Triethylamine → 2-(2'-Nitro-4'-methylsulfonylbenzoyl)-4-propargyl-1,3-cyclohexanedione

HRID 358543Notes

Reaction equation

HRID 358543 reaction equation
[CH2:1]([CH:4]1[CH2:9][CH2:8][C:7](=[O:10])[CH2:6][C:5]1=[O:11])[C:2]#[CH:3].[CH3:12][S:13]([C:16]1[CH:24]=[CH:23][C:19]([C:20](Cl)=[O:21])=[C:18]([N+:25]([O-:27])=[O:26])[CH:17]=1)(=[O:15])=[O:14].C(N(CC)CC)C.[C-]#N.[K+].C1OCCOCCOCCOCCOCCOC1>C(#N)C>[N+:25]([C:18]1[CH:17]=[C:16]([S:13]([CH3:12])(=[O:15])=[O:14])[CH:24]=[CH:23][C:19]=1[C:20]([CH:6]1[C:5](=[O:11])[CH:4]([CH2:1][C:2]#[CH:3])[CH2:9][CH2:8][C:7]1=[O:10])=[O:21])([O-:27])=[O:26]

Participants

7

Reactant 5

HCID 8471TriethylamineHCID 9032Potassium CyanideHCID 2855718-Crown-6HCID 114805364-(Prop-2-yn-1-yl)cyclohexane-1,3-dioneHCID 148001864-(Methanesulfonyl)-2-nitrobenzoyl chloride

Product 1

HCID 200662982-(2'-Nitro-4'-methylsulfonylbenzoyl)-4-propargyl-1,3-cyclohexanedioneYield 44.9%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

4Propargyl-1,3-cyclohexanedione (3.75 g, 25 mmol) and 4-methanesulfonyl-2-nitrobenzoyl chloride (6.06 g, 23 mmol) were dissolved in acetonitrile (100 mL) at 0° C. Triethylamine (9.6 mL, 69 mmol) was added. The mixture was then stirred for 3 hours. To the mixture was then added potassium cyanide (5.0 g) and 18-crown-6 ether (0.5 g) in one portion. The mixture was stirred for 3 days. After dilution with ether, the solution was washed with 1N HC1 and extracted with 5% K2CO3. The basic extract was acidified with concentrated HC1 and extracted with diethyl ether. The ether extract was washed with brine, dried over MgSO4, and concentrated under vacuum, yielding 3.9 g of the desired product, an orange solid, m.p. 65-70° C. The structure was confirmed by nuclear magnetic spectroscopy, infrared spectroscopy, and mass spectroscopy.

Workup

  1. stirringThe mixture was stirred for 3 days
  2. washAfter dilution with ether, the solution was washed with 1N HC1
  3. extractionextracted with 5% K2CO3
  4. extractionThe basic extract
  5. extractionextracted with diethyl ether
  6. extractionThe ether extract
  7. washwas washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-920785c218cf4fe790f3acaf11cbf2de
Source dataset
uspto-grants-1991_03
Patent number
US04997473

Reaction notes

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