Iodine → HCID 12884304, compound

To a stirred solution of 400 ml. of 0.5 M bis-(3-methyl-2-butyl)borane in glyme, prepared from sodium borohydride, 2-methyl-2-butene, and boronitrifluoride etherate as in Example 123, is added 63.7 (0.30 moles) of 4-methyl-4-trimethylsilyloxy-1-octyne (Example 600) at -10°. The solution is stirred at ambient temperature for 2.5 hours, cooled to -10°, and treated during 30 minutes with 158 g. (2.1 moles) of solid trimethylamine oxide with cooling. The mixture is stirred at ambient temperature for 2 hours and then poured into a stirred, ice-cold solution of 15% aqueous sodium hydroxide; the stirred mixture is treated immediately with a solution of 426 g. (1.68 moles) of iodine in 1100 ml. of tetrahydrofuran. After 4 hours the mixture is extracted with ether. The extract is washed successively with water, aqueous sodium thiosulfate, and brine and dried over magnesium sulfate. The extract is concentrated, and the residue is subjected to chromatography on silica gel with hexane to provide an oil, p.m.r. (CDCl3): δ 1.18 (singlet, 4-CH3 group).

1. temperaturecooled to -10°
2. additiontreated during 30 minutes with 158 g
3. stirringThe mixture is stirred at ambient temperature for 2 hours
4. additionthe stirred mixture is treated immediately with a solution of 426 g
5. extractionAfter 4 hours the mixture is extracted with ether
6. washThe extract is washed successively with water, aqueous sodium thiosulfate, and brine
7. dry with materialdried over magnesium sulfate
8. concentrationThe extract is concentrated
9. customto provide an oil, p.m.r

ORD record

ord-d6726def0846435686c32e7470b8e8d0

Source dataset

uspto-grants-1979_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04179451