R. Arvai et al. / Tetrahedron 65 (2009) 5361–5368
5367
3.27. 1-Benzyl-3-methyl-3H-imidazol-1-ium trifluoro-
methanesulfonimide 3r
3.31. Allylethyldiisopropylammonium trifluoro-
methanesulfonimide 10b
RN: [433337-24-7]20k
Prepared from DIEA (0.172 mL, 1 mmol); colourless oil (0.342 g,
0.76 mmol, 76%).
Prepared from 1-methyl-1H-imidazole (0.079 mL, 1 mmol);
yellow oil (0.385 g, 0.85 mmol, 85%).
1H NMR (CDCl3, 300 MHz):
d 5.99–5.86 (m, 1H), 5.59–5.48
1H NMR (CDCl3, 300 MHz):
d
8.68 (s, 1H), 7.37 (s, 5H), 7.29–7.28
(m, 2H), 3.90–3.78 (m, 4H), 3.29 (q, JH–H¼6.0 Hz, 2H), 1.39 (d,
3
(m, 1H), 7.24–7.23 (m, 1H), 5.27 (s, 2H), 3.86 (s, 3H); 13C NMR
3JH–H¼6.8 Hz, 12H), 1.29 (t, JH–H¼6.0 Hz, 3H); 13C NMR (CDCl3,
3
1
(100 MHz, CDCl3):
d
135.4, 132.3, 129.4, 129.2, 128.5, 123.7, 122.0,
50 MHz):
d
126.7, 126.3, 119.8 (q, JC–F¼319.5 Hz), 62.7, 60.1, 52.3,
1
119. 5 (q, JC–F¼319 Hz), 53.1, 35.9; 19F NMR (CDCl3, 282 MHz):
18.2, 18.1, 9.8; 19F NMR (CDCl3, 282 MHz):
d
ꢀ79.48 (s, 1F).
d
ꢀ79.58 (s, 1F).
Anal. Calcd for C13H24F6N2O4S2$0.4H2O: C, 34.12; H, 5.46; N,
Anal. Calcd for C13H13F6N3O4S2: C, 34.44; H, 2.89; N, 9.27; S,
6.12; S, 14.01. Found: C, 34.21; H, 5.27; N, 6.12; S, 14.39.
14.14. Found: C, 34.36; H, 2.78; N, 9.24; S, 14.05.
3.32. Allyltriphenylphosphonium trifluoro-
methanesulfonimide 10c
3.28. Benzyltriphenylphosphonium trifluoromethane-
sulfonimide 3s
Prepared from Ph3P (1 mmol); colourless oil (0.484 g,
0.83 mmol, 83%).
RN: [953415-83-3]20l
1H NMR (CDCl3, 300 MHz):
d
7.82–7.76 (m, 3H), 7.70–7.58 (m,
12H), 5.73–5.58 (m, 1H), 5.41–5.33 (m, 2H), 4.04–3.96 (m, 2H); 13C
NMR (CDCl3, 50 MHz):
Prepared from Ph3P (0.873 mmol); colourless oil (0.431 g,
0.68 mmol, 78%).
1H NMR (CDCl3, 300 MHz):
d
7.81 (qt, J¼7.5, 1.4 Hz, 3H), 7.65 (dt,
d
135.4, 133.5 (d, JC–P¼10.0 Hz), 130.5 (d,
J¼7.8, 3.6 Hz, 6H), 7.53–7.46 (m, 6H), 7.31–7.26 (m, 1H), 7.16 (t,
J¼7.6 Hz, 2H), 6.88 (dd, J¼7.4, 2.0 Hz, 2H), 4.57 (d, J¼14.1 Hz, 2H);
JC–P¼12.5 Hz), 126.1 (d, JC–P¼13.0 Hz), 122.7 (d, JC–P¼9.5 Hz), 119.9
1
(q, JC–F¼320.0 Hz), 117.4 (d, JC–P¼86.0 Hz), 28.4 (d, JC–P¼51.0 Hz);
13C NMR (CDCl3, 50 MHz):
d
135.43 (d, JC–P¼3.0 Hz), 133.9 (d,
19F NMR (CDCl3, 282 MHz):
121 MHz): 21.62 (s, 1P).
d
ꢀ79.32 (s, 1F); 31P NMR (CDCl3,
JC–P¼10.0 Hz), 130.9 (d, JC–P¼5.5 Hz), 130.4 (d, JC–P¼12.5 Hz), 129.1
(d, JC–P¼3.5 Hz), 128.9 (d, JC–P¼4.0 Hz), 126.4 (d, JC–P¼8.5 Hz), 119. 7
(q, JC–F¼320 Hz), 117.0 (d, JC–P¼85.5 Hz), 30.7 (d, JC–P¼47.0 Hz); 19F
Anal. Calcd for C23H20F6NO4PS2: C, 47.34; H, 3.45; N, 2.40; S,
10.99. Found: C, 47.35; H, 3.54; N, 2.52; S, 10.69.
NMR (CDCl3, 282 MHz):
23.66 (s, 1P).
d
ꢀ79.19 (s, 1F), 31P NMR (CDCl3, 121 MHz):
3.33. 1-Allyl-tetrahydrothiophenium trifluoro-
methanesulfonimide 10d
Anal. Calcd for C27H22F6NO4PS2: C, 51.19; H, 3.50; N, 2.21; S,
10.12. Found: C, 51.44; H, 3.62; N, 2.37; S, 9.91.
RN: [949155-08-2]20m
3.29. N-Allyl trifluoromethanesulfonimide 9
Prepared from tetrahydrothiophene (1 mmol); yellow oil
(0.358 g, 0.84 mmol, 84%).
RN: [70869-00-0]15c
1H NMR (CD3CN, 200 MHz):
d 8.89–5.77, (m, 1H), 5.66–5.55 (m,
DIEA (8.14 mL, 46.8 mmol) was added, under inert atmosphere,
to a solution of a freshly distilled allylamine (1.75 mL, 23.40 mmol)
in anhydrous dichloromethane (40 mL). The reaction mixture was
cooled down to ꢀ78 ꢁC, then triflic anhydride (9.83 mL, 58.5 mmol)
was added dropwise. The reaction mixture was slowly warmed up
to room temperature (30 min) and stirred at this temperature for
30 min. Then, 3% aqueous HCl (50 mL) was added. The aqueous
phase was extracted with dichloromethane and the combined or-
ganic layers dried over MgSO4. Filtration and solvent evaporation
left a crude mixture, which was refluxed in pentane. Before cooling
down to room temperature, the pentane phase was collected. This
operation was repeated several times. Evaporation of the combined
pentane fractions left the allyl sulfonimide 9 as a brown oil (0.65 g,
87%).
2H), 3.81 (d, JH–H¼8 Hz, 2H), 3.54–3.24 (m, 4H), 2.39–2.14 (m, 4H);
13C NMR (CD3CN, 50 MHz):
d
127.8, 126.0, 121.0 (q, 1JC–F¼318.5 Hz),
45.2, 43.2, 29.4; 19F NMR (CD3CN, 235 MHz):
Anal. Calcd for C9H13F6NO4S3: C, 26.40; H, 3.20; N, 3.42; S, 23.50.
Found: C, 26.65; H, 3.10; N, 3.53; S, 23.11.
d
ꢀ79.93.
Supplementary data
Supplementary data associated with this article can be found in
References and notes
1H NMR (CDCl3, 300 MHz):
d
5.98–5.84 (m, 1H), 5.49–5.42 (m,
1. (a) Foropoulos, J.; DesMarteau, D. D. Inorg. Chem. 1984, 23, 3720–3723; (b)
DesMarteau, D. D.; Witz, M. J. Fluorine Chem. 1991, 52, 7–12.
2. Xu, K. Chem. Rev. 2004, 104, 4303–4417.
3. (a) Belieres, J. P.; Gervasio, D.; Angell, C. A. Chem. Commun. 2006, 4799–4801;
(b) Susan, B. H.; Noda, A.; Mitsushima, S.; Watanabe, M. Chem. Commun. 2003,
938–939.
2H), 4.53 (d, 3JH–H¼7.0 Hz, 2H); 13C NMR (CDCl3, 50 MHz):
d 129.3,
123.2, 118.8 (q, JC–F¼322.2 Hz), 55.8; 19F NMR (CDCl3, 282 MHz):
d
ꢀ72.60 (s, CF3).
4. Xue, H.; Verma, R.; Shreeve, J. M. J. Fluorine Chem. 2006, 127, 159–176.
5. Olah, G. A.; Prakash, G. K. S.; Sommer, J. Superacids; John Wiley: New York,
NY, 1985.
3.30. Allyldiisopropylammonium trifluoro-
methanesulfonimide 10a
6. (a) Singh, S.; DesMarteau, D. D.; Zuberi, S. S.; Witz, M.; Huang, H.-N. J. Am. Chem.
Soc. 1987, 109, 7194–7196; (b) Zhang, J.; DesMarteau, D. D. J. Fluorine Chem.
2001, 111, 253–257; (c) Lal, G. S.; Pez, G. P.; Syvret, R. G. Chem. Rev. 1996, 96,
1737–1755.
7. Central Glass Co. Ltd, JP 070246338, 1995.
8. Hasegawa, Y.; Ohkubo, T.; Sogabe, K.; Kawamura, Y.; Wada, Y.; Nakashima, N.;
Yanagida, S. Angew. Chem., Int. Ed. 2000, 39, 357–360.
9. (a) Howells, R. D; Lamanna, W. M; Fanta, A. D; Waddell, J.E. WO 9723448 (to
3M), 1997; Chem. Abstr. 1997, 03575; (b) Sakai, S; Takase, H; Sakauchi, H. EP
1029850 (to Central Glass Co. Ltd.), 2000; Chem. Abstr. 2000, 592395.
10. (a) Sakaguchi, H; Fuji, K; Sakai, S; Kobayashi, Y; Kita, Y. FR 2724380 (to Central
Glass Co. Ltd.), 1996; Chem. Abstr. 1996, 311263; (b) Morizaki, K; Sasaki, M. JP
2000086617 (to Kanto Denka Kogyo KK), 2000; Chem. Abstr. 2000, 198018.
Prepared from iPr2NH (0.140 mL, 1 mmol); colourless oil
(0.329 g, 0.78 mmol, 78%).
1H NMR (CDCl3, 300 MHz):
d 6.71 (br s, 1H), 6.03–5.80 (m, 1H),
5.62–5.42 (m, 2H), 3.95–3.83 (m, 1H), 3.61–3.77 (m, 3H), 1.33 (d,
3JH–H¼6.8 Hz, 12H); 13C NMR (CDCl3, 50 MHz):
d 127.6, 124.5, 119.6
(q, 1JC–F¼318.5 Hz), 55.3, 50.2, 18.2, 17.1; 19F NMR (CDCl3, 282 MHz):
d
ꢀ79.55 (s, 1F).
Anal. Calcd for C11H20F6N2O4S2: C, 31.28; H, 4.77; N, 6.63; S,
15.18. Found: C, 31.46; H, 4.76; N, 6.64; S, 14.94.