反应详情

A mixture of 13.9 g (0.14 mole) of phosgene and 17.3 g (0.125 mole) of potassium carbonate in 140 mL of methylene chloride was stirred under nitrogen for 30 min then cooled in an ice water bath while 46.5 g (0.125 mole) of 3-(2-chloro-6-methylphenoxy)-1-(diphenylmethyl)azetidine in 140 mL of methylene chloride was added dropwise. After stirring for 16 h the excess phosgene was destroyed by adding small pieces of ice. Water was added to dissolve the inorganic material and the methylene chloride portion was separated, dried (filtered through Whatman PS paper) and concentrated in vacuo, 65.8 g. The oily residue was triturated with 300 mL of 30/60 pet ether and then with 300 mL of hexanes, both at ambient temperature. The remaining yellow residue was triturated with boiling hexanes and the hot solution decanted (4×200 mL). Upon cooling an orange oil separated which was removed from the hexanes solution by decanting. After decanting again, the hexanes solution was cooled in an ice bath and decanted to remove all traces of the impure orange oil. The volume of hexanes was reduced to 75 mL by heating under a stream of nitrogen. Upon cooling, crystalline product was obtained in 2 fractions (10.8 g and 5.5 g). Rework of the filtrate and the ambient temperature filtrates (300 mL of pet ether and 300 mL of hexanes) yielded an additional 6 g of product for a total yield 22.3 g crude (68.6%), mp 67°-69° . A sample was recrystallized for analysis from hexanes, mp 70°-71.5° C.

1. additionwas added dropwise
2. customwas destroyed
3. additionby adding small pieces of ice
4. additionWater was added
5. dissolutionto dissolve the inorganic material
6. customthe methylene chloride portion was separated
7. customdried
8. filtration(filtered through Whatman PS paper)
9. concentrationconcentrated in vacuo, 65.8 g
10. customThe oily residue was triturated with 300 mL of 30/60 pet ether
11. customat ambient temperature
12. customThe remaining yellow residue was triturated with boiling hexanes
13. customthe hot solution decanted (4×200 mL)
14. temperatureUpon cooling an orange oil
15. customseparated which
16. customwas removed from the hexanes solution
17. customby decanting
18. customAfter decanting again
19. temperaturethe hexanes solution was cooled in an ice bath
20. customdecanted
21. customto remove all traces of the impure orange oil
22. temperatureby heating under a stream of nitrogen
23. temperatureUpon cooling
24. customcrystalline product was obtained in 2 fractions (10.8 g and 5.5 g)