Formaldehyde → HCID 19883771, compound

HRID 1461866Notes

Reaction equation

HRID 1461866 reaction equation
Cl.[CH2:2]([NH:9][OH:10])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.C=O.[C:13](=O)(O)[O-].[Na+].[P:18]([O-:35])([O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>O1CCCC1>[CH2:2]([N:9]([CH2:13][P:18](=[O:35])([O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[OH:10])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 516892Sodium BicarbonateHCID 11332622N-benzylhydroxylamine hydrochlorideHCID 21904359Dibenzylphosphite

Product 1

HCID 19883771HCID 19883771, compoundYield 40.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
59 °C

Procedure

A mixture of 2.0 g (12.5 mmol) of N-benzylhydroxylamine hydrochloride, 0.75 g (25 mmol) of paraformaldehyde, 1.0 g (12 mmol) of sodium bicarbonate and 40 ml of tetrahydrofuran (THF) is stirred at 59° C. for one hour. To the resultant mixture is then added dropwise over a three-hour period a solution of 3.6 g (13.7 mmol) of dibenzyl phosphite in 40 ml of THF. The reaction mixture is then stirred for 14 hours at 55° C. The reaction mixture is concentrated in vacuo to 20 ml volume and 500 ml of ethyl acetate is added. The organic phase is separated and washed sequentially with a saturated solution of sodium bicarbonate and a saturated solution of sodium chloride. The organic phase is dried over anhydrous magnesium sulfate and the solvent removed in vacuo. The residue is purified by column chromatography (silica gel, 20:1, methylene chloride:ethyl acetate eluent) followed by recrystallization from a mixture of methylene chloride, ethyl acetate and hexane to give 1.95 g (40% yield) of a white solid melting at 62°-64° C.

Workup

  1. stirringThe reaction mixture is then stirred for 14 hours at 55° C
  2. concentrationThe reaction mixture is concentrated in vacuo to 20 ml volume and 500 ml of ethyl acetate
  3. additionis added
  4. customThe organic phase is separated
  5. washwashed sequentially with a saturated solution of sodium bicarbonate
  6. dry with materialThe organic phase is dried over anhydrous magnesium sulfate
  7. customthe solvent removed in vacuo
  8. customThe residue is purified by column chromatography (silica gel, 20:1, methylene chloride:ethyl acetate eluent)
  9. customfollowed by recrystallization from a mixture of methylene chloride, ethyl acetate and hexane

Sources & evidence

ORD record
ord-1987e3340c444f74a66ac7e25d910204
Source dataset
uspto-grants-1991_12
Patent number
US05077329

Reaction notes

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