18-Crown-6 → HCID 58524147, compound

HRID 536433Notes

Reaction equation

HRID 536433 reaction equation
[CH3:1][C:2]1[C:3]([NH2:13])=[C:4]([CH:9]=[CH:10][C:11]=1[CH3:12])[C:5]([O:7][CH3:8])=[O:6].B([O-])([O-])[O-].F[N+:19](F)(F)F.F[N+](F)(F)F.F[N+](F)(F)F.N([O-])=O.[Na+].C([O-])(=O)C.[K+].C1OCCOCCOCCOCCOCCOC1>Cl.O.C(Cl)(Cl)Cl>[CH3:8][O:7][C:5]([C:4]1[CH:9]=[CH:10][C:11]([CH3:12])=[C:2]2[C:3]=1[NH:13][N:19]=[CH:1]2)=[O:6]

Participants

9

Reactant 5

HCID 2855718-Crown-6HCID 517044Potassium AcetateHCID 18365523HCID 18365523, compoundHCID 23668193Sodium NitriteHCID 86659464HCID 86659464, compound

Product 1

HCID 58524147HCID 58524147, compoundYield 58.9%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent3×HCID 6212ChloroformSolvent

Procedure

A solution of methyl 3,4-dimethyl-2-aminobenzoate (10 g) in concentrated hydrochloric acid (20 ml) was cooled to 0° C., treated with solution of tetrafluoroammoniumborate (9.4 g) in water (2 ml), a solution of sodium nitrite (7.7 g) in water (2 ml) dropwise, stirred for 2 h, filtered to get a solid. The solid residue was dissolved in chloroform (50 m), treated with potassium acetate (2 mol equivalents) and catalytic amounts of 18-Crown-6, and stirred for 12 h. The reaction mixture was treated with water (50 ml) and extracted with chloroform (2×50 ml). The combined organic layers were dried over sodium sulfate and concentrated. Chromatographic purification (hexane/ethyl acetate 80:20) gave 4-methyl- 1H-indazole-7-carboxylic acid methyl ester (3.2 g). 1H-NMR (400 MHz, CDCl3): 2.68 (s, 3H), 4.00 (s, 3H), 7.02 (d, 1H), 7.97 (d, 1H), 8.15 (s, 1H). LC-MS (methanol): m/z=191 (M+H).

Workup

  1. filtrationfiltered
  2. customto get a solid
  3. extractionextracted with chloroform (2×50 ml)
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. concentrationconcentrated
  6. customChromatographic purification (hexane/ethyl acetate 80:20)

Sources & evidence

ORD record
ord-ef1645ad042841dc9147d42d0c50e55c
Source dataset
uspto-grants-2014_10
Patent number
US08859592B2

Reaction notes

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