3-Chloroaniline → HCID 58313936, compound

HRID 2036917Notes

Reaction equation

HRID 2036917 reaction equation
Cl[C:2]1[CH:7]=[C:6]([NH:8]C(=O)OC(C)(C)C)[N:5]2[N:16]=[CH:17][C:18]([CH:19]=[O:20])=[C:4]2[N:3]=1.O1CCOCC1.[Cl:27][C:28]1[CH:29]=[C:30]([CH:32]=[CH:33][CH:34]=1)[NH2:31].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>O>[NH2:8][C:6]1[N:5]2[N:16]=[CH:17][C:18]([CH:19]=[O:20])=[C:4]2[N:3]=[C:2]([NH:31][C:30]2[CH:32]=[CH:33][CH:34]=[C:28]([Cl:27])[CH:29]=2)[CH:7]=1

Participants

6

Reactant 4

HCID 79323-ChloroanilineHCID 312751,4-DioxaneHCID 521998p-Toluenesulfonic acid monohydrateHCID 58314515HCID 58314515, compound

Product 1

HCID 58313936HCID 58313936, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
95 °C

Procedure

Tert-butyl 5-chloro-3-formylpyrazolo[1,5-a]pyrimidin-7-ylcarbamate (1.1 g, 3.8 mmol) was added to 1,4-dioxane (15 mL) along with 3-chloroaniline (2.4 mL, 22.6 mmol) and p-toluenes ulfonic acid monohydrate (73 mg, 0.4 mmol). The reaction was heated at 95° C. for 12 hours then cooled to room temperature, diluted with water and filtered. Analysis of the recovered solid by LCMS showed product mass (M+1=288), as well as, product with chloro aniline imine mass (M+1=397). To completely convert this mixture to the desired product, the solid was dissolved in 6 mL of MeOH/conc. HCl solution (1:1) and heated at 60° C. for 1.5 hours. The reaction was quenched by slow addition to ice cold 6N NaOH. The mixture was diluted with water then the solid was collected by filtration. The solid was washed several more times with water then dried under vacuum overnight. The product, 7-amino-5-(3-chlorophenylamino)pyrazolo[1,5-a]pyrimidine-3-carbaldehyde, was collected as orange-red solid in 38% yield. LCMS (M+1=288)

Workup

  1. temperaturethen cooled to room temperature
  2. filtrationfiltered
  3. dissolutionthe solid was dissolved in 6 mL of MeOH/conc
  4. temperatureHCl solution (1:1) and heated at 60° C. for 1.5 hours
  5. customThe reaction was quenched by slow addition to ice cold 6N NaOH
  6. additionThe mixture was diluted with water
  7. filtrationthe solid was collected by filtration
  8. washThe solid was washed several more times with water
  9. customthen dried under vacuum overnight
  10. customThe product, 7-amino-5-(3-chlorophenylamino)pyrazolo[1,5-a]pyrimidine-3-carbaldehyde, was collected as orange-red solid in 38% yield

Sources & evidence

ORD record
ord-3fdd36c52edc4d36945acd374c475a29
Source dataset
uspto-grants-2013_11
Patent number
US08575177B2

Reaction notes

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