Triethylamine → HCID 11768642, compound

HRID 1728986Notes

Reaction equation

HRID 1728986 reaction equation
CO[C:3]([C@H:5]1[CH2:10][CH:9]=[CH:8][CH2:7][C@H:6]1[C:11]([OH:13])=[O:12])=O.C(N(CC)CC)C.ClC(OCC)=O>O1CCCC1>[C:11]1(=[O:12])[C@@H:6]2[C@@H:5]([CH2:10][CH:9]=[CH:8][CH2:7]2)[CH2:3][O:13]1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 53259071-Methyl (1S,2R)-4-cyclohexene-1,2-dicarboxylate

Product 1

HCID 11768642HCID 11768642, compoundYield 62.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In a stream of nitrogen gas, 20 g of (1R, 2S)-2-methoxycarbonylcyclohex-4-ene-1-carboxylic acid was dissolved in 120 ml of dry tetrahydrofuran, and to the solution, was added 18.2 ml of triethylamine while the solution being cooled by ice. A dry tetrahydrofuran (40 ml) solution of ethyl chloroformate (12.4 ml) was slowly added dropwise to the mixture. While the mixture was being cooled by ice, the mixture was stirred for 2 hours. After filtration of the resulting triethylamine hydrochloride, the filtrate was added dropwise to a H2O (100 ml) solution of NaBH4 (10.3 g) with ice-cooling and the mixture was stirred for 2 hours at room temperature. Then, 2N-HCl was added to the mixture to adjust the pH thereof to 4-5, and THF was distilled off under a reduced pressure. The residue was extracted by ethyl acetate. The ethyl acetate layer was washed with saturated sodium bicarbonate solution and brine, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under a reduced pressure, and the residue was dissolved in 100 ml of toluene. 2.07 g of p-toluenesulfonic acid monohydrate was added to this solution, and the mixture was stirred for 5 hours at room temperature. The reaction mixture was washed with saturated sodium bicarbonate solution and brine. Then, the organic layer was dried over anhydrous magnesium sulfate, and after filtration, the filtrate was concentrated under a reduced pressure. The residue was distilled under a reduced pressure, and thus 9.35 g of the titled compound was obtained.

Workup

  1. temperaturebeing cooled by ice
  2. temperatureWhile the mixture was being cooled by ice
  3. filtrationAfter filtration of the resulting triethylamine hydrochloride
  4. additionthe filtrate was added dropwise to a H2O (100 ml) solution of NaBH4 (10.3 g) with ice-
  5. temperaturecooling
  6. stirringthe mixture was stirred for 2 hours at room temperature
  7. additionThen, 2N-HCl was added to the mixture
  8. distillationto 4-5, and THF was distilled off under a reduced pressure
  9. extractionThe residue was extracted by ethyl acetate
  10. washThe ethyl acetate layer was washed with saturated sodium bicarbonate solution and brine
  11. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  12. filtrationAfter filtration
  13. concentrationthe filtrate was concentrated under a reduced pressure
  14. dissolutionthe residue was dissolved in 100 ml of toluene
  15. addition2.07 g of p-toluenesulfonic acid monohydrate was added to this solution
  16. stirringthe mixture was stirred for 5 hours at room temperature
  17. washThe reaction mixture was washed with saturated sodium bicarbonate solution and brine
  18. dry with materialThen, the organic layer was dried over anhydrous magnesium sulfate
  19. filtrationafter filtration
  20. concentrationthe filtrate was concentrated under a reduced pressure
  21. distillationThe residue was distilled under a reduced pressure

Sources & evidence

ORD record
ord-d7757887b7c5435e84252c531dc29263
Source dataset
uspto-grants-1994_07
Patent number
US05329042

Reaction notes

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