1,2-Dibromoethane → HCID 9989356、化合物

温度

-78 °C

A solution of lithium di-isopropylamide, prepared by addition of 8.33 mL (20 mmol) of 2.4 M n-butyllithium in hexane to a 0° C. solution of 3.40 g (20 mmol) of di-isopropylamine in 50 mL of dry THF, is cooled to -78° C. and to it is added dropwise over 30 min a solution of 2.60 g (20 mmol) of methyl t-butylacetate in 50 mL of dry THF. The mixture is stirred at -78° C. for 1 h, then 18.8 g (100 mmol) of 1,2-dibromoethane and 10 mL of HMPA is added all at once. The mixture is stirred for 4 h at -78° C., then allowed to warm slowly to room temperature. Water (100 mL) is carefully added, and the mixture is then extracted with three 100-mL portions of hexane. The combined organic extract is washed with water (100 mL) then with satd. NaCl (50 mL) and dried over Na2SO4. The solvent is removed and the product, methyl 2-t-butyl-4-bromobutyrate, is purified by vacuum distillation. The ester is hydrolyzed by refluxing for 2 h with 25 mL (50 mmol) of 2 N NaOH, the water is removed in Vacuo, and the residue is suspended in 25 ml of di-n-butylphthalate in a 200 mL round-bottomed flask with an efficient stirrer, connected to a distillation apparatus, and heated slowly under vacuum (0.5 torr) in an oil bath to 180° C. with vigorous stirring. The distillate is collected and the reaction is terminated when di-n-butylphthalate begins to reflux in the still head. The product, α-t-butyl-γ-butyrolactone, is then purified by vacuum distillation.

1. stirringThe mixture is stirred for 4 h at -78° C.
2. temperatureto warm slowly to room temperature
3. extractionthe mixture is then extracted with three 100-mL portions of hexane
4. extractionThe combined organic extract
5. washis washed with water (100 mL)
6. dry with materialNaCl (50 mL) and dried over Na2SO4
7. customThe solvent is removed
8. distillationthe product, methyl 2-t-butyl-4-bromobutyrate, is purified by vacuum distillation
9. customthe water is removed in Vacuo
10. customthe residue is suspended in 25 ml of di-n-butylphthalate in a 200 mL round-bottomed flask with an efficient stirrer
11. temperatureheated slowly under vacuum (0.5 torr) in an oil bath to 180° C. with vigorous stirring
12. distillationThe distillate is collected
13. customthe reaction is terminated when di-n-butylphthalate
14. temperatureto reflux in the still head
15. distillationThe product, α-t-butyl-γ-butyrolactone, is then purified by vacuum distillation

ORDレコード

ord-e6f9a57eebe24892bbc4ea4f77a7bfa6

出典データセット

uspto-grants-1987_11

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US04707491