Dichloromethane → HCID 86737780, compound

HRID 1680246Notes

Reaction equation

HRID 1680246 reaction equation
[CH3:1][C:2]1[C:3](=[O:23])[CH2:4][C@@:5]23[CH2:18][CH2:17][N:16]([CH3:19])[C@@H:13]([C@@H:14]2[CH:15]=1)[CH2:12][C:11]1[CH:10]=[CH:9][C:8]([O:20][CH3:21])=[C:7]([OH:22])[C:6]3=1.[NH4+].[Cl-].[NH4+].[OH-].[CH2:28](Cl)Cl>CCOCC>[OH:22][C:7]1[C:6]2[C@:5]34[CH2:18][CH2:17][N:16]([CH3:19])[C@@H:13]([C@@H:14]3[C@@H:15]([CH3:28])[C@H:2]([CH3:1])[C:3](=[O:23])[CH2:4]4)[CH2:12][C:11]=2[CH:10]=[CH:9][C:8]=1[O:20][CH3:21]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 14923Ammonium HydroxideHCID 25517Ammonium ChlorideHCID 57237521HCID 57237521, compound

Product 1

HCID 86737780HCID 86737780, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Compound 14 (20.0 g, 64 mmole) in methylene chloride (400 ml) was added to a solution of lithium dimethyl cuprate (165 mmole) prepared in ether (800 ml) with cooling in an ice-salt bath under an argon atmosphere. The mixture was stirred at this temperature for 1 hour after which it was poured into saturated NH4Cl solution (1 liter). After the addition of concentrated NH4OH to pH~12 and stirring for 30 minutes, the organic phase was separated and washed twice with dilute NH4OH. The aqueous phase was extracted with additional methylene chloride and the combined organic phases dried and evaporated to give a quantitative yield of 16b as a thick syrup, NMR: δ 6.63, s, 2H (aromatic); 4.25, d, 1H (H-5α, J=13H); 3.80 (CH3O--); 2.43 (CH3N--); 1.08; unsymmetrical t, 3H (8β-CH3, J=6H); 0.90, symmetrical d, 3H (7α-CH3, J=6H). A portion of this material was converted to the hydrochloride salt by dissolving the syrupy free base in ethanol and adding excess concentrated HCl. The solution was evaporated to dryness and the residue azeotroped with ethanol, 1:1 V/V ethanol:benzene, then benzene. The residue was crystallized from ethyl acetate to give 16b HCl, mp 259°-262°.

Workup

  1. temperaturewith cooling in an ice-salt bath under an argon atmosphere
  2. stirringstirring for 30 minutes
  3. customthe organic phase was separated
  4. washwashed twice with dilute NH4OH
  5. extractionThe aqueous phase was extracted with additional methylene chloride
  6. customthe combined organic phases dried
  7. customevaporated

Sources & evidence

ORD record
ord-699892cdda4643e9822e0d88d6da841b
Source dataset
uspto-grants-1981_06
Patent number
US04272541

Reaction notes

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