Triethylamine → HCID 131723537, compound

HRID 990615Notes

Reaction equation

HRID 990615 reaction equation
C(N(CC)CC)C.[O:8]([C:16]1[CH:17]=[C:18]([CH:23]=[CH:24][CH:25]=1)[C:19]([O:21][CH3:22])=O)[Si:9]([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10].[C:26]1([C:32]2[CH:33]3[C:46](=O)[CH:37]([CH:38]([C:40]4[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=4)[CH:39]=2)[CH2:36][CH2:35][CH2:34]3)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>C1COCC1.CCCCCC.[Zn]>[O:8]([C:16]1[CH:17]=[C:18]([CH2:19][O:21][CH:22]=[C:36]2[CH2:35][CH2:34][CH:33]3[CH2:46][CH:37]2[CH:38]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:39]=[C:32]3[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:23]=[CH:24][CH:25]=1)[Si:9]([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 2728532,4-diphenylbicyclo[3.3.1]non-2-en-9-one2×HCID 11715937Benzoic acid, 3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-, methyl ester

Product 1

HCID 131723537HCID 131723537, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

Into a 1000 mL three-neck flask equipped with magnetic stirrer, pressure-equalizing addition funnel and nitrogen line was charged with 200 mL of anhydrous THF. Ttitanium tetrachloride (17 mL) was added dropwise over a period of 30 minutes. The suspension was stirred for 20 minutes and 25.5 parts of zinc was added in small portions . The reaction mixture was heated under reflux for 2 hours and 42.5 mL of triethylamine was added dropwise. After refluxing one hour, 9 parts of a solution of methyl 3-tert-butyldimethylsiloxybenzoate and 4 parts of ketone (77) in 100 mL of dry THF was added over a period of 60 minutes and the reaction mixture was heated for one hour. The mixture on TLC silica gel plate showed the presence of the starting ester. An additional 1 part of starting ketone (77) in 35 mL of dry THF was added dropwise over 45 minutes and refluxed for two hours. The mixture was cooled to room temperature, diluted with 600 mL of hexane and decanted. The residue was washed with 3×250 mL of hexane. The combined hexane layer was filtered and evaporated under reduced pressure to give an oily material which was purified by chromatography on silica gel column using 5% ethyl acetate/hexane as an eluant. The fractions were checked by TLC on silica gel plate and the desired fractions were combined. The solvent was evaporated under reduced pressure to give an oil, yield 9.6 parts.

Workup

  1. customInto a 1000 mL three-neck flask equipped with magnetic stirrer, pressure-equalizing addition funnel
  2. temperatureThe reaction mixture was heated
  3. temperatureunder reflux for 2 hours
  4. temperatureAfter refluxing one hour
  5. temperaturethe reaction mixture was heated for one hour
  6. temperaturerefluxed for two hours
  7. customdecanted
  8. washThe residue was washed with 3×250 mL of hexane
  9. filtrationThe combined hexane layer was filtered
  10. customevaporated under reduced pressure
  11. customto give an oily material which
  12. customwas purified by chromatography on silica gel column
  13. customThe solvent was evaporated under reduced pressure
  14. customto give an oil
  15. customyield 9.6 parts

Sources & evidence

ORD record
ord-ee8e11ddf7d146269a4cdb4cd06c732f
Source dataset
uspto-grants-2002_10
Patent number
US06461876B1

Reaction notes

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