Ammonia → HCID 57306753, compound

HRID 1659842Notes

Reaction equation

HRID 1659842 reaction equation
[Li].N.[CH2:3]1[CH2:29][O:28][C:5]([C@@H:7]2[C@:24]3([CH3:25])[C@H:10]([C@H:11]4[C@H:21]([CH2:22][CH2:23]3)[C@:19]3([CH3:20])[C:14](=[CH:15][C:16](=[O:27])[C@@H:17]5[O:26][C@@H:18]53)[CH:13]=[CH:12]4)[CH2:9][CH2:8]2)([CH3:6])[O:4]1.C=CC(=C)C.[Cl-].[NH4+]>CCOCC.O1CCCC1.CCOCC>[CH2:29]1[CH2:3][O:4][C:5]([C@@H:7]2[C@:24]3([CH3:25])[C@H:10]([C@H:11]4[C@H:21]([CH2:22][CH2:23]3)[C@:19]3([CH3:20])[C:14]([CH2:15][C@@H:16]([OH:27])[CH2:17][C@@H:18]3[OH:26])=[CH:13][CH2:12]4)[CH2:9][CH2:8]2)([CH3:6])[O:28]1

Participants

8

Reactant 5

HCID 222AmmoniaHCID 6557IsopreneHCID 25517Ammonium Chloride5×HCID 3028194Lithium6×HCID 57220813HCID 57220813, compound

Product 1

HCID 57306753HCID 57306753, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 21868444Ether tetrahydrofuranSolvent

Procedure

A mixture of 0.594 g (0.0856 g-atom) of lithium in 500 ml of dry liquid ammonia of -31° C. to -33° C. is prepared and stirred for 5 minutes. Then, a solution of 4.535 g (0.0122 mol) of 20,20-ethylenedioxy-1α,2α-epoxy-pregna-4,6-dien-3-one in 300 ml of ether/tetrahydrofuran (2:1) is added to the mixture dropwise under argon during 40 minutes. The resulting deep blue mixture (at -33° C.) is stirred for a further 15 minutes and treated with 2 ml of isoprene until the colour changes to yellow. A total of 4.579 g (0.0856 mol) of ammonium chloride are added in portions with stirring. To the mixture is then added 0.654 g (0.0122 mol) of ammonium chloride and subsequently 0.0849 g (0.0122 g-atom) of lithium. As soon as the lithium has dissolved, this procedure, i.e. the addition of 0.0122 mol of ammonium chloride followed by the amount of lithium equivalent thereto is repeated a further fifteen times, for which a total of 9.81 g (0.183 mol) of ammonium chloride and 1.273 g (0.183 g-atom) of lithium are required. As soon as the lithium of the last addition has dissolved, 9.5 g (0.17 mol) of ammonium chloride and then 500 ml of ether are added. Ammonia is evaporated with stirring until an internal temperature of 0° C. has been reached and the remaining suspension is treated with 500 ml of water and 500 ml of ether. The organic phase is separated and the aqueous phase is back-extracted with ethyl acetate. The organic phases are combined, washed with saturated sodium chloride solution, dried over sodium sulphate and evaporated at 40° C. in a water-jet vacuum. The residue yields, by chromatography on 150 g of silica gel with ether/tetrahydrofuran (19.1) and (4:1), 3.9 g (85%) of uniform 20,20-ethylenedioxy-1α,3β-dihydroxy-pregn-5-ene. The analytical sample is obtained by recrystallisation from methanol; melting point 203°-207° C.; [α]D25 =-47° (c=0.5 in chloroform).

Workup

  1. customis prepared
  2. stirringThe resulting deep blue mixture (at -33° C.) is stirred for a further 15 minutes
  3. stirringwith stirring
  4. dissolutionhas dissolved
  5. customAmmonia is evaporated
  6. stirringwith stirring until an internal temperature of 0° C.
  7. additionthe remaining suspension is treated with 500 ml of water and 500 ml of ether
  8. customThe organic phase is separated
  9. extractionthe aqueous phase is back-extracted with ethyl acetate
  10. washwashed with saturated sodium chloride solution
  11. dry with materialdried over sodium sulphate
  12. customevaporated at 40° C. in a water-jet vacuum

Sources & evidence

ORD record
ord-5e67037a13754f8298c270ed4efdd2d4
Source dataset
uspto-grants-1981_12
Patent number
US04305881

Reaction notes

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