Potential Explosion Hazards Associated with the Autocatalytic Thermal Decomposition of Dimethyl Sulfoxide and Its Mixtures

Abstract

Dimethyl sulfoxide (DMSO) is widely used as a solvent for chemical reactions, as a cosolvent for crop protection formulations, and in medicines for topical administration of drugs. The potential explosion hazards associated with thermal decomposition of DMSO have been well-documented, with early reports dating back to the late 1950s. However, these explosion hazards are still underappreciated and inadequately communicated, as indicated by the fact that numerous severe accidents have occurred on both laboratory and industrial scales over the years. Differential scanning calorimetry studies show that decomposition of pure DMSO is detected at ca. 278 °C, while accelerating rate calorimetry analysis indicates that thermal decomposition of DMSO occurs at temperatures around its boiling point of 189 °C. Studies also show that the presence of certain substances can significantly lower the onset temperature of DMSO decomposition and also potentially increase the severity of the decomposition reaction through autocatalytic behavior. Further analysis of literature information indicates that there is a wide range of substances that exacerbate the thermal decomposition of DMSO, including acids, bases, halides, metals, electrophiles, oxidants, and reductants. This comprehensive review of explosion hazards associated with the thermal decomposition of DMSO and its mixtures will serve as an educational resource to alert researchers about the need to mitigate these hazards and to incentivize research toward its replacement with safer and greener solvents in the broader chemistry community.

Depolymerization of Technical‐Grade Polyamide 66 and Polyurethane Materials through Hydrogenation

“…In addition, decomposition of DMSO at elevated temperature raises potential safety issues. [14] Moreover, in their report, hydrogenation of technical-grade polymers was not demonstrated. Here, we disclose our results on rutheniumcatalyzed hydrogenation of polyamides and polyurethanes through cleavage of the CÀ N bond of amide and carbamate groups.…”

Iodine‐Catalyzed Double [4+2] Oxidative Annulations for the Synthesis of Bipyrazines from Ketones and Diamines by a Domino Strategy

“…DMSO has been reported as an effective oxidant. [21] However, only 15% yield of the bipyrazine was afforded when PhNO 2 was replaced with DMSO in this case (entry 6). Other oxidants such as H 2 O 2 , K 2 S 2 O 8 and Selectfluor failed to give the expected dimeric pyrazines (entry 7).…”

“…13 1 Hz, 2H), 3.17 (t, J = 5.2 Hz, 4H), 3.03 (t, J = 5.2 Hz, 4H), 2.05-1.99 (m, 8H). 13 [21] Petroleum ether/ethyl acetate [24] Petroleum ether/ethyl acetate = 1:1; cis-7, yellow solid (100 mg, 32%); mp 131-132 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.44 (d, J = 7.4 Hz, 4H), 7.41-7.28 (m, 6H), 6.15 (s, 2H), 4.50 (dt, J = 13.5, 3.4 Hz, 1H), 2.76 (s, 1H), 1.87-1.76 (m, 1H), 1.68-1.57 (m, 1H), 1.54-1.39 (m, 2H), 1.13-1.04 (m, 4H). 13 The NMR data were identical in all respects to those previously reported.…”

A spectroscopic method for quantitating lignin in lignocellulosic biomass based on the completely dissolved solution of biomass in LiCl/DMSO

“…During the experiment, it was found that the treated samples can also completely dissolve in the LiCl/DMSO solvent system by direct stirring at 60 °C for only 6 h. It should be noted that the dissolution temperature should not exceed 90 °C to prevent the disproportionation reaction of dimethyl sulfoxide. 39,40 The reason why chemical treatment reduces the dissolving capacity of the lignocellulosic biomass samples in the LiCl/DMSO solvent system and the influence of temperature on the solubility of biomass samples still need further systematic studies. However, the extraordinary solubility of lignocellulosic biomass in the LiCl/DMSO solvent system under mild conditions without chemical pretreatment provides a promising prospect for the development of subsequent green quantitative methods of lignin.…”