Hexamethyldisilazane → HCID 70162033, compound

HRID 1636747Notes

Reaction equation

HRID 1636747 reaction equation
C[Si](C)(C)N[Si](C)(C)C.[CH2:10]([Li])[CH2:11][CH2:12][CH3:13].[CH2:15]([N:18]([CH3:34])[CH2:19]/[CH:20]=[CH:21]/[CH2:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([C:30](=[O:32])[CH3:31])=[CH:26][C:25]=1[F:33])[CH:16]=[CH2:17].[CH2:35](Br)/[CH:36]=[C:37](/[CH2:39][CH2:40][CH:41]=[C:42]([CH3:44])[CH3:43])\[CH3:38].C(=O)(O)[O-].[Na+]>C1COCC1.CCCCCC.CCOCC>[CH2:15]([N:18]([CH3:34])[CH2:19]/[CH:20]=[CH:21]/[CH2:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([C:30](=[O:32])[CH:31]([CH2:35]/[CH:36]=[C:37](\[CH3:38])/[CH2:39][CH2:40][CH:41]=[C:42]([CH3:44])[CH3:43])[CH2:10]/[CH:11]=[C:12](\[CH3:13])/[CH2:24][CH2:25][CH:26]=[C:27]([CH3:30])[CH3:28])=[CH:26][C:25]=1[F:33])[CH:16]=[CH2:17]

Participants

9

Reactant 5

HCID 13838HexamethyldisilazaneHCID 516892Sodium BicarbonateHCID 53658672,6-Octadiene, 1-bromo-3,7-dimethyl-, (2E)-HCID 18434339HCID 18434339, compoundHCID 178418339Butyllithium

Product 1

HCID 70162033HCID 70162033, compound

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 0.92 ml of hexamethyldisilazane in 2.5 ml of THF is treated dropwise at 0° C. with 2.63 ml of 1.6M butyl-lithium in hexane. After 15 min. the mixture is cooled to -78° C. and 0.6g (Ex. Fa) of (E)-1-[4-[4-(allyl-methyl-amino)-but-2-enyloxy]-3-fluorophenyl]-ethanone (Ha) in 1.9 ml of THF is added dropwise. After 1 hr. at -78° C. 0.5 ml of geranyl bromide in 1 ml of THF is added dropwise. The mixture is left to warm to room temperature, stirred for 1 hr. and poured into saturated sodium bicarbonate solution/ether. The organic phase is washed with 10% sodium chloride solution, dried and evaporated. After silica gel chromatography with (97.5%) methylene chloride/methanol the residue is dissolved in ethanol with 0.87 g of fumaric acid, evaporated and precipitated from ether with pentane. There is obtained 0.24 g of (E)-1-[4-[(E)-4-(allyl-methyl-amino)-but-2-enyloxy]-3-fluoro-phenyl]-2-[(E)-3,7-dimethyl-octa-2,6-dienyl]-5,9-dimethyl-deca-4,8-dien-1-one.fumarate (1:2), MS: m/e 549 (M).

Workup

  1. customat -78° C
  2. waitThe mixture is left
  3. temperatureto warm to room temperature
  4. washThe organic phase is washed with 10% sodium chloride solution
  5. customdried
  6. customevaporated
  7. dissolutionAfter silica gel chromatography with (97.5%) methylene chloride/methanol the residue is dissolved in ethanol with 0.87 g of fumaric acid
  8. customevaporated
  9. customprecipitated from ether with pentane

Sources & evidence

ORD record
ord-12e52a4344b34b35a6b17916f9902fc2
Source dataset
uspto-grants-2000_03
Patent number
US06034275

Reaction notes

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