Potassium t-amyloxide

The interaction of (10) with vinylmagnesiiim chloride yields, after hydrolysis of the ketal group, 46% of the 3a-vinyl-l7-ketone (11b) and 7% of the 3j5-vinyl-17-ketone (12b). Ethynylation of (10) with potassium acetylide in dimethylformamide or with acetylene and potassium t-amyloxide in t-amyl alcohol-ether gives only the 3a-ethynyl derivative (11c) in 63% and 74% yields, respectively. ... 

The direct reaction of androsta-l,4-diene-3,17-dione with acetylene in the presence of potassium t-amyloxide gives the 17a-ethynyl-17j -hydroxyandros-ta-l,4-dien-3-one in only 12% yield. 

Moore [1] prepared polystyrene having a Mn of 130,000 daltons with a PDI of 1.05 by initially drying the monomer and neutralizing impurities with n-butyllithium prior to polymerization. n-Butyl-lithium was also used with potassium t-amyloxide by Malanga [2] in preparing ultra-pure poly(a-methylstyrene). 

OL-Alkylation of ketones. Base-catalyzed alkylation of ketones is often unsatisfactory because of polyalkylation and/or formation of isomeric products, particularly in the case of cyclopentanone. A reexamination of this reaction with a variety of bases and solvents indicates that use of potassium t-amyloxide as base and DME as solvent can lead to satisfactory yields, although a large excess of the alkylating... 

Although ethisterone never attained greater medicinal importance, this compound provided the crucial hint, which led to the synthesis of norethister-one. Carl Djerassi (Fig. 6.16) at Syntex oxidised 19-nortestosterone with chromium trioxide to 19-norandrostene-3,17-dione. Treatment with triethyl orthoformate in presence of pyridinium chloride gave an enol ether, which was reacted with acetylene and potassium t-amyloxide, and could subsequently undergo acid hydrolysis to the desired product. [38]... 

Another initiator system for the preparation of high trans-1,4-polybutadiene is based on the complex formed from dibutyl-magnesium and potassium t-amyloxide (KOAm) in hydrocarbon solvent trans-1,4-Polybutadiene was prepared in variable yields (50-100%) with [KOAm]/[R2Mg] 1, [KOAm]/[Bu3MgK] = 1.5-2.3, and [KOAmJ/lRsMgNa] = 2.4-10. High trans-1,4-polybutadienes were also obtained with initiators... 

Potassium-Graphite, 122, 378, 476 Potassium 3-aminopropylamide, 378-379 Potassium f-amyloxide, 378 379 Potassium benzeneselenolate, 373 Potassium bis(trimethylsilyl)amide, 229 Potassium f-butoxide, 7, 380-381 Potassium f-butoxide-Benzophenone, 382 Potassium carbonate, 382-383 Potassium dichromate, 383 Potassium diisopropylamide-Lithium t-butoxide, 383-384... 

---