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

HRID 1043438노트

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HRID 1043438 반응식
[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

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 74505Methyltriphenyliphosphonium bromide촉매HCID 8028Tetrahydrofuran용매2회

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온도
0 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-1be5fd7427ea4db5949df46316bef10f
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08563505B2

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