3,5-Dinitrobenzoyl chloride → HCID 22618865, compound

HRID 842300Notes

Reaction equation

HRID 842300 reaction equation
Cl.[NH2:2][C:3]([CH2:25][CH3:26])([CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][CH2:15][CH2:16][CH2:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:10][CH:9]=1)[CH2:4][OH:5].[C:27](=[O:30])([O-])O.[K+].[N+:32]([C:35]1[CH:36]=[C:37]([CH:41]=[C:42]([N+:44]([O-:46])=[O:45])[CH:43]=1)[C:38](Cl)=[O:39])([O-:34])=[O:33]>C(OCC)(=O)C.O>[N+:32]([C:35]1[CH:36]=[C:37]([CH:41]=[C:42]([N+:44]([O-:46])=[O:45])[CH:43]=1)[C:38]([O:5][CH2:4][C:3]([CH2:25][CH3:26])([NH:2][C:27](=[O:30])[C:37]1[CH:36]=[C:35]([N+:32]([O-:34])=[O:33])[CH:43]=[C:42]([N+:44]([O-:46])=[O:45])[CH:41]=1)[CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][CH2:15][CH2:16][CH2:17][CH2:18][C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)=[CH:10][CH:9]=1)=[O:39])([O-:34])=[O:33]

Participants

6

Reactant 3

HCID 74323,5-Dinitrobenzoyl chlorideHCID 516893Potassium BicarbonateHCID 22618723HCID 22618723, compound

Product 1

HCID 22618865HCID 22618865, compoundYield 50.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-amino-2-ethyl-4-(4-(4-phenylbutyloxy)phenyl)butanol hydrochloride (3.0 g) in ethyl acetate (100 ml) were added a solution of potassium hydrogencarbonate (1.6 g) in water (50 ml) and 3,5-dinitrobenzoyl chloride (3.6 g). The mixture was stirred vigorously at room temperature for 2.5 hours and extracted with ethyl acetate. The ethyl acetate layer was washed with an aqueous sodium hydrogencarbonate solution and a saturated brine, dried over anhydrous sodium sulfate and the solvent was distilled away under reduced pressure. The yellow residue obtained was subjected to the same procedure as mentioned above, and the resulting residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=2:1) to give the subject compound (1.5 g) and 2-ethyl-2-(3,5-dinitrobenzamido)-4-(4-(4-phenylbutyloxy)phenyl)butyl 3,5-dinitrobenzoate (2.9 g) as a by-product. To a solution of the by-product (2.7 g) in a mixed solvent of methanol (50 ml) and tetrahydrofuran (30 ml) was added a solution of lithium hydroxide monohydrate (0.15 g) in water (10 ml) and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate, the ethyl acetate layer was washed with water and a saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure and the residue obtained was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=1:1) to give the subject compound (2.4 g). The combined subject compound was recrystallized from ethyl acetate and hexane to give the subject compound (2.6 g) as pure white crystals, melting at 121-122° C.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe ethyl acetate layer was washed with an aqueous sodium hydrogencarbonate solution
  3. dry with materiala saturated brine, dried over anhydrous sodium sulfate
  4. distillationthe solvent was distilled away under reduced pressure
  5. customThe yellow residue obtained
  6. customwas purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-679497401d7a4bffb505f03f745091af
Source dataset
uspto-grants-2002_04
Patent number
US06372800B1

Reaction notes

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