Subscribe to RSS
DOI: 10.1055/s-2005-862396
TEMPO-Derived Task-Specific Ionic Liquids for Oxidation of Alcohols
Publication History
Publication Date:
22 February 2005 (online)
![](https://www.thieme-connect.de/media/synlett/200504/lookinside/thumbnails/10.1055-s-2005-862396-1.jpg)
Abstract
A novel 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical bearing an ionic liquid-type appendage has been prepared, and its catalytic activity for the selective oxidation of alcohols to the corresponding carbonyl compounds in ionic liquid-aqueous biphasic conditions has been investigated. The ionic liquid-supported TEMPO radical shows catalyst properties similar to those of non-supported counterpart in terms of activity and selectivity, and can be easily recycled and reused without loss of activity and selectivity.
Key words
ionic liquids - alcohols - carbonyl compounds - oxidation - TEMPO
- 1
Hudlicky M. Oxidations in Organic Chemistry American Chemical Society; Washington DC: 1990. - 2
Degonneau M.Kagan ES.Mikhailov VI.Rozantsev EG.Sholle VD. Synthesis 1984, 895 - 4
de Nooy A.Besemer A.van Bekkum H. Synthesis 1996, 35: 1153 - 5
Anelli PL.Biffi C.Montanari F.Quici S. J. Org. Chem. 1987, 52: 2559 - 6
Zhao M.Li J.Mano E.Song Z.Tschaen DM.Grabowski EJJ.Reider PJ. J. Org. Chem. 1999, 64: 2564 - 7
Einhorn J.Einhorn C.Ratajczak F.Pierre JL. J. Org. Chem. 1996, 61: 7452 -
8a
Cella JA.Kelley JA.Kenehan EF. J. Org. Chem. 1975, 40: 1860 -
8b
Cella JA.McGrath JP.Kelley JA.El Soukkary O.Hilpert L. J. Org. Chem. 1977, 42: 2077 -
9a
Anelli PL.Biffi C.Montanari F.Quici S. J. Org. Chem. 1989, 54: 2970 -
9b
Anelli PL.Montanari F.Quici S. Org. Synth. 1990, 69: 212 -
10a
Heeres A.van Doren HA.Gotlieb KF.Bleeker IP. Carbohydr. Res. 1997, 299: 221 -
10b
Bolm C.Fey T. Chem. Commun. 1999, 1795 -
10c
Brunel D.Lentz P.Sutra P.Fajula F.Nagy JB. Stud. Surf. Sci. Catal. 1999, 125: 237 -
10d
Verhoef MJ.Peters JA.van Bekkum H. Stud. Surf. Sci. Catal. 1999, 125: 465 -
10e
Ciriminna R.Blum J.Avnir D.Pagliaro M. Chem. Commun. 2000, 1441 -
10f
Fey T.Fischer H.Bachmann S.Albert K.Bolm C. J. Org. Chem. 2001, 66: 8154 - 11
Dijksman A.Arends IWCE.Sheldon RA. Chem. Commun. 2000, 271 -
12a
Cornils B. Catalysis from A to Z: A Concise Encyclopedia Wiley-VCH; Weinheim: 2000. -
12b
Czarnik AW. Solid Phase Organic Synthesis Wiley; New York: 2001. - 13
Dijksman A.Arends IWCE.Sheldon RA. Chem. Commun. 2000, 271 - 14
Tanyeli C.Gümüs A. Tetrahedron Lett. 2003, 44: 1639 - 15
Pozzi C.Cavazzini M.Quici S.Benaglia M.Dell’Anna G. Org. Lett. 2004, 6: 441 - 16
Wasserscheid P.Welton T. Ionic Liquids in Synthesis Wiley-VCH; Weinheim: 2003. - 17
Wierzbicki A.Davis JH. Proceedings of the Symposium on Advances in Solvent Selection and Substitution for Extraction, 5-9 March 2000 AIChE; New York: 2000. - 18
Fuller RT.Carlin HC.de Long HC.Haworth D. J. Chem. Soc., Chem. Commun. 1994, 299 - 21
Anelli PL.Biffi C.Montanari F.Quici S. J. Org. Chem. 1987, 52: 2559
References
LD50 (oral rat, 4-hydroxy-TEMPO) = 1053 mg Kg21; CAS database.
19
General Procedure for the Attachment of One TEMPO Unit.
To a stirred solution of 4-hydroxy-2,2,6,6-tetramethyl-piperdine-1-oxyl (1, 0.86 g, 5 mmol) and chloroactic acid (0.40 g, 5 mmol) in CH2Cl2 (25 mL) at 0 °C under argon, DCC (1.03 g, 5 mmol) and DMAP (0.15 g, 1.25 mmol) were added and the reaction mixture was stirred for 12 h at r.t. The solid materials formed were filtered off and the filtrate was washed with 1 M HCl (5 mL) followed by sat. NaHCO3 (10 mL) and brine (10 mL). The organic phase was dried over MgSO4 and evaporated under reduced pressure, and then filtered through a short flash chromatography (EtOAc-hexanes 1:4) providing chloroacetic acid 2,2,6,6-tetra-methyl-1-oxy-piperidin-4-yl ester(2) as a red powder (1.14 g, 92%). Then 1-methylimidazole (0.46 g, 5.6 mmol) was added to a solution of 2 (1.00 g, 4 mmol) in MeCN (30 mL) and the resulting solution was stirred for 48 h at 80 °C. After that, the solvent was removed in vacuum and the residue was washed with acetone to give 3 as a light red powder (1.30 g, 98%). Compound 4 was prepared by stirring 3 (1.00 g, 3 mmol) with KPF6 (0.66 g, 3.6 mmol) in acetone (30 mL) at r.t. for 48 h. After this, the insoluble by-products were filtered off and the acetone was removed in vacuum to afford 4 as a pink powder (1.27 g, 96%). As excepted, this charged TEMPO 4 is preferentially soluble in [bmim]PF6 and insoluble in water. All these novel compounds were stable in air and characterized by 1H NMR, 13C NMR, FTIR spectro-metry, mass spectrometry and elemental analyses ref. 20.
To samples containing nitroxyl radical residues was added one drop of neat phenylhydrazine to the NMR sample tube immediately prior to analysis in order to reduce in situ the paramagnetic center to the corresponding hydroxylamine species.
Compound 2: mp 55 °C. 1H NMR (400 MHz, CDCl3): δ = 5.14 (s, 1 H), 4.10 (s, 2 H), 1.97 (t, 2 H, J = 0.8 Hz), 1.83 (t, 2 H, J = 1.2 Hz), 1.28 (s, 6 H), 1.14 (s, 6 H). 13C NMR (400 MHz, CDCl3): δ = 20.37, 31.93, 41.21, 43.29, 68.47, 166.79. IR (KBr, selected data): 1751.93, 1204.23, 1161.84, 791.67 cm-1. Anal. Calcd for C11H19ClNO3: C, 53.12; H, 7.70; Cl, 14.25; N, 5.63. Found: C, 53.17; H, 7.74; N, 5.67. MS (ESI): m/z calcd [M]+: 248.73; found: 248.40.
Compound 3: mp 191 °C. 1H NMR (400 MHz, DMSO): δ = 9.14 (s, 1 H), 7.54 (s, 1 H), 7.36 (s, 1 H), 5.24 (s, 2 H), 5.04 (s, 3 H), 3.90 (s, 3 H), 1.90 (t, 2 H, J = 0.8 Hz), 1.50 (t, 2 H, J = 1.2 Hz), 1.10 (s, 6 H), 1.07 (s, 6 H). 13C NMR (400 MHz, DMSO): δ = 166.43, 137.73, 123.66, 123.27, 68.92, 57.93, 49.54, 43.37, 35.89, 32.06, 20.32. IR (KBr, selected data): 1745.13, 1175.20, 1221.89 cm-1. Anal. calcd for C15H25ClN3O3: C, 54.46; H, 7.62; N, 12.70. Found: C, 54.58; H, 7.59; N, 12.72. MS (FAB): m/z calcd [M]+: 295.38; found: 294.7.
Compound 4: mp 53 °C. 1H NMR (400 MHz, DMSO): δ = 9.04 (s, 1 H), 7.36 (s, 1 H), 7.27 (s, 1 H), 5.20 (s, 2 H), 5.04 (s, 3 H), 3.89 (s, 3 H), 1.91 (t, 2 H, J = 0.8 Hz), 1.50 (t, 2 H, J = 1.2 Hz), 1.10 (s, 6 H), 1.08 (s, 6 H). 13C NMR (400 MHz, DMSO): δ = 166.38, 137.69, 123.68, 123.29, 69.09, 58.03, 49.59, 43.41, 35.87, 32.09, 20.37. IR (KBr, selected data): 1745.13, 1225.18, 1178.83, 839.76 cm-1. Anal. calcd for C15H25F6N3O3P: C, 40.91; H, 5.72; N, 9.54; P, 7.03. Found: C, 40.81; H, 5.62; N, 9.30; P, 7.23. MS (FAB): m/z calcd [M]+: 295.38; found: 294.9.
General Procedure for all Oxidation Runs.
An alcohol (0.80 mmol), 4 (0.008 mmol, 3.54 mg) and dodecane (0.24 mmol) used as the internal standard in GC-analysis were dissolved in [bmim]PF6 (2 mL) followed by 0.16 mL aq KBr (0.5 M). After cooling the mixture at 0 °C, 2.7 mL of aq NaOCl diluted to a concentration of 0.37 M and buffered to pH 8.6 by NaHCO3 was added and the reaction mixture stirred vigorously. After the oxidation, the IL phase was separated and the resultant carbonyl compounds could easily be separated from the IL medium by simple extraction with Et2O (4 × 5 mL), which was analyzed by GC. The IL containing catalyst can subsequently be re-used for a new reaction cycle. The combined organic extracts were dried with Na2SO4, and evaporated to dryness. The residue was purified by silica gel flash chromatography eluting with EtOAc-petroleum ether.