Benzaldehyde → HCID 59243437, compound

HRID 1039138Notes

Reaction equation

HRID 1039138 reaction equation
[CH2:1]([C@@:8]12[CH2:21][CH2:20][C:19](=[O:22])[CH2:18][C@H:17]1[CH2:16][CH2:15][C:14]1[CH:13]=[C:12]([C:23]([OH:25])=[O:24])[CH:11]=[CH:10][C:9]2=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].[CH:28](=O)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.Cl>O.CCOC(C)=O>[CH2:1]([C@@:8]12[CH2:21]/[C:20](=[CH:28]\[C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)/[C:19](=[O:22])[CH2:18][C@H:17]1[CH2:16][CH2:15][C:14]1[CH:13]=[C:12]([C:23]([OH:25])=[O:24])[CH:11]=[CH:10][C:9]2=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 59243441HCID 59243441, compound2×

Product 1

HCID 59243437HCID 59243437, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
25 °C

Procedure

(4bS,8aR)-4b-benzyl-7-oxo-4b,5,6,7,8,8a,9,10-octahydrophenanthrene-2-carboxylic acid (6.5 g, 19.44 mmol) was suspended in water (65 mL). 2.5 M NaOH (11.7 mL, 29.16 mmol) was added followed by benzaldehyde (2.16 mL, 21.38 mmol). Over time (at 50° C. for 4 hours or at 25° C. over night) the mixture became homogeneous. The reaction was considered complete when there was less than 2% of (4bS,8aR)-4b-benzyl-7-oxo-4b,5,6,7,8,8a,9,10-octahydrophenanthrene-2-carboxylic acid (Preparation 5) remaining. The mixture was cooled to 25° C. if it was not already at 25° C. EtOAc (65 mL) was added to the mixture followed by aqueous 2 M HCl (29 mL). Crystallization normally occurred during the acid addition or shortly thereafter. The mixture was stirred for 60 minutes. Heptane (65 mL) was added and the mixture was stirred for an additional 60 minutes. Do not worry about separating out the aqueous phase; filter the entire mixture and wash the solid with water followed by heptane. A pale yellow solid (6.55 g, 80% yield) was obtained. 1H NMR (DMSO): δ 1.70 (m, 1H), 1.85 (m, 1H), 2.45 (m, 3H), 2.65 (d, 3H), 2.95 (m, 2H), 3.50 (d, 1H), 6.15 (d, 2H), 6.25 (d, 1H), 6.70 (t, 2H), 6.90 (t, 1H), 7.30 (d, 1H), 7.50 (m, 5H), 7.70 (d, 2H), 12.75 (s, 1H).

Workup

  1. customOver time (at 50° C. for 4 hours or at 25° C. over night)
  2. customwas not already at 25° C
  3. customCrystallization
  4. additionnormally occurred during the acid addition
  5. additionHeptane (65 mL) was added
  6. stirringthe mixture was stirred for an additional 60 minutes
  7. customabout separating out the aqueous phase
  8. filtrationfilter the entire mixture
  9. washwash the solid with water

Sources & evidence

ORD record
ord-a206f54e5b5e4528999c135f3dc5d9d5
Source dataset
uspto-grants-2013_10
Patent number
US08552035B2

Reaction notes

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