3-trimethylsilylaniline

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

実験手順: More specifically, compound 1 is 2,3-dichloro pyridine (2 g); compound 2 is (R)-2-methyl-piperazine; the synthesized compound 3 is 1-(3-chloro-2-pyridyl)-3-methyl-piperazine (8 g, yield 86.8%). From p-dimethyl(vinyl)silyl phenyl isocynate (compound 7c, 200 mg), it gave about 250 mg of compound A-15 (yield about 61.2%).

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

実験手順: Compound A-11 can be synthesized according to method 1. Just of Scheme 1, R1 is —Cl; R2 is —H; R3 is m-SiMe3. More specifically, compound 1 is 2,3-dichloro pyridine (2 g); compound 2 is piperazine; the synthesized compound 3 is 1-(3-chloro-2-pyridyl)piperazine (2.3 g, yield about 86.8%). Compound A-11 can be synthesized

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

実験手順: Compound A-10 can be synthesized according to method 1. Just of Scheme 1, R1 is —Cl; R2 is -Me; R3 is m-SiMe3. More specifically, compound 1 is 2,3-dichloro pyridine (6 g); compound 2 is (R)-2-methyl piperazine; the synthesized compound 3 is 3-methyl-1-(3-chloro-2-pyridyl)piperazine (8 g, yield about 93.2%). Compound A-10 can be synthesized

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

実験手順: More specifically, compound 1 is 2-chloro-3-trifluoromethylpyridine (2 g); compound 2 is (R)-2-methyl piperazine; the synthesized compound 3 is 3-methyl-1-(3-trifluoromethyl-2-pyridyl)piperazine (2.5 g, yield about 92.6%).

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

実験手順: Compound A-07 can be synthesized according to method 1. Just of Scheme 1, R1 is —CF3; R2 is —H; R3 is p-SiMe3. More specifically, compound 1 is 2-chloro-3-(trifluoromethyl)pyridine (2 g); compound 2 is piperazine; the synthesized compound 3 is 1-(3-(trifluoromethyl)-2-pyridyl)piperazine (2.3 g, yield about 90.1%). Compound A-07 can be synthesized

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

実験手順: Compound A-03 can be synthesized according to method 1. Just of Scheme 1, R1 is —CF3; R2 is -Me; R3 is p-SiMe3. More specifically, compound 1 is 2-chloro-3-(trifluoromethyl)-pyridine (2 g); compound 2 is (R)-2-methylpiperazine; the synthesized compound 3 is 3-methyl-1-(3-trifluoromethyl-2-pyridyl)piperazine (2.5 g, yield about 92.6%). Compound A-03 can be synthesized

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

実験手順: Compound A-02 can be synthesized according to method 1. Just R1, R2, and R3 of Scheme 1 are respectively —Cl, -Me and p-SiMe3. More specifically, compound 1 is 2,3-dichloro-pyridine (6 g), compound 2 is (R)-2-methylpiperazine, the synthesized compound 3 is 1-(3-chloro-2-pyridyl)-3-methyl-piperazine (38 g, yield about 93.2%). Compound A-02 can be synthesized

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

実験手順: Compound A-01 can be synthesized according to method 1. Just R1, R2, and R3 of Scheme 1 are respectively —Cl, —H and p-SiMe3. More specifically, compound 1 is 2,3-dichloro-pyridine (2 g); compound 2 is piperazine; compound 3 is 1-(3-chloro-2-pyridyl)piperazine (2.3 g, yield 86.8%); compound 7 is compound 7a-p-(trimethylsilyl)phenyl isocynate. Compound A-01 can be synthesized

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

実験手順: To a solution of 135 mg (0.817 mmol) of m-trimethylsilylaniline in 8 ml of dry benzene were added 1.0 ml of dry pyridine and 179 mg (0.900 mmol) of methyl p-chloroformylbenzoate, successively. The mixture was stirred at room temperature for 20 hours. To the reaction mixture was added water and the aqueous solution was extracted with AcOEt. The extract was washed successively with water, sat.eq.NaHCO3 and sat.aq.NaCl, dried and evaporated to give 272 mg of white powder, which was purified by column chlomatography on silica gel (eluent: methylene chloride) to give 266 mg of white powder (yield: 99%). Recrystallization of the powder from a mixture of methylene chloride, n-hexane and chloroform gave 120 mg of white needles, m.p.125-126° C. (yield 45%). the aqueous solution was extracted with AcOEt The extract was washed successively with water, sat.eq NaCl, dried evaporated

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

実験手順: m-Nitrotrimethylsilylbenzene (200 mg) was catalytically hydrogenated over Pd-C in 7.5 ml of benzene at atmospheric pressure for 40 minutes. The catalyst was filtered off and washed with benzene and dry MeOH, successively. The filtrate and washings were mixed and evaporated. The residue was purified by column chromatography on silica gel [eluent: methylene chloride] to give 169 mg of pale brown liquid. The catalyst was filtered off washed with benzene and dry MeOH The filtrate and washings were mixed evaporated The residue was purified by column chromatography on silica gel [eluent: methylene chloride]

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

実験手順: m-Nitrotrimethylsilylbenzene (200 mg) was catalytically hydrogenated over Pd-C in 7.5 ml of benzene at atmospheric pressure for 40 minutes. The catalyst was filtered off and washed with benzene and dry MeOH, successively. The filtrate and washings were mixed and evaporated. The residue was purified by column chromatography on silica gel [eluent: methylene chloride] to give 169 mg of pale brown liquid. The catalyst was filtered off washed with benzene and dry MeOH The filtrate and washings were mixed evaporated The residue was purified by column chromatography on silica gel [eluent: methylene chloride]

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

実験手順: 283 mg (1.75 mmol) 1,1′-Carbonyl-diimidazol (CDI) were given to a solution of 262 mg (1.59 mmol) 3-trimethylsilanyl-phenylamine (Kimes, A. S., J. Med. Chem. 35 (1992) 4683-4689) in 4.0 ml dichloro-methane and stirred for 12 h. A solution of 413 mg (1.59 mmol) 3-[4-(4-Amino-phenoxy)-pyrimidin-2-ylamino]-propan-1-ol in 6 ml dichloromethane was added within 30 min. and the mixture stirred for 12 h at r.t. The reaction mixture was evaporated and the residue was purified by chromatography on silica gel (dichloromethane/ethanol 96:4). The obtained material was washed with ether, the precipitate was isolated by filtration and dried. The reaction mixture was evaporated the residue was purified by chromatography on silica gel (dichloromethane/ethanol 96:4) The obtained material was washed with ether the precipitate was isolated by filtration dried