Allyl--chloro phenol

2 -Chlorophenyl allyl ether (p. 81) is placed in a flask equipped with a reflux condenser and a thermometer placed in the liquid. The liquid is heated to reflux until its temperature has risen to 256°. 

This requires about 20-25 minutes. The material is then distilled and nearly all goes over in the range 256-260°. If large quantities of material are used, the reflux period should be no longer than absolutely necessary, and the subsubsequent distillation should be carried out under vacuum instead of at atmospheric pressure. The distillate solidifies on standing, and it is pressed to remove small amounts of oil and recrystallized from petroleum ether. The product melts at 48°, and the yield is nearly quantitative. 

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In a similar way, numerous P-chloroalkylphosphonic acids undergo fast and quantitative hydrolysis at pH > 5 94). A typical example is the fragmentation of 2-chloro-decyl-l-phosphonic acid in the presence of cyclohexylamine with formation of 1-decene (in contrast, other bases such as pyridine, triethylamine, and dimethylaniline effect only HC1 elimination to form 1-decene-l-phosphonic acid). Added alcohols, such as ethanol, allyl alcohol, cyclohexanol, tert-butanol, and phenol are phosphorylat-ed. 

The extent of C-alkylation as a side reaction in etherification varies about 1% of allyl 2-allylphenyl ether is formed when phenol is used in the acetone and potassium carbonate method with allyl bromide with cinnamyl bromide or 7,7-dimethylallyl bromide the extent of C-alkylar tion is greater.16 A complicated mixture of C- and O-alkylation products results from the treatment of phenol with 4-bromo-2-hexene and 4-chloro-2-hexene. 9 4-Hexenylresordnol has been obtained in about 40% yield from the reaction of l-bromo-2-hexene, resorcinol, and potassium carbonate in boiling acetone.99 An appreciable amount of C-alkylation occurs when 2,6-dimethyIphenol is treated with allyl bromide and sodium ethoxide in ethanol.70 Since, in general, the ampunt of C-alkylation is greatly increased by carrying out the alkylation on the sodium salt of the phenol in benzene,16 this method is unsuitable for the preparar tion of allyl aryl ethers. 

Alcohols are appreciably harder than phenols to alkylate with dialkyl sulfates. Here an essential point for success is complete exclusion of water.691 Alkylation of alcohols is relatively smooth only if they contain activated hydroxyl groups, as in allyl alcohol, benzyl alcohol,692 acetylenic alcohols,693 cyanohydrins, trifluoroethanol,694 mandelic acid,695 2-chloro-ethanol,696 or 2-alkoxyethanols.697... 

Chloro allyldiisobulyl 4-Chlorophenol 1 moles of NaOH in THF then telluronium bromide added phenol telluronium mixture stirred (5h.) under Nj to give allyl 4-chlorophenyl ether, bromide... 

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