Dimethyl Sulfate → HCID 91097000, compound

HRID 897051Notes

Reaction equation

HRID 897051 reaction equation
[O:1]1[C@H:3]2[CH2:4][C@@:5]3([CH3:35])[CH:9]([CH:10]4[CH2:11][C@H:12]([F:21])[C:13]5[C@@:18]([CH3:19])([C@:2]124)[CH:17]=[CH:16][C:15](=[O:20])[CH:14]=5)[CH2:8][C@@H:7]([CH3:22])[C@:6]3([O:26][C:27]([C:29]1[S:30][CH:31]=[CH:32][C:33]=1[CH3:34])=[O:28])[C:23]([OH:25])=[O:24].[CH2:36]1CCN2C(=NCCC2)CC1.S(OC)(OC)(=O)=O>C(OCC)(=O)C>[O:1]1[C@H:3]2[CH2:4][C@@:5]3([CH3:35])[CH:9]([CH:10]4[CH2:11][C@H:12]([F:21])[C:13]5[C@@:18]([CH3:19])([C@:2]124)[CH:17]=[CH:16][C:15](=[O:20])[CH:14]=5)[CH2:8][C@@H:7]([CH3:22])[C@:6]3([O:26][C:27]([C:29]1[S:30][CH:31]=[CH:32][C:33]=1[CH3:34])=[O:28])[C:23]([O:25][CH3:36])=[O:24]

Participants

5

Reactant 3

HCID 6497Dimethyl SulfateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 86589030HCID 86589030, compound

Product 1

HCID 91097000HCID 91097000, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

The product of Step 1 (11.1 g) is dissolved in ethyl acetate (200 mL). DBU (4.05 g) and dimethyl sulphate (3.36 g) are added sequentially and the reaction mixture is stirred at room temperature for 2 hours, then partitioned between ethyl acetate and water. The organic layer is washed with water and brine, dried over magnesium sulphate and evaporated. Crystallisation from methanol affords 3-methylthiophene-2-carboxylic acid (6S,9S,10S,11S,13S,16R,17R)-9,11-epoxy-6-fluoro-17-methoxycarbonyl-10,13,16-trimethyl-3-oxo-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-17-yl ester. Selected 1H-NMR signals (CDCl3) δ 0.90 (3H, d), 0.92 (3H, s), 1.40 (3H, s), 2.40 (3H, s), 3.65 (3H, s).

Workup

  1. custompartitioned between ethyl acetate and water
  2. washThe organic layer is washed with water and brine
  3. dry with materialdried over magnesium sulphate
  4. customevaporated
  5. customCrystallisation from methanol

Sources & evidence

ORD record
ord-86d177cb7a07456d9d4970820a5ea220
Source dataset
uspto-grants-2005_07
Patent number
US06921757B2

Reaction notes

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