Benzaldehyde → Diethyl 2-benzylpropanedioate

HRID 983770Notes

Reaction equation

HRID 983770 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].C([Mg]Cl)(C)C.[CH:17](=O)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.Cl>C(O[Ti](OC(C)C)(OC(C)C)OC(C)C)(C)C.CCOCC>[CH2:17]([CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 178418918HCID 178418918, compound

Product 1

HCID 69090Diethyl 2-benzylpropanedioate

Reagents, catalysts & solvents 2

HCID 178460666HCID 178460666, compoundCatalystHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-40 °C

Procedure

To an ether solution (7.5 ml) containing tetraisopropoxytitanium (0.284 g, 1.0 mmol) and diethyl malonate (0.145 g, 0.5 mmol) was added dropwise at −50° C. 1.53 ml of 1.31M ether solution containing isopropylmagnesium chloride (2 mmol). Upon stirring at −40° C. for 1 hour, the reaction liquid turned from yellow into brown. The reaction liquid was stirred together with benzaldehyde (0.080 g, 0.75 mmol) at 0° C. for 1 hour. With 1N hydrochloric acid added, the reaction liquid was stirred at room temperature for 15 minutes. After treatment and purification as in Referential Example 1, there was obtained diethyl benzylmalonate in deallylated form (yields: 97%).

Workup

  1. additionwas added dropwise at −50° C
  2. customthe reaction liquid
  3. customThe reaction liquid
  4. customthe reaction liquid
  5. stirringwas stirred at room temperature for 15 minutes
  6. customAfter treatment and purification as in Referential Example 1

Sources & evidence

ORD record
ord-6aec2b690c5d4574bfff4efad2c15e7e
Source dataset
uspto-grants-2005_03
Patent number
US06867161B1

Reaction notes

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