Nitrogen → 2-Chloro-N-(3-nitrophenyl)pyridine-4-amine

HRID 1402480Notes

Reaction equation

N#N.[Cl:3][C:4]1[CH:9]=[C:8](I)[CH:7]=[CH:6][N:5]=1.[N+:11]([C:14]1[CH:15]=[C:16]([CH:18]=[CH:19][CH:20]=1)[NH2:17])([O-:13])=[O:12].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:3][C:4]1[CH:9]=[C:8]([NH:17][C:16]2[CH:18]=[CH:19][CH:20]=[C:14]([N+:11]([O-:13])=[O:12])[CH:15]=2)[CH:7]=[CH:6][N:5]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To a degassed (15 min, N2) suspension of 2-chloro-4-iodopyridine (3.0 g, 12.53 mmol), 3-nitroaniline (1.82 g, 13.18 mmol), BINAP (0.39 g, 0.626 mmol) and Cs2CO3 (8.16 g, 25.04 mmol) in toluene (72 mL) was added Pd(OAc)2 (0.084 g, 0.374 mmol). The reaction tube was sealed and the mixture stirred at 90° C. for 18 h. The mixture was cooled to rt and filtered, washing with EtOAc. The orange/yellow solid collected was washed with CH2Cl2 until all the product washed through into the filtrate. The filtrate was concentrated to afford 2-Chloro-N-(3-nitrophenyl)pyridine-4-amine as a bright yellow solid. Additional product was collected from the solid collected upon concentration of the previous filtrate, after washing with CH2Cl2. No further purification. Total amount of product collected was 2.85 g (91% yield).

Workup

customTo a degassed
customThe reaction tube was sealed
temperatureThe mixture was cooled to rt
filtrationfiltered
washwashing with EtOAc
customThe orange/yellow solid collected
washwas washed with CH2Cl2 until all the product
washwashed through into the filtrate
concentrationThe filtrate was concentrated

Sources & evidence

ORD record: ord-e41336eb5668465ebb2a9179796fef04
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08906944B2

Reaction notes

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