Diethyl methylphosphonate → HCID 88605040, compound

HRID 2166493Notes

Reaction equation

HRID 2166493 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:14])([O:11][CH2:12][CH3:13])[O:8][CH2:9][CH3:10].[C:15]1([CH2:21][O:22][C@@H:23]([C@@H:27]([C@@H:36]([CH2:38][O:39][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)O)[O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C:24]([OH:26])=[O:25])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CCCCCC.O1CCCC1>[CH2:9]([O:8][P:7]([O:11][CH2:12][CH3:13])([CH2:6][C:24]1([O:26][C@H:36]([CH2:38][O:39][CH2:40][C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)[C@@H:27]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@@H:23]1[O:22][CH2:21][C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[OH:25])=[O:14])[CH3:10]

Participants

6

Reactant 3

HCID 12685Diethyl methylphosphonateHCID 54253136HCID 54253136, compoundHCID 178418339Butyllithium

Product 1

HCID 88605040HCID 88605040, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 15.6 ml of 1.6M n-butyllithium in hexane and 20 ml of tetrahydrofuran at -78° C., was added a solution of 3.80 g of diethyl methylphosphonate in 10 ml of tetrahydrofuran during 10 minutes. After 15 minutes at -78° C., a solution of 4.18 g of 2,3,5-tris-O-(phenylmethyl)-D-arabinonic acid, qamma-lactone [Y. Rabinsohn & H. G. Fletcher, J. Org. Chem., 32, 3452-3457 (1967)] in 15 ml of tetrahydrofuran was added during 5 minutes. After 30 minutes at -78° C. the solution was warmed to 0° C. during 5 minutes, stirred at 0° C. for 2 minutes, recooled to -78° C. and quenched with 3.0 ml of glacial acetic acid. The mixture was partitioned with dichloromethane-water. The organic layer was washed successively with water, sodium bicarbonate solution, water and brine, dried and concentrated. The residue was subjected to column chromatography on silica gel (ethyl acetate-heptane) giving the desired compound as an oil, CMR δ 101.2 and 104.3 (doublets, corresponding to anomeric carbon of minor and major anomer, respectively).

Workup

  1. customrecooled to -78° C.
  2. customquenched with 3.0 ml of glacial acetic acid
  3. customThe mixture was partitioned with dichloromethane-water
  4. washThe organic layer was washed successively with water, sodium bicarbonate solution, water and brine
  5. customdried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-849f7cfb6aeb40bbb9001fecf7f8c18c
Source dataset
uspto-grants-1990_07
Patent number
US04945158

Reaction notes

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