Methyl propiolate → HCID 53842172, compound

HRID 2199020Notes

Reaction equation

HRID 2199020 reaction equation
[C:1]([O:5][CH3:6])(=[O:4])[C:2]#[CH:3].[Cl-].[Cl-].C([Al+2])C.[C:12]([O:15][C@@H:16]1[C@@:34]2([CH3:35])[C:20](=[CH:21][CH2:22][C@@H:23]3[C@@H:33]2[CH2:32][CH2:31][C@@:30]2([CH3:36])[C@H:24]3[CH2:25][CH2:26]/[C:27]/2=[CH:28]/[CH3:29])[CH2:19][C@@H:18]([O:37][C:38](=[O:40])[CH3:39])[CH2:17]1)(=[O:14])[CH3:13].P([O-])(O)(O)=O.[Na+]>C1(C)C=CC=CC=1.C(Cl)Cl.C(OCC)(=O)C>[CH3:6][O:5][C:1](=[O:4])[CH:2]=[CH:3][C@H:28]([C:27]1[C@:30]2([CH3:36])[C@H:24]([C@H:23]3[C@H:33]([CH2:32][CH2:31]2)[C@:34]2([CH3:35])[C:20]([CH2:19][C@@H:18]([O:37][C:38](=[O:40])[CH3:39])[CH2:17][C@@H:16]2[O:15][C:12](=[O:14])[CH3:13])=[CH:21][CH2:22]3)[CH2:25][CH:26]=1)[CH3:29]

Participants

8

Reactant 4

HCID 13536Methyl propiolateHCID 12851145HCID 12851145, compoundHCID 16686341Ethyl aluminium dichlorideHCID 23672064Monosodium phosphate

Product 1

HCID 53842172HCID 53842172, compoundYield 89%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a magnetically-stirred solution of 3.9 ml (45 mmol) of methyl propiolate and 150 ml of dry methylene chloride under an argon atmosphere was added by syringe 58 ml (107 mmol) of 25% ethylaluminum dichloride in toluene, followed as rapidly as possible by a solution of 12.0 g (30 mmol) of Z-pregna-5,17(20)-diene-1α,3β-diol diacetate in 150 ml of dry methylene chloride. The temperature rose to 35° after the catalyst addition. After 1.75 hr., the yellow reaction solution was poured into a well-stirred, ice-cold 1 l. of saturated sodium dihydrogen phosphate solution. About 600 ml of ethyl acetate was added, and the phases were separated. The aqueous phase was extracted with 2×600 ml of ethyl acetate, and the organic phases were washed in a countercurrent manner with 500 ml of water and 500 ml of brine, dried (Na2SO4), filtered and evaporated to give 15.32 g of crude product. High-pressure liquid chromatography on 1 kg of silica gel using 9:1 hexane--ethyl acetate for elution afforded after three passes 12.9 g (89%) of 1α,3β-diacetyloxychola-5,16,22-trien-24-oic acid methyl ester as an amorphous solid.

Workup

  1. customrose to 35°
  2. additionafter the catalyst addition
  3. customthe phases were separated
  4. extractionThe aqueous phase was extracted with 2×600 ml of ethyl acetate
  5. washthe organic phases were washed in a countercurrent manner with 500 ml of water and 500 ml of brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated
  9. customto give 15.32 g of crude product
  10. washHigh-pressure liquid chromatography on 1 kg of silica gel using 9:1 hexane--ethyl acetate for elution

Sources & evidence

ORD record
ord-b4f0946f18d84cc9aba5fab4e520cafc
Source dataset
uspto-grants-1982_11
Patent number
US04360470

Reaction notes

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