Oxalyl Chloride: A Versatile Reagent in Organic Transformations

Abstract

Oxalyl chloride, (COCl)2, as an inexpensive commercially available chemical is one of the most versatile applicable organic reagents in chemical transformations. It is also employed extensively in various chemical industries. It is employed in various chemical transformations such as chlorination, oxidation, reduction, dehydration, decarboxylation, and formylation reactions as well as ring cleavage of epoxides. During the past decades, numerous procedures using (COCl)2 as reagent have been developed and published. However, its importance has largely been overlooked by the absence of a comprehensive review in chemical literature dealing with its application in organic transformations and its utilization in the chemical industry. This Review aims to provide an overview for the applications of oxalyl chloride in organic synthesis, including its physical properties, synthesis, as well as its unique roles as the reagent in organic reactions, covering the literature over the past 103 years (from 1916 to date).

Synthesis and Anticancer Activity of Hybrid Molecules Based on Lithocholic and (5Z,9Z)-Tetradeca-5,9-dienedioic Acids Linked via Mono(di,tri,tetra)ethylene Glycol and α,ω-Diaminoalkane Units

“…The synthesis of LA-fatty acid conjugates linked via diaminoalkane units of different lengths was carried out in several stages. Compounds 9 and 12 bearing the carboxyl group were first converted to chloroanhydrides 17 and 18 using oxalyl chloride in dichloromethane [ 28 ]. Chloroanhydrides 17 and 18 without preliminary purification were involved in reactions with diaminoalkanes to form amides 19a – d and 20a – d .…”

“…Subsequent deprotection of 1,14-bis-tetrahydropyranyl-5Z,9Z-diene-1,14-diol 3 formed after hydrolysis of magnesacyclopentane 2 in the presence of catalytic amounts of p-toluenesulfonic acid or its oxidation with Jones reagent led to compounds 4 and 5, respectively (Scheme 1). methane [28]. Chloroanhydrides 17 and 18 without preliminary purification were involved in reactions with diaminoalkanes to form amides 19a-d and 20a-d.…”

Curcumin-Piperlongumine Hybrids with a Multitarget Profile Elicit Neuroprotection in In Vitro Models of Oxidative Stress and Hyperphosphorylation

“…Several attempts to use thionyl chloride for this transformation met with failure, and thus established adequate reaction conditions for the synthesis of the required acyl chlorides required some experimentation. Finally, the transformation could be performed with a mixture of oxalyl chloride and dimethylformamide [ 49 ] using as solvent hexane, which extracted the unstable cinnamyl chloride as it was formed.…”

Potential Safety Hazards Associated with Using N,N-Dimethylformamide in Chemical Reactions

“…Furthermore, noncondensable gases are formed during the reactions of DMF with chlorination reagents. More specifically, sulfur dioxide (SO 2 ) and hydrogen chloride (HCl) are released during the reaction of DMF with SOCl 2 , while CO, CO 2 , and HCl are the byproducts from the reaction of DMF with oxalyl chloride . The formation of these noncondensable gases can cause a dramatic pressure rise without proper venting as well as a possible need for scrubbing due to environmental emission limits, increasing the severity of the hazards.…”

“…More specifically, sulfur dioxide (SO 2 ) and hydrogen chloride (HCl) are released during the reaction of DMF with SOCl 2 , while CO, CO 2 , and HCl are the byproducts from the reaction of DMF with oxalyl chloride. 49 The formation of these noncondensable gases can cause a dramatic pressure rise without proper venting as well as a possible need for scrubbing due to environmental emission limits, increasing the severity of the hazards. Under certain conditions, i.e., an "all-in" scenario in which all of the reactants are accumulated and the reaction is heated at elevated temperatures, the heat release rate could overwhelm the ability of the reactors to remove heat from the reaction system and result in runaway scenarios or even explosions.…”