Dimethyl methylphosphonate → HCID 11119485, compound

HRID 1576166Notes

Reaction equation

HRID 1576166 reaction equation
CP(=O)([O:5][CH3:6])OC.[CH2:8]([Li])CCC.[CH3:13][O:14][C:15]1[CH:32]=[CH:31][C:30]2[C:29]3[CH2:28][CH2:27][C@@:25]4(C)[C:21](=[CH:22]O[C:24]4=O)[C:20]=3[CH2:19][CH2:18][C:17]=2[CH:16]=1>CCCCCC.O1CCCC1.O>[CH3:13][O:14][C:15]1[CH:32]=[CH:31][C:18]2[C:19]3[CH2:28][CH2:27][C@@:25]4([CH3:24])[C@H:21]([CH:22]=[CH:8][C:6]4=[O:5])[C:20]=3[CH2:29][CH2:30][C:17]=2[CH:16]=1.[CH3:13][O:14][C:15]1[CH:32]=[CH:31][C:18]2[C:19]3[CH2:28][CH2:27][C@@:25]4([CH3:24])[C@@H:21]([CH:22]=[CH:8][C:6]4=[O:5])[C:20]=3[CH2:29][CH2:30][C:17]=2[CH:16]=1

Participants

8

Reactant 3

HCID 12958Dimethyl methylphosphonateHCID 53957683HCID 53957683, compoundHCID 178418339Butyllithium

Product 2

HCID 11119485HCID 11119485, compoundHCID 68137148HCID 68137148, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To a solution of 5 g. of dimethyl methylphosphonate in 100 ml. of dry tetrahydrofuran cooled to about -78° under nitrogen, there is added with stirring one equivalent of n-butyl lithium in hexane. After about 10 minutes, there is added one molar equivalent of 3-methoxy-16-oxaestra-1,3,5(10), 8,14-pentaen-17-one in dry tetrahydrofuran while maintaining the temperature at about -78°. The mixture is allowed to warm to room temperature and then left to stand at room temperature for 5 hours. The mixture is diluted with water and then extracted with ether. The ether extracts are combined and concentrated to furnish a residue which is chromatographed on neutral alumina eluting with benzene to afford 3-methoxy-14β-estra- 1,3,5(10),8,15 -pentaen-17-one and 3-methoxy-14α-estra-1,3,5(10),8,15-pentaen-17-one which can be further purified by recrystallization from aqueous methanol.

Workup

  1. additionthere is added
  2. temperaturewhile maintaining the temperature at about -78°
  3. waitleft
  4. waitto stand at room temperature for 5 hours
  5. extractionextracted with ether
  6. concentrationconcentrated
  7. customto furnish a residue which
  8. customis chromatographed on neutral alumina eluting with benzene

Sources & evidence

ORD record
ord-9cc2fdb2e31d4625b6d575c4a73a33cd
Source dataset
uspto-grants-1976_09
Patent number
US03979458

Reaction notes

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