4-((Trimethylsilyl)ethynyl)aniline

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

Procedure: As shown in the following Reaction 2, 250 mg (1.32 mmol) of 4-trimethylsilylethynylaniline obtained in A of Example 1-1 was melted in 3 mL of hydrochloric acid at the temperature of 0° C., and 94 mg (1.37 mmol, 1.04 eq) of sodium nitrite was added thereto, and then the reaction solution was stirred for 1 hour. After completion of stirring, 280 mg (1.69 mmol, 1.28 eq) of potassium iodide was added to the reaction solution, and then the reaction solution was stirred at room temperature for 12 hours. Next, the reaction solution was extracted with ether 2 times and 1 time with 1M sodium chloride aqueous solutions 1 time. The organic solvent layer was dehydrated with magnesium sulfate, filtered, and then distilled under reduced pressure. The compound distilled under reduced pressure was purified with an alumina column chromatography (mobile phase: hexane) to obtain 360 mg of 4-trimethylsilylethynyl iodobenzene with the yield of 92%. NMR data of the obtained compound is as follows. [1H NMR (400 MHz, CDCl3): δ 0.23-0.27 (m, 9H), 7.16 (d, 2H), 7.69 (d, 2H)]. obtained in A of Example 1-1 was added After completion of stirring the reaction solution was stirred at room temperature for 12 hours Next, the reaction solution was extracted with ether 2 times and 1 time with 1M sodium chloride aqueous solutions 1 time filtered distilled under reduced pressure The compound distilled under reduced pressure was purified with an alumina column chromatography (mobile phase: hexane)

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

Procedure: As shown in the following Reaction 2, 250 mg (1.32 mmol) of 4-trimethylsilylethynylaniline obtained in A of Example 1-1 was melted in 3 mL of hydrochloric acid at the temperature of 0° C., and 94 mg (1.37 mmol, 1.04 eq) of sodium nitrite was added thereto, and then the reaction solution was stirred for 1 hour. After completion of stirring, 280 mg (1.69 mmol, 1.28 eq) of potassium iodide was added to the reaction solution, and then the reaction solution was stirred at room temperature for 12 hours. Next, the reaction solution was extracted with ether 2 times and 1 time with 1M sodium chloride aqueous solutions 1 time. The organic solvent layer was dehydrated with magnesium sulfate, filtered, and then distilled under reduced pressure. The compound distilled under reduced pressure was purified with an alumina column chromatography (mobile phase: hexane) to obtain 360 mg of 4-trimethylsilylethynyl iodobenzene with the yield of 92%. NMR data of the obtained compound is as follows. [1H NMR (400 MHz, CDCl3): δ 0.23-0.27 (m, 9H), 7.16 (d, 2H), 7.69 (d, 2H)]. obtained in A of Example 1-1 was added After completion of stirring the reaction solution was stirred at room temperature for 12 hours Next, the reaction solution was extracted with ether 2 times and 1 time with 1M sodium chloride aqueous solutions 1 time filtered distilled under reduced pressure The compound distilled under reduced pressure was purified with an alumina column chromatography (mobile phase: hexane)

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

Procedure: As shown in the following Reaction 1, 300 mg (1.37 mmol) of 4-iodoaniline was melted in 5 mL of trimethylamine, and 0.20 mL (1.46 mmol, 1.07 eq) of trimethylsilylacetylene, 4 mg (0.0068 mmol, 0.5 mol %) of dichlorobis-(triphenylphosphine)palladium(II), and 2 mg (0.013 mmol, 1 mol %) of copper iodide were added thereto, and then the reaction solution was stirred under nitrogen atmosphere for 12 hours. Next, the reaction solution was filtered with ether, and was extracted with 10 mL of 2M ammonium chloride aqueous solution 2 times and with 1M sodium chloride aqueous solution 1 time. The organic solvent layer was dehydrated with magnesium sulfate, filtered, and then distilled under reduced pressure. The compound distilled under reduced pressure was purified with a column chromatography (mobile phase volume ratio; ethylacetate:n-hexane=1:4) to obtain 246 mg of 4-trimethylsilylethynylaniline with the yield of 98%. NMR data of the obtained compound is as follows. [1H NMR (400 MHz, CDCl3): δ 0.24-0.27 (m, 9H), 3.81 (s, 2H), 6.58 (d, 2H), 7.29 (d, 2H)]. Next, the reaction solution was filtered with ether was extracted with 10 mL of 2M ammonium chloride aqueous solution 2 times and with 1M sodium chloride aqueous solution 1 time filtered distilled under reduced pressure The compound distilled under reduced pressure was purified with a column chromatography (mobile phase volume ratio; ethylacetate:n-hexane=1:4)

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

Procedure: As shown in the following Reaction 1, 300 mg (1.37 mmol) of 4-iodoaniline was melted in 5 mL of trimethylamine, and 0.20 mL (1.46 mmol, 1.07 eq) of trimethylsilylacetylene, 4 mg (0.0068 mmol, 0.5 mol %) of dichlorobis-(triphenylphosphine)palladium(II), and 2 mg (0.013 mmol, 1 mol %) of copper iodide were added thereto, and then the reaction solution was stirred under nitrogen atmosphere for 12 hours. Next, the reaction solution was filtered with ether, and was extracted with 10 mL of 2M ammonium chloride aqueous solution 2 times and with 1M sodium chloride aqueous solution 1 time. The organic solvent layer was dehydrated with magnesium sulfate, filtered, and then distilled under reduced pressure. The compound distilled under reduced pressure was purified with a column chromatography (mobile phase volume ratio; ethylacetate:n-hexane=1:4) to obtain 246 mg of 4-trimethylsilylethynylaniline with the yield of 98%. NMR data of the obtained compound is as follows. [1H NMR (400 MHz, CDCl3): δ 0.24-0.27 (m, 9H), 3.81 (s, 2H), 6.58 (d, 2H), 7.29 (d, 2H)]. Next, the reaction solution was filtered with ether was extracted with 10 mL of 2M ammonium chloride aqueous solution 2 times and with 1M sodium chloride aqueous solution 1 time filtered distilled under reduced pressure The compound distilled under reduced pressure was purified with a column chromatography (mobile phase volume ratio; ethylacetate:n-hexane=1:4)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-[2-(Trimethylsilyl)ethynyl]aniline (Takahashi et al. (1980) Synthesis, 8: 627-630) (1.0 g, 5.3 mmol) was suspended in a mixture of conc. HCl (2.4 mL) and H2O (10 mL) and cooled to 0° C. under stirring. A solution of NaNO2 (0.40 g, 5.8 mmol) in H2O (2 mL) was added while the temperature was carefully maintained between 0-5° C. After the addition was complete, the mixture was stirred for 30 min at 0° C. The resulting diazonium salt solution was then added slowly to a solution of ferrocene (0.49 g, 2.7 mmol) in toluene (100 mL) at 0° C., resulting in gas evolution. After the addition was complete, the mixture was stirred for 1 h at 0° C., warmed to rt and stirring was continued for an additional 16 h. The layers were separated and the aqueous layer was extracted with toluene (3×50 mL). The combined organic layers were washed with satd aq NaHCO3 (3×50 mL), brine (3×50 mL), dried (MgSO4) and filtered. The solvent was removed under reduced pressure and the resulting residue was purified by column chromatography (silica, CH2Cl2/hexanes, 1:1) to remove unreacted ferrocene. Elution with CH2Cl2 afforded 0.42 g (44%) of compound 3. 1H NMR δ 0.27 (s, 9H), 4.02 (s, 5H), 4.35 (A2B2, J=1.5 Hz, 2H), 4.65 (A2B2, J=1.5 Hz, 2H), 7.40 (s, 4H); 13C NMR δ 0.04, 66.5, 69.3, 69.7, 84.1, 94.0, 105.5, 120.2, 125.6, 132.0, 140.1; FAB-MS obsd 358.0851, calcd exact mass 358.0840 (C21H22FeSi). was carefully maintained between 0-5° C After the addition the mixture was stirred for 30 min at 0° C resulting in gas evolution After the addition the mixture was stirred for 1 h at 0° C. warmed to rt stirring The layers were separated the aqueous layer was extracted with toluene (3×50 mL) The combined organic layers were washed with satd aq NaHCO3 (3×50 mL), brine (3×50 mL) dried (MgSO4) filtered The solvent was removed under reduced pressure the resulting residue was purified by column chromatography (silica, CH2Cl2/hexanes, 1:1) to remove unreacted ferrocene Elution with CH2Cl2

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-[2-(Trimethylsilyl)ethynyl]aniline (Takahashi et al. (1980) Synthesis, 8: 627–630) (1.0 g, 5.3 mmol) was suspended in a mixture of conc. HCl (2.4 mL) and H2O (10 mL) and cooled to 0° C. under stirring. A solution of NaNO2 (0.40 g, 5.8 nmol) in H2O (2 mL) was added while the temperature was carefully maintained between 0–5° C. After the addition was complete, the mixture was stirred for 30 min at 0° C. The resulting diazonium salt solution was then added slowly to a solution of ferrocene (0.49 g, 2.7 mmol) in toluene (100 mL) at 0° C., resulting in gas evolution. After the addition was complete, the mixture was stirred for 1 h at 0° C., warmed to rt and stirring was continued for an additional 16 h. The layers were separated and the aqueous layer was extracted with toluene (3×50 mL). The combined organic layers were washed with satd aq NaHCO3 (3×50 mL), brine (3×50 mL), dried (MgSO4) and filtered. The solvent was removed under reduced pressure and the resulting residue was purified by column chromatography (silica, CH2Cl2/hexanes, 1:1) to remove unreacted ferrocene. Elution with CH2Cl2 afforded 0.42 g (44%) of compound 3. 1H NMR δ 0.27 (s, 9H), 4.02 (s, 5H), 4.35 (A2B2, J=1.5 Hz, 2H), 4.65 (A2B2, J=1.5 Hz, 2H), 7.40 (s, 4H); 13C NMR δ 0.04, 66.5, 69.3, 69.7, 84.1, 94.0, 105.5, 120.2, 125.6, 132.0, 140.1; FAB-MS obsd 358.0851, calcd exact mass 358.0840 (C21H22FeSi). was carefully maintained between 0–5° C After the addition the mixture was stirred for 30 min at 0° C resulting in gas evolution After the addition the mixture was stirred for 1 h at 0° C. warmed to rt stirring The layers were separated the aqueous layer was extracted with toluene (3×50 mL) The combined organic layers were washed with satd aq NaHCO3 (3×50 mL), brine (3×50 mL) dried (MgSO4) filtered The solvent was removed under reduced pressure the resulting residue was purified by column chromatography (silica, CH2Cl2/hexanes, 1:1) to remove unreacted ferrocene Elution with CH2Cl2