Nitrogen → HCID 25139185, compound

HRID 1669107Notes

Reaction equation

HRID 1669107 reaction equation
[Sn](CC)(CC)(CC)[CH2:2][CH3:3].N#N.[Si:12]([O:19][CH2:20][CH:21]1[CH2:35][C:34]2[C:23](=[CH:24][C:25]3[N+:30]([O-:31])=[N:29][C:28](I)=[N:27][C:26]=3[CH:33]=2)[CH2:22]1)([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13]>O1CCOCC1.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>[Si:12]([O:19][CH2:20][CH:21]1[CH2:35][C:34]2[C:23](=[CH:24][C:25]3[N+:30]([O-:31])=[N:29][C:28]([CH2:2][CH3:3])=[N:27][C:26]=3[CH:33]=2)[CH2:22]1)([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13]

Participants

6

Reactant 3

HCID 947NitrogenHCID 11704Tetraethyltin2×HCID 25139184HCID 25139184, compound

Product 1

HCID 25139185HCID 25139185, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 312751,4-DioxaneSolvent

Procedure

Et4Sn (1.47 mL, 7.5 mmol) and Pd(PPh3)4 (154 mg, 0.99 mmol) were added to a N2-purged, stirred solution of iodide 133 (2.27 g, 4.97 mmol) in dry dioxane (30 mL) at 20° C. and the reaction mixture was stirred at reflux temperature under N2. After 5 h more Et4Sn (1.5 mL, 7.5 mmol) and Pd(PPh3)4 (150 mg, 0.98 mmol) were added and the mixture stirred at reflux temperature for 5 h. The mixture was cooled and partitioned between EtOAc and water. The organic layer was separated, dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-5%) of EtOAc/pet. ether, to give 1-oxide 135 (1.57 g, 88%) as a yellow solid: mp (EtOAc/pet. ether) 63-65° C.; 1H NMR δ 8.23 (s, 1H, H-9), 7.72 (s, 1H, H-5), 3.59-3.66 (m, 2H, CH2O), 3.14-3.24 (m, 2H, CH2), 2.92-3.06 (m, 4H, H-6, H-8), 2.72-2.83 (m, 1H, H-7), 1.43 (t, J=7.5 Hz, 3H, CH3), 0.87 [s, 9H, SiC(CH3)3], 0.04 [s, 6H, Si(CH3)2]. Anal. calcd for C19H29N3O2Si: C, 63.5; H, 8.1; N, 11.7. Found: C, 63.3; H, 8.2; N, 11.4%.

Workup

  1. custompurged
  2. temperatureat reflux temperature under N2
  3. stirringthe mixture stirred
  4. temperatureat reflux temperature for 5 h
  5. temperatureThe mixture was cooled
  6. custompartitioned between EtOAc and water
  7. customThe organic layer was separated
  8. customdried
  9. customthe solvent evaporated
  10. customThe residue was purified by chromatography
  11. washeluting with a gradient (0-5%) of EtOAc/pet. ether

Sources & evidence

ORD record
ord-282dfe4493eb4b05916b379f8b622762
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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