Ethyl 2-methylacetoacetate → HCID 86587764, compound

HRID 2086145Notes

Reaction equation

HRID 2086145 reaction equation
[NH2:1][C:2]1[CH:18]=[C:17]([CH3:19])[C:5]([O:6][C:7]2[CH:12]=[CH:11][C:10]([OH:13])=[C:9]([CH:14]([CH3:16])[CH3:15])[CH:8]=2)=[C:4]([CH3:20])[CH:3]=1.[N:21]([O-])=O.[Na+].[CH3:25][CH2:26][O:27][C:28]([CH:30]([C:32](C)=O)C)=[O:29]>C(O)C.Cl.O.[OH-].[Na+]>[CH2:26]([O:27][C:28](=[O:29])[C:30](=[N:21][NH:1][C:2]1[CH:3]=[C:4]([CH3:20])[C:5]([O:6][C:7]2[CH:12]=[CH:11][C:10]([OH:13])=[C:9]([CH:14]([CH3:16])[CH3:15])[CH:8]=2)=[C:17]([CH3:19])[CH:18]=1)[CH3:32])[CH3:25]

Participants

8

Reactant 3

HCID 701Ethyl 2-methylacetoacetateHCID 121141794-(4-Amino-2,6-dimethyl-phenoxy)-2-isopropyl-phenolHCID 23668193Sodium Nitrite

Product 1

HCID 86587764HCID 86587764, compoundYield 100.4%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolvent2×HCID 702EthanolSolvent2×HCID 962WaterSolvent2×HCID 14798Sodium HydroxideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4-(4-amino-2,6-dimethyl-phenoxy)-2-isopropyl-phenol (136 mg, 0.50 mmol) in a mixture of ethanol (2 mL) and hydrochloric acid (12M, 0.17 mL) at 0° C. was added slowly a solution of sodium nitrite (45 mg, 0.65 mmol) in water (0.5 mL). After stirring at 0° C. for 30 minutes, the diazonium solution was added dropwise into a solution of ethyl-2-methyl acetoacetate (87 mg, 0.60 mmol) in ethanol (1 mL) and 1N sodium hydroxide (2.26 mL) at 0° C. The resulting mixture was warmed to room temperature, stirred for 1 hour, then diluted with water (10 mL) and 1M hydrochloric acid (1 mL), and extracted with ethyl acetate (15 mL). The organic layer was separated, washed with 1M hydrochloric acid (15 mL), brine (15 mL), dried (Na2SO4), filtered, and concentrated to give the title compound (193 mg) which was used in the next step without further purification. MS (APCI−) Calc: 384.2, Found: 383.3 (M−1).

Workup

  1. temperatureThe resulting mixture was warmed to room temperature
  2. stirringstirred for 1 hour
  3. extractionextracted with ethyl acetate (15 mL)
  4. customThe organic layer was separated
  5. washwashed with 1M hydrochloric acid (15 mL), brine (15 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-06502293dbf7413fa07c766fa75fec97
Source dataset
uspto-grants-2004_04
Patent number
US06723744B2

Reaction notes

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