Formaldehyde → 2-Nitro-2-(4-octylphenethyl)propane-1,3-diol

HRID 1028875Notes

Reaction equation

HRID 1028875 reaction equation
[CH2:1]=[O:2].C(N(CC)CC)C.C(O[CH:14]([C:20]1[CH:25]=[CH:24][C:23]([CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[CH:22][CH:21]=1)[CH2:15][CH2:16][N+:17]([O-:19])=[O:18])(=O)C.O.[O:35]1CCOC[CH2:36]1>>[N+:17]([C:16]([CH2:15][CH2:14][C:20]1[CH:21]=[CH:22][C:23]([CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[CH:24][CH:25]=1)([CH2:1][OH:2])[CH2:36][OH:35])([O-:19])=[O:18]

Participants

6

Reactant 5

HCID 712FormaldehydeHCID 962WaterHCID 8471TriethylamineHCID 312751,4-Dioxane2×HCID 569680573-Nitro-1-(4-octylphenyl)propyl acetate

Product 1

HCID 668372762-Nitro-2-(4-octylphenethyl)propane-1,3-diol

Procedure

To a mixture of paraformaldehyde (0.13 mol, 9 eq), 4 ml (1.5 eq) of triethylamine in 40 ml of 1,4-dioxane, 3-nitro-1-(4-octylphenyl)propyl acetate (13) (5 g, 0.015 mol) in 50 ml of 1,4-dioxane was added dropwise with stirring at RT, the mixture was slowly heated to 70° C., and stirred for 24 h at this temperature, under TLC control. To the reaction mixture was added water and the mixture, pH adjusted to ˜9-10 and stirred 16 h at 40° C. for deprotection (TLC and HPLC monitoring). After reaction completion (˜2-3 h) the mixture was extracted with ethyl acetate and washed successively with 1 N HCl, sodium bicarbonate solution and brine. The ethyl acetate solution was dried over sodium sulfate and concentrated. The residue was pure enough for transformation to the next step or can be purified by crystallization or silica gel column chromatography using hexane-ethyl acetate as eluent to afford a white solid with mp. 80-82° C., ESIMS 376.2 [M+Na]+

Workup

  1. additionwas added dropwise
  2. temperaturethe mixture was slowly heated to 70° C.
  3. stirringstirred for 24 h at this temperature, under TLC control
  4. stirringstirred 16 h at 40° C. for deprotection (TLC and HPLC monitoring)
  5. customAfter reaction completion (˜2-3 h) the mixture
  6. extractionwas extracted with ethyl acetate
  7. washwashed successively with 1 N HCl, sodium bicarbonate solution and brine
  8. dry with materialThe ethyl acetate solution was dried over sodium sulfate
  9. concentrationconcentrated
  10. customcan be purified by crystallization or silica gel column chromatography
  11. customto afford a white solid with mp. 80-82° C., ESIMS 376.2 [M+Na]+

Sources & evidence

ORD record
ord-ff6d7c37f5e84f76985ad4b5c83062ac
Source dataset
uspto-grants-2014_05
Patent number
US08735627B2

Reaction notes

Loading…