Reaction with chloroform

Ahyl alcohol undergoes reactions typical of saturated, aUphatic alcohols. Ahyl compounds derived from ahyl alcohol and used industriahy, are widely manufactured by these reactions. For example, reactions of ahyl alcohol with acid anhydrides, esters, and acid chlorides yield ahyl esters, such as diahyl phthalates and ahyl methacrylate reaction with chloroformate yields carbonates, such as diethylene glycol bis(ahyl carbonate) addition of ahyl alcohol to epoxy groups yields products used to produce ahyl glycidyl ether (33,34). 

Aliphatic Alcohols and Thiols. Ahphatic alcohols on reaction with chloroformates give carbonates and hydrogen chloride. Frequendy, the reaction proceeds at room temperature without a catalyst or hydrogen chloride acceptor. However, faster reactions and better yields are obtained in the presence of alkaU metals or their hydroxides, or tertiary amines. Reactions of chloroformates with thiols yield monothiolocarbonates (14). 

Heterocyclic Alcohols. Thek reactions with chloroformates lead to carbonates. Thus furan- and tetrahydrofuran-derived alcohols give the corresponding carbonates in 75% yield (15). Inorganic bases and tertiary amines as acid acceptors increase the rate and yield in this reaction. 

Benzoin, reaction with chloroform to give 1,1,3 tnchloro n nonane, 45, 104... 

Diethylammonium chloride, reaction with chloroform to give 1,1,3-trichloro- -nonane, 45,104 Diethylazelate, 46, 31 Diethylbenzene as solvent for decomposition of diphenyliodonium-2-carboxylate in preparation of... 

Reaction with chloroform under basic conditions is a common test for primary amines, both aliphatic and aromatic, since isocyanides have very strong bad odors. The reaction probably proceeds by an SnIcB mechanism with dichlorocarbene as an intermediate ... 

Prior and Wiegrebe (52,53) examined the von Braun degradation of 7,8-secoberbines. It proceeded analogously to the reaction with chloroformates... 

Since arylazoamidoximes release nitric oxide when incubated in rat liver microso-mial fraction [172], 3-arylazo-l,2,4-oxadiazol-5-ones 136 have been prepared from the corresponding arylazoamidoximes 134 as their potential pro-drugs [172]. Reaction with chloroformate afforded compounds 135 which underwent cyclisation to 136 in alkaline medium (Scheme 6.26). 

Aminophenols, 2 652-678 analysis, 2 661-662 chelating agents, 5 712t chemical reactions, 2 656-658 derivatives, 2 664-671 economic aspects, 2 661 health and safety factors, 2 663-664 manufacture and processing, 2 658-661 physical properties of, 2 653-656, 666t reactions with chloroformates, 6 296 salts, 2 656t... 

FIGURE 3.14 Protection of amino groups as urethanes by reaction with chloroformates (path... 

The tropone ring of cyclohepta[c]thiophen-6-one reacts preferentially at the C=C bond, instead of at the carbonyl group, with both dichloro- and dibromocarbene to give mono- and bis-adducts in relatively low yields (5-40%) [60]. Benzoquinones produce anfi-bis-insertion adducts in their reaction with chloroform (95%), or bromoform (57%), under basic conditions [29]. 

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