Tertiary acetylenic alcohols

Table 5. Commercial Secondary and Tertiary Acetylenic Alcohols and Glycols...

Economic Aspects. A number of secondary and tertiary acetylenic alcohols and glycols are manufactured by Air Products and Chemicals Co. In 1990, U.S. bulk prices of ethyloctynol, methylbutynol, and tetramethyldecynediol were about 8.35/kg, 3.95/kg, and 8.00/kg, respectively. 

Later, the method of cleavage of the tertiary acetylenic alcohols in boiling benzene or toluene in the presence of NaOH or KOH was reported (88M253 2001UP1). 

The carbamates of tertiary acetylenic alcohols have also been made by reaction of these alcohols with sodium cyanate in tri-fluoroacetic acid.9 The yields by this procedure are significantly lower than those obtained by the present modification, which is essentially that described by Loev and Kormendy.5... 

The nonfluorinated tertiary acetylenic alcohol 2-methylbut-3-yn-2-ol (13) reacts explosively to give a mixture of 3-fluoro-3-methylbut-l-yne and 2-methylbut-l-en-3-yne.56... 

In an H2O/DMSO medium (1 2 by volume) tertiary acetylenic alcohols are formed from ketoximes and acetylene in yields of up to 50% (76ZOR1180), i.e., in this case the authors encountered an analog of the Favorsky reaction (cf. Section III.G). 

Toda, F., and Tanaka, K. (1981) ANew Optical Resolution Method of Tertiary Acetylenic Alcohol Utilizing Complexation with Brucine, Tetrahedron Lett., 22, 4669-4672. 

The acid catalyzed rearrangement of tertiary acetylenic alcohols, the Rupe reaction, is a viable procedure for the preparation of a,p-unsaturated carbonyl compounds. Under standard acidic conditions, however, the products can polymerize and various by-products can be produced. With solid acids these problems are minimized. The reaction of an acetylenic tertiary alcohol with Nafion-H gave the a,P-unsaturated ketone in good to very good yields (Eqns. 22.24—25). When this reaction was run using a vanadium pillared... 

Chemical/Pharmaceutical/Other Class Tertiary acetylenic alcohol... 

Brucine is recommended as a convenient and effective reagent for the resolution of tertiary acetylenic alcohols. The evidence available to date indicates that the acetylenic alcohol must have two aryl groups, or one aryl group and one bulky alkyl group, attached to the hydroxyl-bearing carbon atom. The X ray crystal structure analysis of one such brucine complex was also reported. 

Tertiary acetylenic alcohols can also be esterified by that method819 although they react too slowly for other methods to be successful. 

Tertiary acetylenic alcohols react with isopropenyl ethers in the presence of a small amount of acid to yield 2-oxoalkyl allenes 9... 

We found that some kinds of alcohols form channel-type inclusion compounds with alkaloids such as brucine (72) and sparteine (75), and that the alcohols are easily resolved utilizing inclusion formation. We also found that sparteine can be resolved by inclusion formation with an optically active tertiary acetylenic alcohol. 

This reaction was initially reported by Favorskii in 1905 and subsequently extended by Babayan in 1939. It is a base-promoted or -catalyzed ethynylation of aldehydes and ketones to produce secondary or tertiary acetylenic alcohols or glycols using anhydrous KOH or NaOH. Therefore, it is generally known as the Favorskii-Babayan reaction or Favorskii reaction. Although it has been proposed that this reaction might involve a reaction between acetylene and the adduct from the ketone and KOH or a coupling of potassium acetylide with the carbonyl compounds, the most recent experimental results indicate that potassium hydroxide and acetylene first form a complex, rather than potassium acetylide in liquid ammonia, which then reacts with carbonyl compounds to form the acetylenic alcohols, where ammonia functions as a co-catalyst. The experimental evidence includes... 

It is believed that a strong base such as KOH or potassium alkoxide will deprotonate the active hydrogen from the reactants, such as alcohols, thiols, amines, carboxylic acids, and phenols, to generate the nucleophiles that add to acetylene, as illustrated by the formation of vinyl ether from alcohol and acetylene. This can qualitatively explain the reactivity order among primary, secondary, and tertiary alcohols, without considering the steric hindrance. It is known that tertiary alcohol is less acidic than secondary and primary alcohol, therefore, less potassium f-butoxide will be formed than primary potassium alkoxide from KOH. ... 

Methylbutynyl alcohol is a tertiary acetylenic alcohol with an isoprenaid structure. 

NON-IONIC SURFACTANTS Polyoxyethylenated alkylphenols, alkylphenol ethoxylates Polyoxyethylenated straight- chain alcohols, alcohol ethoxylates Polyoxyethylenated polyoxypropylene glycols Polyoxyethylenated mercaptans Long-chain carboxylic acid esters Alkanolamine condensates, alkanolamides Tertiary acetylenic glycols Polyoxyethylenated silicones N-alkylpyrrolidones Alkylpolyglycosides... 

ABSTRACT. Novel optical resolutions of guest compounds by inclusion complex formation with optically active host compound are reviewed Tertiary acetylenic alcohols, cyanohydrins, and secondary alcohols were resolved by complexation with alkaloids such as brucine or sparteine. Cycloalkanones, 2,3 -epoxycyclohexanones, and some other neutral compounds were resolved by complex formation with optically active diacetylenic diol. Mutual optical resolution of bis-g-naphthol and sulfoxides by complex formation was also reviewed. 

Optical Resolution of Tertiary Acetylenic Alcohols by Complex Formation with Brucine... 

An optically active acetylenic alcohol is an useful starting material to prepare various chiral compounds, because it has two functional groups. However, the optical resolution of an acetylenic alcohol by the diastereomeric method for its phthalic acid half-ester is complicated and successful only in a few cases,1 Recently, the preparation of optically active secondary acetylenic alcohol by the enantioselective reduction of ethynyl ketone or by the enantioselective addition of lithium acetylide to aldehyde has been reported. However, these methods are not applicable to the preparation of optically active tertiary acetylenic alcohols. 

We found that some tertiary acetylenic alcohols form a 1 1 complex with brucine, and that the acetylenic alcohols v ere easily resolved by utilizing the complexation. As an example, the experimental detail of the resolution of 1,1-di-methyl-2-phenyl-3-pentyn-2-ol is described. A solution... 

---