Acetonitrile → HCID 70237051, Verbindung

To a solution of 1,1,1,3,3,3-hexamethyldisilazane (4.13 ml, 19.6 mmol) in THF (80 ml) was added dropwise, under argon atmosphere at −78° C., a 1.56M solution of n-butyllithium hexane solution (12.5 ml, 19.6 mmol). The mixture was stirred for 10 minutes, to which was added acetonitrile (0.94 ml, 17.9 mmol), and the mixture was stirred for further 15 minutes. To the mixture was added a solution of 6-methoxy-2,2-dimethyl-1-indanone (3.00 g, 16.3 mmol) in THF (10 ml), which was stirred for 15 minutes. To the reaction mixture was added water so that the temperature was gradually reverted to room temperature. The reaction mixture was subjected to extraction with ethyl acetate. The extract solution was washed with brine, which was dried over anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was dissolved in toluene (100 ml). To the solution was added 10-camphor sulfonic acid (0.5 g), and the mixture was heated for 1.5 hours under reflux. The reaction mixture was cooled, to which was added water. The mixture was subjected to extraction with ethyl acetate. The extract solution was washed with brine, which was dried over anhydrous magnesium sulfate, followed by distilling off the solvent under reduced pressure. The residue was subjected to a silica gel column chromatography (hexane/ethyl acetate, 97:3→9:1) to give 1.03 g (yield 30%) of (Z)-(6-methoxy-2,2-dimethylindan-1-ylidene)acetonitrile as an oily product.

1. stirringthe mixture was stirred for further 15 minutes
2. stirringwas stirred for 15 minutes
3. customwas gradually reverted to room temperature
4. extractionThe reaction mixture was subjected to extraction with ethyl acetate
5. washThe extract solution was washed with brine, which
6. dry with materialwas dried over anhydrous magnesium sulfate
7. distillationby distilling off the solvent under reduced pressure
8. dissolutionThe residue was dissolved in toluene (100 ml)
9. additionTo the solution was added 10-camphor sulfonic acid (0.5 g)
10. temperaturethe mixture was heated for 1.5 hours
11. temperatureunder reflux
12. temperatureThe reaction mixture was cooled, to which
13. additionwas added water
14. extractionThe mixture was subjected to extraction with ethyl acetate
15. washThe extract solution was washed with brine, which
16. dry with materialwas dried over anhydrous magnesium sulfate
17. distillationby distilling off the solvent under reduced pressure

ORD-Eintrag

ord-8ec23e3d66f6437790f45a37d6345d68

Quelldatensatz

uspto-grants-2001_05

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06235789B1