Formaldehyde → HCID 13578833, compound

HRID 1285310Notes

Reaction equation

HRID 1285310 reaction equation
C[O-].[Na+].[CH3:4][C@:5]12[CH2:22][CH:21]=[C:20]3[C@@H:10]([CH2:11][CH2:12][C:13]4[C@:18]3([CH3:19])[CH:17]=[CH:16][C:15](=[O:23])[CH:14]=4)[C@@H:9]1[CH2:8][CH2:7][C:6]2=[O:24].[CH3:25]OC(=O)C(OC)=O.C=O>CO.C1COCC1.C(Cl)Cl.O.C(N(CC)CC)C.C(O)(=O)C>[CH2:25]=[C:7]1[CH2:8][C@H:9]2[C@H:10]3[C:20](=[CH:21][CH2:22][C@:5]2([CH3:4])[C:6]1=[O:24])[C@:18]1([CH3:19])[C:13](=[CH:14][C:15](=[O:23])[CH:16]=[CH:17]1)[CH2:12][CH2:11]3

Participants

11

Reactant 4

HCID 712FormaldehydeHCID 11120Dimethyl oxalateHCID 10265807Androsta-1,4,9(11)-triene-3,17-dioneHCID 10942334Sodium Methoxide

Product 1

HCID 13578833HCID 13578833, compound

Reagents, catalysts & solvents 6

HCID 176Acetic AcidSolventHCID 887MethanolSolvent2×HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

Sodium methoxide in methanol (25%, 6.85 ml) is added dropwise to a mixture of androst-1,4,9(11)-triene-3,17-dione (IB, 7.05 g) in THF (80 ml) and methylene chloride (8 ml) containing dimethyloxalate (4.38 g) previously cooled to 4°. After one hour at 4°, the preparation of the 16-oxalate salt is complete and the following reagents were added sequentially: acetic acid (0.5 ml), triethylamine (2.6 ml), methanol (10 ml), and aqueous formaline (37%, 2.8 ml). The reaction mixture was warmed to 20°-25° and after one hour the reaction was complete. The reaction mixture was poured into water and extracted twice with ethyl acetate. The ethyl acetate extracts were combined, washed with water, dried over sodium sulfate, and concentrated under reduced pressure to a solid. The solid was dissolved in methylene chloride (2.5 ml), following which the methylene chloride was evaporated. The solid was again dissolved in dry THF (25 ml), following which the THF was evaporated. The solid was then dissolved in dry THF (50 ml) for use in the following reaction.

Workup

  1. temperaturepreviously cooled to 4°
  2. additionthe following reagents were added sequentially
  3. temperatureThe reaction mixture was warmed to 20°-25° and after one hour the reaction
  4. extractionextracted twice with ethyl acetate
  5. washwashed with water
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure to a solid
  8. dissolutionThe solid was dissolved in methylene chloride (2.5 ml)
  9. customwas evaporated
  10. dissolutionThe solid was again dissolved in dry THF (25 ml)
  11. customwas evaporated
  12. dissolutionThe solid was then dissolved in dry THF (50 ml) for use in the following reaction

Sources & evidence

ORD record
ord-45c51960a26d4961abdf2d8e6e0fa701
Source dataset
uspto-grants-1986_01
Patent number
US04567001

Reaction notes

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