1H-1,2,4-Triazole → HCID 90411586, compound

HRID 1754615Notes

Reaction equation

HRID 1754615 reaction equation
[C:1]([Si:5]([CH3:29])([CH3:28])[O:6][CH2:7][C@H:8]([CH2:19][N:20]1[CH:25]=[CH:24][C:23](=O)[NH:22][C:21]1=[O:27])[C@H:9]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[CH3:10])([CH3:4])([CH3:3])[CH3:2].[NH:30]1[CH:34]=[N:33][CH:32]=[N:31]1>N1C=CC=CC=1>[C:1]([Si:5]([CH3:29])([CH3:28])[O:6][CH2:7][C@H:8]([CH2:19][N:20]1[CH:25]=[CH:24][C:23]([N:30]2[CH:34]=[N:33][CH:32]=[N:31]2)=[N:22][C:21]1=[O:27])[C@H:9]([O:11][Si:12]([C:15]([CH3:17])([CH3:16])[CH3:18])([CH3:13])[CH3:14])[CH3:10])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 92571H-1,2,4-TriazoleHCID 90411588HCID 90411588, compound

Product 1

HCID 90411586HCID 90411586, compoundYield 66.6%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a cold (ice/water bath) solution of 42 (2.7 g, 6.08 mmol) and 1,2,4-triazole (5.8 g, 84 mmol) in 37 ml of anhydrous pyridine was added dropwise over 5 min 4.2 g (17.11 mmol) of 4-chlorophenyldichlorophosphate (via syringe). The reaction was allowed to warm up and kept at room temperature for 3 days. The reaction was concentrated and partitioned between ethyl acetate (150 ml) and water (150 ml). The organic phase was washed with 10% citric acid, saturated NaCl and dried over Na2SO4. The crude material (brown oil) obtained after concentration of the extract was chromatographed on silica eluting with a gradient of ethyl acetate (50-66%) in hexane. Concentration of the pure product fractions afforded 2.0 g (66%) of 43 as a light tan solid. 1H NMR (DMSO-d6): δ 9.40 (s, 1H), 8.38 (s, 1H), 8.37 (d, J=7 Hz, 1H), 6.90 (d, J=7 Hz, 1H), 4.05 (m, 2H), 3.83 (m, 1H), 3.60 (d, J=6.3 Hz, 2H), 2.22 (m, 1H), 1.15 (d, J=6 Hz, 3H), 0.81 (s, 9H), 0.79 (s, 9H), 0.01 (s, 6H), −0.04 (s, 6H).

Workup

  1. temperatureto warm up
  2. concentrationThe reaction was concentrated
  3. custompartitioned between ethyl acetate (150 ml) and water (150 ml)
  4. washThe organic phase was washed with 10% citric acid, saturated NaCl
  5. dry with materialdried over Na2SO4
  6. customThe crude material (brown oil) obtained after concentration of the extract
  7. customwas chromatographed on silica eluting with a gradient of ethyl acetate (50-66%) in hexane

Sources & evidence

ORD record
ord-d074b1ddb6a44ff2a2e90d779c12742b
Source dataset
uspto-grants-2015_10
Patent number
US09169256B2

Reaction notes

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