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

HRID 1043438Notes

Reaction equation

HRID 1043438 reaction equation
[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

Participants

5

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-1be5fd7427ea4db5949df46316bef10f
Source dataset
uspto-grants-2013_10
Patent number
US08563505B2

Reaction notes

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