Journal of the Korean Chemical Society 2017, Vol. 61, No. 4
Printed in the Republic of Korea https://doi.org/10.5012/jkcs.2017.61.4.1
SUPPORTING INFORMATION
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines
Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf*
Laboratory of Applied Organic Chemistry, Bioorganic Chemistry Group, Department of Chemistry, Sciences Faculty, - Badji Mokhtar - Annaba University, Box 12, 23000 Annaba, Algeria
*E-mail: [email protected]; [email protected] (Received March 28, 2017; Accepted June 15, 2017)
Table of Contents
1. Apparatus··· 4
2. Typical experimental procedure for the benzyloxy- carbonylation of amines ··· 4
3. Spectral Data··· 4
1H NMR spectrum: N-Carbobenzyloxyaniline ··· 5
13C NMR spectrum: N-Carbobenzyloxyaniline ··· 5
IR spectrum: N-Carbobenzyloxyaniline ··· 6
1H NMR spectrum: N-Carbobenzyloxybenzylamine ··· 6
IR spectrum: N-Carbobenzyloxybenzylamine ··· 7
1H NMR spectrum: N-Carbobenzyloxy-4-methoxyani- line ··· 7
13C NMR spectrum: N-Carbobenzyloxy-4-methoxyani- line ··· 8
IR spectrum: N-Carbobenzyloxy-4-methoxyaniline ···· 8
1H NMR spectrum: N-Carbobenzyloxy-2-methoxyani- line ··· 9
13CNMR spectrum: N-Carbobenzyloxy-2-methoxyani- line ··· 9
IR spectrum: N-Carbobenzyloxy-2-methoxyaniline ·· 10
1H NMR spectrum: N-Carbobenzyloxyurea ···10
13C NMR spectrum: N-Carbobenzyloxyurea ···11
IR spectrum: N-Carbobenzyloxyurea···11
Mass spectrum: N-Carbobenzyloxyurea··· 12
1H NMR spectrum: N-Carbobenzyloxydipenylamine ··· 12
13C NMR spectrum: N-Carbobenzyloxydipenylamine ···13
IR spectrum: N-Carbobenzyloxydipenylamine ··· 13
1H NMR spectrum: N-Carbobenzyloxymorpholine ···· 14
13C NMR spectrum: N-Carbobenzyloxymorpholine···· 14
IR spectrum: N-Carbobenzyloxymorpholine··· 15
1H NMR spectrum: N-Carbobenzyloxyphenylpipirazine ··· 15
13C NMR spectrum: N-Carbobenzyloxyphenylpipirazine ··· 16
IR spectrum: N-Carbobenzyloxyphenylpipirazine ···· 16
Mass spectrum: N-Carbobenzyloxyphenylpipirazine··· 17
1H NMR spectrum: N-Carbobenzyloxypropylamine··· 17
13C NMR spectrum: N-Carbobenzyloxypropylamine·· 18
IR spectrum: N-Carbobenzyloxypropylamine ··· 18
1H NMR spectrum: N-Carbobenzyloxycyclohexylamine ··· 19
13C NMR spectrum: N-Carbobenzyloxycyclohexylamine ··· 19
IR spectrum: N-Carbobenzyloxycyclohexylamine ···· 20
1H NMR spectrum: (S)-N-Carbobenzyloxyphenylalani- nol··· 20
13C NMR spectrum: (S)-N-Carbobenzyloxyphenylalani- nol··· 21
IR spectrum: (S)-N-Carbobenzyloxyphenylalaninol ·· 21
1H NMR spectrum: (S)-N-Carbobenzyloxyvalinol···· 22
13C NMR spectrum: (S)-N-Carbobenzyloxyvalinol··· 22
IR spectrum: (S)-N-Carbobenzyloxyvalinol··· 23
Mass spectrum: (S)-N-Carbobenzyloxyvalinol ··· 23
1H NMR spectrum: (S)-N-Carbobenzyloxyphenylala- ninemethyl ester ··· 24
13C NMR spectrum: (S)-N-Carbobenzyloxyphenylala- ninemethyl ester ··· 24
IR spectrum: (S)-N-Carbobenzyloxyphenylala- ninemethyl ester··· 25
Mass spectrum: (S)-N-Carbobenzyloxyphenylala- ninemethyl ester ··· 25
1H NMR spectrum: (S)-N-Carbobenzyloxyprolineethyl ester ··· 26
13C NMR spectrum: (S)-N-Carbobenzyloxyprolineethyl ester ··· 26
IR spectrum: (S)-N-Carbobenzyloxyprolineethyl ester ··· 27
2 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Mass spectrum: (S)-N-Carbobenzyloxypro- lineethyl ester
··· 27
1H NMR spectrum: (S)-N-Carbobenzyloxyleucineethyl ester··· 28
13C NMR spectrum: (S)-N-Carbobenzyloxyleucineethyl ester··· 28 IR spectrum: (S)-N-Carbobenzyloxyleucineethyl ester
··· 29 Mass spectrum: (S)-N-Carbobenzyloxyleucineethylester ··· 29
1H NMR spectrum: (S)-Benzyl-N-(1-hydroxy-3-methyl- butan-2-yl) sulfamoylcarbamate ··· 30 IR spectrum: (S)-Benzyl-N-(1-hydroxy-3-methylbutan-2- yl) sulfamoylcarbamate··· 30 Mass spectrum: (S)-Benzyl-N-(1-hydroxy-3-méthylbu- tan-2-yl) sulfamoylcarbamate ··· 31
1H NMR spectrum: (S)-Benzyl-N-(1-hydroxy-4-méthyl- pentan-2-yl) sulfamoylcarbamate. ···31
13C NMR spectrum: (S)-Benzyl-N-(1-hydroxy-4-methyl- pentan-2-yl) sulfamoylcarbamate32 Mass spectrum: (S)- Benzyl-N-(1-hydroxy-4-methylpentan-2-yl) sulfamoyl- carbamate ···32
1. Instruments and Materials
All reagents and solvents were of commercial quality and were used without further purification. All reactions were carried out in a SAMSUNG microwave oven type M1610N, 230-50Hz, and 2450 Hz MW at 50 °C. All reaction were monitored by TLC on Silica gel Merck 60 F254 (Art. 5554)
percolated aluminum plates and were developed by spray- ing with ninhydrine solution. Melting points were deter- mined in open capillary tubes on an Electrothermal apparatus and uncorrected. Mass spectra were recorded on a SHIMADZU QP 1100 Ex mass spectrometer. IR spec- tra were recorded on a Perkin-Elmer FT-600 spectrome- ter. Proton nuclear magnetic resonance were determined 250 Or 400 MHz Brücker spectrometer using CDCl3 as a solvent and TMS as an internal standard. Chemical shifts are reported in δ units (ppm). All coupling constants (J) are reported in Hertz. Multiplicity is indicated as s (sin- glet), d (doublet), t (triplet), q (quartet), m (multiplet) and combination these signals.
2. Typical experimental procedure of N-benzyloxycar- bonylation protection on amines derivatives promoted by microwave irradiation
Benzylcholoroformate Cbz-Cl (1 mmol) was added to amine (1 mmol) and the mixture was subjected to the microwave irradiation (100W) for the appropriate time (Tables 2, 3, 4 and 5). After completion of the reaction (monitored by TLC) dichloromethane: methanol (98/2), the reaction mix- ture was treating with n-hexane (15 – 20 mL) and was allowed to stand at room temperature overnight. The solid products were collected by filtration, washed with n-hex- ane and dried to give the N-Cbz derivatives in good to excellent yields.
3. Spectral Data
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 3
Figure S1. 1H NMR spectrum: N-Carbobenzyloxyaniline (entry 1a).
Figure S2. 13C NMR spectrum: N-Carbobenzyloxyaniline (entry 1a).
4 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S3. IR spectrum: N-Carbobenzyloxyaniline (entry 1a).
Figure S4. 1H NMR spectrum: N-Carbobenzyloxybenzylamine (entry 2a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 5
Figure S5. IRspectrum: N-Carbobenzyloxybenzylamine (entry 2a).
Figure S6. 1H NMR spectrum: N-Carbobenzyloxy-4-methoxyaniline (entry 4a).
6 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S7. 13C NMR spectrum: N-Carbobenzyloxy-4-methoxyaniline (entry 4a).
Figure S8. IRspectrum: N-Carbobenzyloxy-4-methoxyaniline (entry 4a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 7
Figure S9. 1H NMR spectrum: N-Carbobenzyloxy-2-methoxyaniline (entry 5a).
Figure S10. 13C NMR spectrum: N-Carbobenzyloxy-2-methoxyaniline (entry 5a).
8 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S11. IR spectrum: N-Carbobenzyloxy-2-methoxyaniline (entry 5a).
Figure S12. 1H NMR spectrum: N-Carbobenzyloxyurea (entry 9a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 9
Figure S13. 13C NMR spectrum: N-Carbobenzyloxyurea (entry 9a).
Figure S14. IR spectrum: N-Carbobenzyloxyuree (entry 9a).
10 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S15. Mass spectrum: N-Carbobenzyloxyurea (entry 9a).
Figure S16. 1H NMR spectrum: N- Carbobenzyloxydipenylamine (entry 10a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 11
Figure S17. 13C NMR spectrum: N-Carbobenzyloxydiphenylamine (entry 10a).
Figure S18. IR spectrum: N-Carbobenzyloxydiphenylamine (entry 10a).
12 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S19. 1H NMR spectrum: N-Carbobenzyloxymorpholine (entry 12a).
Figure S20. 13C NMR spectrum: N-Carbobenzyloxymorpholine (entry 12a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 13
Figure S21. IR spectrum: N-Carbobenzyloxymorpholine (entry 12a).
Figure S22. 1H NMR spectrum: N-Carbobenzyloxyphenylpiperazine (entry 13a).
14 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S23. 13C NMR spectrum: N-Carbobenzyloxyphenylpiperazine (entry 13a).
Figure S24. IR spectrum: N-Carbobenzyloxyphenylpiperazine (entry 13a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 15
Figure S25. Mass spectrum: N-Carbobenzyloxyphenylpiperazine (entry 13a).
Figure S26. 1H NMR spectrum: N-Carbobenzyloxypropylamine (entry 16a).
16 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S27. 13C NMR spectrum: N-Carbobenzyloxypropylamine (entry 16a).
Figure S28. 13C NMR spectrum: N-Carbobenzyloxypropylamine (entry 16a).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 17
Figure S30. 13C NMR spectrum: N-Carbobenzyloxycyclohexylamine (entry 18a).
Figure S29. 1H NMR spectrum: N-Carbobenzyloxycyclohexylamine (entry 18a).
18 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S31. IR spectrum: N-Carbobenzyloxycyclohexylamine (entry 18a).
Figure S32. 1H NMR spectrum: (S)-N-Carbobenzyloxyphenylalaninol (entry 1b).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 19
Figure S33. 13C NMR spectrum: (S)-N-Carbobenzyloxyphenylalaninol (entry 1b).
Figure S34. IR spectrum: (S)-N-Carbobenzyloxyphenylalaninol (entry 1b).
20 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S35. 1H NMR spectrum: (S)-N-Carbobenzyloxyvalinol (entry 2b).
Figure S36. 13C NMR spectrum: (S)-N-Carbobenzyloxyvalinol (entry 2b).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 21
Figure S37. IR spectrum: (S)-N-Carbobenzyloxyvalinol (entry 2b).
Figure S38. Mass spectrum: (S)-N-Carbobenzyloxyvalinol (entry 2b).
22 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S39. 1H NMR spectrum: (S)-N-Carbobenzyloxyphenylalaninemethyl ester (entry 2c).
Figure S40. 13C NMR spectrum: (S)-N-Carbobenzyloxyphenylalaninemethyl ester (entry 2c).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 23
Figure S41. IR spectrum: (S)-N-Carbobenzyloxyphenylalaninemethyl ester (entry 2c).
Figure S42. Mass spectrum: (S)-N-Carbobenzyloxyphenylalaninemethyl ester (entry 2c).
24 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S43. 1H NMR spectrum: (S)-N-Carbobenzyloxyprolineethyl ester (entry 3c).
Figure S44. 13C NMR spectrum: (S)-N-Carbobenzyloxyprolineethyl ester (entry 3c).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 25
Figure S45. IR spectrum: (S)-N-Carbobenzyloxyprolineethyl ester (entry 3c).
Figure S46. Mass spectrum: (S)-N-Carbobenzyloxyprolineethyl ester (entry 3c).
26 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S48. 13C NMR spectrum: (S)-N-Carbobenzyloxyleucineethyl ester (entry 4c).
Figure S47. 1H NMR spectrum: (S)-N-Carbobenzyloxyleucineethyl ester (entry 4c).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 27
Figure S50. Mass spectrum: (S)-N-Carbobenzyloxyleucineethyl ester (entry 4c).
Figure S49. IR spectrum: (S)-N-Carbobenzyloxyleucineethyl ester (entry 4c).
28 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S52. IRspectrum: (S)-Benzyl-N-(1-hydroxy-3-methylbutan-2-yl) sulfamoylcarbamate (entry 2d).
Figure S51. 1H NMR spectrum: (S)-Benzyl-N-(1-hydroxy-3-methylbutan-2-yl) sulfamoylcarbamate (entry 2d).
A Simple, Efficient, Catalyst-Free and Solvent-Less Microwave-Assisted Process for N-Cbz Protection of Several Amines 29
Figure S54. 1H NMR spectrum: (S)-Benzyl-N-(1-hydroxy-4-methylpentan-2-yl) sulfamoylcarbamate (entry 3d).
Figure S53. Mass spectrum: (S)-Benzyl-N-(1-hydroxy-3-methylbutan-2-yl) sulfamoylcarbamate (entry 2d).
30 Zineb Aouf, Rachida Mansouri, Salah Lakrout, Malika Berredjem, and Nour-Eddine Aouf
Figure S55. 13C NMR spectrum: (S)-Benzyl-N-(1-hydroxy-4-methylpentan-2-yl) sulfamoylcarbamate (entry 3d).
Figure S56. Mass spectrum: (S)-Benzyl-N-(1-hydroxy-4-methylpentan-2-yl) sulfamoylcarbamate (entry 3d).
