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Synlett 2003(5): 0631-0634
DOI: 10.1055/s-2003-38358
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Catalytic Lewis Acid Activation of Thionyl Chloride: Application to the Synthesis of Aryl Sulfinyl Chlorides Catalyzed by Bismuth(III) Salts

Magali Peyronneaua, Nicolas Roquesb, Stéphane Mazières*a, Christophe Le Roux*a
a Hétérochimie Fondamentale et Appliquée (UMR CNRS 5069), Université Paul-Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex, France
Fax: +33(5)61558204; e-Mail: leroux@chimie.ups-tlse.fr;
b Rhodia Organique Fine, Centre de Recherche de Lyon, 85 rue des Frères Perret, 69192 Saint-Fons Cedex, France
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Publication History

Received 10 January 2003
Publication Date:
28 March 2003 (online)

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Abstract

The catalytic Lewis acid activation of thionyl chloride (1) has been achieved and applied to the preparation of aryl sulfinyl chlorides using BiCl3 (2), or Bi(OTf)3·xH2O (with 1 < x ≤ 4) (3) as catalysts. 3 is by far more efficient than 2 and the scope of this reaction is restricted to electron rich aromatics.

Key words

catalysis - electrophilic activation - thionyl chloride - bismuth reagents - Friedel-Crafts reactions

    References

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    When a 10:2:0.4 molar mixture of 1, 4 and 3 was stirred at -5 °C for 2 h, the 1H NMR signals of 4 remained unchanged.

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    Unfortunately in our hands, using scandium triflate purchased from Aldrich Chemical Co., used as received and following the procedure reported, [19a] 1 failed to react with some selected aromatic compounds (anisole, veratrole, biphenyl, fluorobenzene, benzene, chlorobenzene).
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17

From our experience the stability of aryl sulfinyl chlorides seems highly unpredictable.

20

General procedure. CAUTION: Aromatic sulfinyl chlorides are thermolabile compounds and have been reported to explode during distillation. [4a] [5a] Thus, distillation was not attempted in our experiments and all the yields reported have been determined by 1H NMR (250 MHz) after addition of a known amount of dibromomethane. To a 50 mL flask equipped with a septum inlet and magnetic stirring bar was added 160 mg (507 µmol) of bismuth(III) chloride. The flask was connected to an argon line and 18 mL (247 mmol) of freshly distilled thionyl chloride were added by syringe. To this suspension was added 2.74 g (25.3 mmol) of anisole. The flask was equipped with a condenser, connected to an oil bubbler and the reaction mixture was heated in an oil bath at 60 °C for 1 h. During this time the color of the solution became red-orange and HCl evolved from the solution. The flask was cooled in an ice bath and the excess of thionyl chloride was removed in vacuum (0.1 mm Hg) yielding to an orange liquid. In order to remove the catalyst, 50 mL of pentane were added, the organic phase was collected and evaporated under reduced pressure to give a yellow liquid, which was characterized as 4-methoxybenzenesulfinyl chloride(4). 1H NMR (CDCl3): δ 3.84 (s, 3 H, OMe), 7.03 (d, 2 H, H3,5, J = 8.9 Hz), 7.79 (d, 2 H, H2,6, J = 8.9 Hz); 13C NMR (CDCl3): δ 55.9 (OMe), 114.9, 126.1 (CH phenyl), 139.9 (C-OMe), 164.1 (C-SO phenyl); IR (neat): 2976, 1587, 1488, 1310, 1260, 1146, 1078, 1021, 831 cm-1. The formation of 4 was proved after characterization of its corresponding sulfinamide (N,N-diisopropyl-4-methoxybenzenesulfinamide was isolated after flash chromatography over silica gel G60, eluant: ethyl acetate) as previously reported. [7a] Mp = 57-58 °C; 1H NMR (CDCl3): δ 1.09 (d, 6 H, CHMe2, J = 6.7 Hz), 1.38 (d, 6 H, CHMe2, J = 6.7 Hz), 3.58 (spt, 2 H, CHMe2, J = 6.7 Hz), 3.83 (s, 3 H, Me), 6.98 (m, 2 H, H3,5), 7.53 (d, 2 H, H2,6); 13C NMR (CDCl3): δ 23.7, 23.8 (CHMe2), 46.7 (CHMe2), 55.4 (OMe), 114.0, 128.1 (CH phenyl), 135.7 (C-OMe), 161.2 (C-SO phenyl); IR(neat): 2966, 1461, 1376, 1245, 1180, 1087, 831 cm-1; MS (EI): m/z (%) = 255 (8) [M+], 240 (8), 155 (100), 58 (18), 43 (17).
4-Methoxy-2-methylbenzenesulfinyl chloride: 1H NMR (CDCl3): δ 2.27 (s, 3 H, C-Me), 3.56 (s, 3 H, OMe), 6.53 (d, 1 H, H3, J = 2.3 Hz), 6.69 (dd, 1 H, H5, J = 2.3 Hz and 8.8 Hz), 7.78 (d, 1 H, H6, J = 8.8 Hz); 13C NMR (CDCl3): δ 18.1 (C-Me), 55.9 (OMe), 113.0, 117.0, 126.0 (CH phenyl), 138.2, 138.6 (C-Me and C-OMe phenyl), 164.4 (C-SO phenyl); IR (neat): 2940, 1590, 1568, 1480, 1456, 1323, 1291, 1249, 1148, 1058, 851, 814 cm-1.
N,N -diisopropyl-4-methoxy-2-methylbenzenesulfin-amide: 1H NMR (CDCl3): δ 1.05 (d, 6 H, CHMe2, J = 6.7 Hz), 1.38 (d, 6 H, CHMe2, J = 6.7 Hz), 2.31 (s, 3 H, C-Me), 3.56 (spt, 2 H, CHMe2, J = 6.7 Hz), 3.80 (s, 3 H, OMe), 6.67 (d, 1 H, H3, J = 2.4 Hz), 6.87 (dd, 1 H, H5, J = 2.4 Hz and 8.5 Hz), 7.92 (d, 1 H, H6, J = 8.5 Hz); 13C NMR (CDCl3): δ 19.1 (C-Me), 23.5, 23.9 (CHMe2), 47.1 (CHMe2), 55.3 (OMe), 111.0, 116.7, 128.7 (CH phenyl), 132.6, 137.1 (C-Me and C-OMe phenyl), 161.3 (C-SO phenyl); IR (neat): 2970, 1597, 1481, 1240, 1069, 1055, 940, 861 cm-1; MS (EI): m/z (%) = 269 (16) [M+], 169 (100), 141 (19), 108 (48), 58(35), 43 (51).
4-Methoxy-3-methylbenzenesulfinyl chloride: 1H NMR (CDCl3): δ 2.06 (s, 3 H, C-Me), 3.58 (s, 3 H, OMe), 6.72 (d, 1 H, H5, J = 8.5 Hz), 7.5 (m, 1 H, H2), 7.54 (dd, 1 H, H6, J = 2.4 Hz and 8.5 Hz); 13C NMR (CDCl3): δ 18.7 (C-Me), 56.1 (OMe), 110.5, 124.3, 126.2 (CH phenyl), 128.8, 139.6 (C-Me and C-OMe phenyl), 162.6 (C-SO phenyl); IR (neat): 2974, 1588, 1492, 1458, 1317, 1255, 1135, 1080, 1024, 808 cm-1.
N,N -diisopropyl-4-methoxy-3-methylbenzenesulfin-amide: 1H NMR (CDCl3): δ 1.00 (d, 6 H, CHMe2, J = 6.7 Hz), 1.28 (d, 6 H, CHMe2, J = 6.7 Hz), 2.13 (s, 3 H, Me), 3.44 (spt, 2 H, CHMe2, J = 6.7 Hz), 3.74 (s, 3 H, CH3), 6.78 (d, 1 H, H5, J = 8.5 Hz), 7.26 (m, 1 H, H2), 7.30 (dd, 1 H, H6, J = 2.4 Hz and 8.5 Hz); 13C NMR (CDCl3): δ 16.3 (C-Me), 23.7, 23.8 (CHMe2), 46.2 (CHMe2), 55.4 (OMe), 109.6, 125.6 (CH phenyl), 127.1 (C-Me or C-OMe phenyl), 128.4 (CH phenyl), 134.8 (C-Me or C-OMe phenyl), 159.3 (C-SO phenyl); IR(neat): 2967, 1594, 1488, 1458, 1365, 1252, 1182, 1123, 1067, 944 cm-1; MS (EI): m/z (%) = 269(10) [M+], 254 (6), 169 (100), 58 (13), 43 (13).
3,4-Dimethoxybenzenesulfinyl chloride: 1H NMR (CDCl3): δ 3.97 (s, 3 H, OMe), 3.98 (s, 3 H, OMe), 7.00 (d, 1 H, H3, J = 8.9 Hz), 7.42 (m, 2 H, H2,5); 13C NMR (CDCl3): δ 56.0 and 56.1 (OMe), 105.5, 110.7, 117.9 (CH phenyl), 139.7, 149.8 (C-Me and C-OMe phenyl), 153.8 (C-SO phenyl); IR(neat): 2954, 1574, 1503, 1461, 1261, 1231, 1133, 1077, 1015 cm-1.
N,N -diisopropyl-3,4-dimethoxybenzenesulfinamide: 1H NMR (CDCl3): δ 0.93 (d, 6 H, CHMe2, J = 6.7 Hz), 1.20 (d, 6 H, CHMe2, J = 6.7 Hz), 3.38 (spt, 2 H, CHMe2, J = 6.7 Hz), 3.72 (s, 3 H, OMe), 3.73 (s, 3 H, OMe), 6.77 (d, 2 H, H3, J = 8.8 Hz), 6.94-7.10 (m, 2 H, H2-6); 13C NMR (CDCl3): δ 23.6, 23.8 (CHMe2), 46.2 (CHMe2), 55.9 (OMe), 109.1, 110.7, 119.3 (CH phenyl), 136.0, 149.0 (C-Me and C-OMe phenyl), 150.4 (C-SO phenyl); IR (neat): 2964, 1588, 1504, 1268, 1254, 1229, 1182, 1088 cm-1; MS (EI): m/z (%) = 285 (9) [M+], 185 (100), 58 (8), 43(11).
4-Ethoxybenzenesulfinyl chloride: 1H NMR (CDCl3): δ 1.39 (t, 3 H, Me, J = 7.5 Hz), 4.07 (q, 2 H, CH2, J = 7.5 Hz), 6.98 (m, 2 H, H3,5), 7.74 (d, 2 H, H2,6); 13C NMR (CDCl3): δ 14.7 (CH2-Me), 64.3 (CH2-Me), 109.9 (C-Me phenyl), 115.3, 126.1 (CH phenyl), 139.7 (C-OEt phenyl), 163.5 (C-SO phenyl); IR(neat): 2975, 1587, 1489, 1310, 1261, 1142, 1077, 1039, 832 cm-1.
N,N -diisopropyl-4-ethoxybenzenesulfinamide: 1H NMR (CDCl3): δ 0.97 (d, 6 H, CHMe2, J = 6.7 Hz), 1.25 (d, 6 H, CHMe2, J = 6.7 Hz), 1.28 (t, 3 H, Me, J = 7.0 Hz), 3.41 (spt, 2 H, CHMe2, J = 6.7 Hz), 3.91 (q, 2 H, CH2, J = 7.0 Hz), 6.82 (d, 2 H, H3,5), 7.39 (d, 2 H, H2,6); 13C NMR (CDCl3): δ 14.7 (CH2-Me), 23.7, 23.8 (CHMe2), 46.2 (CHMe2), 63.6 (CH2-Me), 114.4, 128.0 (CH phenyl), 135.3 (C-OEt phenyl), 160.6 (C-SO phenyl); MS (EI): m/z (%) = 269 (9) [M+], 254 (6), 169 (89), 141 (51), 86 (72), 84 (100); IR (neat): 2964, 1590, 1487, 1472, 1385, 1364, 1303, 1246, 1179, 1113, 1082, 1061, 949, 836 cm-1.
2,4,6-trimethylbenzenesulfinyl chloride: 1H NMR (CDCl3): δ 2.34 (s, 3 H, 4-Me), 2.63 (s, 6 H, 2,6-Me), 6.93 (s, 2 H, H3,5); 13C NMR (CDCl3): δ 18.7 (2,6-Me), 21.5 (4-Me), 131.2, 138.0 (CH phenyl), 141.0 (C-Me), 144.6 (C-SO phenyl); IR(neat): 2919, 1598, 1454, 1379, 1292, 1151, 1052, 852 cm-1.
N,N -diisopropyl-2,4,6-trimethylbenzenesulfinamide: 1H NMR (CDCl3): δ 1.04 (d, 6 H, CHMe2, J = 6.7 Hz), 1.42 (d, 6 H, CHMe2, J = 6.7 Hz), 2.19 (s, 3 H, 4-Me), 2.46 (s, 6 H, 2,6-Me), 6.75 (br s, 2 H, H3,5); 13C NMR (CDCl3): δ 20.5 (C2,6-Me), 21.0 (C4-Me), 23.7, 24.4 (CHMe2), 48.9 (CHMe2), 131.3 (CH phenyl), 134.8, 138.3, 139.9 (C2,4,6-Me and C-SO phenyl); MS (EI): m/z (%) = 267 (60) [M+], 167 (66), 139 (100), 106 (94), 58 (80), 43 (97); IR (nujol): 2868, 1598, 1460, 1366, 1172, 1120, 1085, 935, 848 cm-1.