O-Xylene → 4-Cyclopropyl-3-nitropyridine
Reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[CH:11]1(B(O)O)[CH2:13][CH2:12]1.C1(C)C(C)=CC=CC=1.C(=O)([O-])[O-].[K+].[K+]>CCCCCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OC(=O)C)C>[CH:11]1([C:2]2[CH:7]=[CH:6][N:5]=[CH:4][C:3]=2[N+:8]([O-:10])=[O:9])[CH2:13][CH2:12]1Participants
8
Reactant 4
Product 1
Reagents, catalysts & solvents 3
Conditions
- Temperature
- 130 °C
Procedure
4-Chloro-3-nitropyridine (100 mg, 0.630 mmol) and cyclopropyl boronic acid (10.0 mg, 0.091 mmol) were added to a solution of xylene (3 mL) previously purged with argon (10 minutes). The reaction mixture was purged with argon for a further 15 minutes, followed by the addition of potassium carbonate (174.35 mg, 1.26 mmol) and Pd(PPh3)4 (34.5 mg, 0.063 mmol). The resulting mixture was heated to reflux at 130° C. overnight. The reaction was monitored by TLC (30% ethylacetate in hexane). The reaction mixture was cooled and concentrated to afford the crude product. Purification by column chromatography on silica gel (15% ethyl acetate in hexane) afforded 110 mg of the product (100% yield). LCMS Purity: 99%, m/z=165 (M+1)
Workup
- custompreviously purged with argon (10 minutes)
- customThe reaction mixture was purged with argon for a further 15 minutes
- temperatureThe resulting mixture was heated
- temperatureThe reaction mixture was cooled
- concentrationconcentrated
- customto afford the crude product
- customPurification by column chromatography on silica gel (15% ethyl acetate in hexane)
Sources & evidence
- ORD record
- ord-09fbe57d94aa4f698b6bb7f10e4c5711
- Source dataset
- uspto-grants-2015_05
- Patent number
- US09029399B2
Reaction notes
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