Hydrochloric Acid → (2-Aminophenyl)(pyridin-4-yl)methanone

HRID 1463776Notes

Reaction equation

HRID 1463776 reaction equation
B(Cl)(Cl)Cl.[NH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[C:12]([C:14]1[CH:19]=[CH:18][N:17]=[CH:16][CH:15]=1)#N.[Cl-].[Cl-].[Cl-].[Al+3].Cl.[OH-:25].[Na+]>ClC(Cl)C(Cl)Cl>[NH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[C:12]([C:14]1[CH:19]=[CH:18][N:17]=[CH:16][CH:15]=1)=[O:25]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 6115AnilineHCID 75064-CyanopyridineHCID 14798Sodium HydroxideHCID 25135Boron TrichlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 14005182(2-Aminophenyl)(pyridin-4-yl)methanoneYield 35%

Reagents, catalysts & solvents 1

HCID 65911,1,2,2-TetrachloroethaneSolvent2×

Conditions

Temperature
100 °C

Procedure

A 1M solution of boron trichloride (in dichloromethane, 130 ml, 130 mmol) was added dropwise to a stirred, cooled (0° C.) solution of aniline (10.92 ml, 120 mmol) in 1,1,2,2-tetrachloroethane (160 ml). After addition a solution of 4-cyanopyridine (16.63 g, 160 mmol) in 1,1,2,2-tetrachloroethane (240 ml) was added followed by solid aluminium trichloride (17.33 g, 130 mmol) and further 1,1,4,4-tetrachloroethane (100 ml). The reaction mixture was heated to 100° C. for 6 hours, cooled to 0° C. then treated cautiously with 2M hydrochloric acid (100 ml). After addition the mixture was heated at 100° C. for 30 minutes, cooled to room temperature then basified with 2M sodium hydroxide solution. The organic layer was separated and the aqueous exhaustively extracted with dichloromethane. The combined organics were dried (sodium sulphate) and evaporated to give the crude product which was triturated with propan-2-ol to afford the title compound as a yellow solid (8.22 g, 35%). mp 153°-161° C.; IR (nujol) 1620 cm-1 ; 1H NMR (250MHz, CDCl3) δ 6.30 (2H, broad s), 6.60 (1H, ddd, J1 =1Hz, J2 =J3 =8Hz), 6.73 (1H, dd, J1 =1Hz, J2 =8Hz), 7.29-7.37 (2H, m), 7.43 (2H, dd, J1 =2Hz, J2 =4.5Hz), 8.75 (2H, dd, J1 =2Hz, J2 =4.5Hz).

Workup

  1. additionwas added
  2. temperaturecooled to 0° C.
  3. additionAfter addition the mixture
  4. temperaturewas heated at 100° C. for 30 minutes
  5. temperaturecooled to room temperature
  6. customThe organic layer was separated
  7. extractionthe aqueous exhaustively extracted with dichloromethane
  8. dry with materialThe combined organics were dried (sodium sulphate)
  9. customevaporated
  10. customto give the crude product which
  11. customwas triturated with propan-2-ol

Sources & evidence

ORD record
ord-567f9330d9cd491598c39dedaa330813
Source dataset
uspto-grants-1994_04
Patent number
US05302591

Reaction notes

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