Data analysis of “krokodil” samples obtained by street-like synthesis

Abstract

The data described in this work is related to be the subject of an article in the Forensic Science International, titled: “The harmful chemistry behind “krokodil”: street-like synthesis and product analysis” (http://dx.doi.org/10.1016/j.forsciint.2015.07.042) [1]. The data presented here provides additional description of the chemical profile of “krokodil”. Physicochemical and organoleptic characteristics, TLC profile, UV/Vis, 1H NMR and FTIR spectrum are presented. These data validate the proposed synthetic procedure and pathway and give further information about the contaminants present in “krokodil”.

Street-Like Synthesis of Krokodil Results in the Formation of an Enlarged Cluster of Known and New Morphinans

“…Morphinans detected in krokodil samples are summarized in Table . Morphinans were identified with high accuracy (Δ m / z = −1.89–2.81 ppm) and similar to what is reported for other Orbitrap-based methods. − In addition, for each validated hit, the mass of the three most abundant fragments obtained from MS 2 fragmentation are reported. These fragments were considered in order to fulfill the requirements of EU Decision (implementing, 2002) concerning the performance of analytical methods and the interpretation of results …”

“…Mass Frontier uses a set of general fragmentation rules and a fragmentation library to predict the structure of the different fragments . Manual interpretation of spectra was conducted accordingly with mass fragmentation rules and with morphine and codeine fragmentation pathways described in the literature. ,− The three morphinans showed a similar fragmentation behavior. All three show the piperidine ring loss, leading to the base peak ( m / z 215) in desomorphine and to the intense peaks in codeine ( m / z 243) and morphine ( m / z 229).…”

“…The identification of other morphinans could represent a pivotal importance to fully understand the psychotropic effects of krokodil, but it is even more interesting to explain the apparent profound analgesia to tolerate the injection of a corrosive and caustic formulation (pH < 1). , It is clear that all morphinans present in krokodil have to be originated from codeine, the only possible precursor of this class of compounds present in the starting materials. From the codeine precursor, three types of conditions can be outlined in eight different chemical transformations (Figure a–i): (a) The codeine to desomorphine synthetic pathway; three different reactions are involved (a, b, and c), dehydroxylation at position number 6, reduction of double bond between positions 7 and 8, and O-demethylation of the methoxyl group at position 3; (b) the previously reported desomorphine byproducts, dehydroxylation at position number 3 and N-demethylation (d,e); , (c) codeine byproducts; considering the highly reductive environment of krokodil manufacture, it is reasonable to assume that a 4,5-epoxy cleavage can also occur as is the case with the already described methoxyl cleavage at position 3.…”

Repeated subcutaneous administrations of krokodil causes skin necrosis and internal organs toxicity in Wistar rats: putative human implications

“…The nature of the krokodil synthesis process and its precursors create the opportunity for the formation of a great variety of by‐products with phosphate structure. Indeed, 31 P‐RMN of krokodil samples presents different phosphorus species (Alves et al, ; Neves et al, ). The signals were compatible with the presence of phosphanes or phosphorous and/or phosphoric acid derivatives, such as phosphate esters, phosphonate esters, or phosphates salts, probably produced by phosphorous and phosphoric acids conversion during the extremely harsh reaction conditions (Alves et al, ).…”

“…Recently, our group deeply studied the production of krokodil by mimicking the street synthetic route (Alves et al, ; Tetradze, Shavishvili, Otiashvilli, & Grund, ). This work allowed the detection of other morphinans (dihydromorphine‐3,6‐dideoxy and morphinan‐4,5‐epoxy‐3‐ol) in the mixture besides desomorphine, which is the main psychoactive ingredient (Alves et al, ; Neves et al, ). The damage caused in PWIK are due to, in one hand, the harmful starting materials applied in the home production of the drug and, on the other hand, the lack of an effective purification method of the final product (Alves et al, , ; Katselou et al, ).…”