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Neopentyl and isobutyl chlorosulfate can be easily prepared in large scale by the reaction of the respective alcohols with sulfuryl chloride. The crude chlorosulfates can be distilled and then stored under argon at -20 °C for several months without detectable decomposition. Buncel, E. Chem. Rev. 1970, 70, 323-337.
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note
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Initial reactions of phenol with neopentyl chlorosulfate in the presence of a tertiary amine base gave diester 1, but in unsatisfactory yields (<50%), even with reaction times of up to 3 days. Lithium aryloxides, produced using n-butyllithium or lithium bis(trimethylsilyl)amide, reacted slowly with neopentyl chlorosulfate. These reactions did not go to completion, even with extended reaction times.
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21
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32244448703
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note
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Multiple equivalents of isobutyl chlorosulfate were used to increase the reaction rate and protect the diester product from degradation under the reaction conditions. Lithium phenoxides reacted with isobutyl chlorosulfate to give isobutyl ethers almost exclusively.
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23
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32244431834
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note
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1H NMR, IR, and MS.
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24
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0000356854
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25
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32244435268
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note
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Triethylamine was used to keep the reaction mixture slightly basic and prevent decomposition of sulfate monoester products.
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27
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0043045262
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A similar result was observed in the solvolysis of the analogous p-bromobenzenesulfonate esters of tetrahydrofuran-2-methanol and tetrahydropyran-2-methanol. Kwiatkowski, G. T.; Kavarnos, S. J.; Closson, W. D. J. Heterocycl. Chem. 1965, 2, 11-14.
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Closson, W.D.3
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