Triethylamine → HCID 20069081, compound

HRID 982121Notes

Reaction equation

HRID 982121 reaction equation
CS(Cl)(=O)=O.[N:6]([CH2:9][C@H:10]1[C:15]2[C:16]([CH3:22])=[CH:17][CH:18]=[C:19]([O:20][CH3:21])[C:14]=2[CH2:13][C@@H:12]([CH2:23]O)[O:11]1)=[N+:7]=[N-:8].[CH2:25]([N:27](CC)[CH2:28][CH3:29])[CH3:26]>C(Cl)Cl.C(OCC)C>[N:6]([CH2:9][CH:10]1[C:15]2[C:16]([CH3:22])=[CH:17][CH:18]=[C:19]([O:20][CH3:21])[C:14]=2[CH2:13][CH:12]([CH2:23][N:27]2[CH2:28][CH2:29][CH2:26][CH2:25]2)[O:11]1)=[N+:7]=[N-:8]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 86744625HCID 86744625, compound2×

Product 1

HCID 20069081HCID 20069081, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Methanesulfonyl chloride (0.146 mL, 1.89 mmol) is added dropwise to a solution of 0.453 g (1.72 mmol) of [1R,3S] 1-azidomethyl-3,4-dihydro-3-hydroxymethyl-5-methoxy-8-methyl-1H-2-benzopyran, the product of Step 4 of Example 142, and 0.36 mL (2.58 mmol) of triethylamine in 15 mL of methylene chloride at 0° C. The reaction mixture is stirred for 30 min at 0° C. then transferred to a separatory funnel and diluted with 45 mL of diethyl ether. The layers are separated and the organic layer is washed with 2×20 mL of water, 2×20 mL of 1 N hydrochloric acid and 20 mL of brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue is dissolved in 20 mL of N,N-dimethyl formamide (DMF) and an excess amount of pyrrolidine is added to this solution. The reaction mixture is heated at 95° C. for 2.5 h then poured into 75 mL of water. The aqueous solution is extracted with 3×40 mL of diethyl ether. The combined ether extracts are washed with 2×30 mL of water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue is purified by column chromatography on silica gel eluted to give the title compound.

Workup

  1. customat 0° C
  2. customthen transferred to a separatory funnel
  3. customThe layers are separated
  4. washthe organic layer is washed with 2×20 mL of water, 2×20 mL of 1 N hydrochloric acid and 20 mL of brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. dissolutionThe residue is dissolved in 20 mL of N,N-dimethyl formamide (DMF)
  9. additionan excess amount of pyrrolidine is added to this solution
  10. temperatureThe reaction mixture is heated at 95° C. for 2.5 h
  11. additionthen poured into 75 mL of water
  12. extractionThe aqueous solution is extracted with 3×40 mL of diethyl ether
  13. washThe combined ether extracts are washed with 2×30 mL of water and brine
  14. dry with materialdried over anhydrous magnesium sulfate
  15. concentrationconcentrated in vacuo
  16. customThe residue is purified by column chromatography on silica gel
  17. washeluted

Sources & evidence

ORD record
ord-e6989968065e4f26895314d9d05bda06
Source dataset
uspto-grants-1991_02
Patent number
US04994486

Reaction notes

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