Hydrochloric Acid → Ethyl-4-(3-isopropyl-2-methoxyphenyl)-4-methyl-2-oxo-pentanoate

HRID 1869418Notes

Reaction equation

HRID 1869418 reaction equation
[Sn](Cl)(Cl)(Cl)Cl.[CH:6]([C:9]1[C:10]([O:19][CH3:20])=[C:11]([C:15](O)([CH3:17])[CH3:16])[CH:12]=[CH:13][CH:14]=1)([CH3:8])[CH3:7].[CH2:21]([O:23][C:24](=[O:32])[C:25]([O:27][Si](C)(C)C)=[CH2:26])[CH3:22].C(=O)([O-])[O-].[Na+].[Na+].Cl>ClCCl.O>[CH2:21]([O:23][C:24](=[O:32])[C:25](=[O:26])[CH2:27][C:15]([C:11]1[CH:12]=[CH:13][CH:14]=[C:9]([CH:6]([CH3:8])[CH3:7])[C:10]=1[O:19][CH3:20])([CH3:17])[CH3:16])[CH3:22]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 10340Sodium Carbonate2×HCID 24287Tin tetrachlorideHCID 111168062-Trimethylsilanyloxy-acrylic acid ethyl esterHCID 179891992-(3-Isopropyl-2-methoxyphenyl)propan-2-ol

Product 1

HCID 17989132Ethyl-4-(3-isopropyl-2-methoxyphenyl)-4-methyl-2-oxo-pentanoateYield 49.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-72 °C

Procedure

15.3 ml (129.71 mmol) of tin tetrachloride is added in drops to a mixture, cooled to −72° C., that consists of 28.16 g (135.19 mmol) of 2-(3-isopropyl-2-methoxyphenyl)-propan-2-ol and 50.9 g (270.38 mmol) of 2-trimethylsilanyloxy-acrylic acid ethyl ester in 420 ml of dichloromethane. In this case, the temperature increased to −65° C. After 30 minutes of stirring in this temperature interval, the reaction mixture is poured into a mixture that consists of saturated sodium carbonate solution and dichloromethane (in each case 250 ml). After 30 minutes of stirring at room temperature, the batch is transferred into a spherical separating funnel and a 1:1 mixture that consists of water and dichloromethane is added until a phase separation takes place. After the organic phase is shaken with sodium carbonate, 1N HCl and water, it is dried with sodium sulfate. According to the conventional procedure, the residue is chromatographed on silica gel (mobile solvent ethyl acetate/hexane). 20.44 g (48.35%) of the desired compound is obtained.

Workup

  1. temperatureIn this case, the temperature increased to −65° C
  2. additionthe reaction mixture is poured into a mixture that
  3. stirringAfter 30 minutes of stirring at room temperature
  4. customthe batch is transferred into a spherical separating funnel
  5. additionis added until a phase separation
  6. dry with materialis dried with sodium sulfate
  7. customthe residue is chromatographed on silica gel (mobile solvent ethyl acetate/hexane)

Sources & evidence

ORD record
ord-680579338f704ae9b6487b84472b6fd3
Source dataset
uspto-grants-2009_12
Patent number
US07638515B2

Reaction notes

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