1,2-Dichloroethane → (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one

HRID 1401002Notes

Reaction equation

HRID 1401002 reaction equation
[Cl-].[CH3:2][C@:3]12[C@@:20]3([CH3:21])[C@@H:11]([C@:12]4([CH3:25])[C@@H:17]([CH2:18][CH2:19]3)[C:16]([CH3:23])([CH3:22])[C:15](=[O:24])[CH2:14][CH2:13]4)[CH2:10][CH2:9][C@@H:8]1[C@H:7]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:6]1([NH3+:32])[CH2:5][CH2:4]2.[O-]P(OP(OP([O-])([O-])=O)([O-])=O)(=O)[O-].[K+].[K+].[K+].[K+].[K+].Cl[CH2:52][CH2:53]Cl>C(#N)C>[N:32]1([C@:6]23[CH2:28][CH2:27][C@@H:26]([C:29]([CH3:31])=[CH2:30])[C@@H:7]2[C@@H:8]2[C@@:3]([CH3:2])([CH2:4][CH2:5]3)[C@@:20]3([CH3:21])[C@@H:11]([C@:12]4([CH3:25])[C@@H:17]([CH2:18][CH2:19]3)[C:16]([CH3:22])([CH3:23])[C:15](=[O:24])[CH2:14][CH2:13]4)[CH2:10][CH2:9]2)[CH2:53][CH2:52]1

Participants

5

Reactant 3

HCID 111,2-DichloroethaneHCID 61695Pentapotassium TriphosphateHCID 86692354(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-aminium chloride

Product 1

HCID 71698573(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
130 °C

Procedure

A mixture of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-aminium chloride (1.09 g, 2.359 mmol) and potassium triphosphate (2.7 g, 12.72 mmol) in 1,2-dichloroethane (12 mL) and acetonitrile (24 mL) was placed in a thick-walled resealable vessel. The reaction vessel with its contents were flushed with nitrogen, sealed, and warmed to 130° C. for 36 hours. The crude reaction mixture was cooled to RT, filtered through a short bed (−1″ thick) of silica gel type-H, washed with ethyl acetate (150 mL). The filtrate was concentrated into a free flowing solid (1.1 g, quantitative) which was taken to the next step without further purification. MS: m/e 452.35 (M+H)+, 3.12 min (method 21). 1H NMR (400 MHz, CHLOROFORM-d) δ 4.77 (d, J=2.5 Hz, 1H), 4.62 (dd, J=2.5, 1.5 Hz, 1H), 2.74-2.56 (m, 2H), 2.55-2.36 (m, 3H), 2.10-2.00 (m, 1H), 1.96-1.86 (m, 1H), 1.85-1.75 (m, 1H), 1.74-1.67 (m, 2H), 1.68 (s, 3H), 1.55-1.24 (m, 16H), 1.16-1.10 (m, 1H), 1.08 (s, 3H), 1.07 (s, 3H), 1.04 (s, 3H), 0.98 (s, 3H), 0.96 (d, J=2.8 Hz, 2H), 0.94 (s, 3H).

Workup

  1. customwas placed in a thick-walled resealable vessel
  2. customThe reaction vessel with its contents were flushed with nitrogen
  3. customsealed
  4. customThe crude reaction mixture
  5. temperaturewas cooled to RT
  6. filtrationfiltered through a short bed (−1″ thick) of silica gel type-H
  7. washwashed with ethyl acetate (150 mL)
  8. concentrationThe filtrate was concentrated into
  9. customwas taken to the next step without further purification
  10. customm/e 452.35 (M+H)+, 3.12 min (method 21)

Sources & evidence

ORD record
ord-f7943c77fe0240319c21d0dc038f1e03
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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