60 cyrene (3),-valerolactone (11) 3 3.60 4.20 2-MeTHF (12) 2 4.20 4.80 cyclopentanone (7), NMP, CH2Cl2, DMF 1 4 groups Swelling range Solvents Rank propylene carbonate (2), D-limonene (18), p-cymene (19), 1.80 2.55 4 MeOH (20), EtOH (21), isopropanol (22) ethylene carbonate (1), acetone (4), EtOAc (8), 2.55 3.30 3 dimethyl carbonate (16), diethyl carbonate (17) 3.30 4.05 cyrene (3),-valerolactone (11), 2-MeTHF (12) 2 4.05 4.80 cyclopentanone (7), NMP, CH2Cl2, DMF 1 S10 NovaGel resin Maximum swelling 5.8 mL g-1; 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