Water → cis-4-(4-Bromophenoxy)tetrahydrofuran-3-amine

HRID 2060828Notes

Reaction equation

HRID 2060828 reaction equation
[N:1]([C@H:4]1[C@@H:8]([O:9][C:10]2[CH:15]=[CH:14][C:13]([Br:16])=[CH:12][CH:11]=2)[CH2:7][O:6][CH2:5]1)=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>O1CCCC1>[Br:16][C:13]1[CH:14]=[CH:15][C:10]([O:9][C@H:8]2[CH2:7][O:6][CH2:5][C@H:4]2[NH2:1])=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 962WaterHCID 11776TriphenylphosphineHCID 86653048cis-3-Azido-4-(4-bromophenoxy)tetrahydrofuran

Product 1

HCID 67193588cis-4-(4-Bromophenoxy)tetrahydrofuran-3-amineYield 59.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of cis-3-azido-4-(4-bromophenoxy)tetrahydrofuran (286.7 g, 1.01 mol) in tetrahydrofuran (1.25 L) was cooled to 0° C. and treated with triphenylphosphine (278 g, 1.06 mol). The reaction was allowed to warm to room temperature and stirred for 18 hours. Water (53 mL) was added and the reaction was stirred at room temperature for 66 hours. Solvent was removed under reduced pressure and the residue was mixed with diethyl ether. The supernatant was decanted and concentrated in vacuo, providing a residue, which was filtered through a short plug of silica gel (Gradient: 0% to 5% methanol in methylene chloride) to afford cis-4-(4-bromophenoxy)tetrahydrofuran-3-amine (155 g) and 366 grams of impure product. An acid/base extraction was carried out on the impure material, providing additional product (48.5 g). Total yield: 203.5 g, 0.788 mol, 68% over four steps. 1H NMR (300 MHz, CDCl3) δ 3.6 (m, 1H), 3.7 (m, 1H), 3.9 (m, 1H), 4.0 (m, 1H), 4.1 (m, 1H), 4.6 (m, 1H), 6.8 (m, 2H), 7.3 (m, 2H).

Workup

  1. stirringthe reaction was stirred at room temperature for 66 hours
  2. customSolvent was removed under reduced pressure
  3. additionthe residue was mixed with diethyl ether
  4. customThe supernatant was decanted
  5. concentrationconcentrated in vacuo
  6. customproviding a residue, which
  7. filtrationwas filtered through a short plug of silica gel (Gradient: 0% to 5% methanol in methylene chloride)

Sources & evidence

ORD record
ord-e39d0177cd184026aaa27e95dcacd761
Source dataset
uspto-grants-2012_10
Patent number
US08278457B2

Reaction notes

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