2-methylbut-2-enoyl chloride

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To 20 ml of tetrahydrofuran were added 2.4 g of 4-amino-6,7-dimethoxy-2-(1-piperazinyl)quinazoline hydrochloride and 2.6 g of triethylamine, after which the mixture was stirred for 20 minutes. There was then added 0.7 g of 2,3-dimethylacryloyl chloride, after which the mixture was stirred at room temperature for 12 hours. The crystals which were produced were collected by filtration, washed with water and recrystallized from ethanol, to give 1.04 g of the desired Compound No. 3 in the form of pale yellow prisms melting at 219.5°-221.5° C. after which the mixture was stirred at room temperature for 12 hours The crystals which were produced were collected by filtration washed with water recrystallized from ethanol

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

Procedure: Method a) A mixture of 11.81 g 2-methyl-but-2-enoyl chloride (0.10 mol) and 1.36 g zinc chloride (0.01 mol, 0.1 eq.) in 100 ml ethylene chloride was treated with a soln. of 136 g α-pinene ((1S)-(−)/(1R)-(+) 90:10, 1 mol, 10 eq.) in 150 ml ethylene chloride and the resulting mixture was stirred 45 min. at 25° C., 2.5 h at 50° C., and 1 h at 80°. After cooling, the reaction mixture was washed with aq. sat. NaCl soln. and aq. sat. NaHCO3 soln. The aq. phases were extracted with Et2O, dried (Na2SO4), and concentrated. The crude product (48 g) filtered (SiO2, hexane/Et2O 200:6→200:13) and the residue (5.1 g) treated with 1 g LiOH.H2O in 75 ml MeOH at 25° C. for 48 h. The resulting mixture was poured into aq. sat. NaCl soln. and extracted with hexane. The combined org. phases were dried (Na2SO4), concentrated and purified by FC (SiO2, hexane/Et2O 100:3) gave 1.6 g (7.1%) of compound 11. was treated with a soln 1 h at 80° After cooling the reaction mixture was washed with aq. sat. NaCl soln The aq. phases were extracted with Et2O dried (Na2SO4) concentrated The crude product (48 g) filtered (SiO2, hexane/Et2O 200:6→200:13) the residue (5.1 g) treated with 1 g LiOH.H2O in 75 ml MeOH at 25° C. for 48 h The resulting mixture was poured into aq. sat. NaCl soln and extracted with hexane phases were dried (Na2SO4) concentrated purified by FC (SiO2, hexane/Et2O 100:3)