Acetone → HCID 89545285, compound

HRID 1750753Notes

Reaction equation

HRID 1750753 reaction equation
[Si:1]([C:8]1C(C)=[C:16]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=[CH:15]2)[C:9]=1[CH3:19])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].ClC1C(=O)C(C#N)=C(C#N)C(=[O:28])C=1Cl.S([O-])([O-])(=O)=S.[Na+].[Na+].C[C:42]([CH3:44])=[O:43]>>[Si:1]([C:8]1[C:44]([CH:42]=[O:43])=[C:16]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=[CH:15]2)[C:9]=1[CH:19]=[O:28])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 4

HCID 180AcetoneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 24477Sodium ThiosulfateHCID 10468384HCID 10468384, compound

Product 1

HCID 89545285HCID 89545285, compoundYield 89%

Procedure

90 mg of 40 (0.33 mmol) was dissolved in 5 ml of acetone at room temperature. To this solution was added 359 mg of DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (1.58 mmol) in one portion. The reaction mixture immediately turned color from blue to red as it was stirred in the dark for 1 hour. When all reactant was gone the reaction mixture was stirred with 15 ml of saturated sodium thiosulfate solution to remove unreacted DDQ for 2 min and then 15 ml of saturated sodium bicarbonate was added, and then it was stirred for 2 min to remove acidic DDQH2. The reaction mixture was then extracted with chloroform (5×40 ml). The combined bottom red organic phases were subsequently washed with 15 ml of saturated NaCl solution, dried over anhydrous MgSO4, filtered and evaporated. The red residue was then purified by column chromatography using 7:3 hexane:ethylacetate to provide 88.4 mg of bis-aldehyde 32 in 89% yield as red crystals. 1H NMR δ 10.59 (s, 2H), 10.12 (dd, 2H, J=10), 8.11 (tt, 1H, J=10), 7.94 (t, 1H, J=10), 1.05 (s, 9H), 0.61 (s, 6H); 13C NMR δ 190.28, 162.4, 144.9, 142.75, 140.94, 134.14, 132.73, 27.06, 17.99, 0.98; LRMS (LC/MS-ESI, MeOH) m/e 299 (MH+)

Workup

  1. customto remove unreacted DDQ for 2 min
  2. addition15 ml of saturated sodium bicarbonate was added
  3. stirringit was stirred for 2 min
  4. customto remove acidic DDQH2
  5. extractionThe reaction mixture was then extracted with chloroform (5×40 ml)
  6. washThe combined bottom red organic phases were subsequently washed with 15 ml of saturated NaCl solution
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationfiltered
  9. customevaporated
  10. customThe red residue was then purified by column chromatography

Sources & evidence

ORD record
ord-5dcf0a65d66e4675ba46b53b065cb422
Source dataset
uspto-grants-2015_10
Patent number
US09156862B2

Reaction notes

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