Hydrochloric Acid → 7-(4-Chlorobenzyl)-4-(2-chloropropenyl)-4-methyl-1-oxaspiro[2.4]heptane

HRID 1752012Notes

Reaction equation

HRID 1752012 reaction equation
I[CH2:2]CI.[Cl:5][C:6](=[CH2:23])[CH2:7][C:8]1([CH3:22])[CH2:12][CH2:11][CH:10]([CH2:13][C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=2)[C:9]1=[O:21].ICI.[OH-].[Na+].Cl>C1COCC1>[Cl:20][C:17]1[CH:18]=[CH:19][C:14]([CH2:13][CH:10]2[C:9]3([O:21][CH2:2]3)[C:8]([CH:7]=[C:6]([Cl:5])[CH3:23])([CH3:22])[CH2:12][CH2:11]2)=[CH:15][CH:16]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 6346DiiodomethaneHCID 122241,2-DiiodoethaneHCID 14798Sodium HydroxideHCID 866706832-(2-Chloro-2-propenyl)-5-(4-chlorobenzyl)-2-methylcyclopentanone2×

Product 1

HCID 866706827-(4-Chlorobenzyl)-4-(2-chloropropenyl)-4-methyl-1-oxaspiro[2.4]heptane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Under argon atmosphere, anhydrous THF (9 ml) was combined with Sm (1.01 g, 6.71 mmol), and then, at room temperature, 1,2-diiodoethane (1.05 g, 3.73 mmol) was added. The reaction solution was stirred for 1 hour at room temperature, and then cooled to −7 degrees C. to −2 degrees C., and 2-(2-chloro-2-propenyl)-5-(4-chlorobenzyl)-2-methylcyclopentanone (Compound (V), (Ra)Xana=CH3, (Rb)Xbnb=CH2CCl═CH2, Ym=4-Cl) dissolved in diiodomethane (0.90 g, 0.00168×2.0 mol) and THF (5 ml) was added, and stirred for 1.5 hours at the same temperature. To this, a 2N aqueous solution of NaOH (8 ml) was added, and stirring was conducted for 1 hour while cooling with ice. A 2N aqueous solution of hydrochloric acid (8 ml) was added, and then extraction with hexane (100 ml×2) was conducted. The organic layer was washed with water (50 ml) and saturated brine (30 ml), and then dried over anhydrous sodium sulfate and concentrated to obtain a crude intended substance (0.44 g), which was used in the next reaction as it was.

Workup

  1. temperaturecooled to −7 degrees C
  2. customto −2 degrees C
  3. stirringstirred for 1.5 hours at the same temperature
  4. stirringstirring
  5. waitwas conducted for 1 hour
  6. temperaturewhile cooling with ice
  7. extractionextraction with hexane (100 ml×2)
  8. washThe organic layer was washed with water (50 ml) and saturated brine (30 ml)
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated
  11. customto obtain a crude
  12. customwas used in the next reaction as it

Sources & evidence

ORD record
ord-9c83bc208e2243e1b5e7970c2d54f104
Source dataset
uspto-grants-2015_10
Patent number
US09162966B2

Reaction notes

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