Diethyl Ether → 3,3-Bis(bromomethyl)-1-(4-methylbenzenesulfonyl)azetidine

HRID 874726Notes

Reaction equation

HRID 874726 reaction equation
[Br:1][CH2:2][C:3]1([CH2:17]O)[CH2:6][N:5]([S:7]([C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)(=[O:9])=[O:8])[CH2:4]1.C(Br)(Br)(Br)[Br:20].CCOCC>C(Cl)Cl>[Br:1][CH2:2][C:3]1([CH2:17][Br:20])[CH2:6][N:5]([S:7]([C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)(=[O:9])=[O:8])[CH2:4]1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 11205Carbon tetrabromideHCID 56776986[3-(Bromomethyl)-1-tosylazetidin-3-yl]methanol

Product 1

HCID 567769853,3-Bis(bromomethyl)-1-(4-methylbenzenesulfonyl)azetidineYield 67%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

(3-(Bromomethyl)-1-(p-toluenesulfonyl)azetidin-3-yl)methanol (10.2 g, 30.6 mmol) was dissolved in DCM (100 mL) and CBr4 (16.9 g, 51 mmol) was added. The solution was cooled to 0° C. and then PPh3 (13.4 g, 51 mmol) was added in one portion. The resulting mixture was stirred at 0° C. for 2 h, then warmed to rt and stirred for 4 h. Et2O (100 mL) was added and the yellow precipitate was filtered. The filtrate was concentrated under reduced pressure and purification by flash chromatography (Biotage Isolera, 100 g KP-SIL, 0-30% EtOAc in hexanes) gave the title compound as colourless crystals (8.05 g, 67%). 1H NMR (400 MHz, CDCl3) δ ppm 7.74 (d, J=8.3 Hz, 2H), 7.41 (d, J=8.0 Hz, 2H), 3.60 (s, 4H), 3.54 (s, 4H), 2.48 (s, 3H); MS ESI 398.1 [M+H]+, calcd for [C12H15Br2NO2S+H]+397.9.

Workup

  1. temperaturewarmed to rt
  2. stirringstirred for 4 h
  3. filtrationthe yellow precipitate was filtered
  4. concentrationThe filtrate was concentrated under reduced pressure and purification by flash chromatography (Biotage Isolera, 100 g KP-SIL, 0-30% EtOAc in hexanes)

Sources & evidence

ORD record
ord-099adcbf12644981914f88b312105bd1
Source dataset
uspto-grants-2015_03
Patent number
US08980934B2

Reaction notes

Loading…