Calcium Carbonate → (3alpha,5alpha)-3-(Acetyloxy)-20-oxo-pregnane-18-carbonitrile

HRID 505020Notes

Reaction equation

HRID 505020 reaction equation
C([O-])([O-])=O.[Ca+2].[C:6]([O:9][C@@H:10]1[CH2:29][CH2:28][C@@:27]2([CH3:30])[C@@H:12]([CH2:13][CH2:14][C@@H:15]3[C@@H:26]2[CH2:25][CH2:24][C@@:23]2([CH3:31])[C@H:16]3[CH2:17][CH2:18][C@@H:19]2[C:20](=[O:22])[CH3:21])[CH2:11]1)(=[O:8])[CH3:7].[C:32]([O:35][C@@H:36]1[CH2:57][CH2:56][C@@:55]2([CH3:58])[C@@H:38]([CH2:39][CH2:40][C@@H:41]3[C@@H:54]2[CH2:53][CH2:52][C@@:51]2([CH3:59])[C@H:42]3[CH2:43][CH2:44][C@@H:45]2[C:46]([OH:50])([C:48]#[N:49])[CH3:47])[CH2:37]1)(=[O:34])[CH3:33]>C1CCCCC1>[C:6]([O:9][C@@H:10]1[CH2:29][CH2:28][C@@:27]2([CH3:30])[C@@H:12]([CH2:13][CH2:14][C@@H:15]3[C@@H:26]2[CH2:25][CH2:24][C@@:23]2([CH2:31][C:48]#[N:49])[C@H:16]3[CH2:17][CH2:18][C@@H:19]2[C:20](=[O:22])[CH3:21])[CH2:11]1)(=[O:8])[CH3:7].[C:32]([O:35][C@@H:36]1[CH2:57][CH2:56][C@@:55]2([CH3:58])[C@@H:38]([CH2:39][CH2:40][C@@H:41]3[C@@H:54]2[CH2:53][CH2:52][C@@:51]2([CH3:59])[C@H:42]3[CH2:43][CH2:44][C@@H:45]2[C:46](=[O:50])[CH3:47])[CH2:37]1)(=[O:34])[CH3:33]

Participants

6

Reactant 3

HCID 10112Calcium CarbonateHCID 11463359(3alpha,5alpha)-3-(Acetyloxy)-20-hydroxypregnane-20-carbonitrileHCID 53835422Allopregnan-3alpha-ol-20-one acetate

Product 2

HCID 11246136(3alpha,5alpha)-3-(Acetyloxy)-20-oxo-pregnane-18-carbonitrileHCID 53835422Allopregnan-3alpha-ol-20-one acetate

Reagents, catalysts & solvents 1

HCID 8078CyclohexaneSolvent

Procedure

Compound 8a was prepared using a reported procedure. (See, Kalvoda, J., et al., Reactions of Steroid Hypoiodites. VII. 1,4-Shift of the Nitrile Group (18-Cyanopregnanes), Helv. Chim. Acta 1966, 49: 424-436)12 (1.6 g, 6.30 mmol) was added to a refluxing mixture of Pb(OAc)4 (6.0 g, 13.5 mmol) and CaCO3 (2 g, 20.0 mmol) in cyclohexane (200 mL). The purple solution was refluxed for 1 h and the mixture of compound 6a and 7a obtained in last step [prepared from 6a (1.0 g, 2.77 mmol)] was added. The reaction mixture was refluxed while irradiated with a 300 W tungsten lamp for 3 h and then cooled to room temperature. After filtration, the precipitate was washed thoroughly with ether. The combined filtrate was washed successively with 10% Na2S2O3 and brine, and dried over Na2SO4. Removal of solvent under reduced pressure gave a residue which was purified by column chromatography (silica gel; hexanes/EtOAc, 4:1) to give compound 8a (400 mg, 40% from 6a) and recovered compound 6a (400 mg).

Workup

  1. temperatureThe purple solution was refluxed for 1 h

Sources & evidence

ORD record
ord-9c2869f7c5f845dcbf038fb5d24a604f
Source dataset
uspto-grants-2010_08
Patent number
US07781421B2

Reaction notes

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