Studies on ferrocene derivatives. Part XIII. Ligand exchange reactions of benzoferrocenes

Reactions between benzoferrocenes and substituted benzenes gave products resulting from intramolecular and intermolecular ligand exchange. The product ratios were influenced by the number of methyl substituents on the benzene ring; the larger the number, the greater the ratio of intermolecular products.     

Free-Radical copolymerization of N-vinylsuccinimide with butyl acrylate in the presence of zinc chloride and aluminum chloride

The free-radical copolymerization of N-vinylsuccinimide with butyl acrylate performed in dimethyl sulfoxide and benzyl alcohol in the presence of zinc chloride and aluminum chloride as complexing agents is studied. Under the given conditions, the reactivity ratios are determined. It is shown that zinc chloride influences the electron-density distribution only in butyl acrylate molecules. It is found that benzyl alcohol retards the total rate of polymerization. The character of the monomer-unit distribution in copolymer macromolecules is described.     

Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride

The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes.     

Reactions ofN-pentafluorophenylcarbonimidoyl dichloride with aromatic hydrocarbons in the presence of aluminum chloride

N-Pentafluorophenylcarbonimidoyl dichloride reacts with aromatic hydrocarbons (benzene, toluene, xylenes, and mesitylene) in the presence of AlCl₃ to give stableN-pentafluorophenylbenzimidoyl chlorides, which can further react with aromatic hydrocarbons to give azomethine derivatives. An increase in the number of methyl groups in the molecule of a hydrocarbon favors the reaction.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1605–1611, September, 1993.     

Regiochemistry of the reactions of phenylenedioxytrichlorophosphorane with phenylacetylene and propargyl chloride in the presence of benzyltrimethylammonium chloride

NMR studies revealed that the reactions of phenylenedioxytrichlorophosphorane with phenylacetylene and propargyl chloride in the presence of benzyltrimethylammonium chloride predominantly yield derivatives of 2,7-dichloro-2-oxobenzo[e]-1,2-oxaphosphorinine, i.e., the benzene ring is selectively chlorinated in the meta-position to the endocyclic O atom of the phosphorinine heterocycle.     

Functionalization of syndiotactic polystyrene with succinic anhydride in the presence of aluminum chloride

Syndiotactic polystyrene has been chemically modified with succinic anhydride by use of Friedel-Crafts acylation reaction in the presence of anhydrous aluminum chloride in carbon disulfide. The modified syndiotactic polystyrene containing -COCH₂CH₂COOH fragments in side phenyl rings, named succinoylated syndiotactic polystyrene (s-sPS), was characterized by FTIR and ¹H NMR spectroscopy. The effects of reaction conditions on the degree of succinoylation of s-sPS were investigated. In addition, the effects of incorporation of carboxyl groups into syndiotactic polystyrene on the thermal behavior were studied by differential scanning calorimetry in comparison with pure syndiotactic polystyrene. It was found that the crystallization temperature, melting temperature, and degree of crystallinity of the modified polymer decreased with increasing the degree of succinoylation, while the glass transition temperature increased.     

Bromination of 2-benzoylthiophene in the presence of excess aluminum chloride

Russian Chemical Bulletin -     

Transfer hydrogenation of phenanthrene in the presence of boron modified alumina or silica-alumina

Reactions of phenanthrene with hydrogen donors carried out in the presence of boron trifluoride etherate modified catalysts: silica, alumina or silica-alumina have been studied. Di-, tetra- and octahydrophenanthrenes as well as some bicyclic hydrocarbons were the reactions products. Their yields were strongly influenced by hydrogen donor polarity.     

Halogen exchange reactions of silicon tetrafluoride with phosphorus trichloride and phosphoryl chloride

Silicon tetrafluoride undergoes halogen exchange reactions with both phosphorus trichloride and phosphoryl chloride at temperatures of 500–600°C yielding mixed chlorofluorides of silicon and phosphorus. It is interesting to note that, at these high temperatures, PCl₃ undergoes complete exchange to form PF₃ while POCl₃ reacts only with partial substitution, the major products being phosphorus chloride difluoride and silicon trichloride fluoride.     

Spectrofluorimetric determination of thallium in silicate rocks with rhodamine b in the presence of aluminum chloride

A sensitive spectrofluorimetric procedure with rhodamine B in the presence of aluminum chloride is given for determining submicrogram and microgram quantities of thallium in silicate rocks. Samples are decomposed with a mixture of hydrofluoric and nitric acids and then treated with hydrochloric acid. Thallium is extracted as its dithizonate with chloroform from an alkaline medium containing ascorbate, citrate, and cyanide and then back-extracted with dilute nitric acid. After destruction of the organic matter and treatment with bromine, hydrochloric acid, aluminum chloride, and rhodamine B, the

T001. Determination of thallium in U.S. Geological Survey standard rocks by different laboratories

Thallium (p.p.m.)		Method	Ref.
G-1	W-1
1.06	0.102	Neutron activation analysis	1
1.08	0.121, 0.116	Neutron activation analysis	2
1.3	0.17	Neutron activation analysis	3
1.3	0.11	Spectrographic	4
	0.105–0.110	Flameless atomic absorption spectroscopy	5
1.3a	0.13a		19
1.24b	0.110b		20
1.09 ± 0.01	0.110 ± 0.005	Spectrofluorimetric	Present method

a

Values given by Fleischer.

b

Average value given by Flanagan. fluorescence intensity of the benzene-extracted rhodamine B chlorothallate is measured. The limit of determination is approximately 0.01 p.p.m. for a 1.0-g sample. The thallium contents of U.S. Geological Survey standard rocks G-1 and W-1 were found to be 1.09 ± 0.01 and 0.110 ± 0.005 p.p.m., respectively.

     

Action of bromine and tert-butyl chloride on methyl-2-furyl ketone in the presence of excess aluminum chloride

Summary Methyl 2-furyl ketone is brominated in the nucleus in the presence of 3 moles of aluminum chloride without solvent.     

Transformation of 1,1,3,3-tetramethyl-1,3-disilacyclobutane in presence of aluminum chloride

Conclusions The reaction of equimolar amounts of 1,1,3,3-tetramethyl-1,3-disilacyclobutane and aluminum chloride gives tetramethylsilane and a mixture of linear and cyclic silmethylene compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 953–955, April, 1975.     

Ligand exchange in the complexone-porphyrin macrocycle system in reactions of copper(II) ethylenediaminetetraacetate with porphyrins and phthalocyanines

Complexation between 5,10,15,20-tetraphenylporphine H₂TPP and tetra(tert-butyl)phthalocyanine H₂(t-Bu)₄Pc with copper(II) ethylenediaminetetraacetate in DMSO was studied by spectrophotometry. The kinetic parameters of the reaction were calculated and the mechanism of ligand exchange in the complexone-porphyrin macrocycle system was proposed. The reactivities of H₂TPP and H₂(t-Bu)₄Pc in reactions with copper ethylenediaminetetraacetate and some other copper chelate complexes were compared.     

Mathematical modeling of the catalytic degradation of polystyrene in the presence of aluminum chloride

We model the effect of the catalyst AlCl₃ on polystyrene (PS). Detailed experimental studies were previously carried out on the effect of AlCl₃ on PS, as part of an effort to understand how to minimize the degradation of PS during the Friedel-Crafts alkylation performed to obtain a graft copolymer from immiscible blends of PS and a polyolefin (PO). In the present work three mathematical models for the catalytic degradation of PS are proposed, all of which consider that reaction starts with the elimination of a phenyl group from the PS chain, followed by either chain scission or a change in the chain structure. The models vary in the way they consider the strength of the main chain bonds, or the reactivity of modified PS chains. Kinetic parameters for each model are estimated. Although the three proposed models could be used to represent our own experimental data, one is more accurate. Experimental data from other authors are used to evaluate its capabilities. Based on the predictions of the better model, we discuss conditions to minimize PS scission, such as operating at low temperatures and AlCl₃ concentrations, and using short processing times.