Page 1 of 18 An Acyclic Trialkylamine Virtually Planar at Nitrogen. Some Chemical Consequences of Nitrogen Planarity. Yuanping Jie, Peter Livant,* Hui Li, Minmin Yang, Wei Zhu, Vince Cammarata, Phillip Almond, Tyler Sullens, Yu Qin, Eric Bakker Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849-5312 Supporting Information Table of Contents Figure S1. ORTEP drawing of compound 9...2 Figure S2. ORTEP drawing of compound 9H + Cl...3 Figure S3. H-bonding contacts involving Cl in 9H + Cl...4 Figure S4. 1 H NMR Spectrum of 13...5 Figure S5. 1 H NMR Spectrum of 16...6 Figure S6. 13 C NMR Spectrum of 16...7 Figure S7. 1 H NMR Spectrum of 17...8 Figure S8. 13 C NMR Spectrum of 17...9 Figure S9. DEPT-135 NMR Spectrum of 17...10 Figure S10. 1 H NMR Spectrum of 9...11 Figure S11. Expanded 1 H NMR Spectrum of 9...12 Figure S12. 13 C NMR Spectrum of 9...13 Figure S13. 1 H NMR Spectrum of 18...14 Figure S14. 13 C NMR and DEPT-135 Spectra of 18....15 Figure S15. 1 H NMR Spectrum of 9H + Cl...16 Figure S16. 13 C NMR and DEPT-135 Spectra of 9H + Cl...17 Table S1. Effect on 15 N chemical shift of one N-C-CH 3 N-C-CH 2 OH transformation, A...18
Figure S1. ORTEP plot of 9 at the 50% probability level Page 2 of 18
Figure S2. ORTEP plot of 9H + Cl at the 50% probability level Page 3 of 18
Page 4 of 18 Figure S3. H-bonding contacts involving Cl in 9H + Cl. Atoms are represented by spheres of arbitrary size. Hydrogens bonded to carbon have been omitted.
Figure S4. 1 H-NMR spectrum of 13. (400 MHz; CDCl 3 ) Page 5 of 18
Figure S5. 1 H-NMR spectrum of 16. (400 MHz; CDCl 3 ) Page 6 of 18
Figure S6. 13 C-NMR spectrum of 16. (100 MHz; CDCl 3 ) Page 7 of 18
Figure S7. 1 H-NMR spectrum of 17. (400 MHz; CDCl 3 ) Page 8 of 18
Figure S8. 13 C-NMR spectrum of 17. (100 MHz; CDCl 3 ) Page 9 of 18
Figure S9. 13 C-DEPT-135 spectrum of 17. (100 MHz; CDCl 3 ) Page 10 of 18
Page 11 of 18 Figure S10. 1 H-NMR spectrum of 9. (400 MHz; D 2 O) Methanol, added as a chemical shift standard, appears at 3.34 ppm.
Page 12 of 18 Figure S11. Expanded 1 H-NMR spectrum of 9. (400 MHz; D 2 O) The spectrum has been resolution-enhanced by Gaussian multiplication. Added methanol appears at 3.34 ppm.
Page 13 of 18 Figure S12. 13 C-NMR spectrum of 9. (100 MHz; D 2 O) Methanol was added to provide a chemical shift standard (49.5 ppm).
Figure S13. 1 H NMR Spectrum of 18. (400 MHz; CDCl 3 ) Page 14 of 18
Figure S14. 13 C NMR and DEPT-135 Spectra of 18. (100 MHz; CDCl 3 ) Page 15 of 18
Page 16 of 18 Figure S15. 1 H-NMR Spectrum of 9H + Cl. (400 MHz; D 2 O). Methanol, added as a chemical shift standard, appears at 3.34 ppm.
Page 17 of 18 Figure S16. 13 C and DEPT-135 Spectra of 9H + Cl. (100 MHz; D 2 O). Methanol, added as a chemical shift standard, appears at 49.5 ppm.
Page 18 of 18 Table S1. Effect on 15 N chemical shift of one N-C-CH 3 N-C-CH 2 OH transformation, A Entry 1 2 Amine Š355.4 (CH NH 3 OH) a Š365.7 (no solvent) b HO 2 NH Š8.38 2 Š355.1 (cyclohexane) a Š361.7 (no solvent) c Š363.5 (no solvent) d NH 2 Š338.1 (CH 3 OH) a NH 2 HO Š337.2 (cyclohexane) a β-hydroxyamine Š346.0 (no solvent) b A (ppm) Š8.35 3 NH 2 Š324.3 (CH 3 OH) a NH 2 HO Š322.4 (cyclohexane) a Š332.9 (no solvent) b Š9.55 4 NH 2 Š342.2 (CH 3 OH) a HO NH 2 Š342.4 (cyclohexane) a Š351.0 (no solvent) b Š8.7 5 N H Š334.0 (no solvent) b HO NH 2 Š351.4 (no solvent) d Š8.7 6 Š332.0 (CH N 3 OH) a HO Š6.55 Š333.6 (cyclohexane) a N Š345.9 (no solvent) d 2 7 HO N 2 Š345.9 (no solvent) d HO N 3 Š354.0 (no solvent) d Š352.3 (D 2 O) e Š7.25 8 N Š340.5 (CH 3 OH) a Š343.1 (cyclohexane) a HO N 2 Š353.2 (no solvent) d Š5.7 9 N Š351.3 (CH 3 OH) a Š355.2 (cyclohexane) a HO N Š358.0 (no solvent) d Š4.75 Average A = Š7.4 ± 1.5 ppm a Duthaler, R. O.; Roberts, J. D. J. Am. Chem. Soc. 1978, 100, 3889-3895. b Lichter, R. L.; Roberts, J. D. J. Am. Chem. Soc. 1972, 94, 2495-2500. c Levy, G. C.; Holloway, C. E.; Rosanske, R. C.; Hewitt, J. M.; Bradley, C. H. Org. Magn. Reson. 1976, 8, 643-647. d Liepins, E.; Birgele, I.; Zelcans, G.; Urtane, I.; Lukevics, E. Zh. Obshch. Khim. 1980, 50, 2733-2737. e This work. Note: Each A value was obtained by subtracting the average of all chemical shift entries for the amine from the average of all chemical shift entries for the corresponding β-hydroxylamine and dividing by the number of β methyls altered.