* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0 - 20℃; for 0.333333h;Product distribution / selectivity;
10 ml (0.1 mol) of 3-methyl-3-(hydroxymethyl)oxetane and 36.58 g (0.11 mol) of carbone tetrabromide were dissolved in 100 ml of CH2Cl2. The solution was cooled to 0C under nitrogen atmosphere, and 31.56 g (0.12 mol) of triphenylphosphine was gradually added thereto. The mixture was heated to room temperature and stirred for 20 minutes. After the reaction terminated, the solvent was removed under reduced pressure. 100 ml of ethylene acetate was added thereto and the mixture was filtered using celite to remove impurities. After the solvent was removed from the mixture, hexane was added thereto. The mixture was filtered using celite, and concentrated under reduced pressure. The resultant product was fractionally distilled to obtain 16 g of 3-methyl-3-(bromomethyl)oxetane (Yield: 95%). NMR spectroscopy of the resulting product was: 1H NMR (CDCl3, 300MHz): delta4.46-4.38 (d+d, 4H), 3.65(s, 2H), 1.44(s, 3H).
With carbon tetrabromide; triphenylphosphine; In dichloromethane; at 0 - 23℃; for 1.33333h;
3-Bromomethyl-3-methyl-oxetane; To a dichloromethane (600 ml) solution of (3-Methyl-oxetan-3-yl)-methanol (50 g, 0.4896 mol, prepared as in Corey, E. J., Raju, N., Tetrahedron Lett., 1983, 5571) at about 0 C. was added carbon tetrabromide (165.35 g, 0.4986 mol) followed by the addition of triphenyl phosphine (179 g, 0.683 mol) slowly in portions over about 20 minutes. The reaction was allowed to warm to about 23 C. and was stirred at that temperature for about 1 hour then was concentrated in vacuo. The residue was diluted with diethyl ether and cooled to about 0 C., then was filtered through Celite and the organic layer was concentrated in vacuo. The residue was then diluted with hexanes and filtered then concentrated in vacuo and distilled under vacuum to give 124.3 g of 3-bromomethyl-3-methyl-oxetane as a colorless oil.
3-Bromomethyl-3-methyl-oxetane To a dichloromethane (600 ml) solution of (3-Methyl-oxetan-3-yl)-methanol (50 g, 0.4896 mol, prepared as in Corey, E.J., Raju, N., Tetrahedron Lett.,1983, 5571) at about 0C was added carbon tetrabromide (165.35 g, 0.4986 mol) followed by the addition of triphenyl phosphine (179 g, 0.683 mol) slowly in portions over about 20 minutes. The reaction was allowed to warm to about 23C and was stirred at that temperature for about 1 hour then was concentrated in vacuo.The residue was diluted with diethyl ether and cooled to about 0C, then was filtered through Celite and the organic layer was concentrated in vacuo.Theresidue was then diluted with hexanes and filtered then concentrated in vacuoand distilled under vacuum to give 124.3 g of 3-bromomethyl-3-methyl-oxetane as a colorless oil.
NaH (60percent in oil, 1.24 g, 30.9 mmol) was washed twice with pentane and dried under vacuum. Dioxane (50 mL) was added, followed by (3-methyloxetan-3-yl)methanol (3.0 mL, 30.9 mmol) dropwise. This was allowed to stir 2 h at room temp before addition of 6-chloropyrazin-2-amine (2.0 g, 15.4 mmol). The reaction was heated to reflux for 16 h, cooled and concentrated. Water was added (50 mL), and the mixture was extracted with EtOAc (3x75 mL), and the combined organics were washed with water and brine, dried with Na2SO4, filtered and concentrated. The crude product was purified by silica gel column chromatography (0-10percent MeOH/CH2 ) to give 6-((3-methyloxetan-3- yl)methoxy)pyrazin-2-amine (3.02 g, quant). MS (ESI) calcd for C9H13N3O2: 195.10; found: 196 [M+H]
100%
NaH (60percent in oil, 1.24 g, 30.9 mmol) was washed twice with pentane and dried under vacuum. Dioxane (50 mL) was added, followed by (3-methyloxetan-3-yl)methanol (3.0 mL, 30.9 mmol) dropwise. This was allowed to stir 2 h at room temp before addition of 6-chloropyrazin-2-amine (2.0 g, 15.4 mmol). The reaction was heated to reflux for 16 h, cooled and concentrated. Water was added (50 mL), and the mixture was extracted with EtOAc (3x75 mL), and the combined organics were washed with water and brine, dried with Na2SO4, filtered and concentrated. The crude product was purified by silica gel column chromatography (0-10percent MeOH/CH2Cl2) to give 6-((3-methyloxetan-3-yl)methoxy)pyrazin-2-amine (3.02 g, quant.). MS (ESI) calcd for C9H13N3O2: 195.10; found: 196 [M+H].
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
120K+ Compounds
Competitive Price
1-2 Day Shipping
