Hydrochloric Acid → (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

HRID 1400999Notes

Reaction equation

HRID 1400999 reaction equation
[N:1]([C@:4]12[CH2:30][CH2:29][C@@H:28]([C:31]([CH3:33])=[CH2:32])[C@@H:5]1[C@@H:6]1[C@@:19]([CH3:22])([CH2:20][CH2:21]2)[C@@:18]2([CH3:23])[C@@H:9]([C@:10]3([CH3:27])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13](=[O:26])[CH2:12][CH2:11]3)[CH2:8][CH2:7]1)=C=O.[ClH:34]>O1CCOCC1>[Cl-:34].[CH3:22][C@:19]12[C@@:18]3([CH3:23])[C@@H:9]([C@:10]4([CH3:27])[C@@H:15]([CH2:16][CH2:17]3)[C:14]([CH3:24])([CH3:25])[C:13](=[O:26])[CH2:12][CH2:11]4)[CH2:8][CH2:7][C@@H:6]1[C@H:5]1[C@H:28]([C:31]([CH3:33])=[CH2:32])[CH2:29][CH2:30][C@:4]1([NH3+:1])[CH2:21][CH2:20]2

Participants

4

Reactant 2

HCID 313Hydrochloric AcidHCID 25426274(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one

Product 1

HCID 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 chlorideYield 72%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one (2.1 g, 4.65 mmol) in dioxane (30 mL) at RT was added 7 mL conc. HCl over a period of 5 minutes. The clear solution was stirred for 10 minutes, forming a slightly turbid mixture. Stirring continued for a total of 6 hours and the reaction mixture turned into a 2-layer mixture. All the volatile solvents were removed under high vacuum. The dried, crude material was dissolved into DCM (15 mL), poured over a short bed (˜1″ thick) of silica gel type-H, washed with 500 mL, 20% ethyl acetate in hexanes, followed by a 2:1 mixture of DCM:Ethyl acetate (0.5 L). Upon concentration, a pale gum was obtained. The material was dried under high vacuum to give 1.55 gm (72% yield). MS: m/e 426.40 M+, 4.11 min (method 11). 1H NMR (400 MHz, CHLOROFORM-d) δ 8.24 (br. s., 3H), 4.83 (br. s., 1H), 4.66 (br. s., 1H), 2.62-2.17 (m, 4H), 2.16-1.78 (m, 5H), 1.77-1.31 (m, 17H), 1.30-1.16 (m, 5H), 1.09 (s, 3H), 1.03 (s, 3H), 0.99 (br. s., 3H), 0.93 (s, 3H).

Workup

  1. customforming a slightly turbid mixture
  2. stirringStirring
  3. customcontinued for a total of 6 hours
  4. customAll the volatile solvents were removed under high vacuum
  5. dissolutionThe dried, crude material was dissolved into DCM (15 mL)
  6. additionpoured over a short bed (˜1″ thick) of silica gel type-H
  7. washwashed with 500 mL, 20% ethyl acetate in hexanes
  8. additionfollowed by a 2:1 mixture of DCM
  9. concentrationUpon concentration
  10. customa pale gum was obtained
  11. customThe material was dried under high vacuum
  12. customto give 1.55 gm (72% yield)
  13. custom4.11 min (method 11)

Sources & evidence

ORD record
ord-e330a9e032f141d9a1bad31fdd7b72e0
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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