Sodium Hydroxide → 3-(3-Quinolyl)-2-propen-1-ol t-butyl carbonate

HRID 1370012Notes

Reaction equation

HRID 1370012 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[C:3]([CH:11]=[CH:12][CH2:13][OH:14])[CH:2]=1.[C:15]([O:22]C(OC(C)(C)C)=O)([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16].[OH-].[Na+].C(OCC)(=O)C.CCCCCCC>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C(Cl)Cl>[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[C:3]([CH:11]=[CH:12][CH2:13][OH:14])[CH:2]=1.[C:15](=[O:16])([O-:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 90495Di-tert-butyl dicarbonateHCID 21899848Ethylacetate heptaneHCID 539384493-(3-Quinolyl)-2-propen-1-ol

Product 1

HCID 865842593-(3-Quinolyl)-2-propen-1-ol t-butyl carbonate

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a 500-mL three-necked round-bottom flask equipped with an overhead mechanical stirrer was charged 3-(3-quinolyl)-2-propen-1-ol (13.03 g, 70.43 mmol) as a mixture of cis- and trans-isomers (81% cis, and 19% trans), di-tert butyl dicarbonate (16.91 g, 77.48 mmol, 1.11 equiv), tetra n-butylammonium hydrogen sulfate (742 mg, 2.17 mmol) and methylene chloride (135 mL). The stirred mixture which resulted was cooled to 0 to 5° C. at which time aqueous 25% sodium hydroxide (33.3 mL) was added over 45 minutes such that the internal temperature did not rise above 20° C. Upon completion of the reaction (1 to 4 hours) as indicated by TLC (3:2 ethyl acetate/heptane), the reaction mixture was diluted with methylene chloride (50 mL) and washed with water (2×125 mL). The organic was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to provide the 3-(3-quinolyl)-2-propen-1-ol-t-butyl carbonate: 18.35 g, 91.4% as an oil. This material can be further purified to remove lower Rf impurities by eluting through a plug of silica gel with heptane/acetone/triethylamine (9:1:0.1). The product eluant is then concentrated under reduced pressure and further dried by the azeodistillation of ethyl acetate. This procedure provides the purified carbonate as a colorless oil which retains the original ratio of cis and trans isomers: 17.50 g, 87.2%.

Workup

  1. customTo a 500-mL three-necked round-bottom flask equipped with an overhead mechanical stirrer
  2. customThe stirred mixture which resulted
  3. additionwas added over 45 minutes such that the internal temperature
  4. customdid not rise above 20° C
  5. customUpon completion of the reaction (1 to 4 hours)
  6. washwashed with water (2×125 mL)
  7. dry with materialThe organic was dried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-aa1c9857fff346aab07b1a91cc9a5ff2
Source dataset
uspto-grants-2003_06
Patent number
US06579986B2

Reaction notes

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