Subscribe to RSS
DOI: 10.1055/s-2004-815402
Simple Synthesis of Tetrabutylammonium and Potassium Salts of Difluorotriorganostannate and Silicate Anions
Publication History
Publication Date:
12 January 2004 (online)
Abstract
The title salts are readily prepared via stirring of triorganotin halides or triorganosilyl fluorides with tetrabutylammonium hydrogen sulfate and potassium, fluoride or sole potassium fluoride.
Key words
tin compounds - silicon compounds - germanium compounds - hypervalent anions
- 1
Gingras M. Tetrahedron Lett. 1991, 32: 7381 - 2
Pilcher A.Ammon H.De Shong P. J. Am. Chem. Soc. 1995, 117: 5166 - 3
Kvíèala J.Mysík P.Paleta O. Synlett 2001, 547 - 4
García Martínez A.Osío Barcina J.Rys AZ.Subramanian LR. Tetrahedron Lett. 1992, 33: 7787 - 5
Soli E.Manoso A.Patterson M.De Shong P.Favor D.Hirschmann R.Smith A. J. Org. Chem. 1999, 64: 3171 -
6a
García Martínez A.Osío Barcina J.del Rosario Colorado Heras M.de Fresno Cereso A. Org. Lett. 2000, 2: 1377 -
6b
Brescia M.-R.DeShong P. J. Org. Chem. 1998, 63: 3156 -
6c
Movery ME.DeShong P. J. Org. Chem. 1999, 64: 3266 - 7
Kerverdo S.Fernandez X.Poulain S.Gingras M. Tetrahedron Lett. 2000, 41: 5841 -
8a
Mkosza M.Bujok R. Tetrahedron Lett. 2002, 43: 2761 -
8b
Mkosza M.Bujok R. Synlett 2002, 1285 - 11
Swain CG.Esteve RM.Jones RH. J. Am. Chem. Soc. 1949, 71: 965
References
Mkosza, M., Bujok, R., manuscript in preparation.
10
Synthesis of Tetrabutylammonium Salts
KF (10-20 equiv, see Table
[1]
), R3MX (3.0 mmol), tetrabutylammonium hydrogensulphate (3.0 mmol) and solvent (7.5 mL) were placed in flask and heated with stirring at 60 ºC for 24 h. The solid was filtered off and washed with the solvent used in the reaction (4 × 5 mL). The combined filtrates were evaporated and the residue was recrystallized from MeCN-Et2O, compounds 1 and 2 were isolated as oils and not purified.
Synthesis of Potassium Salts
KF (10-20 eq; see Table
[2]
), R3MX (1.0 mmol) and DMF (2.5 mL) were placed in flask and heated with stirring at 60 ºC for 24 h. The solid was filtered off and washed with DMF (4 × 3 mL). The combined filtrates were evaporated and the residue was recrystallized from DMF-Et2O.
1: Oil.
1H NMR (DMSO-d
6
): δ = 0.01 (9 H), [Sn satellites:
J (119Sn-1H) = 74.8 Hz, J (117Sn-1H) = 71.5 Hz], 0.94 (t, J = 7.2 Hz, 12 H), 1.21-1.40 (m, 8 H), 1.49-1.62 (m, 8 H), 3.12-3.20 (m, 8 H). 19F NMR (CDCl3): δ = -126.7. 119Sn NMR (CDCl3): δ = -53.7. MS [LSIMS(-) NBA]: m/z calcd for Me3
120SnF2
-: 203; found: 203.
2: Oil.
1H NMR (DMSO-d
6
): δ = 0.68 (m, 6 H), 0.84 (t, J = 7.2 Hz, 9 H), 0.94 (t, J = 7.2 Hz, 12 H), 1.15-1.40 (m, 14 H), 1.42-1.69 (m, 14 H.), 3.14-3.23 (m, 8 H). 19F NMR (CDCl3): δ = -146.3. 119Sn NMR (CD3CN): δ = -107.9. MS [LSIMS (-) NBA]: m/z calcd for Bu3
120SnF2
-: 329; found: 329.
3: mp 189-190.5 ºC (lit.1 189-189.5 ºC). 19F NMR (CDCl3): δ = -162.93 (s), [Sn satellites: J (119Sn-19F) = 1985 Hz, J [117Sn-19F] = 1896 Hz]. Anal. Calcd for C34H51N1F2Sn: C, 64.77; H, 8.15; N, 2.22. Found: C, 64.79; H, 8.22; N, 2.04.
4: mp 148-150 ºC (lit.2 150-151 ºC). 19F NMR (CDCl3): δ = -96.1, [Si satellites: J [29Si-19F] = 250 Hz]. Anal. Calcd for C34H51N1F2Si: C, 75.64; H, 9.52; N, 2.59. Found: C, 75.50; H, 9.52; N, 2.47.
5: mp 162-164 ºC. 1H NMR (CDCl3): δ = 0.89 (t, J = 6.9 Hz, 12 H); 1.20 (br s, 16 H); 2.74 (br s, 8 H), 7.27 (br s, 5 H, Ph). 19F NMR (376 MHz, CDCl3): δ = -118.9 (br s). MS [ESI
(-), MeCN]: m/z calcd for Ph3GeF2
-: 341; found: 341.2. Anal. Calcd for C34H51N1F2Ge: C, 69.88; H, 8.80; N, 2.40. Found: C, 69.62; H, 8.80; N, 2.28.
6: mp 136-137 ºC. 1H NMR (CDCl3): 0.85 (t, J = 6.8 Hz, 12 H), 0.98-1.12 (m, 16 H), 2.26 (s. 9 H), 2.40-2.48 (m, 8 H), 7.05 (6 H), 7.93 [Sn satellites: J (119Sn-1H) = 70 Hz, J (117Sn-1H) = 55 Hz; 6 H). 19F NMR (CDCl3): δ = -161.2 [Sn satellites: J (119Sn-19F) = 1942 Hz, J [117Sn-19F] = 1857 Hz). 119Sn NMR (CDCl3): δ = -333.4 [t,
J (119Sn-19F) = 1938 Hz). MS [LSIMS (-) NBA]: m/z calcd for (4-MePh)3
120SnF2
-: 431; found: 431.5.
7: mp 136-138 ºC. 1H NMR (DMSO-d
6
): δ = 0.92 (t, J = 7.2 Hz, 12 H), 1.26-1.36 (m, 8 H), 1.44-1.58 (m, 8 H), 2.21 (s, 9 H), 3.08-3.12 (m, 8 H), 6.91, 7.74 (AA′XX′, 12 H). 19F NMR (DMSO-d
6
): δ = -97.7 [Si satellites: J [29Si-19F] = 254 Hz, MS [ESI(-) MeCN]: m/z calcd for (4-MePh)3SiF2
-: 339; found: 339. Anal. calcd for C37H57N1F2Si: C, 76.36; H, 9.87; N, 2.41. Found C, 76.13; H, 10.13; N, 2.34.
8: mp 138-140 ºC. 1H NMR (DMSO-d
6
): δ = 0.93 (t, J = 7.4 Hz), 1.25-1.34 (m, 8 H), 1.50-1.59 (m, 8 H), 3.12-3.154 (m, 8 H), 7.18, 7.96 (AA′XX′, 12 H). 19F NMR (DMSO-d
6
): δ = -97.6 [Si satellites: J (29Si-19F) = 255 Hz]. MS [ESI (-) MeCN]: m/z calcd for (4-35ClPh)3SiF2
-: 399; found: 399.
9: mp > 250 ºC. 1H NMR (400 MHz, DMSO-d
6
): δ = 7.25 (br s, 9 H), 7.94 [Sn satellites: J (117,119Sn-1H) = 64 Hz, 6 H). 19F NMR (376 MHz, DMSO-d
6
): δ = -164.3 [Sn satellites: J (Sn-F) = 2021 Hz]. 119Sn NMR (DMSO-d
6
.): δ = -350.0 [t, J [119Sn-19F] = 1938 Hz). MS [LSIMS (-) NBA]: m/z calcd for Ph3
120SnF2
-: 389; found: 389. Anal. Calcd for C18H15F2KSn: C, 50.62; H, 3.54 Found C, 50.25; H, 3.83.
10: mp 225 ºC (decomp.). 1H NMR (400 MHz, DMSO-d
6
): δ = 7.10-7.13 (m, 5 H), 7.31-7.36 (m, 3 H), 7.41-7.44 (m, 4 H), 7.85-7.88 (m, 3 H). 19F NMR (376 MHz, DMSO-d
6
):
δ = -98.2. Anal. Calcd for C18H15F2KSi: C, 64.25; H, 4.49. Found C, 64.51; H, 4.71.
11: mp > 250 ºC. 1H NMR (400 MHz, DMSO-d
6
): δ = 2.26 (s, 9 H), 7.08 (br s, 6 H), 7.80 (br s, 6 H). 19F NMR (376 MHz, DMSO-d
6
): δ = -162.9 [Sn satellites: J (117,119Sn-
19F) = 2020 Hz, 117Sn NMR (DMSO-d
6
): δ = -346.8 [t,
J (117Sn-19F) = 1929 Hz]. MS [ESI (-) MeCN]: Calcd for
(4-MePh)3
120SnF2
-: 431; found 431.3. Anal. calcd for C21H21F2KSn: C, 53.67; H, 4.51. Found C, 52.97; H, 4.53.
12: mp > 250 ºC. 1H NMR (400 MHz, DMSO-d
6
): δ = 7.32 (br s, 6 H), 7.97 [Sn satellites: J (117,119Sn-1H) = 53 Hz, 6 H). 19F NMR (37 MHz, DMSO-d
6
): δ = -164.3 [Si satellites: J (119Sn-19F) = 2089 Hz, J (117Sn-19F) = 1997 Hz]. 117Sn NMR (DMSO-d
6
.): δ = -353.5 [t,
J (117Sn-19F) = 1997 Hz]. MS [ESI (-) MeCN]: m/z calcd for (4-35ClPh)3
120SnF2
-: 491.0; found: 491.0. Anal. Calcd for C18H12Cl3F2KSn: C, 40.76; H, 2.28. Found C, 41.40; H, 2.74
13: mp 164 ºC (decomp.). 1H NMR (400 MHz, DMSO-d
6
): δ = 7.16-7.21 (m, 3 H), 7.48-7.54 (m, 6 H), 7.84-7.90 (m, 3 H). 19F NMR (376 MHz, DMSO-d
6
): -97.6 [Si satellites: J [29Si-19F] = 256 Hz]. Anal. Calcd for C18H12Cl3F2KSi: C, 49.15; H, 2.75. Found C, 49.08; H, 3.04.