Simple Synthesis of Tetrabutylammonium and Potassium Salts of Difluorotriorganostannate and Silicate Anions

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.

tin compounds - silicon compounds - germanium compounds - hypervalent anions

References

<A NAME="RG30003ST-1">1</A> Gingras M. Tetrahedron Lett.  1991,  32:  7381 

<A NAME="RG30003ST-2">2</A> Pilcher A. Ammon H. De Shong P. J. Am. Chem. Soc.  1995,  117:  5166 

<A NAME="RG30003ST-3">3</A> Kvíèala J. Mysík P. Paleta O. Synlett  2001,  547 

<A NAME="RG30003ST-4">4</A> García Martínez A. Osío Barcina J. Rys AZ. Subramanian LR. Tetrahedron Lett.  1992,  33:  7787 

<A NAME="RG30003ST-5">5</A> Soli E. Manoso A. Patterson M. De Shong P. Favor D. Hirschmann R. Smith A. J. Org. Chem.  1999,  64:  3171 

<A NAME="RG30003ST-6A">6a</A> García Martínez A. Osío Barcina J. del Rosario Colorado Heras M. de Fresno Cereso A. Org. Lett.  2000,  2:  1377 

<A NAME="RG30003ST-6B">6b</A> Brescia M.-R. DeShong P. J. Org. Chem.  1998,  63:  3156 

<A NAME="RG30003ST-6C">6c</A> Movery ME. DeShong P. J. Org. Chem.  1999,  64:  3266 

<A NAME="RG30003ST-7">7</A> Kerverdo S. Fernandez X. Poulain S. Gingras M. Tetrahedron Lett.  2000,  41:  5841 

<A NAME="RG30003ST-8A">8a</A> Mkosza M. Bujok R. Tetrahedron Lett.  2002,  43:  2761 

<A NAME="RG30003ST-8B">8b</A> Mkosza M. Bujok R. Synlett  2002,  1285 

<A NAME="RG30003ST-9">9</A>

Mkosza, M., Bujok, R., manuscript in preparation.

<A NAME="RG30003ST-10">10</A>

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.

<A NAME="RG30003ST-11">11</A> Swain CG. Esteve RM. Jones RH. J. Am. Chem. Soc.  1949,  71:  965