dimethylazanide;titanium(4+)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 250 mL Schlenk flask is charged with toluene, 75 mL, and titanium tetrakis(dimethylamide), 2.35 g (10.48 mmole). The mixture is stirred magnetically throughout the procedure. Freshly degassed indene (nitrogen sparged) is added to the Schlenk flask at room temperature in excess, 2.44 mL (20.96 mmole). The mixture is refluxed at least 24 hours giving a blood red solution. All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue. The residue is transferred in a minimum of hexane to a micro scale distillation apparatus and distilled under vacuum. A viscous red oil distills at 60° C. (0.025 mm Hg) which is identified by nuclear magnetic resonance (NMR) as indenyltitanium tris(dimethylamide). The yield is 70% by this method of preparation. The mixture is refluxed at least 24 hours giving a blood red solution All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue The residue is transferred in a minimum of hexane to a micro scale distillation apparatus distilled under vacuum A viscous red oil distills at 60° C. (0.025 mm Hg) which The yield is 70% by this method of preparation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 250 mL Schlenk flask is charged with toluene, 75 mL, and titanium tetrakis(dimethylamide), 2.35 g (10.48 mmole). The mixture is stirred magnetically throughout the procedure. Freshly degassed indene (nitrogen sparged) is added to the Schlenk flask at room temperature in excess, 2.44 mL (20.96 mmole). The mixture is refluxed at least 24 hours giving a blood red solution. All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue. The residue is transferred in a minimum of hexane to a micro scale distillation apparatus and distilled under vacuum. A viscous red oil distills at 60° C. (0.025 mm Hg) which is identified by nuclear magnetic resonance (NMR) as indenyltitanium tris(dimethylamide). The yield is 70% by this method of preparation. The mixture is refluxed at least 24 hours giving a blood red solution All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue The residue is transferred in a minimum of hexane to a micro scale distillation apparatus distilled under vacuum A viscous red oil distills at 60° C. (0.025 mm Hg) which The yield is 70% by this method of preparation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 4.87 g of neopentyllithium in pentane was added to a solution of 7.0 g of titanium tetrakis(dimethylamide) in pentane with stirring. Lithium dimethylamide precipitated rapidly. The total amount of pentane in the reaction mixture was about 50-100 ml. After being stirred for one hour the mixture was filtered, and pentane was evaporated from the filtrate to give 7.5 g (86%) of dineopentyltitanium bis(dimethylamide) as an air-sensitive yellow oil. Nmr C6D6 : δ (NMe) 3.23, δ (CMe3) 1.05 ppm downfield from tetramethylsilane. Lithium dimethylamide precipitated rapidly After being stirred for one hour the mixture was filtered pentane was evaporated from the filtrate

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 4.20 g of titanium tetrakis(dimethylamide) in about 10 ml of pentane was added a solution of 1.77 g of trimethylsilylmethyllithium in pentane. Lithium dimethylamide precipitated immediately. The mixture was stirred for 1 hour and filtered, pentane was removed from the filtrate by rotary evaporation, and the residual pale-yellow oil was distilled through a short still-head under reduced pressure, to give 0.87 g of trimethylsilylmethyltitanium tris(dimethylamide), bp 55° C. (50 μ). Nmr in C6D6 : δ (NMe) 3.07, δ (SiMe) 0.22, δ (CH2) 0.35 ppm downfield from tetramethylsilane. Lithium dimethylamide precipitated immediately filtered pentane was removed from the filtrate by rotary evaporation the residual pale-yellow oil was distilled through a short still-head under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol (0.3 g, 1.3 mmol) in toluene (5.2 mL) was added dropwise a solution of tetrakis(dimethylamido)titanium (0.29 g, 1.3 mmol) in toluene (1.7 mL) at −30° C. The mixture was stirred for 30 min at room temperature and then at 110° C. for 5 hrs. The solvent was distilled off to give 2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitanium bis(dimethylamide) (0.30 g, yield 83.3%). at 110° C. for 5 hrs The solvent was distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol (0.3 g, 1.3 mmol) in toluene (5.2 mL) was added dropwise a solution of tetrakis(dimethylamido)titanium (0.29 g, 1.3 mmol) in toluene (1.7 mL) at −30° C. The mixture was stirred for 30 min at room temperature and then at 110° C. for 5 hrs. The solvent was distilled off to give 2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitanium bis(dimethylamide) (0.30 g, yield 83.3%). at 110° C. for 5 hrs The solvent was distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-(2,3,4,5-tetramethylcyclopentadienyl)benzylalcohol (0.3 g, 1.3 mmol) in toluene (5.2 mL) was added dropwise a solution of tetrakis(dimethylamido)titanium (0.29 g, 1.3 mmol) in toluene (1.7 mL) at −30° C. The mixture was stirred for 30 min at room temperature and then at 110° C. for 5 hrs. The solvent was distilled off to give 2-(2,3,4,5-tetramethylcyclopentadienyl)benzyloxytitanium bis(dimethylamide) (0.30 g, yield 83.3%). at 110° C. for 5 hrs The solvent was distilled off

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 250 mL Schlenk flask is charged with titanium tetrakis(dimethylamide), 3.73 g (16.64 mmole), and toluene, 100 mL. Methylcyclopentadiene, 5.33 g (66.54 mmole), is added to the magnetically stirred solution. The mixture is refluxed 1.5 hours. Solvent and volatiles are removed under vacuum leaving a brown residue. The residue is transferred to a microdistillation apparatus and a forerun of titanium tetrakis(dimethylamide) is distilled from the mixture (at 35°-40° C. and 0.025 mm Hg) followed by a red low melting solid (at 104°-108° C. and 0.025 mm Hg) which is determined to be methylcyclopentadienyltitanium tris(dimethylamide) by proton NMR. The mixture is refluxed 1.5 hours Solvent and volatiles are removed under vacuum leaving a brown residue a forerun of titanium tetrakis(dimethylamide) is distilled from the mixture (at 35°-40° C. and 0.025 mm Hg) followed by a red low melting solid (at 104°-108° C. and 0.025 mm Hg) which

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 250 mL Schlenk flask is charged with titanium tetrakis(dimethylamide), 2.48 g (11.06 mmole), and toluene, 100 mL. Freshly cracked cyclopentadiene monomer, 2.7 mL (33.18 mmole), is added to the magnetically stirred solution. The mixture is refluxed 1 hour giving a deep red solution. All volatiles are removed under vacuum at room temperature leaving a viscous deep red oil. The oil is transferred to a microdistillation apparatus and a low melting solid is distilled at 70° C. under vacuum (0.05 mm Hg). The product is determined to be cyclopentadienyltitanium tris(dimethylamide). The mixture is refluxed 1 hour giving a deep red solution All volatiles are removed under vacuum at room temperature leaving a viscous deep red oil a low melting solid is distilled at 70° C. under vacuum (0.05 mm Hg)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 250 mL Schlenk flask is charged with toluene, 75 mL, and titanium tetrakis(dimethylamide), 2.35 g (10.48 mmole). The mixture is stirred magnetically throughout the procedure. Freshly degassed indene (nitrogen sparged) is added to the Schlenk flask at room temperature in excess, 2.44 mL (20.96 mmole). The mixture is refluxed at least 24 hours giving a blood red solution. All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue. The residue is transferred in a minimum of hexane to a micro scale distillation apparatus and distilled under vacuum. A viscous red oil distills at 60° C. (0.025 mm Hg) which is identified by nuclear magnetic resonance (NMR) as indenyltitanium tris(dimethylamide). The yield is 70% by this method of preparation. The mixture is refluxed at least 24 hours giving a blood red solution All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue The residue is transferred in a minimum of hexane to a micro scale distillation apparatus distilled under vacuum A viscous red oil distills at 60° C. (0.025 mm Hg) which The yield is 70% by this method of preparation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 250 mL Schlenk flask is charged with toluene, 75 mL, and titanium tetrakis(dimethylamide), 2.35 g (10.48 mmole). The mixture is stirred magnetically throughout the procedure. Freshly degassed indene (nitrogen sparged) is added to the Schlenk flask at room temperature in excess, 2.44 mL (20.96 mmole). The mixture is refluxed at least 24 hours giving a blood red solution. All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue. The residue is transferred in a minimum of hexane to a micro scale distillation apparatus and distilled under vacuum. A viscous red oil distills at 60° C. (0.025 mm Hg) which is identified by nuclear magnetic resonance (NMR) as indenyltitanium tris(dimethylamide). The yield is 70% by this method of preparation. The mixture is refluxed at least 24 hours giving a blood red solution All volatiles are removed under vacuum at room temperature leaving a deep red, oily residue The residue is transferred in a minimum of hexane to a micro scale distillation apparatus distilled under vacuum A viscous red oil distills at 60° C. (0.025 mm Hg) which The yield is 70% by this method of preparation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 4.87 g of neopentyllithium in pentane was added to a solution of 7.0 g of titanium tetrakis(dimethylamide) in pentane with stirring. Lithium dimethylamide precipitated rapidly. The total amount of pentane in the reaction mixture was about 50-100 ml. After being stirred for one hour the mixture was filtered, and pentane was evaporated from the filtrate to give 7.5 g (86%) of dineopentyltitanium bis(dimethylamide) as an air-sensitive yellow oil. Nmr C6D6 : δ (NMe) 3.23, δ (CMe3) 1.05 ppm downfield from tetramethylsilane. Lithium dimethylamide precipitated rapidly After being stirred for one hour the mixture was filtered pentane was evaporated from the filtrate