Hydrochloric Acid → Ethyl 6-[2-(2,6,6-trimethylcyclohex-1-enyl)ethynyl]-2-naphthoate

HRID 2399768Notes

Reaction equation

HRID 2399768 reaction equation
[CH3:1][C:2]1[CH2:7][CH2:6][CH2:5][C:4]([CH3:9])([CH3:8])[C:3]=1[C:10]#[CH:11].C([Li])CCC.Br[C:18]1[CH:19]=[C:20]2[C:25](=[CH:26][CH:27]=1)[CH:24]=[C:23]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH:22]=[CH:21]2.Cl>O1CCCC1.CCCCCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1[CH2:7][CH2:6][CH2:5][C:4]([CH3:8])([CH3:9])[C:3]=1[C:10]#[C:11][C:18]1[CH:19]=[C:20]2[C:25](=[CH:26][CH:27]=1)[CH:24]=[C:23]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH:22]=[CH:21]2

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1249959Ethyl 6-bromonaphthalene-2-carboxylateHCID 132969122-Ethynyl-1,3,3-trimethylcyclohex-1-eneHCID 178418339Butyllithium

Product 1

HCID 15297948Ethyl 6-[2-(2,6,6-trimethylcyclohex-1-enyl)ethynyl]-2-naphthoate

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent4×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 0.503 g (3.3916 mmol) 1,3,3-trimethyl-2-ethynylcyclohexene (G. Kobrich et al. Chem Ber., 1966, 99,689.) in 4 ml of dry tetrahydrofuran at 0 degrees C. under argon was added dropwise 2.1 ml of 1.6M (3.36 mmol) of n-butyllithium in hexane. This mixture was stirred at 0 degrees C. for 10 minutes, at room temperature for 10 minutes and cooled again to 0 degrees C. To this was added, via cannula, a solution of 0.480 g (3.52 mmol) fused zinc chloride in 4 ml of tetrahydrofuran with stirring at 0 degrees C. for 40 minutes and at room temperature for 5 minutes. A solution of 0.9186 g (3.29 mmol) of ethyl 6-bromo-2-naphthoate (Anderson, L. C. J. Am. Chem. Soc., 1943, 65,242.) in 5 ml of dry tetrahydrofuran was transferred by cannula into a suspension of 0.410 g (0.3584 mmol) tetrakis(triphenylphosphine)palladium in 5 ml of dry tetrahydrofuran and stirred for 5 minutes at room temperature. This mixture was then treated via cannula with the solution of alkynyl zinc and the resultant mixture stirred at room temperature for 18 hours. Ice and 30 ml of 3N HCl was added and the products extracted with 4×50 ml ether. The combined ether extracts were washed with saturated NaHCO3 and NaCl solution, dried (MgSO4) and concentrated to give a brown oil. This oil was purified by HPLC (Waters 6000; Partisil M-9 10/50; 2% ethyl acetate in hexanes) to give the title compound as a yellow oil.

Workup

  1. customat 0 degrees C
  2. waitat room temperature for 10 minutes
  3. temperaturecooled again to 0 degrees C
  4. additionTo this was added, via cannula
  5. waitfor 40 minutes
  6. waitat room temperature for 5 minutes
  7. stirringstirred for 5 minutes at room temperature
  8. extractionthe products extracted with 4×50 ml ether
  9. washThe combined ether extracts were washed with saturated NaHCO3 and NaCl solution
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated
  12. customto give a brown oil
  13. customThis oil was purified by HPLC (Waters 6000; Partisil M-9 10/50; 2% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-39fdd832084e4f3b845c175a4230bcac
Source dataset
uspto-grants-1995_09
Patent number
US05451605

Reaction notes

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