Reactions of polyhalogenopyridines. 11.* Synthesis of 3-hydroxy-4,6,7-trichloro-2-ethoxycarbonylthieno[3,2-c]pyridine

A derivative of thieno[3,2-c]pyridine was synthesized by intramolecular condensation of the substituents at positions 3 and 4 of the pyridine ring.for Communication 10. see[1].Chernogolovka Institute of Chemical Physics, Russian Academy of Sciences, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 364–365, March, 1996. Original article submitted December 6, 1995.     

Reactions of polyhalopyridines 7. New method of synthesizing carbonyl-containing derivatives of polychloropyridine-2-thiols

A method of synthesizing S-alkylcarbonyl and dicarbonyl substituted polychloropyridine-2-thiols has been developed which is based on the thermally induced decomposition of N,N-dimethyldithiocarbamate derivatives of polychloropyridine N-oxides in the presence of carbonyl compounds. Various pathways were shown for the thermolysis of the starting materials depending on the number of chlorine atoms in the pyridine nucleus.For Communication 6 see [1].Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, Chernogolovka 14232. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 660–665, May, 1994. Original article submitted April 11, 1994.     

Reactions of polyhalogenopyridines. 12. Reactions of 4-pentafluoroethylthio-2,3, 5,6-tetrafluoropyridine with nucleophilic agents

The reactions of 4-perfluoroethylthio-2,3,5,6-tetrafluoropyridine with various nucleophilic agents were investigated. It was shown that the pentafluoroethylthio group is inert toward N- and O-nucleophiles.For Communication 11, see [1].Chernogolovka Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 932–935, July, 1996. Original article submitted June 22, 1996.     

Reactions of polyhalogenopyridines. 14. Reaction of isomeric dichlorocyanopyridines and pentachloropyridine with potassium ethylxanthate

The reactions of isomeric tetrachlorocyanopyridines with potassium ethylxanthate were studied. It was found that tetrachloro-2-cyanopyridine was converted successively into 4-mono- and then 3,4-bisethylxanthate derivatives. In the presence of potassium ethylxanthate the last derivative undergoes intramolecular cyclization with the formation of derivatives of 1,3-dithiolo[4,5-c]pyridine. In the case of other initial polychloropyridines processes involving substitution of the chlorine atoms by the ethylxanthate fragment, sometimes accompanied by the loss of COS molecules, were observed instead of heterocyclization. For Communication 13, see [1]. Chernogolovka Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka 142432. M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1510–1520, November, 1997.     

Reactions of polyhalogenopyridines. 15. Reaction of isomeric tetrachlorocyanopyridines and pentachloropyridine with potassium isopropyltrithiocarbonate

The reaction of isomeric tetrachlorocyanopyridines and pentachloropyridine with potassium isopropyltrithiocarbonate was investigated. It was found that the structure and composition of the reaction products depend both on the initial polychloropyridines and on the solvent in which the process is carried out. The intramolecular transformations of the isopropyltrithiocarbonate derivatives of tetrachloro-2-cyanopyridine in acetonitrile solution lead to 1,3-dithiolo[4,5-c]pyridines. In other cases heterocyclization was not observed. If the reactions were conducted in ethanol (except with tetrachloro-3-cyanopyridine) thioalkylation of the pyridine ring occurred.For Communication 14, see [1].Chernogolovka Institute of Chemical Physics, Chernogolovka 142432, Russia. M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 330–341, March, 1998.     

Stereo- and regioselective cycloaddition of norbornene to 2,4,9-triazidopyridine

4-(3-Azatricyclo[3.2.1.0]oct-3-yl)-2,6-diazido-3,5-dicyanopyridine has been obtained by the reaction of 2,4,6-triazido-3,5-dicyanopyridine with an equimolar quantity of norbornene. The product reacted readily at room temperature with an excess of norbornene giving the corresponding trisazatricyclooctane cycloadduct. An analogous trisadduct was obtained in the reaction of 4-(3-azatricyclo[3.2.1.0]oct-3-yl)-1,6-diazido-3-chloro-5-cyanopyridine with norbornene on boiling in CCl₄, and also in ether at room temperature in the presence of the complexes Rh₂(OAc)₄ and Cu(AcAc)₂. The cycloaddition proceeds stereoselectively in all cases with the exclusive formation of exo-conformers. Calculations have been carried out using the PM3 and RHF/3-21G^* methods on 2,4,6-triazido-3-chloro-5-cyanopyridine and on 2,4,6-triazido-3,5-dicyanopyridine and also on the cycloadducts of these compounds with one or two molecules of norbornene. It was established that the addition of norbornene at the azide groups of pyridine is a dipole-LUMO controlled type of reaction and leads to the formation of cycloadducts having higher LUMO energy than the initial azides. The energy of the LUMO is increased to a lesser extent as a result of the addition of norbornene to a triazide containing identical substituents in the β positions of the pyridine ring, and is due to the special features of the symmetry of the LUMO of the cycloadducts formed. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1521–1532, November, 1997.     

The unusual structure of 3-hydro-2-acetylbenzo[b]thiophene hydrazones

The structure of N,N-disubstituted 3-hydroxy-2-acetylbenzo[b]thiophene hydrazones was investigated by x-ray structural analysis. 2-(N-Methyl-N-phenylhydrazinoethylidene)-3(2H)-benzo[b]thiophenone exists in the E-ketoenehydrazine form, and 2-(N,N-diphenylhydrazinoethylidene)-3(2H)-benzo[b]thiophenone in the crystals forms a structure intermediate between the ketoenehydrazine and hydroxyhydrazone forms.Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 917–922, April, 1992.     

Trisubstituted 1,3,5-triazines. 2. Synthesis of 1,3,5-triazines from 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine

A study was carried out on electrophilic addition and hydrolytic dissociation of 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine. Chloro, bromo, and methyl derivatives of tris[di(tert-butoxycarbonyl)methyl]-1,3,5-triazine were synthesized for the first time as well as 2,4,6-tris-(tert-butoxycarbonylmethyl)-1,3,5-triazine. For Communication 1, see ref. [1]. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow and Institute of Chemical Physics, Russian Academy of Sciences at Chernogolovka, 142432 Chernogolovka, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1407, October, 1998.     

Furopyridines. XVII . Cyanation,chlorination and nitration of furo[3,2-b]pyridine N-oxide

The N-oxide 2 of furo[3,2-b]pyridine ( 1 ) was cyanated by the Reissert-Henze reaction with potassium cyanide and benzoyl chloride to give 5-cyano derivative 3 , which was converted to the carboxamide 4 , carboxylic acid 5 , ethyl ester 6 and ethyl imidate 8 . Chlorination of 2 with phosphorus oxychloride yielded 2-9a , 3- 9b , 5- 9c and 7-chloro derivative 9d . Reaction of 9d with sodium methoxide, pyrrolidine, N,N-dimethylformamide and ethyl cyanoacetate afforded 7-methoxy- 10 , 7-(1-pyrrolidyl)- 11 and 7-dimethylaminofuro[3,2-b]pyridine ( 14 ) and 7-(1-cyano-1-ethoxy-carbonyl)methylene-4,7-dihydrofuro[3,2-b]pyridine ( 12 ). Nitration of 2 with a mixture of fuming nitric acid and sulfuric acid gave 2-nitrofuro[3,2-b]pyridine N-oxide ( 15 ).     

Reactions of polyhalopyridines. 8. Reactions of polychlorotrifluoromethyl-pyridines with sodium N,N-dimethyldithiocarbamate. Structure of the 8-trifluoromethylbis-1,3-dithiolo-[4,5-b:4′,5′-e]-pyridine-2,6-dione molecule

The reaction of the isomeric tetrachloro--, -, and -trifluoromethylpyridines and of 3,4,5-trichloro-2-trifluoromethylpyridine with sodium N,N-dimethyldithiocarbamate dihydrate has been studied. In the case of the -, and -isomers an intramolecular cyclization with the formation of 1,3-dithiol-2-one derivatives occurs and the remaining compounds give only products of mono- or disubstitution of chlorine atoms by a dithiocarbamate fragment at positions 4 or 6 of the pyridine ring. The structure of the compounds synthesized was proved using¹³C NMR and X-ray crystallographic analysis.See [6] for part 7.Institute of Chemical Physics, Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1278–1284, September, 1994. Original article submitted June 25, 1994.     

Lateral Metallation and Redistribution Reactions of Sodium Ferrates Containing Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilide Ligands

Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe₃)(Dipp) (Dipp=2,6-iPr₂-C₆H₃). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS)₃] (HMDS=N(SiMe₃)₂) with an excess of HN(SiMe₃)(Dipp) led to the isolation of heteroleptic [Na(HMDS)₂Fe{N(SiMe₃)Dipp}]_∞ ( 1 ) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe₃)Dipp] and [Fe{N(SiMe₃)Dipp}₂] induces lateral metallation of one Me arm from the SiMe₃ group in the iron amide furnishing tetrameric [NaFe{N(SiCH₂Me₂)Dipp}{N(SiMe₃)Dipp}]₄ ( 2 ). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe₃)Dipp}(HMDS)Fe(C₆F₅)]_∞ ( 4 ). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe₃)Dipp}(HMDS)] ( 5 ), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate.     

Polysulfonylamine. LXXXIV [1]. Zur Isotypie in den Dimesylamid-Komplexreihen [M(H2O)4{(CH3SO2)2N}2] (MMg,Ca, Ni,Cu, Zn,Cd) und [M(py)4{(CH3SO2)2N}2] (MNi,Cu, Zn,Cd)

Polysulfonylamines. LXXXIV. Isotypic Structures in the Dimesylamide Complex Series [M(H₂O)₄{(CH₃SO₂)₂N}₂] (M?Mg, Ca, Ni, Cu, Zn, Cd) and [M(py)₄{(CH₃SO₂)₂N}₂] (M?Ni, Cu, Zn, Cd) The crystal structures of the trans-octahedral complexes [M(H₂O)₄{(CH₃SO₂)₂N}₂] (M?Ca, Cd), in which the dimesylamide anion acts as a monodentate O-ligand and a tetrafunctional hydrogen bond acceptor, were determined by low-temperature X-ray diffraction. Both belong to an isotypic series (triclinic, space group P1 , Z = 1) that had previously been characterized for M?Mg, Ni, Cu and Zn (Z. Anorg. Allg. Chem. 1996 , 622, 1065). In this structure there exists an extended network of strong hydrogen bonds which is probably the underlying reason why the structure type surprisingly persists across the whole series. To support this explanation by indirect evidence from comparison with suitable structures devoid of strong hydrogen bonding, the analogous trans-octahedral complexes [M(py)₄{(CH₃SO₂)₂N}₂] (M?Mn, Co, Ni, Cu, Zn, Cd) were prepared by treating M[(CH₃SO₂)₂N]₂ with pyridine, and the crystal structures of the Ni, Cu, Zn and Cd compounds were studied by low-temperature X-ray crystallography. As anticipated, the four pyridine complexes do not form an isotypic series but instead two isotypic pairs consisting of the Ni and Zn compounds (monoclinic, space group P2₁/n, Z =2) and of the Cu and Cd complexes (triclinic, space group P1, Z = 1). All molecules of the aqua and the pyridine complexes display crystallographic centrosymmetry. In the hydrates, the mean M? OH₂ and the M? O(anion) distances are 232.6 and 232.7 pm for M ? Ca, 225.5 and 230.3 pm für M ? Cd. The mean M? N and the M? O(anion) bond lengths of the pyridine species amount to 211.8 and 213.1 pm for M ? Ni, 217.0 and 218.5 pm for M ? Zn, 232.8 and 234.4 pm for M ? Cd; the corresponding values for the severely Jahn-Teller distorted Cu complex are 203.6 and 254.5 pm. In the crystals of the pyridine complexes, each methyl group is connected through a weak C? H…?O bond to a sulfonyl oxygen atom of an adjacent molecule.     

Nitromethyl derivatives of 1,3,5-triazine. Synthesis and properties

The destructive nitration of 2,4,6-tris[di(carboxy)methylene]hexahydro-1,3,5-triazine and its esters has been investigated. A first representative of the nitromethyl derivatives of 1,3,5-triazine, viz. 2,4,6-tris(nitromethyl)-1,3,5-triazine, has been synthesized.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1254–1259, September, 1997.     

2,6‐Bis[bis(2‐pyridiniomethyl)aminomethyl]‐4‐tert‐butylphenol dichloride diperchlorate hydrate

The title compound, C₃₆H₄₄N₆O⁴⁺·2Cl^?·2ClO₄^?·0.132H₂O, is shown to be protonated at all the pyridine N atoms; the two chloride ions are hydrogen bonded to three pyridine N atoms and to the phenolic O atom of the same cation [Cl?N = 3.045 (2)–3.131 (2) Å and Cl?O = 2.938 (2) Å], and the remaining pyridine N atom is hydrogen bonded to the phenolic O atom [N?O = 2.861 (2) Å]. The mean value of the C—N—C angle of the protonated pyridine rings is 123.4 (1)°, which is significantly larger than that found for unprotonated pyridine rings.     

Reactions of 2,4-disubstituted 5-nitro-1,2,3-triazole 1-oxides. 2. Oxidation of 2-substituted 4-amino(alkylamino)-5-nitro-1,2,3-triazole 1-oxides

The oxidation of substituted aminonitrotriazole oxides to the corresponding dinitro derivatives of triazole and azotriazole oxides has been studied. Communication 1, see ref. [1]. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow, Russia; e-mail: cheminst@mail.psu.ru. Institute of Chemical Physics at Chernogolovka, Russian Academy of Sciences, 124432 Chernogolovka, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1356–1362, October, 1999.     

Bis­[4‐(di­methyl­amino)­pyridinium] hexa­chloro­stannate(IV)

In the title compound, 4‐(di­methyl­amino)­pyridine is proton­ated on the pyridine N atom. The N(CH₃)₂ moiety is twisted 4.4 (2)° from the pyridine‐ring plane. The octahedral [SnCl₆]^2? anion is hydrogen bonded via trans‐Cl atoms to pyridinium N atoms from two cations forming (C₇H₁₁N₂)₂[SnCl₆] structural units.     

The development of phosphinoamine–Pd(II)–imidazole complexes: implications in room‐temperature Suzuki–Miyaura cross‐coupling reaction

The reaction of N‐methylimidazole (N‐MeIm) and N‐butylimidazole (N‐BuIm) with the complexes [PdCl₂(PPh₂py–P,N)] and [PdCl₂(PPh₂Etpy–P,N)] in the presence of NH₄PF₆ under N₂ at room temperature afforded four new cationic Pd(II) complexes [PdCl(PPh₂py–P,N)(N‐MeIm)](PF₆) ( 1 ), [PdCl(PPh₂py–P,N)(N‐BuIm)](PF₆) ( 2 ), [PdCl(PPh₂Etpy–P,N)(N‐MeIm)](PF₆) ( 4 ) and [PdCl(PPh₂Etpy‐P,N)(N‐BuIm)](PF₆) ( 5 ) in good yields, where PPh₂py is 2‐(diphenylphosphino)pyridine and PPh₂Etpy is 2‐{2‐(diphenylphosphino)ethyl}pyridine). The complexes were fully characterized. The catalytic activities of these complexes were investigated for Suzuki–Miyaura cross‐coupling reactions at room temperature. Complex 2 exhibited excellent activity compared to other analogs. Copyright © 2013 John Wiley & Sons, Ltd.     

Complexes of germanium bromides with 4‐picoline and 3,4‐lutidine

The reactions of GeBr₄ with 4‐methyl­pyridine and 3,4‐di­methyl­pyridine lead to tetra­bromo­bis(4‐methyl­pyridine)­germanium, [GeBr₄(C₆H₇N)₂], and tetra­bromo­bis(3,4‐di­methyl­pyridine)­germanium, [GeBr₄(C₇H₉N)₂], respectively. These structures show the same features as the corresponding silicon complexes.     

Reaktionen von Organometallverbindungen. VI1. Bildung von Trichloroplumbaten(II) beim Zerfall von Dimethylbleidichlorid in Pyridin und Homologen

Reactions of organometal compounds. VI. Formation of Trichloroplumbates(II) by decomposition of dimethyl lead dichloride in pyridine and its homologues (CH₃)₂PbCl₂ disproportionates in pyridine, 2-methylpyridine and quinoline solution to give (CH₃)₂PbCl and – as a result of the decomposition of the second disproportionation product CH₃PbCl₃ in the presence of the bases – the trichloroplumbates(II) of the N-methylated bases: [C₅H₅N · CH₃][PbCl₃], [C₆G₇N · CH₃][PbCl₃] and [C₉H₇N · CH₃] · [PbCl₃]. N-methylpyridinium-trichloroplumbate(II) crystallizes orthorhombic, space group Pna2₁ or Pnma.     

trans‐Di­aqua­bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato‐κ2N3,O4)­cobalt(II) 4,4′‐bi­pyridine solvate

In the title compound, [Co(C₅H₃N₂O₄)₂(H₂O)₂]·C₁₀H₈N₂, the Co atom is trans‐coordinated by two pairs of N and O atoms from two monoanionic 4,5‐di­carboxy­imidazole ligands, and by two O atoms from two coordinated water mol­ecules, in a distorted octahedral geometry. The 4,4′‐bi­pyridine solvent molecule is not involved in coordination but is linked by an N—H⋯N hydrogen bond to the neutral [Co(C₅H₃N₂O₄)₂(H₂O)₂] mol­ecule. Both mol­ecules are located on inversion centers. The crystal packing is stabilized by N—H⋯N and O—H⋯O hydrogen bonds, which produce a three‐dimensional hydrogen‐bonded network. Offset π–π stacking interactions between the pyridine rings of adjacent 4,4′‐bi­pyridine molecules were observed, with a face‐to‐face distance of 3.345 (1) Å.