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

HRID 25838

反応式

HRID 25838 の反応式
[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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

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.

後処理

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

出典と根拠

ORDレコード
ord-3c22cd9248e049b0bd5a8dbc307ac7b0
出典データセット
uspto-grants-2005_02
特許番号
US06858600B2

関連ノート

読み込み中…