Nitrogen → HCID 53891980, compound

HRID 1599478Notes

Reaction equation

HRID 1599478 reaction equation
O[C@H]1C[C@H]2[C@H]3[C@H](CC[C@]2(C)C1)[C@]1(C)C(=CC(=O)CC1)N(C)[C@@H]3C.[CH3:24][C@@:25]12[C:33](=[O:34])[CH2:32][CH2:31][C@H:30]1[C@@H:29]1[CH2:35][CH:36]=[C:37]3[CH2:42][C@@H:41]([OH:43])[CH2:40][CH2:39][C@:38]3([CH3:44])[C@H:28]1[CH2:27][CH2:26]2.N#N.N1C(C)=CC=CC=1C.FC(F)(F)S(O[Si:61]([CH:68]([CH3:70])[CH3:69])([CH:65]([CH3:67])[CH3:66])[CH:62]([CH3:64])[CH3:63])(=O)=O>C(Cl)Cl>[CH:62]([Si:61]([CH:68]([CH3:70])[CH3:69])([CH:65]([CH3:67])[CH3:66])[O:43][C@H:41]1[CH2:40][CH2:39][C@@:38]2([CH3:44])[C:37]([CH2:36][CH2:35][C@@H:29]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:24])[C@H:30]3[CH2:31][CH2:32][C:33]2=[O:34])=[CH:42]1)([CH3:64])[CH3:63]

Participants

7

Reactant 5

HCID 947NitrogenHCID 5881DehydroepiandrosteroneHCID 79372,6-LutidineHCID 2724529Triisopropylsilyl trifluoromethanesulfonateHCID 53660279HCID 53660279, compound

Product 1

HCID 53891980HCID 53891980, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of 3β-(hydroxy)androst-5-en-17-one (1, R2 =H) (available from Sigma Chemical Co., St. Louis, Mo., 10.09 g, 35 mmoles, also called dehydroepiandrostenone "DHEA") in methylene chloride (150 mL) in a N2 atmosphere was added lutidine (6.1 mL, 52.5 mmoles) followed by triisopropylsilyl trifluoromethanesulfonate (11.6 mL, 42 mmoles) and the resulting mixture stirred at 0° C. for 25 minutes. The reaction mixture was diluted with methylene chloride (100 mL) and washed with 1N HCl (2 times), H2O, 10% NaHCO3, H2O, brine and dried over MgSO4. Evaporation in vacuo gave 3β-(triisopropylsilyloxy)androst-4-ene-17-one (2, R2 =H) as a white, waxy solid. A mixture of (2) (16.9 g, 35 mmoles), powdered KOH (1.96 g, 35 mmoles) and benzaldehyde (7.83 mL, 77 mmoles) in ethanol (250 mL) was stirred at room temperature in the dark for 18 hours. The mixture was cooled in an ice bath, filtered and the precipitate dried in a vacuum oven at 70° C. for 5 hours to give (3, R2 =H) as a white solid. NMR (CDCl3): δ 1.00 (s, 3H, 18-Me); 1.07 (s, 21H, CH(CH3)2 ; 1.09 (s, 3H, 19-Me); 3.58 (m, 1H, 3-H); 5.38 (d, 1H, 6-H); 7.37-7.57 (m, 6H, =CH--Ph).

Workup

  1. washwashed with 1N HCl (2 times), H2O, 10% NaHCO3, H2O, brine
  2. dry with materialdried over MgSO4
  3. customEvaporation in vacuo

Sources & evidence

ORD record
ord-87c6b07fe408419288c68cd971e0febf
Source dataset
uspto-grants-1998_04
Patent number
US05741795

Reaction notes

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