2-Bromotoluene → 4-o-tolylmorpholine

HRID 1871017Notes

Reaction equation

HRID 1871017 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH3:8].[NH:9]1[CH2:14][CH2:13][O:12][CH2:11][CH2:10]1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[N:9]1[CH2:14][CH2:13][O:12][CH2:11][CH2:10]1

Participants

6

Reactant 3

HCID 72362-BromotolueneHCID 8083MorpholineHCID 83681Tris(1,1-dimethylethyl)phosphine

Product 1

HCID 98153874-o-tolylmorpholineYield 101%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

The above general procedure was followed using 2-bromotoluene (171 mg, 1.10 mmol) and morpholine (87 mg, 1.00 mmol) with 1 mol % Pd(OAc)2 and 0.8 mol % tri-t-butylphosphine in 1.0 mL of toluene. After 6 hours, the reaction mixture was adsorbed onto silica gel and chromatographed using 5% ethyl acetate/hexanes to give 179 mg (>99%) of N-(2-methylphenyl)morpholine. 1H NMR (500 MHz, CDCl3) δ 7.20 (d J=7.4 Hz, 1H), 7.18 (d, J=7.4 Hz, 1H), 7.03 (d, J=7.4 Hz, 1H), 7.01 (d, J=7.4 Hz, 1H), 3.86 (t, J=4.5 Hz, 4H), 2.92 (t, J=4.5 Hz, 4H), 2.33 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 151.4, 132.7, 131.2, 126.7, 123.5, 119.0, 67.5, 52.4, 17.8.

Workup

  1. customchromatographed

Sources & evidence

ORD record
ord-e259ebfa9ade4868b863ece1a372837b
Source dataset
uspto-grants-2000_08
Patent number
US06100398

Reaction notes

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