4-Amino-3-nitrobenzonitrile → HCID 21272872, compound

HRID 1463158Notes

Reaction equation

HRID 1463158 reaction equation
B#B.[NH2:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]#[N:11])=[CH:6][C:5]=1[N+:12]([O-:14])=[O:13]>C1COCC1>[NH2:3][C:4]1[CH:9]=[CH:8][C:7]([CH2:10][NH2:11])=[CH:6][C:5]=1[N+:12]([O-:14])=[O:13]

Participants

4

Reactant 2

HCID 5959014-Amino-3-nitrobenzonitrileHCID 6328200Diboron

Product 1

HCID 21272872HCID 21272872, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

One equivalent of diborane in THF was added to a solution of 1-amino-2-nitro-4-cyanobenzene (500 mg.) in anhydrous THF (20 ml.) under nitrogen at 10°. After 2 hours excess diborane was destroyed by addition of MeOH and the reaction mixture was evaporated to dryness. The residue was dissolved in methanol and methanolic HCl added. The solvent was evaporated, the residue was basified and the product extracted with ether (x3). The combined extracts were dried and evaporated to give impure 1-amino-2-nitro-4-aminomethylbenzene. To a solution of this diamine (350 mg.) in dry dioxan (10 ml.) was added "Boc-On" (Aldrich Chemical Co.) (258 mg.). The reaction mixture was stirred at ambient temperature for 18 hours, concentrated, and the residue purified by chromatography on silica using CH2Cl2 /ether as eluant. There was thus obtained 1-amino-2-nitro-4-(t-butoxycarbonylaminomethyl)benzene. This product was hydrogenated at ambient pressure in THF/ethanol solution using 10% w/w palladium-on-carbon catalyst to give 1,2-diamino-4-(t-butoxycarbonylaminomethyl)benzene which was used without further purification.

Workup

  1. customAfter 2 hours excess diborane was destroyed by addition of MeOH
  2. customthe reaction mixture was evaporated to dryness
  3. dissolutionThe residue was dissolved in methanol
  4. additionmethanolic HCl added
  5. customThe solvent was evaporated
  6. extractionthe product extracted with ether (x3)
  7. customThe combined extracts were dried
  8. customevaporated

Sources & evidence

ORD record
ord-339cbd9a52ae4c6ba024c805562adb13
Source dataset
uspto-grants-1984_07
Patent number
US04463173

Reaction notes

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