Chlorosuccinimide → (Chloro(phenylmethoxy)phosphoryl)oxymethylbenzene

HRID 1597133Notes

Reaction equation

HRID 1597133 reaction equation
[Cl:1]N1C(=O)CCC1=O.[CH2:9]([O:16][P:17]([O-:26])[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>C1(C)C=CC=CC=1>[P:17]([Cl:1])([O:16][CH2:9][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)([O:18][CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)=[O:26]

Participants

4

Reactant 2

HCID 31398ChlorosuccinimideHCID 21904359Dibenzylphosphite

Product 1

HCID 4641201(Chloro(phenylmethoxy)phosphoryl)oxymethylbenzene

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
40 °C

Procedure

Dibenzyl chlorophosphate was prepared by adding N-chlorosuccinimide (2.2 g) to a solution of dibenzylphosphite (4.4 g) in dry toluene (70 ml) at room temperature with stirring. The resulting solid was filtered off and the filtrate concentrated to ca. 10 ml. and added to a solution of 4′-methoxyphenyl 2,3,4-tri-O-acetylmannoside (3.86 g) in pyridine (30 ml) at 0° C. and the mixture allowed to stand over night. The mixture was warmed to 40° C. for 1 h and the solvent evaporated under reduced pressure. The residue was chromatographed on a silica gel 60 chromatography column (2.5×55 cm). The column was first eluted with CHCl3 and this fraction discarded. Subsequent elution with 20% acetone/CHCl3 gave 4′-methoxyphenyl 2,3,4-tri-O-acetylmannoside dibenzylphosphate (2.9 g). (1Hnmr, CDCl3: 2.06, s, 3H; 2.09, s, 3H; 2.13, s, 3H; 3.53, t, 1H; 3.6, s, 3H; 3.88, t, 1H; 3.97, m, 1H; 4.8, d, 1H; 5.12, m, 1H; 5.3, m, 2H; 6.81, d, 2H; 6.97, d, 2H; 7.3, m, 10H.) Starting material (1.46 g) was recovered from the column by elution with 10% EtOH/CHCl3.

Workup

  1. filtrationThe resulting solid was filtered off
  2. concentrationthe filtrate concentrated to ca. 10 ml
  3. additionand added to a solution of 4′-methoxyphenyl 2,3,4-tri-O-acetylmannoside (3.86 g) in pyridine (30 ml) at 0° C.
  4. waitto stand over night
  5. customthe solvent evaporated under reduced pressure
  6. customThe residue was chromatographed on a silica gel 60 chromatography column (2.5×55 cm)
  7. washThe column was first eluted with CHCl3
  8. washSubsequent elution with 20% acetone/CHCl3
  9. customgave 4′-methoxyphenyl 2,3,4-tri-O-acetylmannoside dibenzylphosphate (2.9 g)
  10. customwas recovered from the column by elution with 10% EtOH/CHCl3

Sources & evidence

ORD record
ord-db7ff61294b94fb28f911eb5008695fe
Source dataset
uspto-grants-2001_09
Patent number
US06294521B1

Reaction notes

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