Pyridine → HCID 86749449, compound

HRID 1721308Notes

Reaction equation

HRID 1721308 reaction equation
C(O[C@H:10]1[CH2:35][CH2:34][C@@:33]2([CH3:36])[C@@H:12]([CH2:13][CH2:14][C@@H:15]3[C@@H:32]2[CH2:31][CH2:30][C@@:29]2([CH3:37])[C@H:16]3[CH2:17][CH2:18][C@@H:19]2[C@H](C)CC[C@H](C)C(C)C)[CH2:11]1)(=O)C1C=CC=CC=1.[O:38]=[O+][O-].N1C=C[CH:44]=[CH:43][CH:42]=1>C(Cl)Cl>[CH3:42][CH:43]([CH:44]=[O:38])[C@@H:19]1[C@:29]2([CH3:37])[C@H:16]([C@H:15]3[C@H:32]([CH2:31][CH2:30]2)[C@:33]2([CH3:36])[C@H:12]([CH2:11][CH2:10][CH2:35][CH2:34]2)[CH2:13][CH2:14]3)[CH2:17][CH2:18]1

Participants

5

Reactant 3

HCID 1049PyridineHCID 24823OzoneHCID 677062206424-44-8

Product 1

HCID 86749449HCID 86749449, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of pyridazino 3',4',5',6':7,8,14,15!-3β-benzoyloxy-5α-ergostane (34, 3.2 g, 6.08 mmol) in CH2Cl2 (105 mL) and pyridine (1 mL) was cooled to -78° C. in a dry ice-acetone bath and ozone gas (approximately 0.95 mmol O3/ min) was bubbled through the solution for 25 min. Then the excess O3 was removed by bubbling through argon gas. The reaction mixture was treated with methyl sulfide (3 mL) and stirred at ambient temperature for 20 min. The solvent was evaporated under reduced pressure, leaving 3.90 g of tan fluff. Purification by flash column chromatography on 77 g of Merck grade 60 silica gel using MeOH/CHCl3 (2:98) yielded 1.65 g (59%) of aldehyde (36), mp 248°-252° C. EIMS (m/z): 458 (M+). 1H NMR: δ9.72 (d, 1H, J=2.6 Hz), 8.06 (d, 2H, J=8.3 Hz), 7.57 (dd, 1H, J=7.4, 7.4 Hz), 7.45 (dd, 2H, J=7.4, 7.9 Hz), 5.05 (m, 1H), 3.23 (dd, 1H, J=4.4, 18.7 Hz), 3.22 (dd, 1H, J=7.1, 16.4 Hz), 3.09 (dd, 1H, J=11.0, 16.4 Hz), 2.76 (ddd, 1H, J=2.6, 7.0, 10.8 Hz), 2.67 (dd, 1H, J=13.0, 17.3 Hz), 1.25 (d, 3H, J=7.0 Hz ) , 1.13 (s, 3H) , 0.88 (s, 3H).

Workup

  1. customThen the excess O3 was removed
  2. customby bubbling through argon gas
  3. additionThe reaction mixture was treated with methyl sulfide (3 mL)
  4. customThe solvent was evaporated under reduced pressure
  5. customleaving 3.90 g of tan fluff
  6. customPurification by flash column chromatography on 77 g of Merck grade 60 silica gel

Sources & evidence

ORD record
ord-a9cbde071f28475f95ed1fd1dafeb2b9
Source dataset
uspto-grants-1996_04
Patent number
US05510340

Reaction notes

Loading…