Presence Of Cupric Chloride Research Articles

Vinyl polymerization in the presence of copper salts

AbstractThe radical polymerization of several vinyl monomers has been studied in the presence of cupric chloride. A termination reaction with CuII species leads to the formation of CuI species which can also participate significantly in termination with some, but not all, of the monomers studied. A theoretical treatment of the kinetics of such systems is presented which takes full account of initiator depletion during extended inhibition during extended inhibition periods. Specific velocity constants for reactions of polymer radicals with both CuII and CuI moieties are derived from observations on the nonstationary phase at the end of the inhibition period and from the subsequent steady state of polymerization. On the basis of the results presented here, together with the work of other authors, the patterns‐of‐reactivity approach gives α = −5.4, β = 9.0 as the parameters for copper (II) chloride. The implications of the results in relation to the mechanisms of the reactions between polymer radicals and both copper(II) chloride and copper(I) chloride are discussed. The kinetic treatment also provides an improved method for the determination of the rate of initiator decomposition and the rate of initiation form studies of the inhibition period.

A convenient method for the preparation of mixed diesters of phosphoric acid and pyrophosphates.

It was found that mixed diesters of phosphoric acid and pyrophosphates were obtained in good yields when alcohols and arylphosphates, respectively, were allowed to react with 4-methoxyphenyl N-(2-aminophenyl) phosphoramidate in the presence of cupric chloride.

The cuprous chloride catalyzed addition of halogen compounds to olefins under photo-irradiation

The addition of organic halogen compounds to olefins in the presence of cuprous chloride under U.V. irradiation gave 1:1 adducts.

A NEW METHOD FOR GLYCOSYLATION WITH CARBODIIMIDES; NUCLEOPHILIC SUBSTITUTION OF GLYCOSYLISOUREAS

Abstract A glycosyl isourea, prepared from a sugar derivative with free 1-hydroxyl group and a carbodiimide in the presence of cuprous chloride, was successfully subjected to the reaction with a series of protic nucleophiles to give the corresponding glycosyl compounds, i.e., 1-O-acylglycoses, phenyl glycosides, alkyl glycosides including disaccharides, and purine nucleosides, in good yields.

ChemInform Abstract: STUDIES OF PHOSPHORYLATION. V. 8‐QUINOLYL DIHYDROGEN PHOSPHATE AS A PHOSPHORYLATING REAGENT IN NUCLEOTIDE SYNTHESIS

AbstractDurch Phosphorylierung von Nucleosiden (II) mit 8‐Chinolyldihydrogenphosphat (I), dessen Synthese beschrieben wird, in Gegenwart von Kupfer(II)‐chlorid in wasserfreiem Pyridin erhält man in 59 ‐ 76%iger Ausbeute die Nucleosid‐5′‐phosphate (III).

Polymerization of aromatic nuclei. XVI. Mechanism of chain propagation in the polymerization of benzene by aluminum chloride–cupric chloride

AbstractA study was made of the mechanism of benzene polymerization by aluminum chloride‐cupric chloride. Our main effort was devoted to propagation with the aim of resolving a literature conflict as to whether a cationic or radical pathway is involved. When equimolar mixtures of benzene and haloarene are polymerized, the resulting copolymers are composed almost exclusively of benzene monomer. This approach is based on the known relative reactivities of the monomers toward electrophilic and radical species. The amount of haloaromatic present in the copolymer was determined by elemental analyses and confirmed by infrared spectroscopy. These results are strongly indicative of propagation by an electrophilic moiety. The presence of oxygen in the reaction mixture was found to have no significant effect on the rate or yield of the polymerization, in contrast to a previous published report. The progress of the reaction was followed by titration of the evolved hydrogen chloride. Phenyl radicals, obtained by the thermal decomposition of benzoyl peroxide in benzene, were found to be incapable of initiating the polymerization in the presence of cupric chloride. Increased yields of biphenyl and the presence of chlorobenzene point to oxidation of intermediate radicals by cupric chloride. None of the experimental evidence is satisfactorily interpreted by radical propagation. The data are nicely rationalized on the basis of cationic chain extension, apparently via a radical cation initiator.

8-QUINOLYL NUCLEOSIDE 5′-PHOSPHATES AS A USEFUL INTERMEDIATE FOR THE SYNTHESIS OF NUCLEOSIDE 5′-DI- AND 5′-TRI-PHOSPHATES

Abstract Nucleoside 5′-di- and 5′-tri-phosphates were obtained in high yields by the reaction of 8-quinolyl nucleoside 5′-phosphates with phosphoric or pyrophosphoric acids in the presence of cupric chloride.

Studies of phosphorylation. V. 8-Quinolyl dihydrogen phosphate as phosphorylating reagent in nucleotide synthesis.

Phosphorylation of nucleosides by means of 8-quinolyl dihydrogen phosphate has been described. Phosphorylation of nucleosides with 8-quinolyl dihydrogen phosphate could only be carried out in the presence of cupric chloride. By this method, nucleoside 5'-phosphates were obtained in good yields.

Synthesis and antiviral and antimicrobial activity of certain 1-.beta.-D-ribofuranosyl-4,5-disubstituted imidazoles

Starting with AICA ribonucleoside the following nucleosides were prepared. Methyl 5-amino-1-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)imidazole-4-carboxylate (5) was converted into methyl 5-chloro-1-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)imidazole-4-carboxylate (6) via diazotization in the presence of cuprous chloride. Similarly, 5-amino-1-(2,3,5-tri-O-acetyl-beta-D-ribofuanosyl)imidazole-4-carbonitrile (9) was converted into 5-chloro-, 5-bromo-, and 5-iodo-1-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)imidazole-4-carbonitrile derivatives. These 5-halogenated imidazole nucleosides were treated with several nucleophiles such as ammonia, hydroxylamine, and hydrogen sulfide to provide, respectively, 5-haloimidazole-4-carboxamide, 5-haloimidazole-4-carboxamidoxime, and 5-haloimidazole-4-thiocarboxamide ribonucleosides. 5-Chloro- or 5-bromo-1-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)imidazole-4-carbonitrile was treated with potassium hydrosulfide to yield 5-mercapto-1-beta-D-ribofuranosylimidazole-4-thiocarboxamide (16). The catalytic reduction of 5-chloro- or 5-bromo-1-beta-D-ribofuranosylimidazole-4-carboxamidoxime provided 1-beta-D-ribofuranosylimidazole-4-carboxamidines as their hydrochloride and hydrobromide salts, respectively. These nucleosides were tested for in vitro antiviral, antifungal, and antibacterial activity. The 5-halo analogues of 1-beta-D-ribofuranosylimidazole-4-carboxamide showed significant antiviral activity whereas compound 16 was found inhibitory to fungi.

Radiation‐induced polymerization of acrylic acid in aqueous solution

AbstractAqueous acrylic acid in the presence of cupric chloride has been subjected to γ‐irradiation under various reaction conditions and the molecular weights of the resultant poly(acrylic acid) measured. The results, taken in conjunction with previous findings on the dependence of the rate of polymerization on intensity, monomer concentration, and cupric chloride concentration, indicate chain termination solely by cupric ion (rate constant ktCu) and chain transfer to polymer (rate constant kf). Values have been obtained for ktCu/kp, kf/kp and G(radical) of acrylic acid. On the basis of these data a theoretical chain‐length distribution has been derived which agrees well with distribution measured by gel‐permeation chromatography.

Copper-catalyzed oxidative coupling of diphenylmethanimine promoted by some monodentate pyridines

Aerial oxidation of diphenylmethanimine to benzophenone azine was carried out at room temperature in the presence of cuprous chloride and a monodentate pyridine, such as pyridine, γ-picoline, isoquinoline, or quinoline. Cupric chloride, hydroxide, and nitrate were inactive in the reaction, whereas CuCl 2KOH and Cu(OH) 2HCl were active in the presence of excess pyridine. Bidentate ligands, such as ethylenediamine and monoethanolamine, inhibited the oxidative coupling of imine. Using isoquinoline for the direct synthesis of azine from benzophenone, ammonia and molecular oxygen, the reaction temperature can be lowered and the catalysts recycled.

REACTION OF HALOANTHRAQUINONES WITH TRI-n-BUTYLPHOSPHINE

Abstract New phosphonium salts were obtained by the reaction of 1-amino-2,4-dibromoanthraquinone or sodium 1-amino-4-bromoanthraquinone-2-sulfonate with tri-n-butylphosphine in the presence of cuprous chloride. In these reactions, the bromine atom of anthraquinone derivatives was substituted by the phosphine to give phosphonium salts containing carbon–phosphorus bond.

Leuco Base Determination in the Triphenylmethane Dyes, FD&C Blue No. 1, FD&C Green No. 3, and FD&C Violet No. 1

Abstract The quantitative oxidation of leuco bases in FD&C triphenylmethane dyes was examined. A spectrophotometric method for determining the amount of leuco base, using molecular oxygen in the presence of cupric chloride, was studied. Leuco base recovery was found to be 90.0–103% for FD&C Blue No. 1, 97.2-101.9% for FD&C Green No. 3, and 95.4-100% for FD&C Violet No. 1.

ChemInform Abstract: AROMATIC 2‐THENOYLOXYLATION WITH 2‐THENOYL PEROXIDE IN THE PRESENCE OF CUPRIC CHLORIDE

Chemischer InformationsdienstVolume 5, Issue 11 Heterocyclic Compounds ChemInform Abstract: AROMATIC 2-THENOYLOXYLATION WITH 2-THENOYL PEROXIDE IN THE PRESENCE OF CUPRIC CHLORIDE S. HASHIMOTO, S. HASHIMOTOSearch for more papers by this authorW. KOIKE, W. KOIKESearch for more papers by this authorM. OYAMA, M. OYAMASearch for more papers by this author S. HASHIMOTO, S. HASHIMOTOSearch for more papers by this authorW. KOIKE, W. KOIKESearch for more papers by this authorM. OYAMA, M. OYAMASearch for more papers by this author First published: March 19, 1974 https://doi.org/10.1002/chin.197411315AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume5, Issue11March 19, 1974 RelatedInformation

ChemInform Abstract: THE ACTIVATION OF BIVALENT SULFUR COMPOUNDS WITH CUPRIC CHLORIDE AND ZINC CHLORIDE, THE BENZYLATION AND ACYLATION OF AROMATIC COMPOUNDS WITH SULFIDES AND THIOL ESTERS

AbstractDie Umsetzung der Sulfide (II) mit Anisol (I) in Gegenwart von äquimolaren Gemischen aus Cu(II)‐ und Zn‐chlorid ergibt nach 5‐stündigem Rückflußkochen die Benzylderivate (III).

The Reaction of Fatty Acid Esters, Acid Anhydride, and Acid Chloride with Vinylmagnesium Chloride

Reaction of vinylmagnesium chloride with aliphatic carboxylic acid methyl ester gives a mixture of vinylketone and divinylcarbinol. From methyl pentanoate, a mixture of n-butyl-3-hydroxyl-1, 4-pentadiene and 5-oxo-1-nonene is obtained. While reaction of linear α, β-unsaturated methyl esters with vinylmagnesium chloride yields vinylketones as the main product, the reaction of substituted α, β-unsaturated methyl esters yields triethylenic carbinols. Reaction of acid anhydrides and dibasic acid diesters with vinylmagnesium chloride yields mixtures of alkenones, hydroxy-alkenones and alkenols as the main products. Reaction of acid chloride with excess vinylmagnesium chloride at -40°C to -45°C gives 2-allyl-1, 3-diketones. From propanoyl chloride, a mixture of 4-allylheptane-3, 5-dione (33% yield), 6-heptene-3-one (0.5% yield) and 3-ethyl-1, 4-pentadiene-3-ol (2% yield) is obtained. Reaction of vinylmagnesium chloride with a fatty acid methyl ester in the presence of cuprous chloride gives a 1, 6-diketone. From methyl n-valerate, a mixture of n-tetradecane-5, l0-dione and 5-oxo-1-nonene is obtained.

Arylation of thiourea by aryldiazonium salts

1. In the presence of cupric chloride, aryldiazonium chlorides arylate thiourea to give S-arylisothiuronium compounds. 2. In the absence of CuCl2, the reaction of the p-chlorophenyldiazonium fluoborate and chloride with thiourea gives the p-phenylenediisothiuronium compound, and the p-chlorophenylisothiuronium compound in the presence of CuCl2.

The Activation of Bivalent Sulfur Compounds with Cupric Chloride and Zinc Chloride. The Benzylation and Acylation of Aromatic Compounds with Sulfides and Thiol Esters

Abstract Benzylation of aromatic compounds, such as anisole, m-xylene, toluene, and benzene, with various benzyl sulfides in the presence of equimolar amounts of cupric chloride and zinc chloride was investigated. For example, in the case of benzylation of anisole with 4-benzylthiopyridine, o- and p-benzylanisoles were obtained in 79% yield in the presence of cupric chloride and zinc chloride. On the other hand, when the reaction was carried out in the presence of cupric chloride alone, the yield of benzylanisoles was low. The similar activation with cupric chloride and zinc chloride was successfully applied to the reaction of aromatic compounds with benzaldehyde diethylthioacetal and to the acylation of aromatic compounds with 1,2-bis(acylthio)ethanes.

Formation of hexenes from 1-pentanol in the presence of cupric chloride

The dehydration of 1-pentanol in the presence of CuCl2 at 140–200‡ and a pressure of 5–80 atm, in either a CO or a N2 atmosphere, is accompanied by the formation, along with pentenes, of large amounts of hexenes (mainly cis- and trans-2-hexene).

Reaction of Di-β-naphthoyl Peroxide with Aromatic Compounds in the Presence of Cupric Chloride

In the presence of cupric chloride, the thermal decomposition reaction of di-β-naphthoyl peroxide with substituted benzenes has been investigated. The compositions of isomers and the relative rates for aromatic substrates indicated that the β-naphthoylexylatien proceeded by β-naphthoyloxy radicals possessing electrophilic properties. The partial rate factors for meta and para oxygenations might be correlated with the available σ+-substituent parameters according to the Hammett-Brown relationship. The straight line which was best fited to these points had a slope of -1.88.