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Hydrochloric Acid → 3-(3-Cyclopentyloxy-4-methoxyphenyl)-3-trimethylsilylethynylcyclohexan-1-one

HRID 443200
Notes
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Reaction equation

HRID 443200 reaction equation
C([Li])CCC.[CH3:6][Si:7]([C:10]#[CH:11])([CH3:9])[CH3:8].[Cl-].C[Al+]C.[H-].C([Al+]CC(C)C)C(C)C.[C-]#[C-].[Al+3].[C-]#[C-].[C-]#[C-].[Al+3].[CH:34]1([O:39][C:40]2[CH:41]=[C:42]([C:48]3[CH2:53][CH2:52][CH2:51][C:50](=[O:54])[CH:49]=3)[CH:43]=[CH:44][C:45]=2[O:46][CH3:47])[CH2:38][CH2:37][CH2:36][CH2:35]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Cl>CCOCC.C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Ni+2]>[CH:34]1([O:39][C:40]2[CH:41]=[C:42]([C:48]3([C:11]#[C:10][Si:7]([CH3:9])([CH3:8])[CH3:6])[CH2:53][CH2:52][CH2:51][C:50](=[O:54])[CH2:49]3)[CH:43]=[CH:44][C:45]=2[O:46][CH3:47])[CH2:35][CH2:36][CH2:37][CH2:38]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

11

Reactant 8

HCID 313Hydrochloric AcidHCID 62657Potassium Phosphate, TribasicHCID 66111TrimethylsilylacetyleneHCID 113236313-(3-Cyclopentyloxy-4-methoxyphenyl)cyclohex-2-en-1-oneHCID 16686359Dimethylalumanylium chlorideHCID 21225700Diisobutylaluminumhydride
HCID 178418339
Butyllithium
HCID 178418427HCID 178418427, compound

Product 1

HCID 539837473-(3-Cyclopentyloxy-4-methoxyphenyl)-3-trimethylsilylethynylcyclohexan-1-one

Reagents, catalysts & solvents 2

HCID 9834912Nickel(II) acetylacetonateCatalystHCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
-10 °C

Procedure

n-Butyllithium (2.45 M in hexanes, 5.7 mL, 13.96 mmol) was added dropwise over 5 min to a solution of trimethylsilylacetylene (1.97 mL, 13.96 mmol) dissolved in dry ether (30 mL) at -45° C. under an argon atmosphere. After 1.5 h, this solution was cannulated into a solution of dimethylaluminum chloride (1.0 M in hexanes, 13.96 mL, 13.96 mmol). After 3.5 h at room temperature, the mixture was filtered through Celite® under an argon atmosphere. In a separate flask, diisobutylaluminum hydride (1.0 M in toluene, 1.4 mL, 1.4 mmol) was added dropwise to a stirred mixture of nickel acetylacetonate (360 mg, 1.4 mmol) in dry ether (25 mL) at 0° C. under an argon atmosphere. After 10 min, the mixture was further cooled to -10° C. and the solution of aluminum acetylide was added via cannulation over 15 min. 3-(3-cyclopentyloxy-4-methoxyphenyl)cyclohex-2-en-1 -one (2.0 g, 6.98 mmol, prepared as described in U.S. Pat. No. 5,362,915) dissolved in dry ether (70 mL) was added dropwise over 20 min. After 18 h at room temperature, the mixture was poured into a 100 mL saturated aqueous solution of potassium phosphate (monobasic) at 0° C., 100 mL of aqueous 3N HCl solution was added and the aqueous layer was extracted twice with ether. The combined extract was washed with brine, was dried (magnesium sulfate) and was evaporated. Purification by flash chromatography, eluting with 2:1 hexanes/ether followed. by trituration from ether/hexanes, then firthur purification of the mother liquor by flash chromatography, eluting with 4:1 hexaneslethyl acetate followed by trituration from ether/hexanes, provided a white solid. mp 102-103° C.

Workup

  1. waitAfter 3.5 h at room temperature
  2. filtrationthe mixture was filtered through Celite® under an argon atmosphere
  3. waitAfter 10 min
  4. additionwas added dropwise over 20 min
  5. waitAfter 18 h at room temperature
  6. extractionthe aqueous layer was extracted twice with ether
  7. extractionThe combined extract
  8. washwas washed with brine
  9. dry with materialwas dried (magnesium sulfate)
  10. customwas evaporated
  11. customPurification by flash chromatography
  12. washeluting with 2:1 hexanes/ether
  13. customby trituration from ether/hexanes, then firthur purification of the mother liquor by flash chromatography
  14. washeluting with 4:1 hexaneslethyl acetate
  15. customprovided a white solid

Sources & evidence

ORD record
ord-a3ca63839d954b75bb10569bc3106f31
Source dataset
uspto-grants-1999_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05892098

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes