Alcohols, primary with potassium hydroxide

Terminally unsaturated fluonnated alkenoic acids can be obtained from poly-fluorocycloalkenes by reaction with potassium hydroxide m rert-butyl alcohol [24] (equation 26) The use of a tertiary alcohol is critical because primary and secondar y alcohols lead to ethers of the cycloalkenes The use of a polar aprotic solvent such as diglyme generates enols of diketones [26] (equation 27) The compound where... 

Typical reaction conditions are 120-200°C and pressures of 0.2-0.8 MPa (2-8 bar) with potassium hydroxide or sodium alcoholates as catalyst (83). In the reaction with primary amines, both active hydrogens are replaced before further ethylene oxide addition leading to dipolyoxyethylene derivatives. Polyoxyethylenes have a terminal hydroxyl that may be further functionalized under conditions that do not damage the ether linkages, for example, sulfation. 

It is often advisable to determine to which class an amine belongs. There are many ways of distinguishing between and separating primary, secondary, and tertiary amines. Only a few will be mentioned here. Acetyl chloride reacts at ordinary temperatures with primary and secondary amines. Heat is evolved, and in most cases solids are formed from liquid amines. Inactivity with this reagent indicates that the substance, previously shown to be an amine, is a tertiary amine. If an acetyl derivative is formed, the carbylamine test (206) is applied. Some of the original substance is warmed with chloroform and an alcoholic solution of potassium hydroxide. The production of the characteristic, disagreeable odor is evidence that the substance is a primary amine. 

The primary amines unite with alkyl halides to form salts of secondary and tertiary amines and of the quarternary ammonium bases, the reactions being analogous to those already described in connection with the aliphatic amines. Like the latter they are converted into isocyanides when warmed with potassium hydroxide and an alcoholic solution of chloroform. 

The derivatives of anthranilic acid 179 (the products from the condensation of primary amines and the respective isatoic anhydrides) were treated with orthocarbonic ester, and the obtained compounds 180 were cyclized to the derivatives of 2,4-quinazolinedione 181 by the action of an alcohol solution of potassium hydroxide [67, 96, 104, 105],... 

Waxes are esters of fatty acids with long chain primary alcohols (Figure 12.2). The fatty acid is usually straight chain which may be saturated or mono-unsat-urated although occasionally branched chain or hydroxy acids are found. They are extremely non-polar compounds and are relatively inert chemically but they can be hydrolysed using a strong alkali, such as potassium hydroxide, a process called saponification. 

ABT-594 is reported to be in clinical trials for the treatment of neuropathic pain (Thatte, 2000 Sorbero et al. 2001). Its precursor (f )-N-Boc-azetidin-2-yl-methanol is accessible in a short sequence starting from commercially available D-aspartic acid dibenzyl ester. The synthesis is concluded by Mitsunobu coupling with 6-chloropyridin-3-ol and subsequent acidic deprotection. On a larger scale the primary alcohol is activated as a mesylate prior to coupling with 6-chloropyridin-3-ol in the presence of potassium hydroxide, so that Mitsunobu conditions can be avoided (Meyer et al., 2000). 

Potassium hydroxide in DMSO has proved a useful reagent to promote the reaction of activated aryl and heteroaryl chlorides with long chain primary alcohols, to form the corresponding ethers (equation 16).157 The procedure failed with secondary alcohols. 

Acetylenic tertiary alcohols are prepared from sodium acetylides or acetylenic Grignard reagents and ketones in the same manner as described for primary and secondary alcohols (method 88). Dimethylethynylcarbinol is prepared from acetone, aqueous potassium hydroxide, and acetylene in an autoclave at 100° and 300 p.s.i. Ketones ate sometimes treated with an acetylide prepared from acetylene and a solution of sodium or potassium alkoxide in /-amyl alcohol. " Another procedure utilizes... 

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