Diethyl Ether → (5-Bromo-2-methoxy-phenyl)-napthalen-1-yl-methanol

HRID 971351Notes

Reaction equation

HRID 971351 reaction equation
[Br:1][C:2]1[C:11]2[C:6](=CC=CC=2)[CH:5]=[CH:4][CH:3]=1.[CH2:12]([Li])[CH2:13][CH2:14][CH3:15].Br[C:18]1(OC)[CH:25]=[CH:24][C:21]([CH:22]=[O:23])=[CH:20][CH2:19]1.C[CH2:29][O:30]CC>C1COCC1.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:30][CH3:29])=[C:6]([CH:22]([C:21]2[C:20]3[C:19](=[CH:12][CH:13]=[CH:14][CH:15]=3)[CH:18]=[CH:25][CH:24]=2)[OH:23])[CH:11]=1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 70011-BromonaphthaleneHCID 865871414-Bromo-anisaldehydeHCID 178418339Butyllithium

Product 1

HCID 22565251(5-Bromo-2-methoxy-phenyl)-napthalen-1-yl-methanolYield 88.15%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 1.70 ml (12.22 mmol) 1-Bromonaphthalene (61) in 40 ml dry THF 7.64 ml (12.22 mmol, 1.00 eq.) of a 1.6 M solution of n-Butyllithium in hexanes were added at −78° C. via syringe. After stirring this mixture for 1 h at −78° C. a solution of 2.63 g (12.23 mmol, 1.00 eq.) 4-bromo-anisaldehyde (60) in 30 ml dry THF was added dropwise via a dropping funnel. The resulting mixture was stirred for another 60 min at −78° C., then for 2 h at −30° C. and finally 15 h at r. t. After quenching the reaction with 1 M aq. HCl-solution and adding ether the org. phase was washed subsequently with water and brine before it was dried over MgSO4 and evaporated. Column chromatography (CH2Cl2) yielded 3.70 g (10.77 mmol, 88.15%) (5-Bromo-2-methoxy-phenyl)-napthalen-1-yl-methanol (62) as pale greenish foam. Rf (CH2Cl2)=0.37. 1H-NMR (500 MHz, CDCl3): δ=3.84 (s, 3H, OMe), 6.80 (d, J=8.51 Hz, 1H), 6.81 (s, 1H, HO—CH), 7.18 (d, 1H, J=2.68 Hz), 7.34 (dd, 1H, J1=8.82 Hz, J2=2.52 Hz), 7.42-7.48 (m, 3H), 7.55 (d, 1H, J=7.09 Hz), 7.79 (d, 1H, J=8.20 Hz), 7.83-7.87 (m, 1H), 7.96-8.00 (m, 1H). MS (EI): m/z=345 (14), 344 (76), 343 (17), 342 (77), 326 (14), 325 (12), 324 (14), 311 (10), 309 (10), 245 (25), 217 (12), 215 (88), 213 (84), 202 (19), 201 (12), 157 (18), 155 (37), 141 (21), 129 (66), 128 (100), 127 (42), 108 (12), 101 (24), 77 (14), 63 (11). HR-MS (EI): Calcd. for C18H15BrO2: 342.025541. Found: 342.025182.

Workup

  1. additionwas added dropwise via a dropping funnel
  2. waitfor 2 h at −30° C.
  3. customfinally 15 h
  4. customAfter quenching
  5. customthe reaction with 1 M aq. HCl-solution
  6. washphase was washed subsequently with water and brine before it
  7. dry with materialwas dried over MgSO4
  8. customevaporated

Sources & evidence

ORD record
ord-4cf3d82183ae4fcdbb15945724df80d4
Source dataset
uspto-grants-2007_12
Patent number
US07312246B2

Reaction notes

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