Benzoyl Peroxide → HCID 10858468, compound

HRID 2188500

Reaction equation

HRID 2188500 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:11]=[C:10]([C:18](O)=[O:19])[N:9]=1.ClC1C=CC=CC=1C1C2C(=CC=CC=2)C=C(C)N=1.BrN1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:11]=[C:10]([CH:18]=[O:19])[N:9]=1

Participants

6

Reactant 4

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 110005543-Isoquinolinecarboxylicacid, 1-(2-chlorophenyl)-HCID 11128841Isoquinoline, 1-(2-chlorophenyl)-3-methyl-

Product 1

HCID 10858468HCID 10858468, compound

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

Then 1-(2-clorophenyl)-3-isoquinolinecarboxylic acid 81 is formed by the following process. A mixture of 1-(2-clorophenyl)-3-methylisoquinoline 77 (6.68 g, 19.88 mmol), N-bromo-succinimide (NBS) (8.896 g, 19.98 mmol), and benzoyl peroxide (BPO) (0.57 g) in CCl4 was heated to reflux while being illuminated by a flood lamp for 5 hours. The reaction was cooled to room temperature and filtered. The filtrate was washed with saturated NaHCO3 (1×40 mL), dried with Na3SO4, filtered and concentrated in vacuo. The crude dibromide yellow product 79 was used in the next step. To a refluxing solution of the crude dibromide 79. (10.13 g) in EtOH (140 mL) and THF (70 mL) was added dropwise a solution of AgNO3 (10.595 g) in H2O (6 mL). The mixture was refluxed for 1 hour and filtered hot. The filter cake was washed with hot THF (2×20). The combined filtrate was concentrated in vacuo to give crude 1-(2-clorophenyl)-3-isoquinolinecarboxaldehyde as a dark yellow oil. (9 g) This oil was used without purification. To a solution of the crude aldehyde in absolute EtOH (100 mL) was slowly added a solution of AgNO3 (11.11 g) in 10 mL H2O. to this stirred solution was added dropwise a solution of NaOH (9.43 g) in H2O (140 mL). The resulting black slurry was stirred at room temperature for 2 hours. The solution was then filtered through a Celite column. The filter cake was washed with ether. The ether was evaporated and the aqueous solution was made slightly acidic with concentrated HCl. The precipitate was collected by filtration, then washed with H2O. It was then recrystallized from CH3CN affording pale yellow crystals (2.63 g, 35%).

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. customwhile being illuminated by a flood lamp for 5 hours
  4. filtrationfiltered
  5. washThe filtrate was washed with saturated NaHCO3 (1×40 mL)
  6. dry with materialdried with Na3SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. addition(10.13 g) in EtOH (140 mL) and THF (70 mL) was added dropwise a solution of AgNO3 (10.595 g) in H2O (6 mL)
  10. temperatureThe mixture was refluxed for 1 hour
  11. filtrationfiltered hot
  12. washThe filter cake was washed with hot THF (2×20)
  13. concentrationThe combined filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-95350870ea704ca8b89f118bb687f30f
Source dataset
uspto-grants-2012_12
Patent number
US08323621B2

Linked notes

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