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Hydrochloric Acid → (1S, 2R)-1-phenyl-2-hydroxymethylcyclopropane carboxylic anhydride

HRID 54041
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HRID 54041 반응식
[NH2-].[Na+].[C:3]1([CH2:9][C:10]#N)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[CH2:12]([C@@H:14]1[O:16][CH2:15]1)Cl.[OH-:17].[K+].Cl.[C:20](=[O:23])([O-])[OH:21].[Na+].C([O:28][CH2:29][CH3:30])(=O)C>C1C=CC=CC=1.C(O)C>[C:3]1([C@:9]2([C:10]([O:21][C:20]([C@@:9]3([C:3]4[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=4)[CH2:10][C@H:30]3[CH2:29][OH:28])=[O:23])=[O:17])[CH2:12][C@H:14]2[CH2:15][OH:16])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

10

반응물 7

HCID 313Hydrochloric AcidHCID 8794PhenylacetonitrileHCID 8857Ethyl AcetateHCID 14797Potassium HydroxideHCID 24533Sodium amideHCID 516892Sodium BicarbonateHCID 2734062(-)-Epichlorohydrin

생성물 1

HCID 131719977
(1S, 2R)-1-phenyl-2-hydroxymethylcyclopropane carboxylic anhydride
수율 58%

시약·촉매·용매 2

HCID 241Benzene용매3회HCID 702Ethanol용매

실험 절차

8.58 g (0.22 mmol) of sodium amide was suspended in 40 ml of anhydrous benzene. To the resultant suspension was dropwise added a solution of 11.5 ml (0.10 mol) of phenylacetonitrile in 20 ml of anhydrous benzene in a stream of argon gas at 0° C. After completion of the addition, the resultant mixture was stirred at room temperature for 3 hours to effect a reaction. To the resultant reaction mixture was dropwise added a solution of 6.8 ml (0.087 mol) of (R)-(-)-epichlorohydrin in 20 ml of anhydrous benzene while cooling with ice. After completion of the addition, the resultant mixture was stirred at room temperature for 2 hours to effect a reaction. After completion of the reaction, the resultant reaction mixture was subjected to distillation under reduced pressure to thereby remove the solvent and obtain a residue. 20 ml of ethanol and 10 ml of an aqueous 1N-KOH solution were added to the obtained residue, and the resultant mixture was refluxed for 15 hours to effect a reaction. After completion of the reaction, 12N hydrochloric acid was added to the mixture which cooling with ice to thereby acidify the mixture. The acidified mixture was concentrated under reduced pressure to thereby obtain a residue. A saturated aqueous sodium hydrogencarbonate solution was added to the obtained residue, and ethyl acetate was further added for extraction to obtain an organic layer. The organic layer was separated, washed with saturated saline, dried over anhydrous sodium sulfate, and subjected to distillation under reduced pressure to thereby remove the solvent and obtain a residue. The obtained residue was purified by silica gel column chromatography (the composition of the developing solvent was; ethyl acetate:hexane=1:3). As a result, 10.1 g (0.058 mol) of compound 1 (yield: 58%) was obtained as a yellow oily product.

후처리

  1. additionAfter completion of the addition
  2. customa reaction
  3. customTo the resultant reaction mixture
  4. temperaturewhile cooling with ice
  5. additionAfter completion of the addition
  6. customa reaction
  7. customAfter completion of the reaction
  8. customthe resultant reaction mixture
  9. distillationwas subjected to distillation under reduced pressure
  10. customto thereby remove the solvent
  11. customobtain a residue
  12. customa reaction
  13. additionwas added to the mixture which
  14. temperaturecooling with ice
  15. concentrationThe acidified mixture was concentrated under reduced pressure
  16. customto thereby obtain a residue
  17. additionwas further added for extraction
  18. customto obtain an organic layer
  19. customThe organic layer was separated
  20. washwashed with saturated saline
  21. dry with materialdried over anhydrous sodium sulfate
  22. distillationsubjected to distillation under reduced pressure
  23. customto thereby remove the solvent
  24. customobtain a residue
  25. customThe obtained residue was purified by silica gel column chromatography (the composition of the developing solvent

출처 및 근거

ORD 기록
ord-1457c8c4416f476ebdfe4b051baeb527
출처 데이터셋
uspto-grants-1997_04
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05621142

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