Sodium Hydroxide → HCID 66714730, compound

HRID 1405073Notes

Reaction equation

HRID 1405073 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[C:11]1[CH:12]=[N:13][CH:14]=[CH:15][C:16]=1N.[F:18][B-](F)(F)F.[H+].N([O-])=O.[Na+].[OH-].[Na+]>>[F:18][C:16]1[CH:15]=[CH:14][N:13]=[CH:12][C:11]=1[C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[CH3:1]

Participants

5

Reactant 4

HCID 14798Sodium HydroxideHCID 28118Tetrafluoroboric acidHCID 23668193Sodium NitriteHCID 66714222HCID 66714222, compound

Product 1

HCID 66714730HCID 66714730, compoundYield 17.42%

Conditions

Temperature
0 °C

Procedure

To a solution of Intermediate 19A (340 mg, 1.483 mmol) in tetrafluoroboric acid (1 mL, 7.65 mmol) at −10° C. was added sodium nitrite (179 mg, 2.60 mmol) in small portions, keeping the temperature below −5° C. After the addition was complete, the mixture was stirred at 0° C. for 45 min and then warmed slowly to room temperature over a period of 30 min to decompose the preparation of diazonium salt. The temperature of the mixture was rose to 30-35° C. and nitrogen was evolved for about 30 min. The resulting mixture was cooled to −10° C. and neutralized with 1M sodium hydroxide precooled to 0-5° C. The mixture was extracted with ethyl acetate (2×25 mL), washed with cooled water (25 mL), and dried over magnesium sulfate. The crude material was purified by silica gel chromatography (40 g ISCO column, eluting with 100% hexanes to 100% CH2Cl2) to provide Intermediate 19B (60 mg, 0.258 mmol, 17.42% yield) as a yellow solid. MS (ES): m/z=233.0 [M+H]+. 1H NMR (400 MHz, MeOD) δ ppm 2.34 (s, 3 H) 7.44 (dd, J=9.66, 5.65 Hz, 1 H) 7.55 (d, J=8.28 Hz, 1 H) 8.20 (dd, J=8.16, 2.13 Hz, 1 H) 8.28 (d, J=2.26 Hz, 1 H) 8.57 (d, J=9.79 Hz, 1 H) 8.70 (dd, J=7.65, 5.65 Hz, 1 H).

Workup

  1. customthe temperature below −5° C
  2. additionAfter the addition
  3. temperaturewarmed slowly to room temperature over a period of 30 min
  4. customto 30-35° C.
  5. waitnitrogen was evolved for about 30 min
  6. customprecooled to 0-5° C
  7. extractionThe mixture was extracted with ethyl acetate (2×25 mL)
  8. washwashed with cooled water (25 mL)
  9. dry with materialdried over magnesium sulfate
  10. customThe crude material was purified by silica gel chromatography (40 g ISCO column, eluting with 100% hexanes to 100% CH2Cl2)

Sources & evidence

ORD record
ord-1d7aeff441c44429aca6e8bb40f451f9
Source dataset
uspto-grants-2014_12
Patent number
US08916553B2

Reaction notes

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