Chlorosulfonic acid → 6-Allyl-5-ethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine

HRID 1887186Notes

Reaction equation

HRID 1887186 reaction equation
ClS(O)(=O)=O.[NH2:6][C:7]1[N:11]=[CH:10][NH:9][N:8]=1.[C:12]([CH:16]([CH2:19][CH:20]=[CH2:21])[C:17]#[N:18])(=O)[CH2:13][CH3:14]>O.CC1C=CC=CC=1C>[CH2:19]([C:16]1[C:12]([CH2:13][CH3:14])=[N:6][C:7]2[N:8]([N:9]=[CH:10][N:11]=2)[C:17]=1[NH2:18])[CH:20]=[CH2:21]

Participants

6

Reactant 3

HCID 24638Chlorosulfonic acidHCID 866412382-Propionylpent-4-enenitrileHCID 178418311HCID 178418311, compound

Product 1

HCID 685931496-Allyl-5-ethyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamineYield 84%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 7237O-XyleneSolvent

Conditions

Temperature
130 °C

Procedure

In a 20 l jacketed vessel fitted with reflux condenser and water separator, 14650 g of o-xylene were initially charged, and 411 g of chlorosulfonic acid were added. 2074 g of 3-amino-1,2,4-triazole and 3690 g of a solution of 2-propionylpent-4-enenitrile (87.4% in o-xylene) were added, and the mixture was heated to reflux. The mixture was stirred under reflux for 14 hours, and the water of reaction formed was removed via a phase separator. Once no more water separated off, the mixture was cooled to 130° C. and 634 g of triethylamine were added. On further cooling, the product precipitated in the form of colorless crystals. At a temperature of 100° C., 2350 g of isopropanol were added. The mixture was cooled further to 20° C., and the solid formed was separated off. The filtercake was washed with 1500 ml of a 1:1 mixture of isopropanol and water and then dried under reduced pressure. This gives 4057 g of a colorless powder. Melting point: 258° C. (decomposition), 1H-NMR: 1.35 (t, 3H); 2.88 (q, 2H); 3.45 (d, 2H); 5.09 (d, 2H); 5.20 (d, 2H); 5.6 (s, broad, 2H); 5.8-6.0 (m, 1H); 8.30 (s, 1H). Yield: 84.0%.

Workup

  1. customfitted
  2. temperaturewith reflux condenser
  3. temperaturethe mixture was heated to reflux
  4. temperatureunder reflux for 14 hours
  5. customformed
  6. customwas removed via a phase separator
  7. customOnce no more water separated off
  8. addition634 g of triethylamine were added
  9. customOn further cooling, the product precipitated in the form of colorless crystals
  10. additionAt a temperature of 100° C., 2350 g of isopropanol were added
  11. temperatureThe mixture was cooled further to 20° C.
  12. customthe solid formed
  13. customwas separated off
  14. washThe filtercake was washed with 1500 ml of a 1:1 mixture of isopropanol and water
  15. customdried under reduced pressure

Sources & evidence

ORD record
ord-8680dd27871e472fb61847f9c47fca91
Source dataset
uspto-grants-2013_08
Patent number
US08501748B2

Reaction notes

Loading…