Carbon Dioxide → HCID 276227, compound

HRID 1889232Notes

Reaction equation

HRID 1889232 reaction equation
[CH:1](=[N:8][NH:9][CH:10]([CH3:12])[CH3:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.C(=O)=O.C(O[CH:24]=[C:25]([C:28]#[N:29])[C:26]#[N:27])C>C1COCC1>[CH:1](=[N:8][N:9]([CH:24]=[C:25]([C:28]#[N:29])[C:26]#[N:27])[CH:10]([CH3:12])[CH3:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 280Carbon Dioxide2×HCID 671522-(Ethoxymethylene)propanedinitrileHCID 70307532HCID 70307532, compoundHCID 178418339Butyllithium

Product 1

HCID 276227HCID 276227, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of Intermediate 1-benzylidene-2-isopropylhydrazine (12.9 g, 0.079 mol) in 200 ml anhydrous THF was cooled in a dry ice/acetone bath under an argon atmosphere. To this solution was added n-butyllithium (1.6 M in hexanes, 66 ml, 0.106 mol) via syringe. Following completion of the addition, the mixture was stirred at dry-ice temperature for an additional 5 minutes. A solution of (2-(ethoxymethylene)malononitrile (13.6 g, 0.11 mol) in THF (30 ml) was added. The mixture was stirred at dry-ice temperature for 0.5 h, and then was quenched with saturated aqueous sodium bicarbonate solution. The quenched reaction mixture was allowed to warm to rt and was extracted with ethyl acetate. The organic layers were combined, dried over sodium sulfate, filtered, and concentrated. The residue was suspended in ethanol with sonication. The resulting precipitate was collected via filtration and washed with a small amount of cold ethanol to obtain 2-((2-benzylidene-1-isopropylhydrazinyl)methylene)malononitrile as a yellow solid. The mother liquor was concentrated and the residue purified by silica gel column chromatography (1:1 hexanes/ethyl acetate eluant) to afford additional 2-((2-benzylidene-1-isopropylhydrazinyl)methylene)malononitrile. MS m/z 239.2 (M+1).

Workup

  1. additioncompletion of the addition
  2. customwas quenched with saturated aqueous sodium bicarbonate solution
  3. customThe quenched reaction mixture
  4. extractionwas extracted with ethyl acetate
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was suspended in ethanol with sonication
  9. filtrationThe resulting precipitate was collected via filtration
  10. washwashed with a small amount of cold ethanol

Sources & evidence

ORD record
ord-3d96db3276a341bb9d2c19e889617a57
Source dataset
uspto-grants-2013_08
Patent number
US08501758B2

Reaction notes

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