Hexane → Sodium diethyl phosphite

HRID 2166492Notes

Reaction equation

HRID 2166492 reaction equation
[H-].[Na+:2].[P:3]([O-:10])([O:7][CH2:8][CH3:9])[O:4][CH2:5][CH3:6].[C:11]1([CH2:17][O:18][CH2:19][C@:20]2([O:42][C@H:41]([CH2:43][O:44][CH2:45][C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[C@@H:32]([O:33][CH2:34][C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)[C@@H:23]2[O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:21]O)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.CCCCCC>O1CCCC1.O.CCOCC>[P:3]([O-:10])([O:7][CH2:8][CH3:9])[O:4][CH2:5][CH3:6].[Na+:2].[CH2:5]([O:4][P:3]([O:7][CH2:8][CH3:9])([CH2:21][C@:20]1([CH2:19][O:18][CH2:17][C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[O:42][C@H:41]([CH2:43][O:44][CH2:45][C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=2)[C@@H:32]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C@@H:23]1[O:24][CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)=[O:10])[CH3:6]

Participants

9

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 3780918DiethylphosphiteHCID 703483222,5-anhydro-2-C-[(phenylmethoxy)methyl]-3,4,6-tris-O-(phenylmethyl)-D-glucitol

Product 2

HCID 23684067Sodium diethyl phosphiteHCID 885983302,5-Anhydro-1-deoxy-1-(diethoxyphosphinyl)-2-C-[(phenylmethoxy)methyl]-3,4,6-tris-O-(phenylmethyl)-D-glucitol

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
45 °C

Procedure

A fresh solution of sodium diethyl phosphite was prepared from sodium hydride and diethyl phosphite in tetrahydrofuran at a concentration of 2 milliequivalents/ml and added, as described below, to a solution of 260 mg of 2,5-anhydro-2-C-[(phenylmethoxy)methyl]-3,4,6-tris-O-(phenylmethyl)-D-glucitol, 1-(trifluoromethanesulfonate) in 1 ml of tetrahydrofuran. A 0.5 ml portion of the stock solution was added and the mixture stirred 1.5 hours; 0.25 ml was added and stirring continued for 2.5 hours; 0.22 ml was added, the mixture warmed to 45° C. for 20 minutes then cooled to room temperature. The mixture was worked up with hexane, ether and water, giving an oil. This oil was purified by flash chromatography, eluting with 1% methanol in dichloromethane, giving 203 mg of the desired compound.

Workup

  1. additionadded
  2. additionA 0.5 ml portion of the stock solution was added
  3. addition0.25 ml was added
  4. stirringstirring
  5. waitcontinued for 2.5 hours
  6. addition0.22 ml was added
  7. temperaturethen cooled to room temperature
  8. customgiving an oil
  9. customThis oil was purified by flash chromatography
  10. washeluting with 1% methanol in dichloromethane

Sources & evidence

ORD record
ord-9c9fa870f3a24661b44f2149f621dc78
Source dataset
uspto-grants-1990_07
Patent number
US04945158

Reaction notes

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