Hydrochloric Acid → HCID 19871659, compound

HRID 329803Notes

Reaction equation

HRID 329803 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[Cl:7][CH2:8][C:9](=[O:15])[CH2:10][C:11]([O:13][CH3:14])=[O:12].Cl[CH2:17][C:18](=[O:20])[CH3:19].Cl>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(#N)C>[Cl:7][CH2:8][C:9](=[O:15])[CH:10]([CH2:17][C:18]([CH3:19])=[O:20])[C:11]([O:13][CH3:14])=[O:12]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6571ChloroacetoneHCID 10340Sodium CarbonateHCID 36240Methyl 4-chloroacetoacetate

Product 1

HCID 19871659HCID 19871659, compoundYield 15.6%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6342AcetonitrileSolvent2×

Procedure

127.2 g (1.2 mol) of sodium carbonate and 4.6 g (0.02 mol) of benzyltriethylammonium chloride are suspended in 800 ml of acetonitrile. While stirring there is added dropwise thereto within 8 hours a solution of 150.5 g (1 mol) of methyl 4-chloroacetoacetate and 138.8 g (1.5 mol) of chloroacetone in 200 ml of acetonitrile. The mixture is stirred at 20°-25° C. for a further 15 hours. The reaction mixture is poured into 750 ml of 2N HCl (pH value=1) and extracted three times with 300 ml of ether. The combined organic phases are dried over magnesium sulphate and concentrated on a rotary evaporator. The residue is treated with 200 ml of ether, the precipitated 2,5-bimethoxycarbonyl-1,4-cyclohexanedione is filtered off under suction and the filtrate is again concentrated. The crude product is column chromatographed on silica gel with ether/hexane 1:1 and gives 32.28 g (15.6%) of methyl 4-chloro-2-acetonylacetoacetate.

Workup

  1. additionis added dropwise
  2. stirringThe mixture is stirred at 20°-25° C. for a further 15 hours
  3. extractionextracted three times with 300 ml of ether
  4. dry with materialThe combined organic phases are dried over magnesium sulphate
  5. concentrationconcentrated on a rotary evaporator
  6. additionThe residue is treated with 200 ml of ether
  7. filtrationthe precipitated 2,5-bimethoxycarbonyl-1,4-cyclohexanedione is filtered off under suction
  8. concentrationthe filtrate is again concentrated
  9. customchromatographed on silica gel with ether/hexane 1:1

Sources & evidence

ORD record
ord-f65039864f5143679cb9657a02b345f9
Source dataset
uspto-grants-1990_01
Patent number
US04892966

Reaction notes

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