Toluene → HCID 69017910, compound

HRID 1821004Notes

Reaction equation

HRID 1821004 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([C:13]([NH:15][NH:16][C:17](=O)[C:18]2[CH:23]=[CH:22][C:21]([Br:24])=[CH:20][C:19]=2[CH3:25])=O)[CH:6]=[CH:7][C:8]=1[O:9][CH:10]([CH3:12])[CH3:11])#[N:2].C1(C)C=CC=CC=1.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:43])=CC=1>N1C=CC=CC=1>[C:1]([C:3]1[CH:4]=[C:5]([C:13]2[S:43][C:17]([C:18]3[CH:23]=[CH:22][C:21]([Br:24])=[CH:20][C:19]=3[CH3:25])=[N:16][N:15]=2)[CH:6]=[CH:7][C:8]=1[O:9][CH:10]([CH3:12])[CH3:11])#[N:2]

Participants

5

Reactant 3

HCID 1140TolueneHCID 87949Lawesson's reagentHCID 68853800HCID 68853800, compound

Product 1

HCID 69017910HCID 69017910, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
125 °C

Procedure

In an oven-dried high-pressure tube, 240 mg (0.58 mmol) of N′-(3-cyano-4-isopropyloxyphenylcarbonyl)-4-bromo-2-methylbenzhydrazide (from Step A) was combined with 40 mL of anhydrous toluene, 300 mg of Lawesson's Reagent (0.74 mmol), and 100 μL of pyridine. The tube was sealed with a plastic/teflon cap and the reaction mixture was heated to 125° C. for 2 h. The resulting mixture was cooled down to rt, solvents were removed under reduced pressure and residual solids were dissolved in 10 mL of pyridine. To this mixture, 0.5 g of phosphorous pentasulfide was added and the mixture heated to 110° C. The reaction mixture was combined with ice-water and extracted 2×100 mL of EtOAc. Combined organic layers were dried over sodium sulfate, and solvents removed under reduced pressure. Pure title compound was isolated by flash chromatography using Biotage 40S (eluant: hexanes/EtOAc-4/1) to yield 239 mg: 1H NMR (500 MHZ, CDCl3) δ 1.49 (d, J=6.5, 6H), 2.65 (s, 3H), 4.79 (sep, J=6.5, 1H), 7.13 (dd, J=9.0, 2.0, 1H), 7.50 (dd, J=9.0, 2.0, 1H), 7.56 (d, J=2.0, 1H), 7.63 (d, J=8.0, 1H), 8.17 (d, J=2.0, 1H), 8.24 (dd, J=8.0, 2.0, 1H).

Workup

  1. customcap
  2. temperatureThe resulting mixture was cooled down to rt
  3. customsolvents were removed under reduced pressure and residual solids
  4. dissolutionwere dissolved in 10 mL of pyridine
  5. additionTo this mixture, 0.5 g of phosphorous pentasulfide was added
  6. temperaturethe mixture heated to 110° C
  7. extractionextracted 2×100 mL of EtOAc
  8. dry with materialCombined organic layers were dried over sodium sulfate, and solvents
  9. customremoved under reduced pressure

Sources & evidence

ORD record
ord-586c9abb4530454791a2a4dc25c8a8fb
Source dataset
uspto-grants-2009_10
Patent number
US07605171B2

Reaction notes

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