4-[(4,5-dihydro-2-thiazolyl)amino]tetrahydro-3,5-bis(phenylmethylene)-2H-thiopyran-4-ol → 2,3,8,9-Tetrahydro-5-phenyl-9-(phenylmethylene)-5H,6H-thiazolo[3,2-a]thiopyrano[4,3-d]pyrimidine

HRID 65663Notes

Reaction equation

HRID 65663 reaction equation
[S:1]1[CH2:5][CH2:4][N:3]=[C:2]1[NH:6][C:7]1(O)[C:12](=[CH:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH2:11][S:10][CH2:9][C:8]1=[CH:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1(C)C=CC=CC=1.Cl[Ti](Cl)(Cl)Cl>[C:21]1([CH:20]2[N:3]3[CH2:4][CH2:5][S:1][C:2]3=[N:6][C:7]3[C:12](=[CH:13][C:14]4[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=4)[CH2:11][S:10][CH2:9][C:8]2=3)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

4

Reactant 1

HCID 543093604-[(4,5-dihydro-2-thiazolyl)amino]tetrahydro-3,5-bis(phenylmethylene)-2H-thiopyran-4-ol

Product 1

HCID 217866722,3,8,9-Tetrahydro-5-phenyl-9-(phenylmethylene)-5H,6H-thiazolo[3,2-a]thiopyrano[4,3-d]pyrimidineYield 79%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 1140TolueneSolvent2×

Procedure

A slurry of the 4-[(4,5-dihydro-2-thiazolyl)amino]tetrahydro-3,5-bis(phenylmethylene)-2H-thiopyran-4-ol (2.0 g, 5.1 mmole) from part A in 20 ml dry toluene under nitrogen at room temperature is treated with 12 ml of a solution of TiCl4 in toluene (1.29 g, TiCl4 in 25 ml). The resulting mixture is heated at reflux temperature for 2 hours. Upon cooling, the solid mass is pulverized and collected by filtration. The solids are partitioned between CHCl3 and aqueous NaHCO3. The aqueous layer is extracted with additional CHCl3. The extracts are washed (H2O), combined, dried (CaCl2) and concentrated on a steam bath; a volume of 75-100 ml is maintained by periodic addition of MeOH. When precipitation commences, the flask is cooled to room temperature. The product is collected, washed (MeOH) and dried in vacuo (80°) for several hours to give 1.5 g (79%) of product, m.p. 195°-196° d.

Workup

  1. temperatureThe resulting mixture is heated
  2. temperatureat reflux temperature for 2 hours
  3. temperatureUpon cooling
  4. filtrationcollected by filtration
  5. customThe solids are partitioned between CHCl3 and aqueous NaHCO3
  6. extractionThe aqueous layer is extracted with additional CHCl3
  7. washThe extracts are washed (H2O)
  8. dry with materialdried (CaCl2)
  9. concentrationconcentrated on a steam bath
  10. temperaturea volume of 75-100 ml is maintained by periodic addition of MeOH
  11. customWhen precipitation commences
  12. customThe product is collected
  13. washwashed (MeOH)
  14. customdried in vacuo (80°) for several hours

Sources & evidence

ORD record
ord-203c6c4139cf449cb72873cbbb921676
Source dataset
uspto-grants-1978_12
Patent number
US04128647

Reaction notes

Loading…