Hydrochloric Acid → HCID 68599037, compound

HRID 1952276Notes

Reaction equation

HRID 1952276 reaction equation
[OH:1][C:2]1[C:15](=[O:16])[C:14]2[C:5](=[CH:6][CH:7]=[C:8]3[C:13]=2[CH2:12][CH2:11][CH2:10][CH2:9]3)[C:4](=[O:17])[CH:3]=1.[H-].[Li+].[H][H].[CH2:22](Br)[CH:23]=[C:24]([CH3:26])[CH3:25].[Li+].[I-].Cl>CS(C)=O.CCOC(C)=O.O>[CH2:22]([C:3]1[C:4](=[O:17])[C:5]2[C:14]([C:15](=[O:16])[C:2]=1[O:1][CH2:3][CH:4]=[C:5]([CH3:14])[CH3:6])=[C:13]1[C:8]([CH2:9][CH2:10][CH2:11][CH2:12]1)=[CH:7][CH:6]=2)[CH:23]=[C:24]([CH3:26])[CH3:25]

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 62714Lithium hydrideHCID 66321Lithium iodideHCID 700922-Butene, 1-bromo-3-methyl-HCID 178418361HCID 178418361, compoundHCID 178516605HCID 178516605, compound

Product 1

HCID 68599037HCID 68599037, compoundYield 27%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
45 °C

Procedure

3-Hydroxy-5,6,7,8-tetrahydro-1,4-phenanthrenequinone (8.4 g, 37 mM) was dissolved in 70 ml of DMSO, and 560 g (75 mM) of LiH was gradually added thereto. The reaction solution was stirred, and after confirming no further production of hydrogen, was additionally stirred for another 30 min. Then, 12.0 g (80 mM) of prenyl bromide (1-bromo-3-methyl-2-butene) and 3.35 g (0.025 M) of LiI were gradually added thereto. The reaction solution was heated to 45° C. and then stirred vigorously for 12 hours at that temperature. The reaction solution was cooled below 10° C., and 100 ml of cold water was first added. Thereafter, 1N HCl was gradually added to maintain the resulting solution at an acidic pH>3. 200 ml of EtOAc was added to the reaction mixture which was then shaken vigorously thereafter, an organic layer was separated. The organic layer was washed with 100 ml of 5% NaHCO3, and was concentrated. The resulting concentrates purified by chromatography on silica gel to give 1.81 g (4.9 mM) of 2-Prenyl-3-prenyloxy-5,6,7,8-tetrahydro-1,4-phenanthrenequinone. The resulting was mixed with 5 ml of sulfuric acid, and the mixture was vigorously stirred at room temperature for 10 min and 20 g of ice was added thereto to complete the reaction. 60 ml of CH2Cl2 was added to the reaction materials which were then shaken vigorously. Thereafter, a CH2Cl2 layer was separated and washed with 5% NaHCO3. An aqueous layer was extracted once again using 10 ml of CH2Cl2, washed with 5% NaHCO3 and combined with the previously extracted organic layer. The organic layer was concentrated MgSO4 and the resulting concentrates purified by chromatography on silica gel to give 0.83 g (2.8 mM) of Compound 6.

Workup

  1. stirringwas additionally stirred for another 30 min
  2. stirringstirred vigorously for 12 hours at that temperature
  3. temperatureThe reaction solution was cooled below 10° C.
  4. temperatureto maintain the resulting solution at an acidic pH>3
  5. stirringwas then shaken vigorously
  6. customan organic layer was separated
  7. washThe organic layer was washed with 100 ml of 5% NaHCO3
  8. concentrationwas concentrated
  9. customThe resulting concentrates purified by chromatography on silica gel

Sources & evidence

ORD record
ord-fe105d6a0bf74dfd963a30c7272cb364
Source dataset
uspto-grants-2013_03
Patent number
US08404869B2

Reaction notes

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