Sodium Hydroxide → 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(ethylamino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid

HRID 85670Notes

Reaction equation

HRID 85670 reaction equation
[CH2:1]([NH:3][C@:4]12[CH2:39][CH2:38][C@@H:37]([C:40]([CH3:42])=[CH2:41])[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([CH3:36])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]2[CH:35]=[CH:34][C:29]([C:30]([O:32]C)=[O:31])=[CH:28][CH:27]=2)=[CH:12][CH2:11]3)[CH2:8][CH2:7]1)[CH3:2].[OH-].[Na+]>O1CCOCC1.CO>[CH2:1]([NH:3][C@:4]12[CH2:39][CH2:38][C@@H:37]([C:40]([CH3:42])=[CH2:41])[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([CH3:36])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]2[CH:27]=[CH:28][C:29]([C:30]([OH:32])=[O:31])=[CH:34][CH:35]=2)=[CH:12][CH2:11]3)[CH2:8][CH2:7]1)[CH3:2]

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 86676614HCID 86676614, compound

Product 1

HCID 683581554-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(ethylamino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acidYield 61.5%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
75 °C

Procedure

To a solution of methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(ethylamino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (0.037 g, 0.065 mmol) in 1,4-dioxane (1.5 mL) was added NaOH (1N) (0.3 mL, 0.300 mmol). The mixture was heated to 75° C. for 18.5 h then was cooled to rt, was diluted with methanol and 1,4-dioxane, was filtered through a plug of glass wool and was purified by prep HPLC. The fractions containing the expected product were combined and were concentrated under reduced pressure to give 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(ethylamino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid (0.023 g, 0.040 mmol, 61.2% yield) as a white solid. LCMS: m/e 558.6 (M+H)+, 1.77 min (method 2). 1H NMR (400 MHz, Acetic acid d4) δ 7.99 (d, J=8.53 Hz, 2H), 7.26 (d, J=8.28 Hz, 2H), 5.33 (d, J=4.52 Hz, 1H), 4.82 (s, 1H), 4.69 (s, 1H), 3.23 (q, J=7.11 Hz, 2H), 2.81-2.92 (m, 1H), 1.72 (s, 3H), 1.40 (t, J=7.15 Hz, 3H), 1.19 (s, 3H), 1.09 (s, 3H), 1.05 (s, 3H), 0.98 (s, 3H), 0.96 (s, 3H), 0.83-2.24 (m, 22H).

Workup

  1. temperaturethen was cooled to rt
  2. filtrationwas filtered through a plug of glass wool
  3. customwas purified by prep HPLC
  4. additionThe fractions containing the expected product
  5. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-f21df1b5bf444565a8376194af272b8b
Source dataset
uspto-grants-2014_09
Patent number
US08846647B2

Reaction notes

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