Trimethyl borate → (2-(Benzyloxy)naphthalen-1-yl)boronic acid

HRID 1591948

反応式

HRID 1591948 の反応式
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.[Li]CCCC.[B:25](OC)([O:28]C)[O:26]C>CCOCC>[C:14]1([CH2:13][O:12][C:3]2[CH:4]=[CH:5][C:6]3[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=3)[C:2]=2[B:25]([OH:28])[OH:26])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

参加物

5

反応物 3

HCID 8470Trimethyl borateHCID 3788832-Benzyloxy-1-bromonaphthaleneHCID 178418339Butyllithium

生成物 1

HCID 22715022(2-(Benzyloxy)naphthalen-1-yl)boronic acid収率 83.1%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
0 °C

実験手順

To a suspension of 1-bromo-2-(phenylmethoxy)naphthalene (6.26 g, 20.0 mmol) in Et2O (75 mL) at −78° C. was added n-BuLi (8.0 mL, 2.5 M, 20 mmol) in hexanes and the mixture was stirred at 0° C. for 1 h. After re-cooling to −78° C., the mixture was treated with trimethyl borate (2.5 mL, 22 mmol) and allowed to warm to room temperature overnight. The resulting mixture was quenched with 1M HCl (50 mL) and stirred at room temperature for 45 min. The phases were separated and the extraction was completed with CH2Cl2. The combined organic extracts were dried (MgSO4) and evaporated in vacuo to give the title compound, 2-(pbenylmethoxy)-1-napthaleneboronic acid as a white powder (4.62 g, 83%), which was used in the next step without further purification. For analytical purposes, a small amount of the product was re-crystallised from MeOH/H2O: mp 133.0-135.0° C. (MeOH/H2O); 1H NMR (250MHz, d4-MeOH) δ5.20 (s, 2H), 7.28-7.60 (m, 9H), and 7.56-7.88 (m, 2H); 13C NMR (63 MHz, d4-MeOH) δ71.95, 115.4, 124.8, 127.7 (2C), 128.4, 128.9, 129.5, 129.6, 130.7 (2C?), 131.8, 137.2, 139.0 and 159.7;i IR (CHCl3) νmax 3609, 3490, 1592, 1509, 1386, and 1332 cm−1; MS (EI+) m/z (rel intensity) 278 (10%, M+), 234 (10), and 91 (100); HRMS calcd for C17H15BO3 (M+) 277.1151. found 277.1163. Anal. Calcd for C17H15BO3: C, 73.42; H, 5.44. Found: C, 73.07; H, 5.33.

後処理

  1. temperatureAfter re-cooling to −78° C.
  2. temperatureto warm to room temperature overnight
  3. customThe resulting mixture was quenched with 1M HCl (50 mL)
  4. stirringstirred at room temperature for 45 min
  5. customThe phases were separated
  6. extractionthe extraction
  7. dry with materialThe combined organic extracts were dried (MgSO4)
  8. customevaporated in vacuo

出典と根拠

ORDレコード
ord-e557e6f04b0b426896c92509664d323e
出典データセット
uspto-grants-2007_11
特許番号
US07291739B2

関連ノート

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