Morpholine → 4-(7-vinyl-2H-chromen-4-yl)morpholine

HRID 1506406Notes

Reaction equation

HRID 1506406 reaction equation
[CH:1]([C:3]1[CH:12]=[C:11]2[C:6]([C:7](=O)[CH2:8][CH2:9][O:10]2)=[CH:5][CH:4]=1)=[CH2:2].[NH:14]1[CH2:19][CH2:18][O:17][CH2:16][CH2:15]1>C1(C)C=CC=CC=1.[Ti](Cl)(Cl)(Cl)Cl>[CH:1]([C:3]1[CH:12]=[C:11]2[C:6]([C:7]([N:14]3[CH2:19][CH2:18][O:17][CH2:16][CH2:15]3)=[CH:8][CH2:9][O:10]2)=[CH:5][CH:4]=1)=[CH2:2]

Participants

5

Reactant 2

HCID 8083MorpholineHCID 22323781HCID 22323781, compound

Product 1

HCID 671681804-(7-vinyl-2H-chromen-4-yl)morpholineYield 87%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 1140TolueneSolvent

Procedure

To a mixture of 7-vinylchroman-4-one (Preparation 2D, 0.370 g, 2.12 mmol) and morpholine (0.925 mL, 10.6 mmol) in toluene (8 mL) at 0° C. was added titanium(IV) chloride (1.0 M in toluene) (1.17 mL, 1.17 mmol) dropwise. The ice-bath was removed, and the orange, heterogeneous reaction mixture was stirred at room temperature overnight. The reaction mixture was filtered under reduced pressure through a pad of CELITE®, which was rinsed with toluene (3×10 mL). The pale yellow filtrate was concentrated under reduced pressure to give 4-(7-vinyl-2H-chromen-4-yl)morpholine (0.448 g, 1.84 mmol, 87% yield) as a yellow oil. 1H NMR (500 MHz, CDCl3) δ ppm 2.85-2.90 (m, 4), 3.84-3.89 (m, 4), 4.71 (d, J=4.16 Hz, 2), 5.10 (t, J=4.16 Hz, 1), 5.27 (d, J=11.37 Hz, 1), 5.76 (d, J=17.48 Hz, 1), 6.67 (dd, J=17.62, 10.96 Hz, 1), 6.98-7.03 (m, 2H), and 7.29 (s, 1H).

Workup

  1. customThe ice-bath was removed
  2. filtrationThe reaction mixture was filtered under reduced pressure through a pad of CELITE®, which
  3. washwas rinsed with toluene (3×10 mL)
  4. concentrationThe pale yellow filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-b67477a7cc184dc9ae75731abd4f08b7
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

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