반응 #66818

반응 방정식

sodium chloride

sulfolane

phosphoryl chloride

tert-Butyl 3-cyano-4-hydroxy-5,8-dihydrothieno[2,3-b:5,4-c′]dipyridine-7(6H)-carboxylate

→

title compound

수율 51.0%

tert-Butyl 4-chloro-3-cyano-5,8-dihydrothieno[2,3-b:5,4-c′]dipyridine-7(6H)-carboxylate

수율 51.0%

용매

Triethylamine

triethylamine

반응 조건

후처리

1. 1
   온도with cooling
2. 2
   온도The mixture was cooled to rt
3. 3
   온도whilst cooling with an ice-bath
4. 4
   추출extracted with ethyl acetate
5. 5
   세척The organic layer was washed with water
6. 6
   건조dried over sodium sulfate
7. 7
   기타the solvent was removed in vacuo
8. 8
   workup.ADDITIONToluene was added
9. 9
   세척the mixture was washed with water
10. 10
    건조The organic layer was again dried over sodium sulfate
11. 11
    기타the solvent was removed in vacuo
12. 12
    기타After crystallization
13. 13
    기타the product was triturated with water
14. 14
    여과collected by suction filtration
15. 15
    기타dried

실험 절차

To sulfolane (10 mL) was added phosphoryl chloride (1.39 g, 9.05 mmol) at rt. Triethylamine (0.92 g, 9.05 mmol) was added dropwise with cooling. tert-Butyl 3-cyano-4-hydroxy-5,8-dihydrothieno[2,3-b:5,4-c′]dipyridine-7(6H)-carboxylate from Example 52A (1.00 g, 3.02 mol) was added, and the mixture was heated to 70° C. for 1.5 h. The mixture was cooled to rt, and triethylamine (2.3 mL) was added. A semi-saturated aqueous sodium chloride solution (10 L) was added whilst cooling with an ice-bath. The mixture was stirred at rt for 30 min and then extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and the solvent was removed in vacuo. Toluene was added, and the mixture was washed with water. The organic layer was again dried over sodium sulfate, and the solvent was removed in vacuo. After crystallization, the product was triturated with water, collected by suction filtration and dried to yield 543 mg (51%) of the title compound.

출처