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RSC Advances
chloride ion on the trimethylsilyl intermediate 10, leading to
the chloro derivative (Scheme 3).
6 C. Len and R. Luque, Sustainable Chemical Processes., 2014, 2,
1.
On the other hand, the great difference of reactivity observed
for n-propanol and 1,2-propanediol suggests a different reaction
mechanism for the two substrates. While mono hydroxyl
substrates react through simple nucleophilic substitution
pathways (Scheme 3), for polyols (1,2-propanediol, ethylene
glycol and glycerol) a two-step process involving the formation
of epoxide intermediates 12a–c and 13a–c could be proposed,
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according with some literature data†.2,22–25 In particular, the 10 V. Legros, C. Vanhaverbeke, F. Souard, C. Len and J. Desire,
´
´
intermediate 13a (R ¼ CH2OH) evolves into 1-MCH (2) by a
nucleophilic attack of the chloride ion on the less hindered 11 M. Berthelot and S. De Luca, Il Nuovo Cimento, 1855, 2, 295–
carbon atom (Scheme 4). The formation of the intermediates 297.
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12a–c from activated polyols 11a–c through intramolecular 12 L. Carius, Justus Liebigs Ann. Chem., 1862, 122, 71–77.
nucleophilic substitution can be described as an example of 13 A. Claus, J. Chem. Soc., 1873, 26, 1117–1149.
´
`
symphoria impossible for n-propanol and responsible for the 14 P. Carre and P. Mauclere, Compt. Rend., 1931, 192, 1567–
higher reaction rate observed for 1,2-propanediol, ethylene 1569.
glycol and glycerol. Furthermore, the presence of a 1,2-diol 15 Reboul and Lourenço, Justus Liebigs Ann. Chem., 1861, 119,
system on the a-monochlorohydrin (2) allows a second chlori-
nation to give a,g-dichlorohydrin (3).
233–237.
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4. Conclusions
A new method for glycerol chlorination has been carried out
using trimethylchlorosilane as chlorinating agent and AcOH as
catalyst. The process has shown, under optimized conditions, a
very high selectivity towards a,g-dichlorohydrin (3), an useful
starting material for the production of epichlorohydrin. By
controlling the reaction conditions is also possible to drive the
conversion of glycerol towards a-monochlorohydrin (2). Hex-
amethyldisiloxane (HMDSO) is formed as by-product of the
reaction, that can be quantitatively recovered by distillation and
conveniently transformed back to TMSCl,35 for recycling in the
process. Moreover the present methodology could be easily
integrated in the process for the transesterication of triglyc-
erides with TMSCl,33,34 for the conversion of the mixture glyc-
erol/monochlorohydrin, by-product of the BD production, into
valuable a,g-dichlorohydrin (3).
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† Formation of a cyclic intermediate coming from acetylated polyols could be also
proposed, see ref. 28 and R. Boschan and S. Winstein, J. Am. Chem. Soc., 1956, 78,
4921–4925.
30 D. C. Snyder, J. Org. Chem., 1995, 60, 2638–2639.
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