Toluene → HCID 9797046, compound

HRID 726866Notes

Reaction equation

HRID 726866 reaction equation
Cl[C:2]1[C:3](=[O:14])[C:4]([C:12]#N)=[C:5]([C:10]#N)[C:6](=O)[C:7]=1Cl.C[Si]([N:19]([Si](C)(C)C)[C:20](=O)C(F)(F)F)(C)C.F[C:31](F)(F)S(O)(=O)=O.C[O:39][C:40](=O)[CH2:41][C:42](C)=O.[C:46]1([CH3:52])[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1>CC(C)=O.C(Cl)Cl>[CH3:20][N:19]1[C:40](=[O:39])[CH2:41][CH2:42][C@@:49]2([CH3:31])[C:48]1=[CH:47][C@H:46]([CH3:52])[C@@H:51]1[C@@H:50]2[CH2:12][CH2:4][C@@:5]2([CH3:10])[C@H:6]1[CH2:7][CH2:2][C@@H:3]2[OH:14]

Participants

8

Reactant 5

HCID 1140TolueneHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 7757Methyl acetoacetateHCID 62406Trifluoromethanesulfonic acidHCID 65279N,N-Bis(trimethylsilyl)trifluoroacetamide

Product 1

HCID 9797046HCID 9797046, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 6344DichloromethaneSolvent

Procedure

To a dry toluene solution of the ester 52 (361 mg, 1.0 mmole) under N2 was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (266 mg, 1.13 mmole), bis(trimethylsilyl)trifluoroacetamide (1.07 ml, 4 mmole) and trifluoromethanesulfonic acid (7 ml, 0.077 mmole) and the clear red solution stirred at room temperature for 24 hours. Methylacetoacetate (11 ml, 0.1 mmole) was added and after stirring for 1 hour at room temperature the solution was refluxed for 24 hours. The reaction mix was concentrated in vacuo to a small volume and the residue dissolved in methylene chloride and extracted with an aqueous solution of 1.5% sodium carbonate plus 0.5% sodium sulfite, 5% sodium bicarbonate, dried over magnesium sulfate and concentrated in vacuo to give 328 mg crude product. Purificaton by flash chromatography on silica gel in 9:1 methylene chloride:acetone gave 229 mg of the unsaturated ester 69.

Workup

  1. stirringafter stirring for 1 hour at room temperature the solution
  2. temperaturewas refluxed for 24 hours
  3. additionThe reaction mix
  4. concentrationwas concentrated in vacuo to a small volume
  5. dissolutionthe residue dissolved in methylene chloride
  6. extractionextracted with an aqueous solution of 1.5% sodium carbonate plus 0.5% sodium sulfite, 5% sodium bicarbonate
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customto give 328 mg crude product

Sources & evidence

ORD record
ord-cb60ebfb7c444d6cacf57b7065cf8620
Source dataset
uspto-grants-1998_01
Patent number
US05710275

Reaction notes

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