Lithium Hydroxide → 2,2-Bis(4-nitrobenzyl)malonic acid

HRID 921586Notes

Reaction equation

HRID 921586 reaction equation
CC1(C)[O:7][C:6](=[O:8])[C:5]([CH2:19][C:20]2[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][CH:21]=2)([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][CH:11]=2)[C:4](=[O:29])[O:3]1.C1COCC1.[Li+].[OH-]>O>[N+:16]([C:13]1[CH:12]=[CH:11][C:10]([CH2:9][C:5]([CH2:19][C:20]2[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][CH:21]=2)([C:4]([OH:29])=[O:3])[C:6]([OH:8])=[O:7])=[CH:15][CH:14]=1)([O-:18])=[O:17]

Participants

5

Reactant 3

HCID 3939Lithium HydroxideHCID 8028TetrahydrofuranHCID 46194582,2-Dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione

Product 1

HCID 229285922,2-Bis(4-nitrobenzyl)malonic acidYield 87.2%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

An adaptation of the procedure described by Tiefenbacher and Rebek (2012) was followed. To a suspension of 5.33 g (12.9 mmol) of 2,2-dimethyl-5,5-di(4-nitrobenzyl)-1,3-dioxane-4,6-dione in 60 mL of a 9:1 mixture of THF to water was added 1.11 g (46.3 mmol) LiOH. This suspension was stirred for ˜17 h. After stirring, 100 mL of water was added to the suspension. The aqueous solution was washed twice with 50 mL of diethyl ether. The aqueous solution was then acidified to pH=1. The product was extracted with ethyl acetate. The ethyl acetate solution was washed once with 100 ml of water and once with 100 mL of brine. The ethyl acetate solution was dried with MgSO4 and the solvent was removed in vacuo to yield 4.21 g (87%) of the desired material. IR, 1HNMR, 13CNMR in addition to TLC were used to confirm identity of the product.

Workup

  1. stirringAfter stirring
  2. washThe aqueous solution was washed twice with 50 mL of diethyl ether
  3. extractionThe product was extracted with ethyl acetate
  4. washThe ethyl acetate solution was washed once with 100 ml of water and once with 100 mL of brine
  5. dry with materialThe ethyl acetate solution was dried with MgSO4
  6. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-3ac3855f421a4ab2badeabd480991837
Source dataset
uspto-grants-2016_03
Patent number
US09274395B2

Reaction notes

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