Triethylamine → HCID 11130688, compound

HRID 409511Notes

Reaction equation

HRID 409511 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH:10]3[CH:19]([C:20]([O:22][CH3:23])=[O:21])[CH:18](O)[C:17]4[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=4)[O:11]3)=[CH:9][C:4]=2[O:3][CH2:2]1.C(N(CC)CC)C.CS(Cl)(=O)=O.N12CCCN=C1CCCCC2>ClCCl.C1C=CC=CC=1.C(OCC)(=O)C>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH:10]3[C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:18][C:17]4[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=4)[O:11]3)=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 67155832HCID 67155832, compound

Product 1

HCID 11130688HCID 11130688, compoundYield 58.4%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A suspension of racemic methyl 2-(benzo[d][1,3]dioxol-5-yl)-4-hydroxychroman-3-carboxylate (49 mg, 149 μmol) in dichloromethane (2.0 mL) was stirred on an ice bath and treated with triethylamine (31 μL, 224 μmol), then dropwise with methanesulfonyl chloride (13 μL, 164 μmol). The cooling bath was removed after 90 min and the solution was stirred at rt for 23 h. At the conclusion of this period, the solution was diluted with additional dichloromethane, washed with 1.0 M aqueous HCl, dried over sodium sulfate and concentrated under vacuum to yield a residue. The residue was dissolved in benzene (2.0 mL), treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (30 μL, 224 μmol) and stirred at 60° C. for 3.75 h. After this time, the mixture was cooled to rt and then diluted with ethyl acetate, washed with 1.0 M aqueous HCl, water, and saturated aqueous sodium chloride, dried over sodium sulfate and concentrated under vacuum. The resulting residue was purified by column chromatography (silica gel, 2-10% ethyl acetate/hexane) to provide racemic methyl 2-(benzo[d][1,3]dioxol-5-yl)-2H-chromene-3-carboxylate as a white solid (27 mg, 58%). 1H NMR (400 MHz, CDCl3) δ ppm 3.77 (s, 3 H) 5.91 (m, 2 H) 6.18 (s, 1 H) 6.71 (d, J=8.6 Hz, 1 H) 6.78 (d, J=8.1 Hz, 1 H) 6.85 (m, 2 H) 6.90 (t, J=7.4 Hz, 1 H) 7.19 (m, 2 H) 7.67 (s, 1 H).

Workup

  1. customThe cooling bath was removed after 90 min
  2. stirringthe solution was stirred at rt for 23 h
  3. additionAt the conclusion of this period, the solution was diluted with additional dichloromethane
  4. washwashed with 1.0 M aqueous HCl
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customto yield a residue
  8. stirringstirred at 60° C. for 3.75 h
  9. washwashed with 1.0 M aqueous HCl, water, and saturated aqueous sodium chloride
  10. dry with materialdried over sodium sulfate
  11. concentrationconcentrated under vacuum
  12. customThe resulting residue was purified by column chromatography (silica gel, 2-10% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-b617ca6005724fefbd3e3c790f4e73af
Source dataset
uspto-grants-2014_06
Patent number
US08759390B2

Reaction notes

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