Sodium Hydroxide → 3-(3-Chloropyridazin-6-yl)-2-phenylpyrazolo[1,5-a]pyridine

HRID 276924Notes

Reaction equation

HRID 276924 reaction equation
[Cl:1][C:2]1[N:7]=[N:6][C:5]([C:8]#[C:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.[C:16]1([C:22]#[C:23][C:24]2[N:25]=[N:26][C:27]([C:30]#[C:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[CH:28][CH:29]=2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[I-].[NH2:39][N+:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.[OH-].[Na+]>[Cl-].C([N+](C)(C)C)C1C=CC=CC=1.ClCCl.O>[Cl:1][C:2]1[N:7]=[N:6][C:5]([C:8]2[C:9]([C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=3)=[N:26][N:25]3[CH:24]=[CH:23][CH:22]=[CH:16][C:21]=23)=[CH:4][CH:3]=1.[C:16]1([C:22]#[C:23][C:24]2[N:25]=[N:26][C:27]([C:30]3[C:31]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)=[N:39][N:40]4[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=34)=[CH:28][CH:29]=2)[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

9

Reactant 4

HCID 14798Sodium HydroxideHCID 2733704Pyridinium, 1-amino-, iodide (1:1)HCID 126802603-Chloro-6-(phenylethynyl)pyridazineHCID 126802613,6-Bis(2-phenylethynyl)pyridazine

Product 2

HCID 151581443-(3-Chloropyridazin-6-yl)-2-phenylpyrazolo[1,5-a]pyridineHCID 226292233-[3-(2-Phenylethynyl)pyridazin-6-yl]-2-phenylpyrazolo[1,5-a]pyridine

Reagents, catalysts & solvents 3

HCID 5963Benzyltrimethylammonium chlorideCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

A 4:1 mixture of 6-chloro-3-(2-phenylethynyl)pyridazine and 3,6-bis(2-phenylethynyl)pyridazine (10.2 g) was stirred in a two-phase mixture of N-aminopyridinium iodide (90% purity; 11 g), benzyltrimethylammonium chloride (1.4 g), sodium hydroxide (5.9 g), dichloromethane (51 ml), and water (51 ml) at ambient temperature for an hour. The reaction mixture was diluted with dichloromethane and water. The organic layer was separated, and the aqueous layer was extracted once with dichloromethane. The combined organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The residue was subjected to column chromatography on silica gel (elution with 25:1 dichloromethane-ethyl acetate) to give 3-(3-chloropyridazin-6-yl)-2-phenylpyrazolo[1,5-a]pyridine (0.72 g) and 3-[3-(2-phenylethynyl)pyridazin-6-yl]-2-phenylpyrazolo[1,5-a]pyridine (0.5 g). Some fractions containing the mixture thereof were subjected to flash column chromatography on silica gel (elution with 50:1 dichloromethane-ethyl acetate) gave an additional product of 3-(3-chloropyridazin-6-yl)-2-phenylpyrazolo[1,5-a]pyridine (0.34 g) and 3-[3-(2-phenylethynyl)pyridazin-6-yl]-2-phenylpyrazolo[1,5-a]pyridine (0.50 g).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous layer was extracted once with dichloromethane
  3. washThe combined organic layer was washed with water and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e9c6de11ff9c4910a215abf7d7cb93d0
Source dataset
uspto-grants-2002_03
Patent number
US06355640B1

Reaction notes

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