Tetrakis(chloromethyl)phosphonium chloride monohydrate

Tetrakis­(chloro­methyl)­phospho­nium chloride monohydrate, C₄H₈Cl₄P⁺·Cl^?·H₂O or P(CH₂Cl)₄⁺·Cl^?·H₂O, is the first crystal structure determination of a tetrakis­(halogeno­methyl)­phospho­nium compound to date. The only comparable structures known so far are of phospho­nium ions containing just one halogeno­methyl group. The solvent water mol­ecule interacts with the Cl^? anion via hydrogen bonds, with O?Cl distances of 3.230 (2) and 3.309 (2) Å. The structure also contains several C—H?Cl^? and C—H?O contacts, though with longer D?A distances [D?A 3.286 (3)–3.662 (2) Å] or bent D—H?A angles. For these reasons, the C—H?Cl^? and C—H?O interactions should not be considered as strong hydrogen bonds.     

Synthesis of N-(chloromethyl)-2,6-diethylcarbaniloyl chloride (1) and derivatives

The reaction of N-methylene-2,6-diethylbenzenamine with phosgene furnished the titled compound 1. The reaction of 1 with the potassium salts of various thiazolethiols in an acetone medium afforded the expected N-substituted 2,6-diethylthiolcarbanilates 2–6. Substituting the above thiazolethiols with the potassium salt of 2-mercaptobenzimidazole furnished a novel heterocyclic compound 7 in 98% yield. The rection of 1 with the triethylamine salt of disubstituted-dithiocarbamic acids afforded an alternate method for the synthesis of bis(N-substituted-thiocarbonyl)sulfides 8 and 9.     

Synthesis and transformations of acyloxy(chloromethyl)phosphonates and acyloxy(chloromethyl)phosphinates

The reactions ofO-phenyl chloromethylphosphonochloridate and bis(chloromethyl)phosphinous chloride with sodium acetate afford the corresponding acyloxyphosphonates and acyloxyphosphinates, which are readily transformed due to disproportionation into pyrophosphonates and pyrophosphinates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp 2383–2385, November, 1998.     

聚合氯化铝的盐基度与水解形态

聚合氯化铝(PAC)是国际上近年来发展较快的高效水处理剂之一。与传统药剂相比,具有用量少、成本低、净化水质优、使用方便等一系列特点,目前正迅速取代传统水处理药剂。随着聚合氯化铝的广泛应用,其形态结构成为人们日益关注的焦点。已有研究表明,絮凝剂的凝聚效率很大程度上取决于混     

Catalytic effects of copper(II) chloride and aluminum chloride on the pyrolytic behavior of cellulose

The cellulose without and with catalyst (CuCl₂, AlCl₃) was subjected to pyrolysis at temperatures from 350 to 500 °C with different heating rate (10 °C/min, 100 °C/s) to produce bio-oil and selected chemicals with high yield. The pyrolytic oil yield was in the range of 37–84 wt% depending on the temperature, the heating rate and the amount of metal chloride. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil. The mixing cellulose with both metal chlorides results with a significant decrease of the liquid product. The non-catalytic pyrolysis of cellulose gives the highest mass yield of levoglucosan (up to 11.69 wt%). The great influence of metal chloride amount on the distribution of bio-oil components was observed. The copper(II) chloride and aluminum chloride addition to cellulose clearly promotes the formation of levoglucosenone (up to 3.61 wt%), 1,4:3,6-dianhydro-α-d-glucopyranose (up to 3.37 wt%) and unidentified dianhydrosugar (MW = 144; up to 1.64 wt%). Additionally, several other compounds have been identified but in minor quantities. Based on the results of the GC–MS, the effect of pyrolysis process conditions on the productivity of selected chemicals was discussed. These results allowed to create a general model of reactions during the catalytic pyrolysis of cellulose in the presence of copper(II) chloride and aluminum chloride.     

4,5-Bis(chloromethyl)uracil

A one-step synthesis of 4,5-bis(chloromethyl)uracil from readily available starting materials has been accomplished. This substance is a stable, crystalline solid which undergoes facile nucleophilic attack to produce various di-substituted uracil derivatives.     

Spectra and thermodynamics of the cobalt(II) chloride — aluminum chloride gaseous complexes

The reaction of solid cobalt(II) chloride with gaseous aluminum chloride to form blue gaseous complex(es) has been studied spectrophotometrically, in the range 600–800 K and 1–3 atm. The data are rationalized in terms of the reaction: CoCl₂(s) + Al₂Cl₆(g) → CoAl₂Cl₈(g) (ΔH° = 10.0 ± 0.2 Kcal/mole, ΔS° = 9.8 ± 0.3 e.u.). The electronic absorption spectrum of the gaseous complex was compared with the spectra of Co(II) in different molten salt solvents. Thermodynamic and spectroscopic considerations suggest that the predominant absorbing species in the gaseous phase are Co(AlCl₄)₂ molecules having the Co(II) in a close to octahedral coordination.     

Transformations of α-4,5-epoxycarane under influence of HCl

Conclusions The reaction of -4,5-epoxycarane with HCl proceeds with the preferential opening of the oxide ring at the C₅ atom and the formation of m-menthene derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No 10, pp. 2380–2382, October, 1978.     

Synthesis of boehmite and hematite by joint hydrolysis of carbamide,aluminum chloride,and iron(III) chloride under hydrothermal conditions

The formation of boehmite and hematite in dependence of the conditions of joint hydrothermal hydrolysis of carbamide and a mixture of aluminum and iron(III) chlorides in the presence of K, Na, Ca, and Mg chlorides at T = 160–200°C and P = 0.6–1.6 MPa was studied. It was shown that the amount of boehmite and hematite being formed in hydrolysis of Al and Fe chlorides strongly depends on pressure, temperature, hydrolysis duration, and composition of the model mixture of Al, Fe, Mg, Ca, K, and Na chlorides. It was found that a complete hydrolysis of AlCl₃ and FeCl₃ with 99% yield of boehmite and hematite occurs at the stoichiometric ratio between carbamide and aluminum and iron chlorides in the starting solution, whereas mostly iron oxyhydroxide [goethite FeO(OH)] and aluminum oxychloride [Al₁₇O₁₆(OH)₁₆Cl₃] are formed at nonstoichiometric ratios.     

Transformations of some alkaloids of the carboline series under the influence of alkali

The reaction of quaternized forms of two alkaloids of the -carboline series — harman and brevicarine — with alkali was investigated. It was established that, under the reaction conditions, the harman derivative undergoes recyclization of the pyridine part of the molecule, whereas in the analogous brevicarine derivative the pyridine ring does not undergo transformations.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 530–533, April, 1985.     

Transformations of the sulfur analogs of Β-carbolins under the influence of nucleophiles

The reaction of the quaternary salts of some thienopyridines (the sulfur analogs of -carbolins) with nucleophilic reagents was investigated. It was shown that either the methylene anhydro bases are formed or one or both heterocyclic rings are transformed, depending on the structure of the thienopyridine and on the reaction conditions.For the previous communication, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 398–403, March, 1987.     

Synthesis of bis (chloromethyl)chlorophosphine

Conclusions Synthesis of bis(chloromethyl)chlorophosphine is described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 185–186, January, 1969.The authors wish to thank B.E. Ivanov and I.M Shermergorn for kindly supplying a sample of bis(chloromethyl) phosphoryl chloride.     

Zinc underpotential deposition at Pt(111) and Pt(110) under the influence of boric acid and chloride anions

Zinc underpotential deposition (Zn UPD) was studied by cyclic voltammetry in solutions of various pH and composition, where the effects of the presence of boric acid or chloride in the solution were observed. We have found that the cyclic voltammograms of Zn UPD at Pt(111) were dependent on boric acid concentrations, zinc ion concentrations, and pH in acidic solutions. These suggest that the induced adsorption of borate by releasing of H⁺ is accompanied with Zn UPD. The preadsorbed chloride species on Pt(110) accelerate the UPD process by their removal just before the UPD, making the surface sites available for the process, and the UPD remains at identical electrode potentials, while the chloride ions do not take part in the induced adsorption on UPD Zn at Pt, as clearly found by the radiotracer method. These show that the anions play versatile roles in the process of adlayer formation by their different but essential chemical characteristics. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 6, pp. 745–751 The text was submitted by the authors in English.     

Transformations of 2-(phenylethynyl)isocamphanol under acid catalysis

2-exo-(Phenylethynyl)isocamphanol prepared from lithium phenylacetylide and isocamphanone suffered under conditions of Ritter reaction a conversion predominantly into a mixture of 2-(benzoylmethylene)isocamphane and 2-(benzoylmethylene)bornane that formed as a result of rearrangements of the initial acetylene alcohol by Meyer-Schuster and partially by Wagner-Meerwein. The enones ratio depends on the reaction conditions and varies from 5:4 to 1:3. The product of nucleophilic substitution, N-(4-benzoylmethyl-2-isobornyl)acetamide, formed in a yield no higher than 10%. Analogous rearrangements occurred at treating 2-phenylethynylisocamphanol with formic acid; here the mixture of the above enones formed in a ratio 1:2. The initial acetylene alcohol treated with Beckmann mixture gave rise to the same enones in a ratio 1:1, and the target 2-endo-(phenylethynyl)isocamphanol acetate formed as minor product (～15%). The individual α,β-unsaturated ketones under the Ritter reaction conditions were selectively converted into N-(4-benzoylmethyl-2-isobornyl)acetamide.