Reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[CH:5]=[CH:4][C:3]=1[C:11]([CH3:16])([CH2:14][OH:15])[CH2:12]O.C(C=P(CCCC)(CCCC)CCCC)#N.O.O.[Sn](Cl)Cl>C1C=CC=CC=1>[Br:1][C:2]1[CH:7]=[C:6]([CH:5]=[CH:4][C:3]=1[C:11]1([CH3:16])[CH2:14][O:15][CH2:12]1)[NH2:8]Participants
Procedure
2-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol (0.145 g, 0.500 mmol) was dissolved in 2.5 mL of anhydrous benzene. Cyanomethylenetributylphosphorane (CMBP) (0.181 g, 0.750 mmol) was then added and the solution was allowed to stir at room temperature for 72 hours. The mixture was evaporated to dryness and then re-dissolved in 4 mL of EtOH. Tin(II) chloride dihydrate (0.564 g, 2.50 mmol) was then added and the resulting solution was heated at 70° C. for 1 hour. The mixture was cooled to room temperature and then quenched with a saturated aqueous solution of sodium bicarbonate. The mixture was then extracted three times with ethyl acetate. The combined ethyl acetate extracts were evaporated to dryness and purified by preparative LC/MS to yield 3-bromo-4-(3-methyloxetan-3-yl)aniline as a pale yellow oil (0.032 g, 32%) NMR (400 MHz, CD3CN) δ 7.13 (dd, J=0.7, 1.8 Hz, 1H), 6.94-6.88 (m, 2H), 6.75 (br s, 2H), 4.98 (d, J=5.6 Hz, 2H), 4.51 (d, J=6.1 Hz, 2H), 1.74 (s, 3H). ESI-MS m/z calc. 241.0, found; 242.1 (M+1)+ Retention time 0.53 minutes.
Workup
- customThe mixture was evaporated to dryness
- dissolutionre-dissolved in 4 mL of EtOH
- temperaturethe resulting solution was heated at 70° C. for 1 hour
- temperatureThe mixture was cooled to room temperature
- customquenched with a saturated aqueous solution of sodium bicarbonate
- extractionThe mixture was then extracted three times with ethyl acetate
- customThe combined ethyl acetate extracts were evaporated to dryness
- custompurified by preparative LC/MS
Sources & evidence
- ORD record
- ord-427b3467b8884be3a7d93e7f65856425
- Source dataset
- uspto-grants-2013_09
- Patent number
- US08524767B2
Linked notes
Loading…