Ethanethioic acid, S-(4-iodophenyl) ester

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following a general procedure (Uchiro and Kobayashi (1999) Tetrahedron Lett., 40: 3179-3182), to a stirred suspension of zinc powder (3.80 g, 58.0 mmol) and dichlorodimethylsilane (7.00 mL, 58.0 mmol) in 1,2-dichloroethane (126 mL) was added a solution of 4-iodobenzenesulfonyl chloride (5.00 g, 16.5 mmol) and N,N-dimethylacetamide (4.60 mL, 50.0 mmol) in dichloroethane (126 mL). The mixture was stirred at 75° C. for 2 h until the zinc powder was no longer visible. The reaction mixture was cooled to 50° C. and acetyl chloride (1.53 mL, 21.5 mmol) was added. After 15 min the mixture was poured into water. The water layer was extracted with CH2Cl2 and the combined organic layers were dried (Na2SO4), filtered and evaporated. The colorless oil thus obtained was chromatographed (silica, CH2Cl2/hexanes, 1:4) affording a colorless oil (3.93 g, 85.0%) which solidified at −20° C. mp 56-57° C. (lit. 54-55° C.)43; 1H NMR δ 2.42 (s, 3H), 7.12, 7.73 (AA′BB′, 2×2H); 13C NMR δ 31.0, 96.7, 128.4, 136.7, 139.0, 193.9; Anal. Calcd. for C8H7IOS: C, 34.55; H, 2.54; I, 45.63; S, 11.53. Found: C, 34.69; H, 2.59; I, 45.52; S, 11.59. The water layer was extracted with CH2Cl2 the combined organic layers were dried (Na2SO4) filtered evaporated The colorless oil thus obtained was chromatographed (silica, CH2Cl2/hexanes, 1:4)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: S-Acetylthio-derivatized triple decker (15). Samples of (Pc)Eu(Pc)Eu(E′B-Por) (28) (15 mg, 7.0 μmol), 4-iodo-1-(S-acetylthio)benzene (2.0 mg, 7.0 μmol), Pd2(dba)3 (1.0 mg, 1.1 μmol) and P(o-tolyl)3 (2.5 mg, 8.3 μmol) were added to a Schlenk flask. The flask was evacuated and purged with argon three times. Then deaerated toluene (3 mL) and deaerated N,N-diisopropylethylamine (0.6 mL) were added by syringe. The flask was immersed in an oil bath at 35° C. and stirred under argon. The reaction was monitored by TLC (silica, toluene) and LD-MS. After 24 h, the solvent was removed under vacuum, the residue dissolved in toluene/ether (60:1), and loaded onto a silica gel column packed with the same solvent. Elution with toluene/ether (60:1) afforded the desired product together with trace of unreacted starting material as the first band. The product thus obtained was further purified by a second column chromatography procedure (silica gel, toluene), affording a black solid (15) (3.1 mg, 19%) after removal of the solvent and washing with CH3OH. 1H NMR (CDCl3) δ 1.91 (m, 27H), 2.62 (s, 3H), 3.28 (m, 8H), 4.70-4.80 (m, 3H), 4.98 (d, J=6.6 Hz, 1H), 6.68 (m, 4H), 6.94 (d, J=6.6 Hz, 1H), 7.54 (m, 1H), 7.71 (m, 1H), 8.03 (m, 1H), 8.71 (brs, 8H), 9.05-9.12 (m, 3H), 9.42 (m, 1H), 10.10 (brs, 8H), 11.11 (brs, 8H), 11.56 (m, 2H), 11.72 (m, 1H), 12.02 (m, 1H), 12.98 (brs, 8H); LD-MS obsd 2291.4 (M+), 2250.2 (M+-CH3CO), 1181.0 (M+-(Por)Eu), 1111.6 (M+-(Pc)Eu(Pc)), 1067.8 (M+-(Pc)Eu(Pc)-CH3CO); FAB-MS obsd 2284.59, calcd exact mass 2284.58 (C130H90OSN20Eu2); λabs 341, 419, 523, 618, 721 nm. The flask was evacuated purged with argon three times Then deaerated toluene (3 mL) and deaerated N,N-diisopropylethylamine (0.6 mL) were added by syringe The flask was immersed in an oil bath at 35° C. the solvent was removed under vacuum the residue dissolved in toluene/ether (60:1) Elution with toluene/ether (60:1)

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following a general procedure (Uchiro and Kobayashi (1999) Tetrahedron Lett., 40: 3179–3182), to a stirred suspension of zinc powder (3.80 g, 58.0 mmol) and dichlorodimethylsilane (7.00 mL, 58.0 mmol) in 1,2-dichloroethane (126 mL) was added a solution of 4-iodobenzenesulfonyl chloride (5.00 g, 16.5 mmol) and N,N-dimethylacetamide (4.60 mL, 50.0 mmol) in dichloroethane (126 mL). The mixture was stirred at 75° C. for 2 h until the zinc powder was no longer visible. The reaction mixture was cooled to 50° C. and acetyl chloride (1.53 mL, 21.5 mmol) was added. After 15 min the mixture was poured into water. The water layer was extracted with CH2Cl2 and the combined organic layers were dried (Na2SO4), filtered and evaporated. The colorless oil thus obtained was chromatographed (silica, CH2Cl2/hexanes, 1:4) affording a colorless oil (3.93 g, 85.0%) which solidified at −20° C. mp 56–57° C. (lit. 54–55° C.)43; 1H NMR δ 2.42 (s, 3H), 7.12, 7.73 (AA′BB′, 2×2H); 13C NMR δ 31.0, 96.7, 128.4, 136.7, 139.0, 193.9; Anal. Calcd. for C8H7IOS: C, 34.55; H, 2.54; I, 45.63; S, 11.53; Found: C, 34.69; H, 2.59; I, 45.52; S, 11.59. The water layer was extracted with CH2Cl2 the combined organic layers were dried (Na2SO4) filtered evaporated The colorless oil thus obtained was chromatographed (silica, CH2Cl2/hexanes, 1:4)