Synthesis, Structure, and Reactivity of <i>closo</i>-2,3,4,5,6,7,8,9,10,11-Decahydroxy-1,12-bis(sulfonic acid)-1,12-dicarbadodecaborane(12)

Herzog, A.; Cb, Knobler; Mf, Hawthorne

doi:10.1021/ja011917g

Cited by 23 publications

(13 citation statements)

References 27 publications

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“…The total number of reliable structures of cations with overall composition H 7 O 3 + is 11 [CBZSUL01 (Roziere & Williams, 1978), GIDZEZ (Deacon, et al, 2007), HAZCAN (Jin et al, 2005), JOTQOY03 (Calleja et al, 2001), NITRAN01 (Andersen & Andersen, 1975), ODEBOO (Herzog et al, 2001), SALSUL (Mootz & Fayos, 1970), SINNAF (Ganin et al, 2006), SLBZAC10 (Attig & Mootz, 1976) A view of the asymmetric unit of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.…”

Section: Tablementioning

confidence: 99%

Crystallographic investigations of select cathinones: emerging illicit street drugs known as `bath salts'

2015

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The name `bath salts', for an emerging class of synthetic cathinones, is derived from an attempt to evade prosecution and law enforcement. These are truly illicit drugs that have psychoactive CNS (central nervous system) stimulant effects and they have seen a rise in abuse as recreational drugs in the last few years since first having been seen in Japan in 2006. The ease of synthesis and modification of specific functional groups of the parent cathinone make these drugs particularly difficult to regulate. MDPV (3,4-methylenedioxypyrovalerone) is commonly encountered as its hydrochloride salt (C16H21NO3·HCl), in either the hydrated or the anhydrous forms. This `bath salt' has various names in the US, e.g. `Super Coke', `Cloud Nine', and `Ivory Wave', to name just a few. We report here the structures of two forms of the HCl salt, one as a mixed bromide/chloride salt, C16H22NO3(+)·0.343Br(-)·0.657Cl(-) [systematic name: 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide/chloride (0.343/0.657)], and the other with the H7O3(+) cation, as well as the HCl counter-ion [systematic name: hydroxonium 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one dichloride, H7O3(+)·C16H22NO3(+)·2Cl(-)]. This is one of a very few structures (11 to be exact) in which we have a new example of a precisely determined hydroxonium cation. During the course of researching the clandestine manufacture of MDPV, we were surprised by the fact that a common precursor of this illicit stimulant is known to be the fragrant species piperonal, which is present in the fragrances of orchids, most particularly in the case of the vanilla orchid. We found that MDPV can be made by a Grignard reaction of this heliotropin. This may also explain the unexpected appearance of the bromide counter-ion in some of the salts we encountered (C16H21NO3·HBr), one of which is presented here [systematic name: 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide, C16H22NO3(+)·Br(-)]. Complexation of MDPV with a forensic crystallizing reagent, HAuCl4, yields the tetrachloridoaurate salt of this drug, (C16H22NO3)[AuCl4]. The heavy-metal complexing agent HAuCl4 has been used for over a century to identify common quarternary nitrogen-containing drugs via microscopic identification. Another street drug, called ethylone (3,4-methylenedioxyethylcathinone), is regularly sold and abused as its hydrochloride salt (C12H15NO3·HCl), and its structure is herein described (systematic name: N-{1-[(benzo[d][1,3]dioxol-5-yl)carbonyl]ethyl}ethanaminium chloride, C12H16NO3(+)·Cl(-)). Marketed and sold as a `bath salt', `plant feeder', or `cleaning product', this drug is nothing more than a slight chemical modification of the banned drug methylone (3,4-methylenedioxymethcathinone). As with previously popular synthetic cathinones, the abuse of ethylone has seen a recent increase due to regulatory efforts on previous generations of cathinones that are now banned.

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Section: Tablementioning

confidence: 99%

Crystallographic investigations of select cathinones: emerging illicit street drugs known as `bath salts'

2015

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“…The results indicate that the BH vertices which are the farthest to the cage carbons (B8 to B13) are the most electron-rich and the easiest to be attacked by electrophiles. On the other hand, interaction of μ-1,2-(CH 2 ) 3 -1,2-C 2 B 11 H 11 with H 2 O 2 leads to complete degradation of the cage, resulting in the formation of B(OH) 3 , which differs significantly from its icosahedral cousins [23]. These substitution reactions can be closely monitored by 11 [25].…”

Section: Electrophilic Substitution Reaction Of 13-vertex Carboranementioning

confidence: 99%

Supercarboranes: Achievements and perspectives

Jian

Xie

2012

Pure and Applied Chemistry

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This article highlights the achievements in the chemistry of supercarboranes (carboranes with more than 12 vertices) in the past decade and the future perspectives. The chemistry of boron clusters has been dominated by 12-vertex carboranes for several decades. Only in recent years has significant progress been made in the chemistry of supercarboranes. Such a breakthrough relies on the use of CAd (carbon-atoms-adjacent) 12-vertex nido-carborane anions as starting materials. A series of 13-and 14-vertex carboranes as well as their corresponding 14-and 15-vertex metallacarboranes have been prepared and structurally characterized. Reactions of supercarboranes with reducing agents, electrophiles, and nucleophiles are studied, which reveal a more diverse and richer reaction chemistry than their icosahedral cousins.

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“…Thus, deprotonation of p-carborane 80 with nBuLi gave closo-1,12-bis(lithio)-1,12-dicarbadodecabo-rane (12) 81, which by successive treatment with SO2Cl2 and AlCl3 followed by final hydrolysis led to the 1,12-bis-(sulfonic acid) derivative 82. The exhaustive oxidation of compound 82 in hot aqueous H2O2 (30%) afforded Bdecahydroxy-1,12-bis(sulfonic acid)-p-carborane 83 (Scheme 19) [47].…”

Section: Otbdmsmentioning

confidence: 99%