Hydrogen bromide reaction with alkyl alcohols

Thus reaction with alkyl halides such as allyl bromide or pro-pargyl bromide allow for the introduction of oleflnlc2. . or acetylenic side groups onto the phosphazene ring VI, while alcohol leads to the formation of hydrido-phosphazene complexes VII. The hydrogen in these compounds can be replaced with halogen to yield the first series of iodor-phosphazene compounds VIII. 

The value of thiourea for the preparation of thiols is that on reaction with alkyl halides,271 mixtures of hydrogen bromide and alcohols,272 or suitable aromatic273 or heterocyclic halides274 it readily yields S-alkyl- or S-aryl-thiouronium salts, from which the thiols are usually obtained in good yield by alkaline hydrolysis or by aminolysis with high-boiling, strongly nucleophilic... 

Alkylation of diisopropyl (7 )-malate with benzyl bromide produces a 10 1 mixture of benzylated product 945 in 80—85% yield. Use of the isopropyl ester results in higher yields than in the case of the corresponding methyl or ethyl esters, presumably due to reduced ester— enolate condensation. Purification of the diastereomeric mixture is accomplished by hydrolysis to diacid 946 and recrystallization from either chloroform or ethyl acetate/hexane [52% overall yield from diisopropyl (i )-malate]. Treatment of 946 with acetyl chloride and subsequent reaction with isopropyl alcohol gives monoester 948 in 95% overall yield. Amidation of the free acid followed by Hofmann degradation affords 950 in 90% overall yield. Removal of the Boc group and hydrogenation of the benzene ring provides 952. 

Reaction of alcohols with phosphorus tribromide (Section 4 13) As an alternative to converting alco hols to alkyl bromides with hydrogen bromide the inorganic reagent phosphorus tribromide is some times used... 

Both reactants m the Williamson ether synthesis usually originate m alcohol pre cursors Sodium and potassium alkoxides are prepared by reaction of an alcohol with the appropriate metal and alkyl halides are most commonly made from alcohols by reaction with a hydrogen halide (Section 4 7) thionyl chloride (Section 4 13) or phosphorus tri bromide (Section 4 13) Alternatively alkyl p toluenesulfonates may be used m place of alkyl halides alkyl p toluenesulfonates are also prepared from alcohols as their imme diate precursors (Section 8 14)... 

The initial series of major tranquilizers consists of alkylated derivatives of 4-aryl-4-hydroxypiperidines. Construction of this ring system is accomplished by a set of rather unusual reactions. Condensation of methylstyrenes with formaldehyde and ammonium chloride afford the corresponding hexahydro-1,3-oxazines (119). Heating these oxazines in the presence of acid leads to rearrangement with loss of water to the tetrahydropyridines. Scheme 1 shows a possible reaction pathway for these transformations. Addition of hydrogen bromide affords the expected 4-bromo compound (121). This last is easily displaced by water to lead to the desired alcohol (122) The side chain (123) is obtained by Friedel-Crafts acylation of p-fluorobenzene with 4-chloro-butyryl chloride. Alkylation of the appropriate arylpiperidinol with 123 affords the desired butyrophenone derivative. Thus,... 

In what appears, initially, to be a closely similar reaction, acid chlorides react with alkyl halides under solidtliquid two-phase conditions using sodium hydrogen carbonate in the presence of sodium iodide and tetra-n-butylammonium bromide [45]. Although the mechanism is not clear, it has been proposed that the acid chloride is initially converted into the carboxylate anion. It is also probable that the halogen interchange between the sodium iodide and the alkyl halides enhances their reactivity. Although the yields are high, the availability of the alkyl halides and alcohols are usually similar and there appears to be little to commend this process over the catalysed reaction of the acid chlorides with the alcohols. 

The mechanism for the reactions with phosphorus halides can be illustrated using phosphorus tribromide. Initial reaction between the alcohol and phosphorus tribromide leads to a trialkyl phosphite ester by successive displacements of bromide. The reaction stops at this stage if it is run in the presence of an amine which neutralizes the hydrogen bromide that is formed.9 If the hydrogen bromide is not neutralized the phosphite ester is protonated and each alkyl group is successively converted to the halide by nucleophilic substitution by bromide ion. The driving force for cleavage of the C—O bond is the... 

Alcohols react readily with hydrogen halides to yield alkyl halides and water. The reaction is carried out either by passing the dry hydrogen halide gas into the alcohol, or by heating the alcohol with the concentrated aqueous acid. Sometimes hydrogen bromide is generated in the presence of the alcohol by reaction between sulfuric acid and sodium bromide. 

Organyl tellurols are very unstable compounds owing to their extreme sensitivity to oxygen, giving the corresponding ditellurides. The first short-chain alkyltellurols (C1-C4) have been isolated as yellow liquids with an obnoxious odour, from the reaction of aluminium telluride and hydrogen telluride, respectively, with alcohols and alkyl bromides. Aryltellurols seem not to have been isolated. As shown in Sections 3.1.3.2 and 3.2.2, aryl tellurolates are... 

Alcohols react with hydrogen halides to produce alkyl halides. In these reactions, the —OH group of the alcohol is replaced by the halide ion of the acid. All alcohols react with concentrated HBr and HI solutions to produce alkyl bromide and alkyl iodide. These reactions occur by a specific mechanism as shown below. 

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