Formaldehyde → Diethyl [2-benzyloxy-1-(benzyloxymethyl)ethoxy]methylphoshonate

HRID 6245

Reaction equation

HRID 6245 reaction equation
[CH2:1]([O:8][CH2:9][CH:10]([OH:20])[CH2:11][O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:21]=O.[P:23]([O:30]CC)([O:27][CH2:28][CH3:29])[O:24][CH2:25][CH3:26]>ClCCl.C(OCC)(=O)C>[CH2:13]([O:12][CH2:11][CH:10]([CH2:9][O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[O:20][CH2:21][P:23](=[O:30])([O:27][CH2:28][CH3:29])[O:24][CH2:25][CH3:26])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 712FormaldehydeHCID 31215Triethyl phosphiteHCID 2476141,3-Bis(benzyloxy)propan-2-ol

Product 1

HCID 23055900Diethyl [2-benzyloxy-1-(benzyloxymethyl)ethoxy]methylphoshonate

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
140 °C

Procedure

Dry HCl gas was bubbled through an ice-cooled solution of 1,3-dibenzyloxypropan-2-ol (25 g, 0.092 mol) and paraformaldehyde (2.75 g, 0.092 mol) in dry dichloromethane (100 ml) for 1 hour. The resulting solution was dried (MgSO4) and evaporated to dryness to leave an oil. Triethyl phosphite (15.7 ml, 0.092 mol) was added and the resulting mixture stirred and heated at 140° C. for 16 hours. The liquid obtained was dissolved in ethyl acetate and washed with sodium bicarbonate solution. The organic phase was washed with brine, dried (MgSO4) and evaporated to give a mobile oil, which was chromotographed in silica (hexane/ethyl acetate 50:50 as eluant) to give the title compound as a colourless, mobile oil (19.7 g, 51). IR: νmax (film) 3055, 3020, 2900, 2860, 1490, 1470, 1450, 1390, 1305, 1255, 1095, 1050, 1030, 970, 820, 770, 735, 700 cm-1. 1H NMR: δH (CDCl3) 1.3 (6H, t, J=7 Hz, P-(OCH2CH3)2), 3.6 (4H, d, 2×CH2OCH2Ph),3.8-4.05 (1H, m, CH), 4.05 (2H, d, J=9 Hz, OCH2P), 4.0-4.3 (4H, m, P-(OCH2CH3)2), 4.55 (4H, s, 2×OCH2Ph), 7.38 (10H, s, 2×Ph). C22H31PO6 requires: C, 62.54; H, 7.42. Found: C, 62.75, H, 7.61. m/z: C22H31PO6 requires 422.1858; observed (M+) 422.1864.

Workup

  1. customDry HCl gas was bubbled through an ice-
  2. dry with materialThe resulting solution was dried (MgSO4)
  3. customevaporated to dryness
  4. customto leave an oil
  5. customThe liquid obtained
  6. washwashed with sodium bicarbonate solution
  7. washThe organic phase was washed with brine
  8. dry with materialdried (MgSO4)
  9. customevaporated
  10. customto give a mobile oil, which

Sources & evidence

ORD record
ord-1159650d17344e7fa82a836be2dcb965
Source dataset
uspto-grants-1993_09
Patent number
US05247085

Linked notes

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