Dimethyl methylphosphonate → HCID 131715926, compound

HRID 621755Notes

Reaction equation

HRID 621755 reaction equation
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].C([Li])CCC.[O:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH:14]1[O:19][C@@H:20]1[C@@H:26]([O:27][CH:28]2[CH2:33][CH2:32][CH2:31][CH2:30][O:29]2)[C@H:25]([O:34][CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[C@@H:24]([CH2:41][O:42][CH:43]2[CH2:48][CH2:47][CH2:46][CH2:45][O:44]2)[O:23][C:21]1=[O:22]>C(OCC)C.CCCCCC>[O:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH:14]1[O:19][C@@H:20]1[C@@H:26]([O:27][CH:28]2[CH2:33][CH2:32][CH2:31][CH2:30][O:29]2)[C@H:25]([O:34][CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[C@@H:24]([CH2:41][O:42][CH:43]2[CH2:48][CH2:47][CH2:46][CH2:45][O:44]2)[O:23][C:21]1([OH:22])[CH2:1][P:2]([O:5][CH3:6])([O:3][CH3:4])=[O:7]

Participants

6

Reactant 3

HCID 12958Dimethyl methylphosphonateHCID 14166915HCID 14166915, compoundHCID 178418339Butyllithium

Product 1

HCID 131715926HCID 131715926, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of dimethyl methylphosphonate (15.3 ml) in ethyl ether (300 ml) was added dropwise with cooling (-70° to -78° C.) in a stream of argon a solution of n-butyllithium in n-hexane (1.6M solution, 84 ml), and the mixture was stirred for 30 minutes. To the solution was added dropwise with cooling at the same temperature a solution of 2,3,4,6-tetra-O-(tetrahydropyranyl)-D-glucono-1,5-lactone (23.1 g) in ethyl ether (80 ml). The mixture was stirred for one hour, then the cooling bath was removed, and then the mixture was allowed to warm to 0° C. with stirring. The reaction solution was added to an ice-cooled mixture of 10%(W/V) ammonium chloride solution (250 ml) and ethyl ether (120 ml). The ethyl ether layer was separated. The aqueous layer was subjected to extraction with ethyl ether. The organic layers were combined, washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and dried further under reduced pressure to give 3,4,5,7-tetra-O-(tetrahydropyranyl)-1-deoxy-1-(dimethoxyphosphoryl)-D-gluco-2-heptulopyranose (26.6 g).

Workup

  1. additionTo the solution was added dropwise
  2. stirringThe mixture was stirred for one hour
  3. customthe cooling bath was removed
  4. stirringwith stirring
  5. additionThe reaction solution was added to an ice-
  6. temperaturecooled
  7. additionmixture of 10%(W/V) ammonium chloride solution (250 ml) and ethyl ether (120 ml)
  8. customThe ethyl ether layer was separated
  9. extractionThe aqueous layer was subjected to extraction with ethyl ether
  10. washwashed with water
  11. dry with materialdried over anhydrous magnesium sulfate
  12. concentrationconcentrated under reduced pressure
  13. customdried further under reduced pressure

Sources & evidence

ORD record
ord-2d02d5554d1c40cdb161fc32c85e3b16
Source dataset
uspto-grants-1989_04
Patent number
US04824943

Reaction notes

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