Morpholine → 4-(4-Bromophenyl)morpholine

HRID 1992316Notes

Reaction equation

HRID 1992316 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[NH:9]1[CH2:14][CH2:13][O:12][CH2:11][CH2:10]1.CC(C)([O-])C.[Na+].C1OCCOCCOCCOCCOCCOC1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CCOC(C)=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:9]2[CH2:14][CH2:13][O:12][CH2:11][CH2:10]2)=[CH:4][CH:3]=1

Participants

9

Reactant 5

HCID 8083MorpholineHCID 115221-Bromo-4-iodobenzeneHCID 2855718-Crown-6HCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxide

Product 1

HCID 116228514-(4-Bromophenyl)morpholineYield 5.7%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1-bromo-4-iodobenzene (5.0 g, 18 mmol), morpholine (1.85 mL, 21 mmol), sodium tert-butoxide (2.4 g, 25 mmol), 18-crown-6 (6.6 g, 25 mmol) in THF (150 mL) was purged with Ar for 20 min, then BINAP (0.11 g, 0.18 mmol) and Pd2(dba)3 (0.16 g, 0.18 mmol) was added. The mixture turned dark after stirring at room temperature overnight. The solvent was concentrated under reduced pressure and the residue was dissolved in diethyl ether and washed with water. The organic phase was mixed with silica gel, and the solvent was evaporated to dryness. The residue was purified by silica gel column chromatography (EtOAc in hexanes 5%) to of white precipitate (250 mg, 5% yield). 1H NMR (CDCl3): 7.3 (d, 2H), 6.85 (d, 4H), 3.1 (d, 4H).

Workup

  1. concentrationThe solvent was concentrated under reduced pressure
  2. dissolutionthe residue was dissolved in diethyl ether
  3. washwashed with water
  4. additionThe organic phase was mixed with silica gel
  5. customthe solvent was evaporated to dryness

Sources & evidence

ORD record
ord-b8adaa87b2ab452383786db13ba08ef1
Source dataset
uspto-grants-2010_01
Patent number
US07648986B2

Reaction notes

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