Ammonium Chloride → HCID 54065673, compound

HRID 327021Notes

Reaction equation

HRID 327021 reaction equation
[CH3:1][C:2]1([CH3:15])[CH2:7][O:6][CH:5]([C:8]2[CH:13]=[CH:12][C:11](Br)=[CH:10][CH:9]=2)[O:4][CH2:3]1.[CH2:16]1[CH2:39][O:38][C:18]2([CH2:35][CH2:34][C@:33]34[O:36][C@:20]3([CH2:21][CH2:22][C@@H:23]3[C:32]4=[CH:31][CH2:30][C@@:28]4([CH3:29])[C@@H:24]3[CH2:25][CH2:26][C@H:27]4[OH:37])[CH2:19]2)[O:17]1.[NH4+].[Cl-]>O1CCCC1.Cl[Cu]>[CH2:39]1[CH2:16][O:17][C:18]2([CH2:35][CH2:34][C:33]3[C@@:20]([OH:36])([CH2:21][CH2:22][C@@H:23]4[C:32]=3[C@@H:31]([C:11]3[CH:12]=[CH:13][C:8]([CH:5]5[O:6][CH2:7][C:2]([CH3:15])([CH3:1])[CH2:3][O:4]5)=[CH:9][CH:10]=3)[CH2:30][C@@:28]3([CH3:29])[C@@H:24]4[CH2:25][CH2:26][C@H:27]3[OH:37])[CH2:19]2)[O:38]1

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 137145152-(4-Bromophenyl)-5,5-dimethyl-1,3-dioxaneHCID 86747419HCID 86747419, compound

Product 1

HCID 54065673HCID 54065673, compoundYield 49%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

300 mg of CuCl were added to the Grignard reagent prepared from 4.5 g of 4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl bromide and 0.8 g of Mg in 15 ml of dry tetra-hydrofuran, followed by 2.2 g of (5α,10α,14β,17α)-3,3-ethylenedioxy-5,10-epoxyoestr-9(11)-en-17-ol, prepared in Example 3, in 10 ml of dry tetrahydrofuran. After stirring for 1 hour at room temperature, the mixture was poured into 200 ml of saturated NH4Cl solution. After extraction with ethyl acetate and washing, drying and concentrating the organic phase, the residue was chromatographed on silica gel using hexane/ethyl acetate 1/1 as eluent. After crystallization from diisopropyl ether, 1.7 g of (5α,11β,14β,17α)-3,3-ethylenedioxy-11[4-(5,5-dimethyl-1,3-dioxan-2-yl) phenyl]oestr-9-ene-5,17-diol were obtained; melting point: 176°-177° C. A solution of 1.5 g of this compound in 30 ml of 80% acetic acid was heated for 45 min. at 75° C. After cooling and neutralizing by concentrated NH4OH, the product was extracted with ethyl acetate. The organic phase was washed, dried and concentrated. The residue was chromatographed on silica gel using hexane/ethyl acetate 1/1 as eluent. After crystallization from diisopropyl ether, 0.6 g of (11β,14β,17α)-11-(4-formylphenyl)-17-hydroxyoestra-4,9-dien-3-one was obtained; melting point: 153°-155° C.

Workup

  1. extractionAfter extraction with ethyl acetate
  2. washwashing
  3. customdrying
  4. concentrationconcentrating the organic phase
  5. customthe residue was chromatographed on silica gel
  6. customAfter crystallization from diisopropyl ether

Sources & evidence

ORD record
ord-1aa07358acdf40d0aa835175e820cdaf
Source dataset
uspto-grants-1993_12
Patent number
US05272140

Reaction notes

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