- Thioanalogues of N-1-methylanabasine and nicotine - Synthesis and structure
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The synthesis, spectral characteristics and structures of N-1-methyl-6-(pyridin-3-yl)piperidine-2-thione (1) (thioanalogue of N-1-methylanabasine) and N-1-methyl-(5-pyridin-3-yl)pyrrolidine-2-thione (2) (thioanalogue of nicotine) are reported. Both compounds were obtained using Lawesson's reagent. The structures of compounds 1 and 2 are confirmed by NMR, IR, UV and mass spectroscopy, as well as, by X-ray diffraction analysis. Pyridine ring of compound 1 adopts a pseudo-axial orientation in solution, as well as in a solid state. A substantial lengthening of the C=S bond in the crystals of 1 is interpreted as a sign of an enhanced electron delocalization within the thiolactam group due to the presence of several C-H groups in the nearest vicinity of the sulfur atom. In the crystals of 2, which differ from 1 in that the relatively puckered piperidine-2-thione moiety is replaced by the flat pyrrolidine-2-thione ring, no short CH?S(=C) contacts are observed. Instead, the packing is governed by stacking interactions between pyridine rings. The pyrrolidine and pyridine rings in 2 are nearly perpendicular to each other and the pyrrolidine moiety adopts a flattened half-chair conformation.
- Wojciechowska-Nowak, Marzena,Boczoń, W?adys?aw,Warzajtis, Beata,Rychlewska, Urszula,Jasiewicz, Beata
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Read Online
- Preparation method of artificially synthesized nicotine
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The invention discloses a preparation method of artificially synthesized nicotine, and belongs to the technical field of chemical synthesis. According to the synthesis method of a racemate (+/-)-(R,S)-nicotine and a natural optical active enantiomer (-)-(S)-nicotine, nicotinate and diester of succinic acid (or N-alkyl succinimide) are taken as the primary raw materials; and defects of a conventional nicotine synthesis technology such as difficulty for massive production, high cost, and the like, are overcome. Specifically, the provided synthesis method has the advantages that the primary raw materials are easily available, the preparation technology is simple, the cost is low, the prepared nicotine does not contain any other harmful tobacco compound, and the preparation method is suitable for industrial large-scale production.
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- PHOTOCATALYST SYSTEM AND USE THEREOF IN A PHOTOCATALYTIC PROCESS
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Photocatalyst system and use thereof in a photochemical process The invention relates to a photocatalyst system comprising, in the absence of a further photosensitizer other than the compound of formula (III) or a mixture thereof: (i) a nickel(II) salt, (
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Page/Page column 33; 40; 41
(2019/06/13)
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- Sp3 C-H Arylation and Alkylation Enabled by the Synergy of Triplet Excited Ketones and Nickel Catalysts
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Triplet ketone sensitizers are of central importance within the realm of photochemical transformations. Although the radical-type character of triplet excited states of diaryl ketones suggests the viability for triggering hydrogen-atom transfer (HAT) and single-electron transfer (SET) processes, among others, their use as multifaceted catalysts in C-C bond-formation via sp3 C-H functionalization of alkane feedstocks still remains rather unexplored. Herein, we unlock a modular photochemical platform for forging C(sp3)-C(sp2) and C(sp3)-C(sp3) linkages from abundant alkane sp3 C-H bonds as functional handles using the synergy between nickel catalysts and simple, cheap and modular diaryl ketones. This method is distinguished by its wide scope that is obtained from cheap catalysts and starting precursors, thus complementing existing inner-sphere C-H functionalization protocols or recent photoredox scenarios based on iridium polypyridyl complexes. Additionally, such a platform provides a new strategy for streamlining the synthesis of complex molecules with high levels of predictable site-selectivity and preparative utility. Mechanistic experiments suggest that sp3 C-H abstraction occurs via HAT from the ketone triplet excited state. We believe this study will contribute to a more systematic utilization of triplet excited ketones as catalysts in metallaphotoredox scenarios.
- Shen, Yangyang,Gu, Yiting,Martin, Ruben
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supporting information
p. 12200 - 12209
(2018/09/27)
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- Oil composition
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PROBLEM TO BE SOLVED: To provide a gas oil composition for winter suitable for both diesel combustion and premixed compression ignition combustion. ?SOLUTION: The gas oil composition comprises an FT synthetic base material and has a sulfur content of not more than 5 mass ppm, an oxygen content of not more than 100 mass ppm, a bulk modulus of 1,250 to 1,450 MPa, a Saybolt color of not less than +22, a lubrication ability of not more than 400 μm, an initial boiling point of not lower than 140°C, an end point of not higher than 360°C, such characteristic features that (1) the cetane number of the fraction of lower than 200°C is 20-40 and the constitution ratio of the fraction is 10-20 vol.%, (2) the cetane number of the fraction of 200°C to lower than 280°C is 30-60 and the constitution ratio of the fraction is 30-89 vol.% and (3) the cetane number of the fraction of not lower than 280°C is not more than 50 and the constitution ratio of the fraction is 1-60 vol.%, and is used in a supercharger and a diesel engine with EGR having a geometrical compression ratio of more than 16, and satisfies the JIS No.2 gas oil specifications in the quality item properties other than the sulfur content. ?COPYRIGHT: (C)2008,JPOandINPIT ?
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- Antibody-catalyzed oxidative degradation of nicotine using riboflavin
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Tobacco abuse remains a major cause of death worldwide despite ample evidence linking nicotine to various disease states. Consequently, immunopharmacotherapeutic approaches for the treatment of nicotine abuse have received increasing attention. Although a number of nicotine-binding antibodies have been disclosed, no antibody catalysts exist which efficiently degrade nicotine into pharmacologically inactive substances. Herein, we report the first catalytic antibodies which can oxidatively degrade nicotine. These biocatalysts use the micronutrient riboflavin and visible light as a source of singlet oxygen for the production of reactive oxygen species. Along with various known nicotine metabolites, antibody-catalyzed nicotine oxidations produce two novel nicotine oxidation products that were also detected in control ozonation reactions of nicotine. The reaction is efficient, with multiple turnovers of catalyst observed and total consumption of nicotine attained. These results demonstrate the potential of harnessing riboflavin as an endogenous sensitizer for antibody-catalyzed oxidations and demonstrate a new approach for the development of an active vaccine for the treatment of nicotine addiction using in vivo catalytically active antibodies.
- Dickerson, Tobin J.,Yamamoto, Noboru,Janda, Kim D.
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p. 4981 - 4987
(2007/10/03)
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- Hapten-carrier conjugates for use in drug-abuse therapy and methods for preparation of same
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Hapten-carrier conjugates capable of eliciting anti-hapten antibodies in vivo are disclosed. Methods of preparing the hapten-carrier conjugates and therapeutic compositions are also disclosed. Where the hapten is a drug of abuse, a therapeutic composition containing the hapten-carrier conjugate is particularly useful in the treatment of drug addiction, more particularly, cocaine addiction. Passive immunization using antibodies raised against conjugates of the instant invention is also disclosed. The therapeutic composition is suitable for co-therapy with other conventional drugs.
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- Synthesis of pyrrolidin-2-ones by 5-endo-trigonal radical cyclisation of N-vinyl-2,2-bis(phenylsulfanyl)acetamides
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A series of N-methyl-N-(1-substituted or 1,2-disubstituted vinyl)-2,2-bis(phenylsulfanyl)acetamides, upon treatment with tributyltin hydride in the presence of a catalytic amount of AIBN in boiling toluene, underwent smooth cyclisation in a 5-endo-trig ma
- sato, Tatsunori,Chono, Noriko,Ishibashi, Hiroyuki,Ikeda, Masazumi
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p. 1115 - 1120
(2007/10/02)
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- A NEW APPROACH TO 5-ARYLPYRROLIDIN-2-ONES VIA 5-ENDO-TRIG RADICAL CYCLIZATION OF α-HALO- OR α-THIO-SUBSTITUTED N-(1-ARYLETHENYL)ACETAMIDES
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N-(1-Phenylethenyl)carbamoylmethyl radicals generated by tributyltin hydride-mediated cleavage of carbon-halogen or carbon-sulfur bond underwent smooth cyclization in a "disfavored" 5-endo-trig manner to give 5-phenylpyrrolidin-2-one.This method was applied to the synthesis of (+/-)-cotinine.
- Sato, Tatsunori,Machigashira, Naomi,Ishibashi, Hiroyuki,Ikeda, Masazumi
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p. 139 - 142
(2007/10/02)
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- METABOLIC STUDIES WITH MODEL CYTOCHROME p-450 SYSTEMS
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The biomimetic potential of metalloporphyrin catalysts has been studied using nicotine as the substrate.Results indicate the formation of products identical to those obtained from in vivo metabolism.
- Chauncey, M. A.,Ninomiya, Shin-ichi
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p. 5901 - 5904
(2007/10/02)
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- ON THE GIF OXIDATION OF ALICYCLIC TERTIARY AMINES
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Oxidation of various tertiary amines by the GifIV system based on iron catalyst associated with a reductant (zinc) and molecular oxigen, led to a mixture of the keto-derivatives and the corresponding lactams.Steric hindrance and electron withdrawing substituents exert a deactivating effect on the oxidation.
- Barton, D.H.R,Boivin, J.,Gaudin D.,Jankowski, K.
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p. 1381 - 1382
(2007/10/02)
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- PREPARATION OF LACTAMS VIA OXIDATION OF CYCLIC, TERTIARY AND SECONDARY AMINES WITH Hg(II)-EDTA COMPLEX IN ALKALINE MEDIUM
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Oxidation of N-alkylpiperidines and other cyclic, tertiary amines with Hg(II)-EDTA complex in basic solution yields lactams, similar oxidation of N-hydroxypiperidines gives hydroxamic acids (presumably via nitrones) and oxidation of N-unsubstituted piperidines affords lactams, probably via 1-piperidine trimers.
- Wenkert, Ernest,Angell, E. Charles
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p. 1331 - 1338
(2007/10/02)
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- HYPERVALENT IODINE OXIDATION OF AMINES USING IODOSOBENZENE: SYNTHESIS OF NITRILES, KETONES AND LACTAMS
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Primary aliphatic amines on oxidation with iodosobenzene in CH2Cl2 or H2O yield the corresponding nitriles, while primary cycloalkylamines give the corresponding cyclic ketones.Lactams are obtained by the oxidation of cyclic amines. (S)(-) Nicotine (15) is oxidized to (+/-)-cotinine (16).The intermediary imine involved in these processes was trapped in the case of piperidine as the α-aminonitrile.
- Moriarty, Robert M.,Vaid, Radhe K.,Duncan, Michael P.,Ochiai, Masahito,Inenaga, Minako,Nagao, Yoshimitsu
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p. 6913 - 6916
(2007/10/02)
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- PHOTO-INDUCED ELECTRON-TRANSFER OXIDATION OF NICOTINE
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Irradiation of nicotine in acetonitrile in the presence of TiO2 or 9,10-dicyanoanthracene under oxygen with a 100 W high pressure mercury lamp gave nicotyrine, cotinine,, and dehydronornicotine.A reaction mechanism leading to these products trough nicotine radical cation and superoxide anion is proposed.
- Yamada, Shuzo,Sakai, Toshiaki,Ohashi, Mamoru
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p. 287 - 290
(2007/10/02)
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- Transformations involving the Pyrrolidine Ring of Nicotine
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Nicotine was oxidised to cotinine and this successively alkylated and reduced to a series of 4'-mono- and 4',4'-di-alkylnicotines, the mass spectra of which are discussed.The pyrrolidine ring has been opened with ethyl chloroformate and the product both recyclised to S-nicotine without loss of optical activity and converted to metanicotine.The dihydrochloride of the last, on successive treatment with bromine and sodium hydrogencarbonate, yielded 3'-bromonicotine.Cotinine has been converted into various derivatives, and the demethylation of nicotine has been investigated.
- Acheson, R. Morrin,Ferris, Michael J.,Sinclair, Neil M.
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p. 579 - 585
(2007/10/02)
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