5-chloro-1-methyl-4-nitro-1H-pyrazole → HCID 58465025, compound

HRID 1185314Notes

Reaction equation

HRID 1185314 reaction equation
Cl[C:2]1[N:6]([CH3:7])[N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[CH3:11][N:12]1[CH2:17][CH:16]=[C:15](B2OC(C)(C)C(C)(C)O2)[CH2:14][CH2:13]1.C([O-])([O-])=O.[Na+].[Na+].CC([O-])=O.[K+]>CC#N.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:11][N:12]1[CH2:13][CH:14]=[C:15]([C:2]2[N:6]([CH3:7])[N:5]=[CH:4][C:3]=2[N+:8]([O-:10])=[O:9])[CH2:16][CH2:17]1

Participants

6

Reactant 3

HCID 123448365-chloro-1-methyl-4-nitro-1H-pyrazoleHCID 207733711-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridineHCID 86658407HCID 86658407, compound

Product 1

HCID 58465025HCID 58465025, compoundYield 16%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst2×HCID 6342AcetonitrileSolvent

Conditions

Temperature
130 °C

Procedure

5-Chloro-1-methyl-4-nitro-1H-pyrazole (0.2 g, 1.24 mmol), 1-methyl-1,2,3,6 tetrahydropyridine-4-boronic acid pinacol ester (0.553 g, 2.48 mmol) and Pd(dppf)2Cl2 (0.02 g, 0.025 mmol) were suspended in degassed MeCN (5 mL). Aqueous Na2CO3/KOAc solution (1:1, 1.1 M, 1.5 mL) was added and the mixture was heated at 130° C. in a microwave for 40 min. A further portion of Pd(dppf)2Cl2 (0.1 g, 0.12 mmol) was added and the mixture was heated at 130° C. for a further 90 min. The solvents were removed under reduced pressure and the crude residue dissolved in EtOAc and water. The mixture was extracted with EtOAc and the combined organic layers passed through a phase separator cartridge. The solvent was removed under reduced pressure and the crude product was purified via silica gel column chromatography (0-10% MeOH/DCM) to give 1-methyl-4-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,2,3,6-tetrahydropyridine as a brown oil (44 mg, 16%). 1H NMR (400 MHz, CDCl3) δ 8.08 (s, 1H), 5.89-5.86 (m, 1H), 3.82 (s, 3H), 3.19 (q, J=3.0 Hz, 2H), 2.74 (q, J=5.5 Hz, 2H), 2.47-2.39 (m, 5H)

Workup

  1. temperaturethe mixture was heated at 130° C. for a further 90 min
  2. customThe solvents were removed under reduced pressure
  3. dissolutionthe crude residue dissolved in EtOAc
  4. extractionThe mixture was extracted with EtOAc
  5. customThe solvent was removed under reduced pressure
  6. customthe crude product was purified via silica gel column chromatography (0-10% MeOH/DCM)

Sources & evidence

ORD record
ord-176c2ffa2e8e4d828f8c1d9bf625a8cd
Source dataset
uspto-grants-2014_03
Patent number
US08669361B2

Reaction notes

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