Water → Spiro[5.5]undec-1-ene-2-carboxylic acid methyl ester

HRID 2070583Notes

Reaction equation

HRID 2070583 reaction equation
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:10][CH2:9][CH2:8][C:7]2([CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[C@H:6]1O)=[O:4].C(N(CC)CC)C.CS(Cl)(=O)=O.O>C(Cl)(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[CH2:10][CH2:9][CH2:8][C:7]2([CH2:15][CH2:14][CH2:13][CH2:12][CH2:11]2)[CH:6]=1)=[O:4]

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 57771401trans-1-Hydroxy-spiro[5.5]undecane-2-carboxylic acid methyl ester

Product 1

HCID 15701410Spiro[5.5]undec-1-ene-2-carboxylic acid methyl esterYield 82.3%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

To a solution of trans-1-hydroxy-spiro[5.5]undecane-2-carboxylic acid methyl ester (2.74 g) obtained in Step 3 in chloroform (20 mL) was added triethylamine (2.02 mL). To the reaction mixture was added dropwise a solution of methanesulfonyl chloride (1.03 mL) in chloroform (5 mL) under ice-cooling, followed by stirring the reaction mixture at room temperature overnight. Then, after addition of water, the reaction mixture was washed therewith. The separated organic layer was dried and concentrated. To the residue were added tetrahydrofuran (30 mL) and 1,8-diazabicyclo[5.4.0]undec-7-ene (3.62 mL), followed by heating the reaction mixture at 60° C. for 3 hours. After cooling down to room temperature, the reaction mixture was poured into water, followed by extraction with ethyl acetate. The organic layer was washed successively with 1N aqueous hydrochloric acid solution and saturated brine, dried and concentrated. The residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:8) to give spiro[5.5]undec-1-ene-2-carboxylic acid methyl ester (2.075 g).

Workup

  1. temperaturecooling
  2. washthe reaction mixture was washed
  3. customThe separated organic layer was dried
  4. concentrationconcentrated
  5. additionTo the residue were added tetrahydrofuran (30 mL) and 1,8-diazabicyclo[5.4.0]undec-7-ene (3.62 mL)
  6. temperatureby heating the reaction mixture at 60° C. for 3 hours
  7. temperatureAfter cooling down to room temperature
  8. additionthe reaction mixture was poured into water
  9. extractionfollowed by extraction with ethyl acetate
  10. washThe organic layer was washed successively with 1N aqueous hydrochloric acid solution and saturated brine
  11. customdried
  12. concentrationconcentrated
  13. customThe residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:8)

Sources & evidence

ORD record
ord-f55e676fd6fe45be9ae9022896ab4c6c
Source dataset
uspto-grants-2012_10
Patent number
US08299296B2

Reaction notes

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