p-Toluenesulfonic acid → HCID 131715943, compound

HRID 1761973Notes

Reaction equation

HRID 1761973 reaction equation
[C:1]([Li])([CH3:4])(C)[CH3:2].[F:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[CH2:14][C:15]([CH:26]([CH3:28])[CH3:27])(C=O)[S:16][C:17]=2[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:9][CH:8]=1.C1(C)C=CC(S(O)(=O)=[O:36])=CC=1.C(=O)(O)[O-].[Na+]>C1COCC1.C1COCC1.O>[F:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[C:14]([CH:2]=[CH:1][CH:4]=[O:36])=[C:15]([CH:26]([CH3:27])[CH3:28])[S:16][C:17]=2[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:9][CH:8]=1

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 516892Sodium BicarbonateHCID 86743024HCID 86743024, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 131715943HCID 131715943, compoundYield 259.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 21881883Oxolane--water (1/1)Solvent

Procedure

To a solution of 2.4 g of cis-2-bromo-ethoxyethylene in 75 ml of THF at -78°, was added dropwise 2.0 g of t-butyllithium (2.2 m in pentane). After stirring at -78° for 2 hours, a solution of 3.5 g of the aldehyde product of Step 2, above, in 30 ml of THF was added dropwise. The reaction was stirred at -78° for 10 minutes, then was quenched by the addition of saturated aq. ammonium chloride solution. The mixture was extracted once with MTBE and then once with methylene chloride. The organic solutions were combined, dried over anhyd. magnesium sulfate and concentrated under reduced pressure to obtain a residue. The residue was dissolved in 100 ml of THF/water (90:10). p-toluenesulfonic acid (0.7 g) was added and then the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into 10% aq. sodium bicarbonate solution and the organic material was extracted with MTBE. The solution was dried and the solvent removed under reduced pressure to give 3.7 g (98% yield) of the title product of this step for use in the next step (4). An analytical sample was crystallized from hexane; m.p. 138°-140°;

Workup

  1. stirringThe reaction was stirred at -78° for 10 minutes
  2. customwas quenched by the addition of saturated aq. ammonium chloride solution
  3. extractionThe mixture was extracted once with MTBE
  4. customdried over anhyd
  5. concentrationmagnesium sulfate and concentrated under reduced pressure
  6. customto obtain a residue
  7. stirringthe mixture was stirred at room temperature for 1 hour
  8. extractionthe organic material was extracted with MTBE
  9. customThe solution was dried
  10. customthe solvent removed under reduced pressure

Sources & evidence

ORD record
ord-c9b028a68e65478989b6410055b64f7d
Source dataset
uspto-grants-1989_05
Patent number
US04829081

Reaction notes

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