Chloro Compounds Research Articles

ORGANOPHOSPHORVERBINDUNGEN MIT TERTIÄREN ALKYLSUBSTITUENTEN. IV: VERSUCHE ZUR P-HALOGENIERUNG VON DI-1-ADAMANTYLPHOSPHIN MIT PHOSGEN, BROM UND IOD

Abstract The reaction of (1-Ad)2PH 1 with C(:O)Cl2, Br2 or I2 furnished solid products of the type [(1-Ad)2P(H)X]+[X]− (X = Cl: 2, Br: 3, I: 4). The identity of the iodo compound 4 was confirmed by elemental analysis. While (1-Ad)2PCl 5 was isolated as a product of the reaction of the chloro compound 2 with NEt3, the corresponding bromo and iodo compounds could not be prepared in a similar fashion. Even prolonged heating of 3 and 4 led only to the formation of mixtures of the phosphonium salts and the monohalophosphines 6 or 7, which could not be separated from the reaction mixture; thus, 6 and 7 were only detected by NMR spectroscopy and by mass spectrometry.

Preparation of chlorosyringols and chloropyrogallols-components of pulp bleaching effluents

The preparation and properties of chlorosyringols and chloropyrogallols, components of pulp bleaching effluents, and their acetates are given. The compounds are obtained mainly by direct chlorination of both phenols or of syringol acetate with various chlorinating reagents. 5-Chloropyrogallol and 4,5-dichloropyrogallol were the products of demethylation of 5-chloro-3-methoxycatechol acetate and 4,5-dichloro-3-methoxycatechol acetate, respectively. The acetates of all ten chloro compounds were separated by gas chromatography. Electron impact mass spectra and 1H and 13C NMR data for the acetates are given.

Oxidation reduction reactions involving nitro groups in trifluoromethanesulfonic acid. Part 2. The reactions of chloromethylbenzenes with aromatic nitro Compounds

2-Chloro-1,3-dimethylbenzene reacts with 1,4-dinitrobenzene in trifluoromethanesulfonic acid (99%) at 70 °C to give, after quenching, a 45% yield of tris(4-chloro-3,5-dimethylphenyl)methanol. Some other chloro compounds and a range of aromatic nitro compounds react in a similar manner. From isotopic labelling (13C, 2H), kinetic studies, and substituent effects, the reaction appears to involve a rate-determining hydride transfer from the aromatic chloro compound to the protonated nitro compound followed by a series of benzylations, debenzylations and rebenzylations accompanied by further oxidation reactions and leading finally to the corresponding triarylmethyl cations.

Preparation, thermal, structural and electrical studies of dichlorohexa (anthranilamide) cobalt(II) and dichloro (anthranilamide) copper(II)

The chloro compounds of anthranilamide with cobalt and copper were prepared in aqueous solution. Solid compounds were isolated and characterised by analysis, magnetic moments, and vibrational and electronic spectra. They have octahedral structures. Thermogravimetry and differential thermal analysis show that the compounds lose organic ligand and halogen to give the metal oxide. Electrical conductivities at room temperature show ohmic behaviour and lie in the range from 4.50 × 10 −8Ω −1m −1 (for the cobalt complex) to 8.80 × 10 −8Ω −1 m −1 (for the copper complex). The temperature dependence of conductivity was determined for the compounds and was used to provide a measure of the activation energies for conduction.

Metal-metal interactions in chain compounds of gold(I): syntheses and crystal structures of chlorotetrahydrothiophenegold(I), bromotetrahydrothiophenegold(I) and iodotetrahydroselenophenegold(I)

The crystal structures of the title compounds have been determined from X-ray intensity data collected at 200 K with a CAD 4 diffractometer. Crystal data at 200 K (Mo Kα, \\ ̄ gl = 0.7107 Å) are: [Au(C 4H 8S)Cl], orthorhombic, Pmc2 v , Z = 4, a = 6.540(1), b = 8.192(1), c = 12.794(3) Å and V= 685.5(2) Å 3; [Au(C 4H 8S)Br], orthorhombic, Pmc2 v , Z = 4, a =6.564(1), b = 8.328(2), c = 13.229(4) Å and V= 723.1(2) Å 3; [Au(C 4H 8Se)I], orthorhombic, Pc2 1 n, Z = 8, a = 8.286(2), b = 11.552(3), c = 16.204(6) Å and V= 1551.0(5) Å 3. Full matrix least-squares refinements using reflections obeying I > 2 σ( I) converged to R = 0.053 (652 reflections), R = 0.067 (656 reflections) and R = 0.049 (1453 reflections) for the chloro, bromo and iodo compounds, respectively. [Au(C 4H 8S)Cl] and [Au(C 4H 8S)Br] are isostructural and comprise linear, neutral complexes, [Au(C 4H 8S)X], which are stacked in a staggered conformation forming infinite arrays of gold atoms running along a with gold-gold distances of 3.324(1) and 3.353(1) Å and Au-Au-Au angles of 159.30(6)° and 156.29(8)° for the chloro and bromo complexes, respectively. The Au-S distances are in the range 2.26-2.28 Å for both compounds, indicating that the difference in trans-influence of Cl and Br on the Au-S distance is negligible. [Au(C 4H 8Se)I] is composed of linear complexes, [Au(C 4H 8Se) 2] + and [AuI 2] −, which alternate in infinite zigzag chains running along b, with Au-Au distances of 2.987(2) and 3.001(2) Å and with Au-Au-Au angles of 160.89(4)° and 156.35(4)°. The Au-I and Au-Se distances are in the ranges 2.569(2)–2.571(2) and 2.430(3)–2.436(3) Å, respectively. Since there are no ligand bridges between the gold atoms in any of these compounds, the fairly short gold-gold distances indicate metal-metal bonding. A survey of short Au-Au interactions, not supported by ligand bridges, shows a wide range of distances, 2.97 to 3.78 Å, with a frequency maximum at 3.2–3.4 Å.

Vibrational and conformational analysis of 1-bromo-3,3-dimethylbutane and 1-chloro-3,3-dimethylbutane

Infrared and Raman spectra were obtained for 1-bromo-3,3-dimethylbutane and 1-chloro-3,3-dimethylbutane. Each compound exists as two stable conformations. Vibrational assignments were made for both conformers of each compound with the aid of normal coordinate calculations. Molecular mechanics calculations were made for both conformers of each compound, and semi-empirical molecular orbital calculations were made for the chloro compound. Calculated geometrical parameters are given in this paper.

Carben‐analoge Amidoosmium‐Komplexe mit OsN‐Doppelbindung: Synthese, Struktur und Reaktivität von [(Mes)Os(=NHR)(PiPr3)]PF6

Carbene‐Type Amidoosmium Complexes with an OsN Double Bond: Synthesis, Structure and Reactivity of [(Mes)Os(=NHR)(PiPr3)]PF6*The reaction of [(Mes)Os(PiPr3)Cl2] (1) (Mes1,3,5‐C6H3Me3) with primary amines RNH2 (RPh, Me, Et) in acetone/water (1:1) gives, after addition of KPF6, the amidoosmium(II) complexes [(Mes)Os(=NHR)(PiPr3)]PF6 (2–4) in 60–80% yield. From 1 and Et2NH, the chloro(hydrido)compound [(Mes)1‐OsH(PiPr3)Cl] (5) is formed. The X‐ray structural analysis of 2 reveals that the geometry around the osmium atom is trigonalplanar (with the midpoint of the mesitylene ring as one coordination site) and that the OsN distance of 1.923(4) Å is in agreement with an OsN double bond. Thermolysis of 4 (REt) at 165°C leads to the formation of the aldimino(hydrido)osmium complex [(Mes)OsH(NHCHMe)(PiPr3)]PF6 (6) by β1‐hydride migration from the NCH2 carbon atom to the metal atom. Protonation of 3 (RMe) with HCl gives the amine complex [(Mes)Os(NH2Me)(PiPr3)Cl]PF6 (7), whereas on treatment of 3 and 4 with CD3NO2 the deuterated derivatives [(Mes)Os(=NDR)(PiPr3)]PF6 ([D1]‐3, [D1]‐4) are almost quantitatively formed. Compound 2 (RPh) reacts with KOtBu by proton abstraction and phosphane elimination to give the dinuclear imidoosmium complex [(Mes)2Os2(μ1‐NPh)2] (8).

Na[Fe(CO)2(C5H5)] Mediated Coupling Reactions of Benzyl and Allyl Halides

Abstract The reaction of Fp anion [Fp - Fe(Co)2(C5H5)] with allylic and benzylic halides produces the corresponding Fp-R complex, reduced substrate R-H and/or the coupled dimer R-R in varying yields. The major product of the reaction is dependant on the halogen and the nature of the substrate. Allyl and benzyl bromides produce higher yields of coupled product than the corresponding chloro compounds. Doubly and triply benzylic substrates (Ph2CHX and Ph3CX) yield the corresponding reduction products, R-H, as well.

Dehalogenation of organic compounds. 4. Dechlorination of pentachlorophenol and 1,2,4-trichlorobenzene with transition metal-promoted alkoxyborohydrides

Metal-promoted NaBH 4 and NaBH 2(OCH 2CH 2OCH 3) 2 dechlorinations were carried out on the aromatic chloro compounds pentachlorophenol and 1,2,4-trichlorobenzene. The best results were obtained by dropwise addition of NiCl 2 in solution to NaBH 2(OCH 2CH 2OCH 3) 2 and the substrate in THF solutions.

The Dependence of the Etching Properties of Illuminated InAs , GaP , and Other III – V Semiconductors in Concentrated HCl Solutions on the Formation of Chloro Complexes

The influence of complex formation on the etching characteristics of illuminated and in solutions has previously been considered. To further examine the effect of complex formation, the etching behavior of and in under illumination has been investigated in this work. In the case of , the dissolution rate in solutions increase dramatically with an increase in acid concentration above 6M, and the InI–InIII mixed valence chloro compounds were found on the oxidized surface. In contrast, the dissolution of was severely restricted, even in the most acidic solutions, and no gallium chloro compounds were formed. The kinetics of the semiconductor electrode process were shown not to be important enough to explain the lack of reactivity in and . Speculation on the role of the univalent In and Ga chloro compounds and the driving force of the electron transfer between these intermediates and the redox systems, including electron/hole couple, are given and evaluated. The experimental results obtained with these four III – V compounds are in complete agreement with the mechanistic concepts presented in this paper. The differences in their reactivities can be interpreted in terms of the differences in the stabilities of and which, in turn, determine whether or not the nucleophilic attack by Cl− can occur.

Preparation, structural characterisation, thermal and electrical studies of some first row transition metal complexes of 2,3-bis(2-pyridyl)pyrazine

The chloro compounds of cobalt, nickel and copper with 2,3-bis(2-pyridyl)pyrazine have been prepared in ethanolic solution. The thermal behaviour of these compounds, and of the compound 2,3-bis(2-pyridyl)pyrazine, has been studied by thermogravimetry and differential thermal analysis. Thermal decomposition studies on the complexes show that intermediate compounds are produced before the metal oxides are formed. Electrical measurements show that all of the compounds exhibit ohmic behaviour at room temperature. The small differences in the electrical conductivity observed for each of the metal complexes indicates that the coordinated metal ion plays no part in the conduction process.

Thermal, structural and electrical studies of the chloro complexes of cobalt, nickel and copper with 4,7-phenanthroline

The chloro compounds of 4,7-phenanthroline with cobalt, nickel and copper have been prepared in ethanolic solution and have stoichiometry MLCl 2. Solid compounds were isolated and characterised by elemental analyses, magnetic moments, vibrational and electronic spectra. The cobalt and nickel compounds have tetrahedral structures, whereas the copper compound has an octahedral structure. The thermal behaviour of the compounds has been studied using thermogravimetry and differential thermal analysis. An intermediate compound is observed in the decomposition of the cobalt complex. Electrical conductivities at room temperature are reported and all compounds display ohmic behaviour. The ligand molecules make a major contribution to the conduction process.

Thermal, structural and electrical studies of the chloro complexes of cobalt, nickel and copper with 1,10-phenanthroline

The chloro compounds of 1,10-phenanthroline with cobalt, nickel and copper have been prepared in ethanolic solution and have the stoichiometry ML nCl 2, where n = 2 for cobalt and copper and n = 1 for nickel. Solid compounds were isolated and characterised by analysis, magnetic moments, and vibrational and electronic spectra. The cobalt and copper compounds have octahedral structures, whereas the nickel compound has a tetrahedral structure. The thermal behaviour of the compounds has been studied using thermogravimetry and differential thermal analysis. During the thermal decomposition processes, intermediate compounds are produced. Electrical conductivity measurements were obtained for the 1,10-phenanthroline and its copper complex. No suitable discs could be obtained for electrical measurements on the cobalt and nickel complexes. The electrical measurements show ohmic behaviour at room temperature, with conductivities of 7.58 × 10 −8 Ω −1 m −1 for the 1,10-phenanthroline; and 9.10 × 10 −8Ω −1 m −1 for the copper complex.

Preparation, structural characterisation and thermal analysis studies of complexes of cobalt, nickel and copper with nonylamine

Compounds of nonylamine with the chlorides of cobalt, nickel and copper and with the thiocyanate of cobalt, have been prepared in ethanolic solution. The compounds, which have been characterised by analyses, magnetic moments, vibrational and electronic spectra, show that for the cobalt compounds the cobalt ions are in a tetrahedral environment, whereas for the nickel and copper compounds the metal ions are in an octahedral environment. The thermal behaviour of these compounds has been studied by thermogravimetry and differential thermal analysis. The chloro compounds form intermediate compounds during the decomposition process.

Thermal, spectral and magnetic studies of the chloro complexes of manganese, cobalt, nickel and copper with 3-pyridinealdoxime

Some chloro compounds of manganese, cobalt, nickel and copper with 3-pyridinealdoxime were prepared in ethanolic solution. The compounds have the stoichiometry ML 2Cl 2. Spectral and magnetic studies were used to deduce the stoichiometry. The compounds have polymeric octahedral structures. The thermal behaviour of the compounds was studied by thermogravimetry and differential thermal analysis. Thermal decomposition studies show that the cobalt, nickel and copper compounds each form an intermediate compound before decomposing to the metal halide and finally the metal oxide. The manganese compound decomposes with loss of the organic ligand to give the metal halide, followed by loss of chlorine to give the metal oxide.

Thermal, structural and electrical studies of the chloro complexes of cobalt, nickel and copper with anthranilamide

The chloro compounds of anthranilamide with cobalt, nickel and copper have been prepared in ethanolic solution. Solid compounds have been isolated and characterised by elemental analyses, magnetic moments, vibrational and electronic spectra. They have octahedral structures. Thermogravimetry and differential thermal analysis show that all of the compounds lose organic ligand and halogen to give the metal oxide. Electrical conductivities at room temperature show ohmic behaviour and lie in the narrow range 3.60 × 10 −8 Ω −1 m −1 (for the nickel complex) to 1.00 × 10 −7 Ω −1 m −1 (for the copper complex). The high conductivity of the copper complex, relative to that of the other complexes, is attributed to its polymeric structure. The temperature dependence of conductivity is anomalous. Evidence from IR spectra suggests that such behaviour is a result of premature decomposition which is due to a synergistic effect of applied voltage and temperature.

Zur Chemie der 4,6-Dioxo-1,3,5,2 λ3-triazaphosphinane. / On the Chemistry of 4,6-Dioxo-1,3,5,2 λ3-triazaphosphinanes.

In the reaction of phenylisocyanate, 1, with 1,3-dimethylurea, 2, and 1,3-diphenylurea, 4, 1,3-dimethyl-5-phenyl biuret, 3, and 1,3,5-triphenylbiuret, 5, respectively, were obtained. The reaction of 3, 5 and of 1,3,5-trimethylbiuret 6 with a range of P(III) chloro compounds has furnished the new 4,6-dioxo-1,3,5,2 λ3-triazaphosphinanes, 7-16. The characterization of 7-16 rests, especially, on their 1H, 13C and 31P NMR, and mass spectra.

Charge calculations in molecular mechanics. IX. A general parameterisation of the scheme for saturated halogen, oxygen and nitrogen compounds.

The CHARGE2 program for the calculation of partial atomic charges has been amended to include bond parameters for a number of organic functional groups, including halogens, nitrogen and oxygen. These minor amendments to the original scheme produce dipole moments for the fluoro and chloro compounds which are in complete agreement with the observed values. The less complete data sets for the bromo and iodo compounds are also well reproduced, and the dipole moments of a variety of mixed halo compounds are now in better agreement with experiment than previously. The calculated dipole moments of the saturated nitrogen and oxygen compounds are now in much better agreement than in the original scheme, thus the revised parameterisation may be employed with confidence to predict the electrostatic energies of these compounds. Furthermore, the revised scheme now gives a precise proportionality between the charge on the proton in a CH group and the 1H chemical shift of the corresponding proton, allowing the general prediction, in principle, of 1H chemical shifts. In addition, attempts to include variable electronegativity in the alpha effect are described for fluoro compounds.

Stereochemical aspects of the synthesis and reactivity of (diphosphine)(carbonyl)(cyclopentadienyl)ruthenium complexes

The formation of the carbonyl complexes (S Ru, R C )-[Ru(η 5-C 5H 5)(CO)(prophos)]PF 6 ( 3a) (prophos = Ph 2PCH(CH 3) CH 2PPh 2) and ( R Ru, RC)-[Ru(CO)(η 5-C 5H 5)(prophos)]PF 6 ( 3b) by reaction of the corresponding chloro compounds 1a and 1b with carbon monoxide in the presence of NH 4PF 6 is stereospecific, and takes place with retention of configuration at the ruthenium atom. The carbonyls 3a and 3b are also stereospecifically formed by reaction of the vinylidene complexes ( S Ru, R C)-[Ru(η 5-C 5H 5)(CCHPh)(prophos)]PF 6 ( 2a) and ( R Ru, R C)-[Ru(CCHPh)(η 5-C 5H 5) (prophos)]PF 6 ( 2b) with molecular oxygen. The reaction of 3a with LiAlH 4 to give the methyl derivatives is stereospecific but that of 3b shows extensive epimerization as well as a low chemoselectivity. A similar difference in stereoselectivity for the two diasteromers 3a and 3b is also observed in the reaction with [N(C 2H 5) 4]OH.

Studies on hexolic anhydride based polyesters, III. Mechanistic and comparative aspects of the product distributions in the thermal degradation

AbstractTwo systems of unsaturated polyesters based on maleic anhydride, phthalic anhydride, hexolic anhydride (5,6,7,8,9,9‐hexachloro‐1,2,3,4,4a,5,8,8a‐octahydro‐5,8‐methanonaphthalene‐2,3‐dicarboxylic anhydride) and 2‐butene‐1,4‐diol or 2,3‐dichloro‐2‐butene‐1,4‐diol were synthesized. The polyesters were pyrolysed under programmed heating from 40° to 400°C at a rate of 10 K/min. The volatile pyrolysates were separated and identified by combined gas chromatography/mass spectrometry. The formation of anhydrides, diols, hydrocarbons, chloro compounds and polychlorinated cyclopentadiene compounds etc., is explained in the light of single and double β‐scission, acyl‐oxygen and alkyl‐oxygen bond fission and carbon‐carbon bond homolysis mechanisms. It is observed that β‐scission plays a vital role in the primary degradation process of polyesters. The decreasing number of β‐hydrogens in the diol part of the polyester is reflected in the quantity of anhydrides ejected from the polymer backbone. Further it is observed that hexachlorocyclopentadiene and related compounds are ejected from the hexolic anhydride set free during pyrolysis and not from the hexolic moiety incorporated in the polymer backbone. An approximate calculation shows that about 75% of the total amount of maleic anhydride, formed in the pyrolysis of saturated diol based polyesters having fullest number of β‐hydrogens in the diol part, is derived from β‐scission and the rest via alkyl‐oxygen bond fission mechanism. A similar observation is also noted‐indirectly for the formation of hexolic anhydride.