Ethyl orthoformate → HCID 10109807, compound

HRID 431012Notes

Reaction equation

HRID 431012 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][CH2:9][C@H:8]([CH2:11][O:12][S:13]([C:16]3[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][CH:17]=3)(=[O:15])=[O:14])[O:7][C:6]=2[C:23]=1[CH:24]=[N:25]O.[CH:27](OCC)(OCC)OCC>>[O:7]1[C:6]2=[C:23]3[C:2](=[CH:3][CH:4]=[C:5]2[O:10][CH2:9][CH:8]1[CH2:11][O:12][S:13]([C:16]1[CH:17]=[CH:18][C:19]([CH3:22])=[CH:20][CH:21]=1)(=[O:14])=[O:15])[N:1]=[CH:27][N:25]=[CH:24]3

Participants

3

Reactant 2

HCID 31214Ethyl orthoformateHCID 86586526HCID 86586526, compound

Product 1

HCID 10109807HCID 10109807, compound

Procedure

Toluene-4-sulfonic acid (2R)-7-amino-8-(hydroximino-methyl)-2,3-dihydrobenzo[1,4]dioxin-2-ylmethyl ester (3.0 g, 7.9 mmole) was suspended in triethyl orthoformate under nitrogen, brought to a rapid boil and refluxed for 18 hours. The reaction mixture was cooled and the solvent evaporated. The residue was dissolved in methylene chloride (100 mL) and the solution obtained was washed with saturated sodium chloride (100 mL), dried over magnesium sulfate and evaporated to a brown gum (2.7 g) which contained several impurities. Chromatography on silica gel using 1% methanol in chloroform and then 3% methanol in chloroform as eluants gave 0.9 g (30%) of the (R)-enantiomer of the title compound as an oil. 1H(DMSO-d6) singlet, 9.01 δ(1 H); singlet, 9.19 δ(1 H); doublet, 7.75 δ(2 H); doublet, 7.60 δ(1 H); doublet, 7.50 δ(1 H) doublet, 7.30 δ(2 H); multiplet, 4.75 δ(1 H); double doublet, 4.51 δ(1 H); double doublet, 4.46 δ(1 H) double doublet: 4.32 δ(1 H); double doublet, 4.22 δ(1 H); singlet, 2.32 δ(3 H).

Workup

  1. temperaturerefluxed for 18 hours
  2. temperatureThe reaction mixture was cooled
  3. customthe solvent evaporated
  4. dissolutionThe residue was dissolved in methylene chloride (100 mL)
  5. customthe solution obtained
  6. washwas washed with saturated sodium chloride (100 mL)
  7. dry with materialdried over magnesium sulfate
  8. customevaporated to a brown gum (2.7 g) which

Sources & evidence

ORD record
ord-987aa22be6424ea7834c9dbf29a23aa1
Source dataset
uspto-grants-2003_12
Patent number
US06656947B2

Reaction notes

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