2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 3-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile

HRID 1473406ノート

反応式

HRID 1473406 の反応式
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[O:10][CH3:11].C([Li])CCC.C(O[B:21]1[O:25][C:24]([CH3:27])([CH3:26])[C:23]([CH3:29])([CH3:28])[O:22]1)(C)C>C(OCC)C>[CH3:11][O:10][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:2]=1[B:21]1[O:25][C:24]([CH3:27])([CH3:26])[C:23]([CH3:29])([CH3:28])[O:22]1)[C:6]#[N:7]

参加物

5

反応物 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 225911814-Bromo-3-methoxybenzonitrileHCID 178418339Butyllithium

生成物 1

HCID 689291003-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile収率 53%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

A solution of 4-bromo-3-methoxybenzonitrile (Combi-Blocks, San Diego, Calif., 2.500 g, 11.79 mmol) in 100 mL of diethyl ether was cooled to −78° C. and was treated with n-butyllithium (4.95 ml, 12.38 mmol). After stirring for 10 minutes, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.07 ml, 16.51 mmol) was added, and the cooling bath was removed. After stirring for an additional 2 hours, LC/MS showed mostly product, so the reaction mixture was quenched with saturated NH4Cl solution. After stirring for 20 minutes, the reaction mixture was poured into a separatory funnel charged with EtOAc. The organic layer was separated, dried over MgSO4 and concentrated. Purification of the crude residue by silica gel column chromatography (0 to 100% EtOAc/heptane) gave 3-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (1.62 g, 6.25 mmol, 53.0% yield) with minor impurities. m/z (ESI) 260.1 (M+H)+

後処理

  1. customthe cooling bath was removed
  2. stirringAfter stirring for an additional 2 hours
  3. customso the reaction mixture was quenched with saturated NH4Cl solution
  4. stirringAfter stirring for 20 minutes
  5. additionthe reaction mixture was poured into a separatory funnel
  6. additioncharged with EtOAc
  7. customThe organic layer was separated
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customPurification of the crude residue by silica gel column chromatography (0 to 100% EtOAc/heptane)

出典と根拠

ORDレコード
ord-f8b5c0a46a6a49678dee752a53075be4
出典データセット
uspto-grants-2015_04
特許番号
US09012443B2

反応ノート

読み込み中…