Chloromethyl benzotriazole

E = alkyl, ArCH2, PhCO, PhCHOH, Ph2COH, or ArNHCS 

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All reactions of benzotriazole derivatives of the type Bt-CR RbS discussed above are based on electrophilic or nucleophilic substitutions at the ot-carbon, but radical reactions are also possible. Thus, the first report on unsubstituted carbon-centered (benzotriazol-l-yl)methyl radical 841 involves derivatives of (benzotriazol-l-yl)methyl mercaptan. 3 -(Benzotriazol-l-yl)methyl-0-ethyl xanthate 840 is readily prepared in a reaction of l-(chloromethyl)-benzotriazole with commercially available potassium 0-ethyl xanthate. Upon treatment with radical initiators (lauroyl peroxide), the C-S bond is cleaved to generate radical 841 that can be trapped by alkenes to generate new radicals 842. By taking the xanthate moiety from the starting material, radicals 842 are converted to final products 843 with regeneration of radicals 841 allowing repetition of the process (Scheme 134). Maleinimides are also satisfactorily used as radical traps in these reactions <2001H(54)301>. 

Alkylation of benzotriazole with (chloromethyl)trimethoxysilane 99 provides a mixture of its derivatives 98 and 100 in a ratio of 1 3. In a reaction with tris-(2-hydroxyethyl)amine, compound 100 is converted to derivative 101 in nearly quantitative yield. Compound 98 reacts with tris-(2-hydroxyethyl)amine similarly (Scheme 6) <2003ARK(xiii) 125, 2003CHE1639>. 

Benzene azimide. See 1 H-Benzotriazole Benzenecarbaldehyde. See Benzaldehyde Benzenecarbinol. See Benzyl alcohol Benzene carbonal Benzene carboxaldehyde. See Benzaldehyde Benzenecarboxylic acid. See Benzoic acid Benzene chloride. See Chlorobenzene Benzene, chloromethyl-. See Monochlorotoluene Benzene, (chloromethyl)-. See Benzyl chloride Benzene, 1-chloro-4 (trifluoromethyO. See p-Chlorobenzotrifluoride... 

The VNS is the reaction of choice for incorporation of a-sulfonylalkyl substituents into nitroarenes and their heteroanalogues. Particularly accessible and useful are nitroarylmethyl phenyl sulfones and their heteroanalogues that are efficiently produced in the VNS reactions of carbanions of chloromethyl aryl sulfones with a great variety of nitroarenes and nitroheteroarenes. Nitro derivatives of heterocycles, such as pyrrole [54,55], furan [54], thiophene [54], imidazole [106, 112, 113], pyrazole [114], pyridine [57], indole [115], indazole [116, 117], benzimidazole [118], benzotriazole [119], benzofuroxan [120], quinoline [121], and porphyrins [122, 123], have been shown to enter this reaction. 

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