Sodium 3-carboxy-2,3-dihydroxypropanoate → 15-(3,17beta-Dihydroxyoestra-1,3,5(10)-trien-7alpha-yl)pentadecan-5-one

HRID 543022Notes

Reaction equation

HRID 543022 reaction equation
[CH2:1]([Li])CCC.C([O:9][C@H:10]1[CH2:15][CH2:14][C@H:13]2[C@H:16]3[C@H:25]([CH2:26][CH2:27][C@:11]12[CH3:12])[C:24]1[CH:23]=[CH:22][C:21]([OH:28])=[CH:20][C:19]=1[CH2:18][C@H:17]3[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38]C(O)=O)(=O)C.[C:42]([CH:45]([CH:47]([C:49]([O-:51])=O)O)O)(O)=O.[Na+]>C(OCC)C.O1CCCC1>[OH:28][C:21]1[CH:22]=[CH:23][C:24]2[C@@H:25]3[C@H:16]([C@H:13]4[C@@:11]([CH2:27][CH2:26]3)([CH3:12])[C@@H:10]([OH:9])[CH2:15][CH2:14]4)[C@H:17]([CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][C:49](=[O:51])[CH2:47][CH2:45][CH2:42][CH3:1])[CH2:18][C:19]=2[CH:20]=1

Participants

6

Reactant 3

HCID 23690454Sodium 3-carboxy-2,3-dihydroxypropanoateHCID 7044774211-(17beta-Acetoxy-3-hydroxyoestra-1,3,5(10)-trien-7alpha-yl)undecanoic acidHCID 178418339Butyllithium

Product 1

HCID 7044686715-(3,17beta-Dihydroxyoestra-1,3,5(10)-trien-7alpha-yl)pentadecan-5-one

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

n-Butyl-lithium (0.27 ml. of a 1.5 molar solution in diethyl ether) was added to a stirred solution of 11-(17β-acetoxy-3-hydroxyoestra-1,3,5(10)-trien-7α-yl)undecanoic acid (Example 2; 0.046 g.) in tetrahydrofuran (1 ml.) and the mixture was stirred at laboratory temperature for 2 hours. Saturated aqueous sodium hydrogen tartrate solution (2 ml.) was added and the mixture was extracted three times with ethyl acetate (5 ml. each time). The combined extracts were washed with water, dried and evaporated to dryness and the residue was purified by chromatography on a silica gel column using a 17:3 v/v mixture of toluene and ethyl acetate as eluant. There was thus obtained as an oil 15-(3,17β-dihydroxyoestra-1,3,5(10)-trien-7α-yl)pentadecan-5-one, the structure of which was confirmed by proton magnetic resonance and mass spectroscopy.

Workup

  1. extractionthe mixture was extracted three times with ethyl acetate (5 ml
  2. washThe combined extracts were washed with water
  3. customdried
  4. customevaporated to dryness
  5. customthe residue was purified by chromatography on a silica gel column
  6. additiona 17:3 v/v mixture of toluene and ethyl acetate as eluant

Sources & evidence

ORD record
ord-760a6668a62f495ea1ce7a85c31e1d9b
Source dataset
uspto-grants-1987_04
Patent number
US04659516

Reaction notes

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