Dichloromethane → 4-Amino-5-chloro-2-methylbenzonitrile

HRID 2401464Notes

Reaction equation

HRID 2401464 reaction equation
[Cl:1][C:2]1[C:3]([N+:11]([O-])=O)=[CH:4][C:5]([CH3:10])=[C:6]([CH:9]=1)[C:7]#[N:8].O.O.Cl[Sn]Cl.C(Cl)Cl.[OH-].[Na+]>C(O)C.O>[NH2:11][C:3]1[C:2]([Cl:1])=[CH:9][C:6]([C:7]#[N:8])=[C:5]([CH3:10])[CH:4]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 61436Stannous chloride dihydrateHCID 102417995-Chloro-2-methyl-4-nitrobenzonitrile

Product 1

HCID 194223994-Amino-5-chloro-2-methylbenzonitrileYield 81%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

To 5-chloro-2-methyl-4-nitrobenzonitrile (192 mg, 1 mmol) in ethanol (6 mL) and water (0.6 mL) was added SnCl2.2H2O (903 mg, 4 mmol) and the mixture was heated to 65° C. for 5 h. DCM (10 mL) and 2M NaOH(aq) (10 mL) were added, and the mixture was passed through a hydrophobic frit. The solvent was removed in vacuo to give 4-amino-5-chloro-2-methylbenzonitrile (131 mg, 81%) as an off-white solid. LCMS (10 cm_ESCI_Formic_MeCN): [M+H]+=163 at 3.37 min. 1H NMR (400 MHz, CDCl3): δ 6.89 (s, 1H), 6.52 (s, 1H), 4.21 (br s, 2H), 3.84 (s, 3H), 2.38 (s, 3H).

Workup

  1. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-ae4dce7ffcf1454ea3550e111e7485c5
Source dataset
uspto-grants-2014_08
Patent number
US08796296B2

Reaction notes

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