Hydrochloric Acid → HCID 58266642, compound

HRID 1888379Notes

Reaction equation

HRID 1888379 reaction equation
N[C:2]1[CH:24]=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1.N([O-])=O.[Na+].[ClH:29]>S(=O)(=O)(O)O.CC(O)=O.O.C(Cl)Cl.[Cu]Cl>[Cl:29][C:2]1[CH:24]=[N:23][C:5]2[N:6]([CH2:15][O:16][CH2:17][CH2:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[C:7]3[CH:12]=[N:11][C:10]([C:13]#[N:14])=[CH:9][C:8]=3[C:4]=2[CH:3]=1

Participants

9

Reactant 3

HCID 313Hydrochloric AcidHCID 23668193Sodium NitriteHCID 58266498HCID 58266498, compound

Product 1

HCID 58266642HCID 58266642, compoundYield 43%

Reagents, catalysts & solvents 5

HCID 62652Cuprous chlorideCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 3-amino-9-(2-trimethylsilanylethoxymethyl)-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile (45.4 mg, 0.134 mmol) in 2M aqueous sulfuric acid (2.0 mL) and AcOH (1.0 mL) was cooled to 0° C. and treated with a solution of sodium nitrite (10.2 mg, 0.147 mmol) in water (0.30 mL). After 20 min, the solution of the diazonium salt was added slowly to a cooled (0° C.) solution of copper (I) chloride (29.1 mg, 0.294 mmol) in 1M hydrochloric acid (0.60 mL). The reaction mixture was allowed to warm to ambient temperature then diluted with DCM and water. The layers were separated, the aqueous phase extracted further with DCM, and the combined organic phases were dried over sodium sulfate and concentrated in vacuo. The resultant residue was dissolved in ethyl acetate and pre-absorbed onto silica gel and purified by flash chromatography (silica, 4 g column, Biotage, 1-50% EtOAc in heptane) to afford the title compound as a yellow-orange solid (20 mg, 43%). LCMS (Method D): RT=3.61 min, M+H+=359/361.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous phase extracted further with DCM
  3. dry with materialthe combined organic phases were dried over sodium sulfate
  4. concentrationconcentrated in vacuo
  5. dissolutionThe resultant residue was dissolved in ethyl acetate
  6. custompre-absorbed onto silica gel
  7. custompurified by flash chromatography (silica, 4 g column, Biotage, 1-50% EtOAc in heptane)

Sources & evidence

ORD record
ord-71424b8216614692895399af4bbf1c97
Source dataset
uspto-grants-2013_08
Patent number
US08501765B2

Reaction notes

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