tert-Butyl isocyanate → HCID 68980364, compound

HRID 273542Notes

Reaction equation

HRID 273542 reaction equation
[C:1]1([CH3:19])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[C:17]([NH2:18])=[CH:16][C:10]2[N:11]=[C:12]([NH2:15])[N:13]=[N:14][C:9]=2[CH:8]=1.C[Si]([N-][Si](C)(C)C)(C)C.[K+].[C:30]([N:34]=[C:35]=[O:36])([CH3:33])([CH3:32])[CH3:31].C([O-])(O)=O.[Na+]>O1CCOCC1>[NH2:15][C:12]1[N:13]=[N:14][C:9]2[CH:8]=[C:7]([C:2]3[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=3[CH3:19])[C:17]([NH:18][C:35]([NH:34][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:36])=[CH:16][C:10]=2[N:11]=1

Participants

6

Reactant 4

HCID 62412tert-Butyl isocyanateHCID 516892Sodium BicarbonateHCID 3251421Potassium bis(trimethylsilyl)amideHCID 59837698HCID 59837698, compound2×

Product 1

HCID 68980364HCID 68980364, compoundYield 67%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 7-o-tolyl-benzo[1,2,4]triazine-3,6-diamine (compound 16 on scheme (CCLXIX)) (0.12 mmol, 30 mg) in 5 mL anhydrous 1,4-dioxane was added potassium bis(trimethylsilyl)amide (53 mg, 0.26 mmol) and the mixture was stirred at room temperature under argon for 1.5 h. To the red solution was added tert-butylisocyanate (28.5 μl, 0.36 mmol) and stirring was continued for 2 h at room temperature. The product was poured into saturated aqueous NaHCO3 solution (40 mL) and was extracted with EtOAc (100 mL). The combined organic phases were dried (Na2SO4) and the solvent was evaporated to give 1-(3-amino-7-o-tolyl-benzo[1,2,4]triazin-6-yl)-3-tert-butyl-urea (28 mg, 67%). The title product was prepared as a red solid (27.8 mg, 48%) from the above intermediate and 4-bromo-N-(2-pyrrolidin-1-yl-ethyl)-benzenesulfonamide following the above-described coupling procedure and was purified by reverse phase preparative HPLC. 1H NMR DMSO-d6: δ 1.37 (s, 9H), 1.87 (m, 2H); 2.01 (m, 2H), 2.16 (s, 3H), 3.04 (m, 4H), 3.24 (td, J=6.1 Hz, J=6.1 Hz, 2H), 3.56 (m, 2H), 7.21 (s, 1H), 7.33-7.40 (m, 4H), 7.50 (d, J=9.0 Hz, 2H), 7.75 (d, J=9.0 Hz, 2H), 7.88 (t, J=6.1 Hz, 1H), 7.99 (s, 1H), 8.34 (s, 1H), 8.83 (s, 1H), 9.53 (br s, 1H), 10.21 (s, 1H). MS (ESI+) m/z=603.

Workup

  1. stirringstirring
  2. waitwas continued for 2 h at room temperature
  3. extractionwas extracted with EtOAc (100 mL)
  4. dry with materialThe combined organic phases were dried (Na2SO4)
  5. customthe solvent was evaporated

Sources & evidence

ORD record
ord-65982a58ef9b46e3b9af88b03fe861c4
Source dataset
uspto-grants-2008_11
Patent number
US07456176B2

Reaction notes

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