A convenient and practical preparation of 4-chloromethyl-5-methyl-1,3-dioxol-2-one.

Ikeda, Shoji; Takebe, Yasushi; Hirayama, Ryoichi; Sakamoto, Fumio; Iuchi, Koji; Tsukamoto, Goro

doi:10.1248/cpb.36.394

Cited by 9 publications

(1 citation statement)

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“…Starting from 3-hydroxy-2-butanone ( 3 ), cyclization with phosgene or triphosgene followed by filtration afforded solid product 4 . Various chlorinating reagents including chlorine, trichloroisocyanuric acid (TCCA), trichlorotriazine (TCT), N -chloro-succinimide (NCS), and sulfuryl chloride (SO 2 Cl 2 ) , could chlorinate the conjugate form of 4 to give 5 as an unstable intermediate, which easily underwent allylic rearrangement upon heating, followed by molecular distillation , to give final product 1 , along with other related substances (lower half of Scheme ; the content of related substances was retrieved from one of the suppliers).…”

Section: Introductionmentioning

confidence: 99%

Development of a Triphenylmethyl Alkylation Pre-Column Derivatization Method for HPLC Quantitative Analysis of Chemically Unstable Halogenated Compounds

Lu,

Shi,

et al. 2024

ACS Omega

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The primary limitations of the quantitative analysis of thermally labile halogenated compounds by traditional gas chromatography (GC) are the inadequacy of identifying the insufficiently volatile impurity (often with a high boiling point) and the difficulty in obtaining a standard substance with a reliable standardized assay. Taking the 4-(Chloromethyl)-5-methyl-1,3dioxol-2-one (DMDO-Cl, 1) as an example, we reported a triphenylmethanamino-derivatization method to overcome the challenges of the assay determination of such species. During the quantification of 1, the presence of GC-undetectable polymeric impurity 10 poses a critical challenge in assessing the material quality. Moreover, the standard substance of 1 is not available on the market due to its inherent instability during storage and handling, further complicating the quantitative analysis. In this work, a precolumn HPLC-UV derivatization method based on triphenylmethanamino-alkylation was developed to quantitatively analyze 1. The resulting derivative 2 exhibits excellent crystallinity and superior physical and chemical stability and possesses effective chromophores for UV detection. The conversion from analyte 1 to derivative 2 demonstrates desirable reactivity and purity, facilitating quantitative analysis using the external standard method. The chemical derivatization-chromatographic detection method was optimized and validated, demonstrating its high specificity, good linearity, precision, accuracy, and stability. This method offers a valuable alternative to the general quantitative NMR (qNMR) detection technique, which exhibits reduced specificity in the presence of increased levels of impurities in compound 1.

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