4'-Bromo-4-(dimethylamino)biphenyl-2-carbaldehyde → 4'-bromo-N,N-dimethyl-2-vinylbiphenyl-4-amine

HRID 1043438ノート

反応式

HRID 1043438 の反応式
[Li][CH2:2]CCC.[Br:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[C:14]([CH:22]=O)=[CH:15][C:16]([N:19]([CH3:21])[CH3:20])=[CH:17][CH:18]=2)=[CH:9][CH:8]=1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[Br:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][C:14]=2[CH:22]=[CH2:2])=[CH:9][CH:8]=1

参加物

5

反応物 2

HCID 592665494'-Bromo-4-(dimethylamino)biphenyl-2-carbaldehydeHCID 178418339Butyllithium

生成物 1

HCID 592665464'-bromo-N,N-dimethyl-2-vinylbiphenyl-4-amine収率 58.4%

試薬・触媒・溶媒 2

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

BuLi (2.5M in hexanes, 2.96 mL, 7.40 mmol) was added to a solution of methyltriphenylphosphonium bromide (2.94 g, 8.22 mmol) in THF (20 mL). The mixture was stirred at 0° C. for 1 hr. A solution of 4′-bromo-4-(dimethylamino)biphenyl-2-carbaldehyde (1.25 g, 4.11 mmol) in THF (20 mL) was added dropwise at 0° C. The mixture was stirred overnight from 0° C. to r.t. The reaction was filtered and evaporated. The residue was diluted with diethyl ether and washed with water and brine. The ether layer was dried (MgSO4), filtered and evaporated to give the crude material. The crude material was purified on the Biotage (5-15% EtOAc:Hex) to give 4′-bromo-N,N-dimethyl-2-vinylbiphenyl-4-amine (725 mg, 2.399 mmol, 58% yield) as a yellow solid. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 2.97-3.07 (m, 6H) 5.20 (d, J=10.99 Hz, 1H) 5.69 (d, J=17.40 Hz, 1H) 6.70 (dd, J=17.40, 10.99 Hz, 1H) 6.76 (dd, J=8.55, 2.75 Hz, 1H) 6.95 (d, J=2.44 Hz, 1H) 7.16 (d, J=8.55 Hz, 1H) 7.21 (m, J=8.24 Hz, 2H) 7.50 (m, J=8.55 Hz, 2H).

後処理

  1. stirringThe mixture was stirred overnight from 0° C. to r.t
  2. filtrationThe reaction was filtered
  3. customevaporated
  4. additionThe residue was diluted with diethyl ether
  5. washwashed with water and brine
  6. dry with materialThe ether layer was dried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. customto give the crude material
  10. customThe crude material was purified on the Biotage (5-15% EtOAc:Hex)

出典と根拠

ORDレコード
ord-1be5fd7427ea4db5949df46316bef10f
出典データセット
uspto-grants-2013_10
特許番号
US08563505B2

反応ノート

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