Tetrahydrofuran → HCID 12923596, compound

HRID 1262502Notes

Reaction equation

HRID 1262502 reaction equation
[CH:1]1[C:13]2[C:12](=[O:14])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.O1CCCC1.[CH:20]([NH:23][CH2:24][C:25]#[CH:26])([CH3:22])[CH3:21].C([Li])CCC>O>[CH:20]([NH:23][CH2:24][C:25]#[C:26][C:12]1([OH:14])[C:13]2[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=2[C:6]2[C:11]1=[CH:10][CH:9]=[CH:8][CH:7]=2)([CH3:22])[CH3:21]

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran3×HCID 10241FluorenoneHCID 243521N-(Propan-2-yl)prop-2-yn-1-amineHCID 178418339Butyllithium

Product 1

HCID 12923596HCID 12923596, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 9.0 g. of fluoren-9-one dissolved in 500 ml. of tetrahydrofuran was added dropwise over one hour to a stirred cold (-80° C.) solution of 500 ml. of tetrahydrofuran containing 9.7 g. of 3-isopropylaminopropyne and 75 ml. of a 1.6 molar tetrahydrofuran solution of n-butyl lithium. After the addition was complete, the reaction mixture was warmed to room temperature and then heated to reflux for sixteen hours. The reaction mixture was next cooled to room temperature and diluted by the dropwise addition of 200 ml. of water. The aqueous mixture was extracted several times with diethyl ether, and the ethereal extracts were combined, and the reaction product was converted to the hydrochloride salt by the addition of 300 ml. of 6N hydrochloric acid to the ethereal solution. The aqueous acid layer containing the reaction product was separated, washed once with fresh diethyl ether, and then made alkaline by the addition of 10 percent sodium hydroxide, which effected liberation of the hydrochloride salt back to the free amine. The free amine was extracted into fresh diethyl ether. The ethereal extracts were combined, washed with water and dried. Removal of the solvent by evaporation under reduced pressure then afforded 2.3 g of 9-(3-isopropylaminopropynyl)-9-hydroxyfluorene. M.P. 214°-215° C.

Workup

  1. additionAfter the addition
  2. temperatureheated
  3. temperatureto reflux for sixteen hours
  4. temperatureThe reaction mixture was next cooled to room temperature
  5. additiondiluted by the dropwise addition of 200 ml
  6. extractionThe aqueous mixture was extracted several times with diethyl ether
  7. additionthe reaction product was converted to the hydrochloride salt by the addition of 300 ml
  8. additionThe aqueous acid layer containing the reaction product
  9. customwas separated
  10. washwashed once with fresh diethyl ether
  11. additionby the addition of 10 percent sodium hydroxide, which
  12. extractionThe free amine was extracted into fresh diethyl ether
  13. washwashed with water
  14. customdried
  15. customRemoval of the solvent
  16. customby evaporation under reduced pressure

Sources & evidence

ORD record
ord-51e5d9d24a1e4289bfe33611efb93333
Source dataset
uspto-grants-1984_06
Patent number
US04452745

Reaction notes

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