1,3-Dibromo-5,5-dimethylhydantoin → 11alpha-Acetoxy-estra-4,6-diene-3,17-dione

HRID 1837272Notes

Reaction equation

C([O-])(=O)C.[Na+].BrN1C(C)(C)C(=O)N(Br)C1=O.C([O:20][C:21]1[CH2:38][CH2:37][C@H:36]2[C:23](=[CH:24][CH2:25][C@@H:26]3[C@@H:35]2[C@H:34]([O:39][C:40](=[O:42])[CH3:41])[CH2:33][C@@:31]2([CH3:32])[C@H:27]3[CH2:28][CH2:29][C:30]2=[O:43])[CH:22]=1)(=O)C.S([O-])([O-])=O.[Na+].[Na+].[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>CN1CCCC1=O.C(Cl)Cl>[C:40]([O:39][C@@H:34]1[CH2:33][C@@:31]2([CH3:32])[C@@H:27]([CH2:28][CH2:29][C:30]2=[O:43])[C@H:26]2[C@H:35]1[C@@H:36]1[C:23]([CH:24]=[CH:25]2)=[CH:22][C:21](=[O:20])[CH2:38][CH2:37]1)(=[O:42])[CH3:41]

Participants

Conditions

Temperature: 0 °C

Procedure

48 ml of a 10% aqueous sodium acetate solution and, in portions, 22.3 g of 1,3-dibromo-5,5-dimethylhydantoin are added to 57 g of 3,11α-diacetoxy-estra-3,5-dien-17-one in 470 ml of N-methyl-2-pyrrolidinone while being cooled with ice. After 30 minutes, 16.7 g of sodium sulfite is added, it is stirred for 15 minutes at 0° C., then mixed with 20 g of lithium bromide and 16 g of lithium carbonate and stirred at 100° C. After 2 hours, the reaction mixture is added to ice/water. The precipitated product is suctioned off, dissolved in methylene chloride, washed neutral with water and dried. The crude product is recrystallized from 200 ml of ethyl acetate. 30 g of 11α-acetoxy-estra-4,6-diene-3,17-dione with a melting point of 246-248° C. is obtained.

Workup

temperaturewhile being cooled with ice
stirringstirred at 100° C
waitAfter 2 hours
washwashed neutral with water
customdried
customThe crude product is recrystallized from 200 ml of ethyl acetate

Sources & evidence

ORD record: ord-7855a9f30161411994c0c626736604ca
Source dataset: uspto-grants-2004_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06780855B2

Reaction notes

Loading…