Telomerization of vinyl chloride by benzyl chloride

Conclusions The systems Fe(CO)₅ + hexamethylphosphotriamide and Fe(CO)₅ + DMF are efficient initiators for the telomerization of vinyl chloride by benzyl chloride involving the C-Cl bond of the benzyl chloride, in which connection both the conversion of the telogen and yield of telomers is high. Telomers of general formula C₆H₅CH₂-(CH₂CHCl)_nCl (n=1–3) were isolated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2541–2546, November, 1980.     

Spectroscopic study of vinylidene chloride—Vinyl chloride copolymers

Summary Deuteration technique was applied to study the micro structures of copolymer series VDC/VC by infrared spectroscopy and high resolution NMR. The CH₂ bending modes of chlorine atom containing polymers assigned as follows; –CCl₂CH₂CCl₂– 1405 cm^–1 (cryst.) and 1410 cm^–1 (amorph.), –CHClCH₂CCl₂– 1422 cm^–1, –CHClCH₂CHCl– 1428 cm^–1 (cryst.) and 1432 cm^–1 (amorph.) –CHClCH₂CH₂CHCl– 1445 cm^–1 and –CCl₂CH₂CH₂CCl₂– 1448 cm^–1. This infrared interpretation shows that only the head to tail addition occurs in the copolymerisation. Nine peaks of the methylene protons were observed clearly in the NMR spectra of the copolymers. The study of the deuterated copolymers revealed that the effects of the chemical groups until the third at both sides from the marked methylene and the stereo configuration of long VC part should be considered to assign the NMR spectra. The CCl₂ group made the chemical shift of the methylene proton to appear at lower magnetic field and the CHCl group gave the opposite behavior.

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Zusammenfassung Mit deuterierten Monomeren wurde die Mikrostruktur der Copolymerenserie Vinyliden-Chlorid/Vinyl-Chlorid im Infraroten und mit hochauflösender Kernresonanz untersucht. Für die Biegeschwingung der Chloratome enthaltenden Polymeren der Methylengruppe ergeben sich folgende Werte: –CCl₂CH₂CCl₂– 1405 cm^–1 (krist.) und 1410 cm^–1 (amorph.), –CHClCH₂CCl₂– 1422 cm^–1, –CHClCH₂CHCl– 1428 cm^–1 (krist.) und 1432 cm^–1 (amorph.), –CHClCH₂CH₂CHCl– 1445 cm^–1 und –CCl₂CH₂CH₂CCl₂– 1448 cm^–1.Diese Interpretation des Infraroten zeigt, daß nur die Kopf-Schwanz-Addition bei der Copolymerisation stattfindet. Neun Maxima des Methylenprotons wurden deutlich in den NMR-Spektren der Copolymeren beobachtet. Die Untersuchungen an den deuterierten Copolymeren zeigen, daß die Effekte der chemischen Gruppen bis zur dritten nach beiden Seiten vom markierten Methylen und die Stereokonfiguration von langen Vinyl-Chlorid-Anteilen betrachtet werden müssen, um die NMR-Spektren zu beschreiben. Die CCl₂-Gruppe läßt die chemische Verschiebung des Methylen-protons bei geringeren magnetischen Feldern und die CHCl-Gruppe bei höheren erscheinen.

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With 5 figures in 13 details and 4 tables     

Extraction of pertechnetate by triphenyltin chloride and trioctyltin chloride

The extraction of pertechnetate in form of ionogene associates with triphenyltin and trioctyltin cations into chloroform, benzene, toluene and nitrobenzene was studied. As aqucous phases solutions of^99mTcO ₄ ^? in deionized water and in diluted solutions of NaCl, HCl, NaNO₃, HNO₃ NaClO₄, HClO₄ and NaOH were used. Concerning the organic phases, at the use of triphenyltin chloride the extractibility of pertechnetate increases in the sequence: toluene «chloroform, benzene nitrobenzene and approximately in the sequence: NaOH<NaCl, HCl<NaNO₃<H₂O<NaClO₄ concerning aqueous phases. For trioctyltin chloride in chloroform the extractibility of TcO ₄ ^? increases approximately in the sequence of aqueous phases: NaOH<HCl, NaNO₃, NaClO₄, NaCl«H₂O and in nitobenzene in the sequence NaOH<NaClO₄<HCl<NaNO₃, NaCl«H₂O. The extractibility for trioctyltin chloride is in general slightly lower as compared with triphenyltin chloride. The results of the extraction are presented in the form of graphical plots of technetium distribution ratio (D _Te′ logD _Tc) or extraction yield (E _Tc, %) against concentration of the investigated component in aqueous or organic phase. In some of the systems of the systems studied practically quantitative extraction of pertechnetate into organic phase has been achieved.     

Spectroscopic studies on crotonyl chloride and dimethyl acryl chloride

Infrared spectra of liquid samples of crotonyl chloride and dimethyl acryl chloride in the region 4000-600 cm⁻¹ have been recorded along with the Raman spectra in the region 4000-100 cm⁻¹. From CNDO/2 results and some band splitting, existence of conformers are inferred. A complete assignment of the spectra is made on the basis of reported spectral studies on related compounds and the relative variation of i.r. peak intensity with solvent polarity. Normal coordinate analysis of crotonyl chloride has been carried out for the first time.     

Reactions of methylenecyclopropanes with phenylsulfenyl chloride and phenylselenyl chloride

The reaction of methylenecyclopropanes 1 with phenylsulfenyl chloride or phenylselenyl chloride gives (cyclobut-1-enylsulfanyl)benzene or (cyclobut-1-enylselanyl)benzene along with ring-opened product in good total yields at 0 degrees C in various solvents. A plausible mechanism has been proposed.     

Indirect determination of chloride as chromyl chloride by atomic-absorption spectrophotometry

Summary A method for the determination of chloride in aqueous solution by atomic-absorption Spectrophotometry is described. The chloride is converted into chromyl chloride, which is extracted into carbon tetrachloride and subsequently back-extracted and determined in a solution buffered with NH₄H₂PO₄/(NH₄)₂HPO₄. Calibration plots of the atomic absorption of the aqueous back-extracted phase at the chromium 425.4 nm resonance line are linear in the range 5–270g of chloride. The calibration graph can be obtained directly with aqueous solutions of Cr(VI). The proposed method can be applied directly to mineral and medicinal water samples.

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Indirekte AAS-Bestimmung von Chlorid als Chromylchlorid

Zusammenfassung Eine Methode zur Bestimmung von Chlorid durch Atom-Absorptions-Spektroskopie wurde entwickelt, deren Basis die Bildung von Chromylchlorid, dessen Extraktion mit Cl₄C und die anschließende Bestimmung des rückextrahierten Chroms in einer Lösung von NH₄H₂PO₄/(NH₄)₂HPO₄ ist. Das lineare Verhältnis zwischen Absorbanz und Chromkonzentration ermöglicht die Bestimmung des Chlorids im Bereich 5–270g; zur direkten Eichung dienten wäßrige Lösungen von Chrom(VI). Die vorgeschlagene Methode wurde für die Chlorid-Bestimmung in Mineral-und Medizinalwasser benutzt.

     

Melaminium chloride hemihydrate

The crystals of a new melaminium salt, 2,4,6‐tri­amino‐1,3,5‐triazin‐1‐ium chloride hemihydrate, C₃H₇N₆⁺·Cl^?·0.5H₂O, are built up from single‐protonated melaminium residues, chloride anions and water mol­ecules. The protonated melaminium cations lie on a twofold axis, while the chloride anions and water mol­ecule lie on the m plane. The melaminium residues are interconnected by N—H?N hydrogen bonds, forming chains parallel to the (001) plane. The chains of melaminium residues form a three‐dimensional network through hydrogen‐bond interactions with chloride anions and water mol­ecules.     

An improved spectrophotometric determination of chloride via chromyl chloride formation

Chloride (? 1 μg) is extracted into carbon tetrachloride as chromyl chloride. It is back-extracted into pH 3.2 buffer where it oxidizes iodide to tri-iodide ions, which are measured at 288 nm or 351 nm. The relative standard deviation is 0.8% for 10 μg of chloride.     

Preparation of tricyclohexyltin chloride from dicyclohexylaluminum chloride and SnCl4

Conclusions A new simple method was developed for the synthesis of tricyclohexyltin chloride from SnCl₄ and dicyclohexylaluminum chloride. The latter was obtained by reacting diisobutylaluminum chloride with cyclohexene in the presence of the binary Cp₂ZrCl₂/Ti(OBu)₄ catalyst and a catalytic amount of (i-C₄H₉)₂AlH.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1171–1173, May, 1984.     

Sulfurization polyvinyl chloride

A sulfurized polymer comprising 57.64% of chemically bound sulfur characterizing by paramagnetism with the concentration of paramagnetic centers 2 × 10¹⁹ spins g^?1 and g-factor 2.0043 was resulted n the treatment of industrial polyvinyl chloride by elemental sulfur.