反应详情

A stirred solution of 1,4-diiodobenzene (4.21 g, 12.7 mmol) in dry tetrahydrofuran (20 ml) was cooled under nitrogen by a dry ice-acetone bath. n-Butyllithium (8.5 ml of a 1.55M solution in hexane, 12.7 mmol) was added. After 5 minutes, a solution of 1-[4-(2-dimethylaminoethoxy)phenyl]-2-phenyl-1-butanone (2.0 g, 6.4 mmol) was added and the mixture allowed to warm to room temperature. After 15 hours, the mixture was poured into water (60 ml) and extracted with ether (2×50 ml). The ether extracts were concentrated and the residual oil dissolved in ethanol (20 ml). Concentrated hydrochloric acid (10 ml) was added and the mixture heated under reflux for 4 hours, then cooled, and poured into water (100 ml). The solution was basified with aqueous sodium hydroxide (3M) and extracted with ether (100 ml). The ether extract was dried with sodium sulphate, concentrated, and the residue applied to a column of silica (Merck 15111, 80 g). Elution with 1:1 light petroleum (b.p. 40°-60° C.-ether containing an increasing proportion of triethylamine gave after a forerun of tamoxifen which was discarded, at 5% triethylamine, a mixture of 4-iodotamoxifen and its Z isomer:-

1. waitAfter 15 hours
2. extractionextracted with ether (2×50 ml)
3. concentrationThe ether extracts were concentrated
4. dissolutionthe residual oil dissolved in ethanol (20 ml)
5. additionConcentrated hydrochloric acid (10 ml) was added
6. temperaturethe mixture heated
7. temperatureunder reflux for 4 hours
8. temperaturecooled
9. additionpoured into water (100 ml)
10. extractionextracted with ether (100 ml)
11. extractionThe ether extract
12. dry with materialwas dried with sodium sulphate
13. concentrationconcentrated
14. washElution with 1:1 light petroleum (b.p. 40°-60° C.-ether containing an increasing proportion of triethylamine