Dehydration‐fragmentation mechanism of cathinones and their metabolites in ESI‐CID

Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs.     

Synthesis of cycl[3.2.2]azine and benzo[g]cycl[3.2.2]azine derivatives by use of the [2 + 8] cycloaddition reaction of indolizines and dimethyl acetylenedicarboxylate

The reaction of 1-ethoxycarbonylmethylpyridinium bromides 5a-k with nitro ketene dithioacetal, 1,1-bis-(methylthio)-2-nitroethylene ( 2 ), in the presence of triethylamine in ethanol gave the desired ethyl 2-methyl-thioindolizine-3-carboxylates 3a-k in good yields, along with ethyl 2-methylthio-1-nitroindolizine-3-carboxyl-ates 4a-d . Deesterification of 3 using sodium hydroxide in methanol followed by treatment with polyphosphoric acid gave the corresponding 2-methylthioindolizines 5a-d in good yields. The desulfurization of 5 with Raney-nickel in ethanol occurs smoothly to give the 1,2,3-unsubstituted indolizines 6a-c (a , parent indolizine; b , 8-methylindolzine; c , 6,8-dimethylindolizine). Similarly, pyrrolo[2,1-a]isoquinoline ( 19 ) was also synthesized. These indolizine and pyrrolo[1,2-a]isoquinoline derivatives were allowed to react with dimethyl acetylene to give the corresponding cycl[3.2.2]azine and benzo[g]cycl[3.2.2]azine derivatives in good results.     

Hydroxyapatite-supported copper(II)-catalyzed azide-alkyne [3+2] cycloaddition with neither reducing agents nor bases in water

Copper(II)-exchanged hydroxyapatite, prepared by ion-exchanging of Ca(II) in calcium hydroxyapatite [Ca₁₀(PO₄)₆(OH)₂] with Cu(NO₃)₂ at 70 °C in water, functions as a reusable heterogeneous catalyst with neither reducing agents nor bases for azide-alkyne [3+2] cycloaddition at 50 °C in water under air.     

Probabilistic evaluation of interconnectable capacity for wind power generation

We propose a novel framework for probabilistic evaluation of interconnectable capacity for wind power generation. This is based on mathematical modeling of load frequency control systems, which captures their nonlinear (saturation and rate limiting) dynamical characteristics, and stochastic uncertainty of wind power output deviation. The method called stochastic linearization is used to analyze resulting power quality. The effectiveness of the proposed method is examined by numerical simulation.     

Trifluoromethylation of aliphatic halides with trifluoromethyl copper

A solution of trifluoromethyl copper complex in hexamethylphosphoric triamide was found to be useful for trifluoromethylation of aliphatic halides.     

Concise three-component synthesis of defucogilvocarcin M

[reaction: see text] Concise synthesis of defucogilvocarcin M was achieved via the [2 + 2 + 2] approach to beta-phenylnaphthalene structure.     

Strongly red-fluorescent novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazoles with enhanced two-photon absorption cross-sections

Novel donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) type 2,1,3-benzothiadiazole fluorescent dyes connected to the N,N-diarylamino terminus via various type pi-conjugate spacers exhibits large two-photon absorption cross-sections and high fluorescent quantum yields in orange-red color.     

Application of Dithlol-s-triazine Derivatives to PVC CrossUnking

The effects of crosslinking on PVC are well known in regard to the improvement of mechanical properties, creep behavior, and softening temperature. Little is known, however, on the application of the PVC-crosslinking reaction, because most of crosslinked PVC tends to color easily at elevated temperatures. In this paper, a novel PVC-crosslinking reaction with 2-R-4,6-dithiol-s-triazine (I) has been presented to obtain insoluble products which hardly color on ageing. The reaction rate and induction period of the crosslinking reaction with I are made controllable by selecting the basicity of the substituent R of I as well as that of an acid acceptor in the blends. The utility of I as stabilizer as well as a crosslinking agent is also emphasized.