Ammonium Hydroxide → HCID 19922437, compound

HRID 1463682Notes

Reaction equation

HRID 1463682 reaction equation
[H-].[Na+].[Na].[N:4]1[C:16]2[CH2:15][C:14]3[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:8]=2[CH:7]=[CH:6][CH:5]=1.Cl.[N:18]1[CH:23]=[CH:22][C:21]([CH2:24]Cl)=[CH:20][CH:19]=1.[OH-].[NH4+:27].[Cl-].[NH4+]>O.C(OCC)(=O)C>[N:18]1[CH:23]=[CH:22][C:21]([CH2:24][C:15]2([CH2:9][C:8]3[CH:16]=[CH:15][N:27]=[CH:6][CH:7]=3)[C:16]3=[N:4][CH:5]=[CH:6][CH:7]=[C:8]3[C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][C:14]2=3)=[CH:20][CH:19]=1

Participants

9

Reactant 6

HCID 14923Ammonium HydroxideHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 745704-(Chloromethyl)pyridinium chlorideHCID 5360545SodiumHCID 12226515Azafluorene

Product 1

HCID 19922437HCID 19922437, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

2.0 g (42 mmole) of 50% sodium hydride was suspended in a 250 ml, 4-neck, round-bottom flask fitted with nitrogen inlet, condenser, thermometer, addition funnel, magnetic stirrer, and 25 ml of sodium dried tetrahydrofuran (THF) containing 2.5 g (15 mmol) of 1-azafluorene. The mixture was allowed to stir at room temperature for one hour. 6.6 g (40 mmole) of 4-picolylchloride hydrochloride was dissolved in the minimum amount of water and cooled to 0°-5°. Being very careful to keep the temperature below 5°, it was basified with ammonium hydroxide, quickly extracted with benzene, dried with potassium carbonate and filtered. The benzene solution of 4-picolyl chloride was added to the reaction mixture during 15 min. After completion of addition, the mixture was heated to 60° until TLC showed completion of reaction (ETOAc-CH3OH; 90:10) Rf 0.13. Rf 0.13. The reaction mixture was cooled and decomposed with saturated ammonium chloride solution. The layers were separated and the organic phase extracted with benzene. This was dried with potassium carbonate and evaporated to yield 6.0 g crude product. Flash chromatography (ethyl acetate) yielded 4.0 g of product which was recrystallized from butyl chloride to yield 2.49 g, m.p. 204.7°-206.0°. HRMS calculated mass 349.1528, difference 0.0004, C24H19N3. NMR (200 MHz,CDCl3) δ 3.394-3.718[dd,4H,(-CH2 -pyridyl]; 6.437(d,4H,β-pyridyls); 7.107-7.635 (m,6H,aromatic); 8.027-8.057(d,4H,α-pyridyls); 8.589-8.621(dd,1H,α-CHN-azafluorene).

Workup

  1. custom4-neck, round-bottom flask fitted with nitrogen inlet, condenser
  2. additionthermometer, addition funnel, magnetic stirrer
  3. temperaturecooled to 0°-5°
  4. customthe temperature below 5°, it
  5. extractionquickly extracted with benzene
  6. dry with materialdried with potassium carbonate
  7. filtrationfiltered
  8. additionThe benzene solution of 4-picolyl chloride was added to the reaction mixture during 15 min
  9. additionAfter completion of addition
  10. temperaturethe mixture was heated to 60° until TLC
  11. customcompletion of reaction (ETOAc-CH3OH; 90:10) Rf 0.13
  12. temperatureThe reaction mixture was cooled
  13. customThe layers were separated
  14. extractionthe organic phase extracted with benzene
  15. dry with materialThis was dried with potassium carbonate
  16. customevaporated
  17. customto yield 6.0 g crude product

Sources & evidence

ORD record
ord-33c1647418f64d719781986b41556837
Source dataset
uspto-grants-1994_04
Patent number
US05300642

Reaction notes

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