Acetone → 11beta-Ethyl-17beta-dodecyloxycarbonyloxyestr-4-en-3-one

HRID 1161976Notes

Reaction equation

HRID 1161976 reaction equation
[CH2:1]([C@H:3]1[CH2:20][C@@:18]2([CH3:19])[C@@H:14]([CH2:15][CH2:16][C@@H:17]2[OH:21])[C@H:13]2[C@H:4]1[C@@H:5]1[C:10]([CH2:11][CH2:12]2)=[CH:9][C:8](=[O:22])[CH2:7][CH2:6]1)[CH3:2].N1C=CC=CC=1.Cl[C:30]([O:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH3:44])=[O:31].CC(C)=O>C(Cl)Cl>[CH2:1]([C@H:3]1[CH2:20][C@@:18]2([CH3:19])[C@@H:14]([CH2:15][CH2:16][C@@H:17]2[O:21][C:30]([O:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH3:44])=[O:31])[C@H:13]2[C@H:4]1[C@@H:5]1[C:10]([CH2:11][CH2:12]2)=[CH:9][C:8](=[O:22])[CH2:7][CH2:6]1)[CH3:2]

Participants

6

Reactant 4

HCID 180AcetoneHCID 1049PyridineHCID 90513Dodecyl chloroformateHCID 6864808911beta-Ethyl-17beta-hydroxyestr-4-en-3-one

Product 1

HCID 1154804811beta-Ethyl-17beta-dodecyloxycarbonyloxyestr-4-en-3-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

11β-Ethyl-17β-dodecyloxycarbonyloxyestr-4-en-3-one (9b, CDB-4722) was prepared as follows: Under nitrogen, a solution of 11β-ethylestr-4-en-17β-ol (7b, 0.1 g, 0.33 mmol) in dry CH2Cl2 (5 mL) was cooled to 0° C. in an ice bath. Pyridine (0.1 mL, 97.8 mg, 1.24 mmol) followed by dodecyl chloroformate (0.2 mL, 1.84 mg, 0.74 mmol) were added and the mixture stirred at 0° C. for 15 min and then allowed to warm to room temperature. The reaction was stirred at room temperature overnight, after which time, TLC (2% acetone in CH2Cl2) indicated a complete reaction. The mixture was diluted with additional CH2Cl2 (50 mL) and washed with water (1×), saturated sodium bicarbonate solution (1×), and water (1×). The organic fractions were filtered through anhydrous Na2SO4, combined and concentrated in vacuo to give 0.3 g residue as a clear oil. This crude material was purified by Flash chromatography (2% acetone in CH2Cl2) to give 0.16 g of a clear oil in 94% yield, which resisted crystallization.

Workup

  1. additionwere added
  2. temperatureto warm to room temperature
  3. stirringThe reaction was stirred at room temperature overnight
  4. customa complete reaction
  5. washwashed with water (1×), saturated sodium bicarbonate solution (1×), and water (1×)
  6. filtrationThe organic fractions were filtered through anhydrous Na2SO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ee5d7085c0a64efdb91b9683d704e9db
Source dataset
uspto-grants-2010_10
Patent number
US07820642B2

Reaction notes

Loading…