Hydrogen Sulfide → HCID 86740191, compound

Into a chilled solution (ice bath) of 3 g of (11β)-9-fluoro-11-hydroxyandrosta-1,4-dien-3,17-dione in 12 ml of dimethylformamide and 15 ml of morpholine, there was introduced a stream of hydrogen sulfide. Once the exothermic reaction had ceased, the ice bath was removed, the hydrogen sulfide stream was reduced to about one bubble every two seconds and continued overnight. The next day the reaction mixture was poured into ice water, the resulting solid filtered off, washed with water, and dried to yield 3 g of crude product. HPLC analysis indicated the presence of 11% starting material and 88% product. The above 3 g were combined with 2 g of crude product that had been obtained from two earlier batches and chromatographed on silica gel. Elution with chloroform-20% ethyl acetate yielded 2 g of the title compound as a white solid. Crystallization from acetonitrile furnished the analytically pure sample (1.5 g), melting point 295°-297° C. Further elution gave 1 g of the starting steroid. Recrystallization of the thiol from acetic acid yielded needles.

1. customOnce the exothermic reaction
2. customthe ice bath was removed
3. custombubble every two seconds
4. additionThe next day the reaction mixture was poured into ice water
5. filtrationthe resulting solid filtered off
6. washwashed with water
7. customdried
8. customto yield 3 g of crude product
9. customhad been obtained from two earlier batches
10. customchromatographed on silica gel
11. washElution with chloroform-20% ethyl acetate

ORD record

ord-ff5c3444ecc6480fa791977d71cc117c

Source dataset

uspto-grants-1985_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04529548