Stannous chloride dihydrate → 3-Bromo-4-(3-methyloxetan-3-yl)aniline

HRID 640648Notes

Reaction equation

HRID 640648 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

5

Reactant 3

HCID 61436Stannous chloride dihydrateHCID 4622928CyanomethylenetributylphosphoraneHCID 592061202-(2-Bromo-4-nitrophenyl)-2-methylpropane-1,3-diol

Product 1

HCID 592067863-Bromo-4-(3-methyloxetan-3-yl)anilineYield 32%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

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%) 1H 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

  1. customThe mixture was evaporated to dryness
  2. dissolutionre-dissolved in 4 mL of EtOH
  3. temperaturethe resulting solution was heated at 70° C. for 1 hour
  4. temperatureThe mixture was cooled to room temperature
  5. customquenched with a saturated aqueous solution of sodium bicarbonate
  6. extractionThe mixture was then extracted three times with ethyl acetate
  7. customThe combined ethyl acetate extracts were evaporated to dryness
  8. custompurified by preparative LC/MS

Sources & evidence

ORD record
ord-bf092a1bf74145baa8fc902103b5ce04
Source dataset
uspto-grants-2010_04
Patent number
US07691902B2

Reaction notes

Loading…