ChemInform Abstract: Fluoride Salts-Alcohols-Alumina as Reagents for Nucleophilic Substitution of Chlorine Atoms for Alkoxy Groups in 2,3- Dichlorosubstituted Juglones, Naphthazarines, and Quinizarines.

ChemInform ◽  
2010 ◽  
Vol 26 (31) ◽  
pp. no-no
Author(s):  
V. PH. ANUFRIEV ◽  
V. L. NOVIKOV
Keyword(s):  
Nucleophilic Substitution ◽  
Chlorine Atoms ◽  
Alkoxy Groups ◽  
Fluoride Salts

Nucleophilic substitution of chlorine atoms in polyvinyl chloride

2008 ◽  
Vol 81 (1) ◽  
pp. 131-134 ◽  
Author(s):  
N. S. Shaglaeva ◽  
R. T. Sultangareev ◽  
E. A. Zabanova ◽  
O. V. Lebedeva ◽  
K. S. Trofimova
Keyword(s):  
Nucleophilic Substitution ◽  
Polyvinyl Chloride ◽  
Chlorine Atoms

scholarly journals Transformation of 2H-1,2,3-benzothiadiazine 1,1-dioxides variously substituted at the aromatic ring, via nucleophilic substitution and demethylation reactions

2020 ◽  
Author(s):  
Imre Gyűjtő ◽  
Márta Porcs-Makkay ◽  
Ernák Ferenc Várda ◽  
Gyöngyvér Pusztai ◽  
Gábor Tóth ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Functional Groups ◽  
Aromatic Ring ◽  
Methoxy Group ◽  
Medicinal Chemistry ◽  
Building Blocks ◽  
Chlorine Atoms ◽  
New Methods ◽  
Pharmacological Interest

2H‑1,2,3‑Benzothiadiazine 1,1-dioxides are a class of compounds of pharmacological interest. After earlier studies carried out at our laboratory on various transformations (alkylation, acylation, reduction) at the hetero ring, the present manuscript focuses on the transformation of substituents at the aromatic carbocycle, including nucleophilic substitution of chlorine atoms and demethylation of the methoxy group with amines. The new methods described here allow the introduction of versatile functional groups on the aromatic ring, making these compounds useful building blocks for organic and medicinal chemistry applications.

C-Nucleophilic substitution in tetrachlorophthalonitrile — An approach to some new hexadecasubstituted phthalocyanines

2013 ◽  
Vol 17 (08n09) ◽  
pp. 799-806 ◽  
Author(s):  
Vladimir Negrimovsky ◽  
Konstantin Volkov ◽  
Kyrill Suponitsky ◽  
Evgeny Lukyanets
Keyword(s):  
Nucleophilic Substitution ◽  
Benzene Ring ◽  
Chlorine Atom ◽  
Diethyl Malonate ◽  
Methine Proton ◽  
Chlorine Atoms ◽  
High Acidity ◽  
Zinc Phthalocyanines ◽  
Atoms First

Reaction of tetrachlorophthalonitrile with some C -nucleophiles was studied. Only one chlorine atom was substituted regioselectively in the position 4 of benzene ring with diethyl malonate and malononitrile; no reaction occurred in case of bulkier diethyl ethylmalonate and ethylmalononitrile. In case of dimedone the domino substitution of two chlorine atoms, first with C -nucleophile followed by enolate O -nucleophile led to the mixture of two dibenzofuran derivatives. Remaining chlorine aroms n malonate and dibenzofuran derivatives were substituted with thiols, but in malononitrile derivative high acidity of methine proton led to the formation of stable carbanion under basic conditions that prevents further substitution. Hexadecasubstituted zinc phthalocyanines were synthesized from some new phthalonitriles.

scholarly journals Squalene interactions with some hydrosilanes and hydrogermans

2020 ◽  
Vol 64 (11) ◽  
pp. 42-54
Author(s):  
Dmitry A. Efimenko ◽  
◽  
Irina B. Sokolskaya ◽  
Mihail M. Sibircev ◽  
Valentin G. Lahtin ◽  
...  
Keyword(s):  
Metal Complexes ◽  
Silicon Germanium ◽  
Spectral Study ◽  
Electrophilic Addition ◽  
Addition Reactions ◽  
Hydrogen Atoms ◽  
Chlorine Atoms ◽  
Effect Of Substituents ◽  
Alkoxy Groups

Squalene hydrosilylation by a number of organohydrosilanes R3SiH and Me3GeH, including a mixture of α- and β-isomers of adducts of vinyltrimethylsilane addition to tetramethyldisiloxane: HSi(Me2)O(Me2)Si-C(Me)-SiMe3 and HSi(Me2)O(Me2)Si-(CH2)2-SiMe3, formed both according to Markovnikov's rule and against it, is discussed. We pay attention to the mismatch of values between the electronegativities of carbon, silicon, germanium and hydrogen atoms and the reactivity of C-H, Si-H, and Ge-H bonds. A spectral study of a mixture of α- and β-isomers was carried out. The effect of substituents at elements on its reactivity is discussed: hydrosilanes with chlorine atoms, alkyl and alkoxy groups on silicon are not active in the squalene hydrosilylation. In contrast to them, the α- and β-adducts and their mixture add well to squalene with an unambiguously unknown regioselectivity. The results obtained indicate the special behavior of squalene in electrophilic addition reactions catalyzed by metal complexes, in contrast to substituted ethylenes.

scholarly journals Dehalogenation of polychlorinated biphenyls (PCB) by nucleofile reactants at the presence of ionic liquids and under application of microwaves

2013 ◽  
Vol 13 (1) ◽  
pp. 59-64
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Polyethylene Glycol ◽  
Polychlorinated Biphenyls ◽  
Nucleophilic Substitution ◽  
Reaction Rate ◽  
Microwave Field ◽  
Laboratory Scale ◽  
Chlorine Atoms ◽  
Dielectric Fluids

Laboratory-scale experiments were performed in order to examine the effect of microwave field on the effectiveness of KPEG method (nucleophilic substitution of the chlorine atoms in a molecule of PCBs by alkaline polyethylene glycol PEG) in the removal of PCBs from highly contaminated mineral oils with the content of indicator congeners (No 28,52,101,53,138 and 180) above 5500 mg kg-1. Results show that the microwave field significantly increases the reaction rate and the method’s effectiveness in the removal of chlorine from the molecules of PCBs. Addition of a small amount of an ionic liquid, in this case 1-butyl-3-methylimidazolium hexafluorophosphate–[bmim][PF6], significantly positively affects the results obtained under the influence of microwave field. The KPEG method enhanced by the application of microwaves could be used in practice for decontamination and recycling of PCB-containing dielectric fluids in electric capacitors and transformers. High efficiencies of the reaction were achieved even when microwaves were applied with no PEG added, only by the presence of alkaline hydroxide or by the presence of a small amount, up to ca. 2%, of an ionic liquid [bmim][PF6]. The microwave enhanced KPEG method might has some advantages for practical uses in decontamination applications.

Aromatic nucleophilic substitution with sulphoxides: The interaction of dimethyl sulphoxide with chloronitrobenzenes

1974 ◽  
Vol 27 (4) ◽  
pp. 777 ◽  
Author(s):  
MEC Biffin ◽  
DB Paul
Keyword(s):  
Nucleophilic Substitution ◽  
Benzyl Alcohol ◽  
Sodium Benzoate ◽  
Sodium Acetate ◽  
Dimethyl Sulphoxide ◽  
Substituted Phenols ◽  
Aromatic Nucleophilic Substitution ◽  
Decomposition Products ◽  
Chlorine Atoms ◽  
Kornblum Oxidation

Activated chlorine atoms are displaced by sulphoxide oxygen when di- and tri-nitrochlorobenzenes are heated in dimethyl sulphoxide. The corresponding phenols, thiomethoxymethyl- and formyl- substituted phenols, thioanisoles and decomposition products of chlorodimethyl sulphide are formed. Monochloronitrobenzenes do not undergo reaction with Me2SO even at 190�, but in the presence of added sodium acetate or sodium benzoate, phenols and thioanisoles are obtained together with products derived from the sulphonium ylid CH3S+=CH2. These observations are rationalized mechanistically. The reaction mixtures are shown to oxidize benzyl alcohol to benzaldehyde. These results do not substantiate the presence of an intermediate sulphonium complex, however, because benzyl alcohol competes more favourably for the chloroaromatic system than does Me2SO; benzyl alcohol forms the chloride which then undergoes a Kornblum oxidation to yield benzaldehyde.

scholarly journals Preparative Production of Spinochrome E, a Pigment of Different Sea Urchin Species

2014 ◽  
Vol 9 (7) ◽  
pp. 1934578X1400900 ◽  
Author(s):  
Olga P. Shestak ◽  
Victor Ph. Anufriev ◽  
Vyacheslav L. Novikov
Keyword(s):  
Nucleophilic Substitution ◽  
Sea Urchin ◽  
Sea Urchins ◽  
Target Compound ◽  
Chlorine Atoms ◽  
Methoxy Groups ◽  
Hydrolysis Of

A concise route to spinochrome E (1) (2,3,5,6,7,8-hexahydroxy-1,4-naphthoquinone), a pigment isolated from sea urchins of different species, has been developed starting from either commercially available 5,8-dihydroxy-1,4-naphthoquinone (11) or 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone (12). The protocol involves 3 steps, the chlorination of either 11 or 12 to tetrachloronaphthazarin (13), the total nucleophilic substitution of the chlorine atoms in 13 by methoxy groups, and hydrolysis of tetramethyl ether14; this makes possible the preparation of the target compound in overall yields from 41 to 46%.

scholarly journals Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents—The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s)

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3635
Author(s):  
Genrikh E. Zelinskii ◽  
Ilya P. Limarev ◽  
Anna V. Vologzhanina ◽  
Valentina A. Olshevskaya ◽  
Anton V. Makarenkov ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Cycloaddition Reaction ◽  
Intramolecular Interactions ◽  
Dipolar Cycloaddition ◽  
X Ray Diffraction ◽  
Hybrid Molecule ◽  
Chlorine Atoms ◽  
Synthetic Strategy ◽  
Dihydrogen Bonding ◽  
Derivatives Of

A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their “click” 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28º. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C–H…H–B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C–H…F–B interaction with an adjacent carboranoclathrochelate molecule. The N–H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1Н-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.

scholarly journals High-density insensitive energetic materials: 2,4,6-tris(2-fluoro-2,2-dinitroethoxy)-1,3,5-triazine

RSC Advances ◽  
2016 ◽  
Vol 6 (106) ◽  
pp. 104325-104329 ◽  
Author(s):  
Alexander A. Gidaspov ◽  
Vladimir V. Bakharev ◽  
Kyrill Yu. Suponitsky ◽  
Valery G. Nikitin ◽  
Aleksei B. Sheremetev
Keyword(s):  
Nucleophilic Substitution ◽  
Energetic Materials ◽  
High Density ◽  
Chlorine Atoms ◽  
Excellent Yield

A Na3PO4-promoted nucleophilic substitution of all chlorine atoms of cyanuric with fluorodinitroethanol was achieved with excellent yield. The product demonstrates promising potential for diverse applications like explosives or propellants.

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