Sodium Carbonate → 1-Chloro-4-phenyl-5,6,7,8-tetrahydrophthalazine

HRID 593932Notes

Reaction equation

HRID 593932 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl:10][C:11]1[C:20]2[CH2:19][CH2:18][CH2:17][CH2:16][C:15]=2[C:14](Cl)=[N:13][N:12]=1.O1CCOCC1.C(=O)([O-])[O-].[Na+].[Na+]>CCOC(C)=O.O.[Cl-].[Na+].O.ClCCl.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:10][C:11]1[C:1]2[CH2:6][CH2:5][CH2:4][CH2:3][C:2]=2[C:14]([C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)=[N:13][N:12]=1

Participants

10

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 66827Phenylboronic AcidHCID 126224401,4-Dichloro-5,6,7,8-tetrahydrophthalazine

Product 1

HCID 577562221-Chloro-4-phenyl-5,6,7,8-tetrahydrophthalazine

Reagents, catalysts & solvents 5

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
80 °C

Procedure

1,1′-bis(diphenylphosphino)ferrocene-palladium dichloride (0.270 g, 0.369 mmol), phenylboronic acid (0.900 g, 7.38 mmol) and 1,4-dichloro-5,6,7,8-tetrahydrophthalazine (2.25 g, 11.1 mmol) were combined in a 150 mL sealable vessel under argon. 15 mL dioxane and 2.0 M Sodium carbonate, aqueous (7.38 ml, 14.8 mmol) were added. The vessel was sealed and heated to 80° C. to give a homogenous brown reaction. After 30 min, the reaction was cooled to ambient temperature and was diluted with EtOAc, water, and brine. The layers were separated, and the organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give a red solid. This was taken up in dichloromethane and purified by silica gel chromatography (0-60% EtOAc in hexanes) to give 1-chloro-4-phenyl-5,6,7,8-tetrahydrophthalazine as an off-white solid. MS m/z=245 [M+H]+. Calc'd for C14H13ClN2: 244.7.

Workup

  1. customThe vessel was sealed
  2. customto give
  3. customa homogenous brown reaction
  4. temperaturethe reaction was cooled to ambient temperature
  5. customThe layers were separated
  6. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give a red solid
  10. custompurified by silica gel chromatography (0-60% EtOAc in hexanes)

Sources & evidence

ORD record
ord-e864d3bbc06f448aaab81278697060f8
Source dataset
uspto-grants-2016_01
Patent number
US09242961B2

Reaction notes

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