Oxalic Acid → Gestodene

HRID 2413544Notes

Reaction equation

HRID 2413544 reaction equation
C#C.[CH2:3]([Li])[CH2:4]CC.C[O:9][C:10]1[CH2:28][CH2:27][C@H:26]2[C:12](=[CH:13][CH2:14][C@@H:15]3[C@@H:25]2[CH2:24][CH2:23][C@@:20]2([CH2:21][CH3:22])[C@H:16]3[CH:17]=[CH:18][C:19]2=[O:29])[CH:11]=1.C(O)(=O)C(O)=O>O1CCCC1.O.CO>[C:3]([C@:19]1([OH:29])[CH:18]=[CH:17][C@H:16]2[C@H:15]3[C@H:25]([CH2:24][CH2:23][C@:20]12[CH2:21][CH3:22])[C@@H:26]1[C:27](=[CH:28][C:10](=[O:9])[CH2:11][CH2:12]1)[CH2:13][CH2:14]3)#[CH:4]

Participants

8

Reactant 4

HCID 971Oxalic AcidHCID 6326AcetyleneHCID 67362893HCID 67362893, compoundHCID 178418339Butyllithium

Product 1

HCID 3033968Gestodene

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

At 0° C., acetylene is introduced for 15 minutes into a solution of 40 ml of n-butyllithium (15% in hexane) in 100 ml of absolute tetrahydrofuran and then 4.0 g of 3-methoxy-18-methyl-3,5,15-estratrien-17-one in 40 ml of tetrahydrofuran is added dropwise thereto. After 15 minutes, the mixture is combined with 8 ml of water, 40 ml of methanol and 8 g of oxalic acid, stirred for one hour at 60° C., 600 ml of water is added, and the mixture is extracted with ethyl acetate. The organic phase is washed with water and dried. Recrystallization from ethyl acetate yields 2.4 g of 17α-ethynyl-17β-hydroxy-18-methyl-4,15-estradien-3-one. Melting point 197° C.

Workup

  1. extractionthe mixture is extracted with ethyl acetate
  2. washThe organic phase is washed with water
  3. customdried
  4. customRecrystallization from ethyl acetate

Sources & evidence

ORD record
ord-756645435e3346eeabc5d535640a3254
Source dataset
uspto-grants-1988_01
Patent number
US04719054

Reaction notes

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