反应详情

A solution of 6.0 g. (42.5 mmole) of 1-cyanomethyl-1H-tetrazol-5-thiol and 10.0 g. (6.3 mmole) of tetramethylguanidinium azide in 90 ml. of dioxane was heated at the reflux temperature for 3 hours. After cooling, the reaction mixture was evaporated to dryness in vacuo and the residue dissolved in ethyl acetate:water, 1:1. The ethyl acetate layer was separated, and the pH of the aqueous layer was adjusted to pH 1.8 with 20% hydrochloric acid. The acidified aqueous layer was then extracted 3 times with 75 ml. portions of ethyl acetate, and the extracts were combined. The extract was then washed with 5% hydrochloric acid, with brine, was dried over sodium sulfate, and then evaporated in vacuo to dryness. The red oil obtained as a residue crystallized on seeding. The crystals were washed with ethyl acetate and with diethyl ether and were dried. There were obtained 3.7 g. of the bis-tetrazolmethyl thiol melting at about 173° C. to about 175° C. The filtrate from the first crop was evaporated to an oil and after seeding the oil, 0.3 g. of a second crop crystalline product was obtained. A third crop of 0.3 g. was obtained in the same manner. Total yield of product was 4.3 g. (55% yield).

1. temperatureAfter cooling
2. customthe reaction mixture was evaporated to dryness in vacuo
3. dissolutionthe residue dissolved in ethyl acetate
4. customThe ethyl acetate layer was separated
5. extractionThe acidified aqueous layer was then extracted 3 times with 75 ml
6. washThe extract was then washed with 5% hydrochloric acid, with brine
7. dry with materialwas dried over sodium sulfate
8. customevaporated in vacuo to dryness
9. customThe red oil obtained as a residue
10. customcrystallized on seeding
11. washThe crystals were washed with ethyl acetate and with diethyl ether
12. customwere dried
13. customThere were obtained 3.7 g
14. customThe filtrate from the first crop was evaporated to an oil
15. customof a second crop crystalline product was obtained
16. customwas obtained in the same manner