Nicotinic N-oxide Research Articles

Aromatic N-oxide bridged copper(II) coordination polymers: Synthesis, characterization and magnetic properties

The complexes [Cu 2( o-NO 2–C 6H 4COO) 4(PNO) 2] ( 1), [Cu 2(C 6H 5COO) 4(2,2′-BPNO)] n ( 2), [Cu 2(C 6H 5COO) 4(4,4′-BPNO)] n ( 3), [Cu( p-OH–C 6H 4COO) 2(4,4′-BPNO) 2·H 2O] n ( 4), (where PNO = pyridine N-oxide, 2,2′-BPNO = 2,2′-bipyridyl- N, N′-dioxide, 4,4′-BPNO = 4,4′-bipyridyl- N, N′-dioxide) are prepared and characterized and their magnetic properties are studied as a function of temperature. Complex 1 is a discrete dinuclear complex while complexes 2– 4 are polymeric of which 2 and 3 have paddle wheel repeating units. Magnetic susceptibility measurements from polycrystalline samples of 1– 4 revealed strong antiferromagnetic interactions within the {Cu 2} 4+ paddle wheel units and no discernible interactions between the units. The complex 5, [Cu(NicoNO) 2·2H 2O] n ·4 nH 2O, in which the bridging ligand to the adjacent copper(II) ions is nicotinate N-oxide (NicoNO) the transmitted interaction is very weakly antiferromagnetic.

3D MnIIcoordination polymer with alternating azide/azide/formate/formate bridged chains: synthesis, structure and magnetic properties

A new 3D Mn(II) coordination polymer, [Mn(2)(HCO(2))(L)(2)(N(3)) x MeOH](infinity) (1) (L = nicotinate N-oxide), was synthesized by a solvothermal reaction and characterized magnetically. Complex 1 is a typical antiferromagnet with alternating azide/azide/formate/formate bridges, exhibiting a new -J(1)J(1)J(2)J(2)- coupling sequence. This is the first complex to contain an azide, formate and another type of carboxylate ligand.

Single-Crystal-to-Single-Crystal Transformation in Unusual Three-Dimensional Manganese(II) Frameworks Exhibiting Unprecedented Topology and Homospin Ferrimagnet

A new three-dimensional Mn(II) complex, [Mn(3)(HCO(2))(2)(L)(2)(OCH(3))(2)], 1 (L = nicotinate N-oxide), was synthesized by solvothermal reaction and magnetically characterized. Complex 1 exhibits an unprecedented 3,6-connected 5-nodal net topology with Schlafli notation {4(2);6}4{4(3)}2{4(6);6(6);8(3);10}2{4(8);6(6);8} and was assigned as a homospin ferrimagnet. Interestingly, when 1 was placed in air for ca. one month, the methoxy anions in 1 were gradually exchanged by hydroxyl anions and 1 underwent a single-crystal-to-single-crystal structural transition to a new but similar complex, [Mn(3)(HCO(2))(2)(L)(2)(OH)(2)] x 4 H(2)O, 2. The anion exchange and water molecules filling the channels of 2 affect the magnetic behavior at low temperature compared to that of 1.

Poly[μ-azido-(μ3-nicotinatoN-oxide)zinc(II)

The title compound, [Zn(C6H4NO3)(N3)], has been prepared by the reaction of nicotinate N-oxide acid, zinc(II) nitrate and sodium azide. The Zn atom is five coordinated by two azide anions and three nicotinate N-oxide ligands. Each nicotinate N-oxide bridges three Zn atoms, whereas the azide bridges two Zn atoms, resulting in the formation of a two-dimensional metal–organic polymer developing parallel to (100).

Coordination Polymers with End-On Azido and Pyridine CarboxylateN-Oxide Bridges Displaying Long-Range Magnetic Ordering with Low Dimensional Character

A series of 2D and one 3D transition-metal-azido coordination polymers with pyridine carboxylate N-oxide, isonicotinate N-oxide (INO), and nicotinate N-oxide (NNO) as the coligands were synthesized by a hydrothermal method and structurally and magnetically characterized. These complexes have the formulas [M(L)(N3)(H2O)]n (L = INO and M = Mn, 1.Mn; Co, 2.Co; Ni, 3.Ni and L = NNO and M = Mn, 4.Mn; Co, 5.Co; Ni, 6.Ni) and [Cu(L)(N3)(H2O)(0.5)]n (L = INO, 7.Cu; NNO, 8.Cu). All complexes consist of end-on azido and syn-syn carboxylato mixed-bridged M-N(3)/COO chains that are further linked by the pyridine N-oxide group of the INO or NNO to give rise to 2D layered structures for 1.Mn, 2.Co, 3.Ni, 4.Mn, 5.Co, 6.Ni, and 8.Cu and a 3D framework for 7.Cu. The high-temperature magnetic susceptibilities are dominated by low-dimensional behavior while long-range ordering sets in at low temperatures. The Mn complexes are antiferromagnets, and the others are metamagnets. In addition, 5.Co exhibits slow magnetic relaxation behavior at low temperatures. The metamagnetism in each case is due to strong intrachain ferromagnetic interactions and weak interchain antiferromagnetic ones.

Ligand-controlled dimensionality: 1D, 2D and 3D Gd(iii) coordination polymers based on SO42? and pyridine carboxylate N-oxide ligands

Three Gd(III)-sulfate polymers [Gd(PNO)(H2O)2(SO4)]n (1), [Gd(NNO)(H2O)2(SO4)]n (2), and [Gd(INO)(H2O)(SO4)]n (3) exhibiting a systematic variation in framework dimensionality have been hydrothermally synthesized by using three isomeric pyridine carboxylate N-oxides, PNO = picolinate N-oxide, NNO = nicotinate N-oxide, and INO = isonicotinate N-oxide, as organic components. Compound 1 comprises 1D coordination chains that are unable to propagate to higher dimensionalities due to the convergent endo PNO ligand. The structure of compound 2 consists of hydrogen-bonded layers. The formation of the 2D layer is attributed to the more divergent NNO than PNO. Compound 3 consists of a 2-fold interpenetrating “3D herringbone” framework, in which the most divergent exo ligands of INO connect the individual Gd-sulfate inorganic chains to produce the 3D coordination network. It is demonstrated that the convergence or divergence of the three isomeric ligands of the pyridine carboxylate N-oxide can be used to engineer the dimensionality of the coordination polymers.

Synthesis and reduction of (S)-(-)-nicotine-N’-oxide and N,N’-dioxides by rat liver S-9 fraction

cisAnd trans-Nicotine-N’-oxide (5) and N,N’-dioxide (7) diastereomers were synthesized in good yields from nicotine (1) using m-CPBA. Asymmetric reductions of nicotine N-oxides with rat liver S-9 fraction were investigated.

Alkaloid tolerance in Manduca sexta and phylogenetically related sphingids (Lepidoptera: Sphingidae)

Nicotine tolerance is well known for Manduca sexta. It also occurs in several other sphingids of the subfamilies Macroglossinae and Sphinginae. Only members of the subfamily Smerinthinae appear to be more susceptible to nicotine intoxication. Phylogenetic trees have been reconstructed from mitochondrial 16S rDNA and nuclear DNA to map nicotine tolerance.¶The nicotine binding site of both α-subunits of nicotinic acetylcholine receptors (nAChR) have been amplified and sequenced. No apparent amino acid substitution can be seen in the putative nicotine binding site of the α-subunits of nAChR from nicotine tolerant and nicotine sensitive sphingids. Thus, a simple target-site modification can be ruled out as a cause for nicotine tolerance. This finding agrees with feeding experiments: larvae of M. sexta and other sphingids of the Macroglossinae and Sphinginae not only tolerated nicotine, but also many other alkaloids that affect neuroreceptors other than acetylcholine receptors (nAChR, mAChR).¶Only 10 to 20% of nicotine injected into larvae of nicotine-tolerant taxa could be recovered later as free nicotine, nicotine N-oxide or cotinine, i.e., 80 to 90% must have been converted to polar conjugates or degradation products which are not detectable with the methods applied. Usually more than 98% of the recoverable alkaloids were found in the faeces. Excretion reached a maximum 6 h after injection in tolerant taxa. Larvae of Manduca sexta, which were reared on a nicotine-rich diet, showed higher nicotine degradation and faster nicotine elimination than naive larvae. Application of the cytochrome P450 inhibitor SKF 525A (proadifen) reduced the formation of nicotine N-oxide and the rate of alkaloid degradation. Thus, an inducible detoxification mechanism, coupled with a rapid and inducible excretion, appear to be a strategy in Sphingidae that helps them to live on host plants rich in otherwise toxic secondary metabolites.

Determination of nicotine N-oxide by gas chromatography following thermal conversion to 2-methyl-6-(3-pyridyl)tetrahydro-1,2-oxazine.

Determination of nicotine N-oxide by gas chromatography following thermal conversion to 2-methyl-6-(3-pyridyl)tetrahydro-1,2-oxazine.

Organometallic methylation of nicotine and nicotine N-oxide. Reaction pathways and racemization mechanisms

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOrganometallic methylation of nicotine and nicotine N-oxide. Reaction pathways and racemization mechanismsJeffrey I. Seeman, Henry V. Secor, Charles R. Howe, Charles G. Chavdarian, and Larry W. MorganCite this: J. Org. Chem. 1983, 48, 25, 4899–4904Publication Date (Print):December 1, 1983Publication History Published online1 May 2002Published inissue 1 December 1983https://doi.org/10.1021/jo00173a023RIGHTS & PERMISSIONSArticle Views155Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (795 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The radical and organometallic methylation of nicotine and nicotine n-oxide

2-Methylnicotine is a major product in the reaction of nicotine with methyllithium and methyl radical, in addition to the previously reported 4- and 6-methylnicotines. The reaction of nicotine N-oxide with methylmagnesium bromide furnishes both 2- and 6-methylnicotine.

The structure of polymeric diaquo-di-μ-hydroxo-bis-μ-(nicotinato-N-oxide)-bis-μ-(nicotinato-N-oxide)tricopper(II)

The new unusual polymeric copper(II) complex with nicotinate N-oxide (N-nicO), [Cu 3(N-nicO) 4(OH) 2(H 2O) 2] n was prepared and its crystal and molecular structure was determined from three-dimensional X-ray diffraction data. The crystals belong to the triclinic space group P 1 (No. 2). The cell parameters are a = 7.881(9), b = 9.658(11), c = 10.368(12) Å, α = 97.32(9), β = 110.38(9), γ = 109.53(9)°, V = 670(1) Å 3, d obs = 1.94 ( d calc = 2.02) and Z = 1. The structure was refined to a final R-value of 4.13%. The complex is a polymeric, linear chain along the c-axis, and its structure units are connected with each other through two N-oxide oxygen atoms. There are three copper atoms (Cu1, Cu2, Cu2′) that are very close to each other in the structure unit, and the CuCu distances are 3.035 Å. The coordination around the copper atom Cu1 is square planar and around the copper atoms Cu2 and Cu2′ it is square pyramidal with long axial coordination. Nicotinate-N-oxide acts as a bridging ligand and is coordinated bidentately either through both carboxylate O atoms forming a bridge between Cu1 and Cu2 (Cu2′) or through one carboxylate O atom and the N-oxide O atom forming a double bridge between Cu2 and Cu2′ in separate structural units. Water molecules are coordinated with copper atoms Cu2 and Cu2′, and hydroxide groups form a bridge between Cu1 and Cu2, both Cu1 and Cu2′, respectively.

Ferrous and ferric nicotinate N-oxide complexes

Ferrous and ferric nicotinate N-oxide complexes

Nicotinate N-oxide complexes with dipositive 3d metal ions

Nicotinate N-oxide complexes with dipositive 3d metal ions

Nicotine N-oxides

Nicotine-1-N-oxide, trans and cis isomers of nicotine-1′-N-oxide and of nicotine-1,1′-di-N-oxide have been prepared and characterised by NMR, MS and reduction to nicotine. The trans and cis isomers of nicotine-1′-N-oxide have been identified in leaves, stems and roots of Nicotiana tabacum, N. affinis and N. sylvestris.

Modification of nicotine toxicity by pretreatment with different drugs

Sub-lethal doses of nicotine have been shown to protect mice from the lethal effects of subsequently administered doses of the same drug. The evidence suggests that a metabolic product of nicotine is responsible for the protective action. In an attempt to identify this metabolite it was shown that cotinine had no protective action but that nicotine N-oxide and also the reduction product of cotinine both conferred some protection. The pharmacological basis of the protective effect is not clear but it may involve ganglion-blocking activity; the ganglion-blocking drugs hexamethonium and pempidine also protected mice from the lethal effects of nicotine.

N-oxides of some heterocyclic bases Communication 1. Preparation and properties of N-oxides of nicotine

1. In a study of the oxidation of nicotine with hydrogen peroxide all three possible N-oxides were prepared in the crystalline state; of these, nicotine N,N'-dioxide and nicotine N'-oxide (oxygen on the pyridine nitrogen) have not been described previously. 2. Nicotine N,N'-dioxide was prepared as a crystal hydrate with two molecules of water, and also as the anhydrous base, the monopicrate, the dihydrochloride, and the mercury complex. 3. Nicotine N'-oxide was prepared as the crystalline base, the dihydrochloride, the dipicrate, and the mercury complex. 4. From nicotine N-oxide, which was prepared previously by Pinner and is known in the literature as “oxynicotine”, we obtained the previously undescribed hydrochloride and isolated the anhydrous base.