Hexamethylphosphoramide → HCID 272210, compound

HRID 1194501Notes

Reaction equation

HRID 1194501 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([OH:12])[CH:6]=[CH:5]2.[H-].[Na+].Br[CH2:16][CH2:17][CH:18]=C.CN(C)P(=O)(N(C)C)N(C)C>C1COCC1.CN(C=O)C.O>[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([O:12][CH2:18][CH:17]=[CH2:16])[CH:6]=[CH:5]2

Participants

8

Reactant 4

HCID 12679HexamethylphosphoramideHCID 21241Homoallyl bromide2×HCID 24758Sodium hydride2×HCID 271446-Bromo-2-naphthalenol

Product 1

HCID 272210HCID 272210, compoundYield 36.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 10.00 g (45 mmol, Aldrich) of 6-bromo-2-naphthol and 2.16 g (49.0 mmol, 1.1 eq. 60% in oil, Aldrich) of NaH dispersion in 100 ml of dry THF was stirred at 0° C., until gas evolution ceased. A solution of 4.60 ml (45.0 mmol, Aldrich) of 4-bromo-1-butene in 25 ml of DMF was added dropwise and the solution was warmed to room temperature, then stirred at 70° C. overnight. To this solution was added 2.28 ml (22.5 mmol, 0.5 eq., Aldrich) of 4-bromo-1-butene and 6 ml of hexamethylphosphoric triamide (HMPA). Then 1.00 g (20.8 mmol, 60% in oil, Aldrich) of NaH dispersion in 10 ml of dry THF was added, stirred at 70° C. for 8 hours and finally heated to 90° C. for 12 hours. The mixture was cooled, water was added, this was extracted with EtOAc, dried (MgSO4) and concentrated in vacuo. Purification was achieved via flash chromatography (silica gel, 1:8 EtOAc/petroleum ether) to yield 4.31 g (35%) of title compound as a bright yellow solid, m.p. 35°-37° C.

Workup

  1. stirringstirred at 70° C. for 8 hours
  2. temperaturefinally heated to 90° C. for 12 hours
  3. temperatureThe mixture was cooled
  4. extractionthis was extracted with EtOAc
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customPurification

Sources & evidence

ORD record
ord-7c18f829d9af4b6a94e9c457cffb7d19
Source dataset
uspto-grants-1989_03
Patent number
US04814454

Reaction notes

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