Citric Acid → HCID 66747182, compound

HRID 2410166Notes

Reaction equation

HRID 2410166 reaction equation
[CH:1]1([OH:7])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[H-].[Na+].[N+:10]([C:13]1[CH:20]=[CH:19][CH:18]=[C:17]([N+]([O-])=O)[C:14]=1[C:15]#[N:16])([O-:12])=[O:11].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1COCC1>[CH:1]1([O:7][C:17]2[CH:18]=[CH:19][CH:20]=[C:13]([N+:10]([O-:12])=[O:11])[C:14]=2[C:15]#[N:16])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 311Citric Acid2×HCID 7966CyclohexanolHCID 24758Sodium hydrideHCID 520718Dinitrobenzonitrile

Product 1

HCID 66747182HCID 66747182, compoundYield 84.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of cyclohexanol (46.8 grams, 0.467 mol) in anhydrous THF (1 L) was added sodium hydride (20.3 grams, 0.508 mol) at −40° C. under nitrogen. The reaction mixture was allowed to warm slowly to room temperature and stir for another 1 hour. It was then cooled down to −55° C. and 2,6-dinitrobenzonitrile (78.4 g, 0.406 mol) was added. The reaction was stirred at room temperature overnight, then cooled down to −20° C., and citric acid (23.4 grams, 0.122 mol) was added. The mixture was then poured into ice water (5 L) which contained citric acid (7.8 g, 0.041 mol), stirred for 15 minutes, and the precipitated product was collected by filtration. The crude product was recrystallized from isopropanol (750 mL, heated to boiling, then cooled down to 0° C.), filtered, washed with isopropanol (300 mL), then air dried to give 84.4 g yellow solid. The solid was dissolved in dichloromethane (169 mL) and filtered through a plug of alumina to give the title compound as a pale yellow solid (83.2 g, 83.2%). 1H NMR (400 MHz, DMSO-d6) δ 1.4 (m, 4H), 1.6 (m, 2H), 1.7 (m, 2H), 1.9 (m, 2H), 4.75 (m, 1H), 7.79 (dd, J=2.0, 8.0 Hz, 1H), 7.84-7.91 (m, 2H).

Workup

  1. temperatureIt was then cooled down to −55° C.
  2. stirringThe reaction was stirred at room temperature overnight
  3. temperaturecooled down to −20° C.
  4. stirringstirred for 15 minutes
  5. filtrationthe precipitated product was collected by filtration
  6. customThe crude product was recrystallized from isopropanol (750 mL
  7. temperatureheated
  8. temperaturecooled down to 0° C.),
  9. filtrationfiltered
  10. washwashed with isopropanol (300 mL)
  11. customair dried

Sources & evidence

ORD record
ord-d420ff2db61c4a599f56727203b01abb
Source dataset
uspto-grants-2014_08
Patent number
US08815956B2

Reaction notes

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