79-36-7

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The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.

The invention relates to a synthesis method of difluoroacetyl fluoride, which comprises the following steps: 1. reacting trichloroethylene with oxygen under the catalytic action of trialkyl boron shown in the formula I to generate dichloroacetyl chloride, and 2. reacting dichloroacetyl chloride with inorganic fluoride shown in the formula II under the action of a catalyst to generate difluoroacetyl fluoride. According to the synthetic method of difluoroacetyl fluoride, the raw materials are simple and easy to obtain, high-temperature reaction is not needed, and the yield is high.

Dichloroacetate (DCA) as a mitochondria-targeting small molecule, through inhibition of pyruvate dehydrogenase kinases (PDK1-4), promotes mitochondria-regulated apoptosis and hence, inhibits tumour growth and reduces its proliferation. In this study, a series of novel N-aryl-2,2-dichloroacetamide and aryl-2,2-dichloroacetate derivatives were designed and synthesized. Their cytotoxic activities against various human cancer cell lines including A549, HCA-7, MCF-7, MDA-MB-231, KB and SKOV3 were evaluated. These compounds showed satisfactory potencies with much higher anticancer activity than the parent compound DCA, against the studied cancer cell lines. Molecular docking studies were also done to find their binding site and types of their interactions with PDKs isoenzymes. Among the synthesized compounds, 2,2-dichloro-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)acetamide (f1) can also induce A549 cells apoptosis. Therefore, compound f1 might have a potential value for further study in drug development. QSAR studies of this class of compounds were also explored using a collection of chemometrics methods.

The invention relates to an isoalantolactone derivative, a pharmaceutical composition and application thereof, especially use of the isoalantolactone derivative shown as formula (I) or a salt pharmaceutical compound thereof in preparation of adjuvant drugs treating cancer, a pharmaceutical composition containing a therapeutically effective amount of isoalantolactone derivative (I) or its salt anda pharmaceutically acceptable carrier or a composition with other anticancer drugs.

The invention discloses a synthesis method of chloroacetyl chloride (ClCH2COCl). To be specific, the synthesis method is characterized in that an activated carbon loaded lewis acid catalyst is used for catalyzing gaseous acetyl chloride and chlorine to perform an alpha-halogenation reaction in a contact reactor to generate the chloroacetyl chloride. Lewis acid is specifically ferric chloride or aluminium chloride, and the consumption of the lewis acid is 1-7% of the total material input of acetyl chloride. The synthesis method disclosed by the invention is high in catalyst utilizing rate, highin selectivity, and less in byproducts, and the purity of a product is higher than or equal to 99.5%; the reaction is performed at low temperature; the energy consumption is low; the environmental pollution is small; and the reaction equipment structure is simple, and the operation is easy.

The invention provides a method for preparing ethyl bromodifluoroacetate and relates to a preparation method of a chemical reagent. The method takes trichloro ethylene as a raw material, and comprisesthe following steps: under the action of ultraviolet light of a catalytic medium, an oxidation reaction happens between trichloro ethylene and oxygen in a reactor to synthesize dichloracetyl chloride; an amination reaction happens between dichloracetyl chloride and diethylamine under the action of a catalyst to synthesize dichloroacetyl diethylamine; a fluorination reaction happens between dichloroacetyl diethylamine and anhydrous potassium fluoride under the action of a solvent and a phase transfer catalyst to synthesize difluoroacetyl diethylacetamide; difluoroacetyl diethylacetamide is esterified to synthesize ethyl difluoroacetate; and by taking cupric bromide as a brominating agent, ethyl difluoroacetate is bromized to prepare the end product (ethyl bromodifluoroacetate). The methodhas the characteristics that the equipment investment is low, reaction conditions are mild, the method is safely implemented at normal pressure, and after-treatment is simple.

The new complexes [RuCl2(η6-p-cymene)(κP-Ph2PR)] [R = 4-C6H4OSiMe2tBu, 1; R = 4-C6H4Br, 2; R = OC(O)CHCl2, 3; R = OPh, 4; R = O(2-C6H4SiMe2tBu), 5] and [Ru(C2O4)(η6-p-cymene){κP-Ph2PO(2-C6H4(SiMe2tBu))}], 6, were obtained in 83-98% yield from Ru(ii) arene precursors by three different synthetic strategies. The unprecedented phosphine Ph2P(O(2-C6H4SiMe2tBu)) was synthesized in 86% yield from 2-C6H4Br(OSiMe2tBu) and Ph2PCl, via intramolecular oxygen to carbon 1,3 migration of the silyl group (retro-Brook rearrangement). All the complexes were fully characterized by analytical and spectroscopic methods, and by single crystal X-ray diffraction in the cases of 3, 4, 5 and 6. Complexes 1-6 and the model compounds [RuCl2(η6-p-cymene)(κP-PPh3)] (Ru-PPh3) and [Ru(C2O4)(η6-p-cymene)(κP-PPh3)] (Ru-PPh3-O) underwent slow degradation in chloroform solutions upon air contact; the mixed valence complex [(η6-p-cymene)Ru(μ-Cl)3RuCl2(κP-PPh3)], 7, was isolated from a solution of Ru-PPh3 in CHCl3, and X-ray identified. The antiproliferative activity of 1-6 and Ru-PPh3, Ru-PPh3-O and [RuCl2(η6-p-cymene)(κP-PTA)] (RAPTA-C) was assessed towards the triple-negative breast cancer cell line MDA-MB-231, the ovarian carcinoma cell line A2780 and human skin fibroblasts (HSF). Complexes 1, 2, 5 and 6 displayed IC50 values significantly lower than that of cisplatin, with 2 providing a more potent cytotoxic effect on MDA-MB-231 and A2780 cancer cells compared to the noncancerous cell line (HSF). The stability of all complexes in DMSO/water solution was elucidated by NMR and conductivity measurements, and in particular 35Cl NMR spectroscopy was helpful to check the possible chloride dissociation. The stability studies suggest that the cytotoxic activity in vitro of the compounds is mainly ascribable to Ru(ii) species still bound to the phosphorus ligand.

Abstract The reactions of WCl6 with a selection of carboxylic acids were investigated by using dichloromethane as reaction medium. The addition of pyridine-3-carboxylic acid (niacin) to WCl6 gave [C5H4NHC(O)Cl][WOCl5], 1, in 75% yield via selective Cl/O interchange. WCl6 reacted with RCO2H (R = CH3, CBr3, CHCl2) in 1:2 ratio resulting in the formation of HCl and the respective acyl chlorides, RC(O)Cl. WOCl4(κ1-CH3CO2H), 2, was isolated from WCl6/CH3CO2H in 41% yield. The 1:2 reaction of WCl6 with CCl3CO2H proceeded with HCl release affording a mixture of WCl5(O2CCCl3), 3, and WCl4(O2CCCl3)2, 4. Compound 3 was isolated from WCl6/CCl3CO2H (1:1 ratio) in 60% yield. All the metal products were characterized by analytical and spectroscopic techniques. The crystal structure of 1 was ascertained by X-ray diffractometry. DFT calculations were carried out in order to shed light into structural, mechanistic and thermodynamic features.

Relative rate method at the temperature of 298 K and pressure of 1013 hPa and GC-MS detection were used for the study of kinetics of the reactions of Cl atoms with H2C=CCl2, cis-ClHC=CHCl, trans-ClHC=CHCl, ClHC=CCl2, and Cl2C=CCl2. The reaction products were identified by FTIR spectroscopy. A mechanism for the atmospheric degradation of chloro-ethenes has been suggested.

Visible-light-driven TiO2 photocatalysts doped with nitrogen have been prepared as powders and thin films in a cylindrical tubular furnace under a stream of ammonia gas. The photocatalysts thus obtained were found to have a band-gap energy of 2.95 eV. Electron spin resonance (ESR) under irradiation with visible light (λ ≥ 430 nm) afforded the increase in intensity in the visible-light region. The concentration of trapped holes was about fourfold higher than that of trapped electrons. Nitrogendoped TiO 2 has been used to investigate mechanistically the photocatalytic oxidation of trichloroethylene (TCE) under irradiation with visible light (λ ≥ 420 nm). Cl and O radicals, which contribute significantly to the generation of dichloroacetyl chloride (DCAC) in the photocatalytic oxidation of TCE under UV irradiation, were found to be deactivated under irradiation with visible light. As the main by-product. only phosgene was detected in the photocatalytic oxidation of TCE under irradiation with visible light. Thus, the reaction mechanism of TCE photooxidation under irradiation with visible light clearly differs markedly from that under UV irradiation. Based on the results of the present study, we propose a new reaction mechanism and adsorbed species for the photocatalytic oxidation of TCE under irradiation with visible light. The energy band for TiO2 by doping with nitrogen may involve an isolated band above the valence band.

During direct-photodegradation treatment of trichloroethylene by a low-pressure mercury lamp in a dry air atmosphere, slightly degradable by-products are produced; this production is the most serious issue associated with such treatment. We observed the acceleration of by-products degradation with decrease in an oxygen concentration in a treatment atmosphere.

The invention concerns a method for preparing a benzylic-type ether from an aromatic compound. The inventive method for preparing a benzylic-type ether from an aromatic compound is characterised in that it consists in: in a first step, acylating an aromatic compound by reacting said aromatic compound with an acylating agent, in the presence of an efficient amount of zeolite or a Friedel-Crafts catalyst leading to a ketonic compound; in a second step, reducing the carbonyl group into carbinol leading to a benzylic alcohol; in a third step, etherifying the hydroxyl group, by reacting the benzylic alcohol with another alcohol, in the presence of an efficient amount of zeolite.

The invention concerns a method for functionalizing a phenolic compound bearing an electron-donor group, in said group para position, inter alia a method for the amidoalkylation of a phenolic compound bearing an electron-donor group, and more particularly, a phenolic compound bearing an electron-donor group preferably, in the hydroxyl group ortho position. The method for functionalizing in para position with respect to an electron-donor group carried by a phenolic compound is characterised in that the phenolic compound bearing an electron-donor group is subjected to the following steps: a first step which consists of protecting the hydroxyl group in the form of a sulphonic ester function; a second step which consists in reacting the protected phenolic compound with an electrophilic reagent; optionally, a third step deprotecting the hydroxyl group.

The present invention relates to a process facilitating the regeneration of a catalyst based on a zeolite, employed in an acylation reaction. Another subject of the invention is a process for acylation of an aromatic ether, comprising, in a preferred alternative form, an additional stage of regeneration of the catalyst. The process of the invention, which makes it possible to regenerate more easily a catalyst based on a zeolite, employed in an acylation reaction, is characterized in that the zeolite is modified by addition of an effective quantity of at least one metallic element M chosen from the elements of group 8 of the Periodic Classification of the elements.

A method for acylating an aromatic compound, specifically an activated or deactivated aromatic compound, is disclosed. The method is suitable for preparing aromatic ketones. The preparation of a catalyst and novel bismuth compounds is also disclosed. Said aromatic compound acylation method comprises reacting said aromatic compound with an acylating agent in the presence of a catalyst, and is characterised in that the acylation reaction is performed in the presence of an effective amount of at least one bismuth salt of trifluoromethanesulphonic acid.

The present invention concerns a process for acylation of an aromatic compound.The acylation process of the invention consists of reacting the aromatic compound with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that it consists of:mixing the aromatic compound and the acylation compound in any manner;passing said mixture over a catalytic bed comprising at least one zeolite;recirculating the reaction mixture from the catalytic bed over the catalytic bed for a number of times which is sufficient to obtain the desired degree of conversion of the substrate.

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The present invention concerns a process for the acylation of an aromatic ether. Preferably the invention relates to a process for the acylation of a substituted aromatic ether, in particular veratrol. The acylation process of the invention consists of reacting the ether with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that the acylation reaction is carried out in the presence of an effective quantity of a catalyst comprising a faujasite type zeolite or a Y zeolite with the following physico-chemical characteristics: an atomic ratio denoted "global Si/Me1 " between the number of atoms of the element silicon and the number of atoms of every trivalent element Me1 contained in the zeolite in the range 2.4 to 90, preferably in the range 2.4 to 75, and more preferably in the range 2.4 to 60; an Me2 alkali metal content such that the atomic ratio Me2 /Me1(IV) between the number of atoms of alkali metal Me2 and the number of atoms of every trivalent element Me1(IV) included in the zeolitic network is less than 0.2, preferably less than 0.1, and more preferably less than 0.05.

PCT No. PCT/FR96/01763 Sec. 371 Date Aug. 3, 1998 Sec. 102(e) Date Aug. 3, 1998 PCT Filed Nov. 8, 1996 PCT Pub. No. WO97/17324 PCT Pub. Date May 15, 1997The present invention relates to a process for the acylation of an aromatic thioether. In its preferred variant, the invention resides in a process for the condensation of acetic anhydride or acetyl chloride with thioanisole. The process for the acylation of an aromatic thioether according to the invention is characterised in that it consists in reacting said thioether with an acylating agent chosen from the group formed by the halides of carboxylic acids and the anhydrides of carboxylic acids, in the presence of an effective quantity of an acid zeolite.

Decomposition of trichloroethylene (TCE) in electron beam irradiation was examined in order to get information on treatment of industrial off-gas. Air containing vaporized TCE was sealed into a glass vessel and irradiated with an electron beam. The concentration of TCE exponentially decreased with dose (air-absorbed energy). The doses necessary to decompose 90% of input TCE molecules had a value of 3.6 kGy independent of an initial concentrations ranging from 50 to 1800 ppmv. Between G values of decomposition and initial concentrations, the following equation was obtained: G(-TCE) [μmol J-1] = 1.5 [μmol J-1] + 0.020 [μmol J-1 ppmv-1] × conc [ppmv]. The equation shows that concentrations of Cl radicals remained constant at 6.3 × 10-4 ppmv (at 298 K and 1 bar) independent of concentrations of TCE and products under a dose rate of 2.1 kGy/s. Termination reactions in the decomposition mechanism for EB irradiation of TCE and tetrachloroethylene (PCE) were also clarified on the basis of the relation of G value of decomposition and the initial concentrations. Dichloroacetyl chloride, which was identified as a primary product, was decomposed and oxidized to give CO and CO2. Phosgene was also identified as a primary product. From the proportion of DCAC to COCl2 concentrations, a branching ratio was calculated to be 5.3 in the Cl radical chain reaction of TCE. Formation of HCl and/or Cl2 was analyzed and the collection of the products from the gas phase was examined with alkaline solution. The effect of water (400-25 000 ppmv) on decomposition efficiency was examined. The decomposition efficiencies had the same value as that in dry air.

In situ solid-state NMR methodologies have been employed to investigate the photocatalytic oxidation of trichloroethylene (TCE) over two TiO2-based catalysts, Degussa P-25 powder and a monolayer TiO2 catalyst dispersed on porous Vycor glass. 13C magic angle spinning (MAS) experiments reveal that similar reaction intermediates form on the surfaces of both catalysts. Long- lived intermediates, including dichloroacetyl chloride (Cl2HCCOC1, DCAC), carbon monoxide, and pentachloroethane and final products CO2, phosgene (Cl2CO), and HCl were observed under dry conditions. The presence of molecular oxygen was found to be essential for TCE photooxidation to proceed. Adsorbed water was found to greatly reduce the formation of phosgene. The formation of surface-bound dichloroacetate and trichloroacetate species was observed and identified via 13C cross polarization MAS experiments. Dichloroacetate, which forms from mobile DCAC, appears to be bound to the nonirradiated surfaces of the powdered TiO2 catalysts and further degradation was not possible. Formation of di- and trichloroacetate also takes place on the TiO2/PVG catalyst in the absence of light; however, their concentrations are low. Degradation studies of these surface-bound species indicate that the photooxidation of dichloroacetate, is slow and results in the formation of phosgene and CO2, while trichloroacetate remains resistive to degradation on the TiO2/PVG catalyst. Our results also indicate that the formation of DCAC and phosgene seems to be a general result of TCE degradation which is not limited to TiO2 photocatalysis but instead may be more characteristic of the types of initiating species which are formed by UV irradiation. However, the TiO2 surface is the most effective in terms of the observed initial rates of degradation.

The present invention concerns a process for the acylation of an aromatic ether. Preferably, the invention relates to a process for the acylation of an unsubstituted aromatic ether, in particular anisole. The acylation process of the invention consists of reacting the ether with an acylation agent in the presence of a zeolitic catalyst, and is characterized in that the acylation reaction is carried out in the presence of an effective quantity of a catalyst comprising a beta zeolite with an atomic ratio denoted "global Si/Me1 " between the number of atoms of the element silicon and the number of atoms of every trivalent element Me1 contained in the zeolite of no less than 15, preferably in the range 15 to 55, and more preferably in the range 18 to 35.

Transmission Fourier transform infrared spectroscopy has been used to identify gas-phase and surface-bound products and intermediates formed during the gas-phase photooxidation of trichloroethylene (TCE) on TiO2 and ZnO. Several factors are found to influence the gas-phase product distribution for this reaction. On clean TiO2 and ZnO surfaces and at high TCE and O2 pressures, gas-phase CO, CO2, COCl2, CCl2HCOCl, CHCl3, C2HCl5, and HCl are produced, whereas at low TCE and O2 pressures, TCE is converted to gas-phase CO and CO2 only. In addition to TCE and O2 pressure, the product distribution of the photooxidation of TCE is strongly dependent upon the coverage of adsorbed species on the surface of the photocatalyst. It is shown here that the complete oxidation of adsorbed TCE can occur on clean photocatalytic surfaces whereas only partial oxidation of adsorbed TCE occurs on adsorbate-covered surfaces. The role of adsorbed surface products in TCE photooxidation is discussed.

The halogen atom transfer radical cyclization of a N-allyl-N-benzyl-2,2-dihaloamides to 2-pyrrolidinones has been carried out in high yields under mild conditions, in a reaction promoted by CuCl-TMEDA or Fe0-FeCl3 in acetonitrile or N,N-dimethylformamide, respectively.

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The Cl- and Br- initiated oxidations of CHCl=CCl2 in 700 torr of air at 296 K have been studied using a Fourier transform infrared spectrometer. Rate constants k(Cl + CHCl=CCl2) = (7.2 ± 0.8) × 10-1 and k(Br + CHCl=CCl2) = (1.1 ± 0.4) × 1013 cm3 molecule-1 s-1 were determined using a relative rate technique with ethane and ethylene as references, respectively. The major products observed were CHXClC(O)Cl, (X = Cl or Bl), CHClO, and CCl2O. Combining results obtained for the Cl-initiated oxidation of CHCl2 - CHCl2, we deduced that Cl-addition on trichloroethylene occurs via channel 1a, Cl + CHCl=CCl2 → CHCl2-CCl2, (100 ± 12)%. Self-reaction of the subsequently generated peroxy radicals CHCl2-CCl2O2 leads to CHCl2CCl2O radicals which were found to decompose via channel 8a, CHCl2C(O)Cl + Cl, (91 ± 11)% of the time, and channel 8b, CHCl2 + CCl2O. (9 ± 2)%. The reaction Br + CHCl=CCl2 → CHBrCl-CCl2 (17a) accounted for ≥(96 ± 11)% of the total reaction. Decomposition of the CHBrCl-CCl2O radicals proceeds (≥93 ± 11)% via CHBrClC(O)Cl + Cl. As part of this work, k(Cl + CHCl2C(O)Cl) = (3.6 ± 0.6) × 10-14and k(Cl + CHCl2-CHCl2) = (1.9 ± 0.2) × 10-13 cm3 molecule-1 s-1 were measured. Errors reported above include statistical uncertainties (2σ) and estimated systematic uncertainties.

The photooxidation of trichloroethylene (TCE) on TiO2 has been investigated using infrared spectroscopy for kinetic studies of the production of intermediate species and for investigation of the reaction mechanism. Trichloroethylene is oxidized by chemisorbed molecular O2 when TiO2 band gap radiation (hv > 3.1 ± 0.1 eV) is incident. An intermediate species, dichloroacetyl chloride, HCl2CCOCl, was identified. At 300 K, Cl2CO, CO, CO2, HCl, and H2O are final photooxidation products. At 473 K, Cl2CO undergoes a thermal side reaction on TiO2 to produce Cl2C=CCl2. Studies in which oxygen-labeled H2O was present indicated no incorporation of the oxygen label into any of the intermediates, showing that the OH· driven oxidation mechanism proposed by others is not operative. At 150 K, TCE blocks TiO2 sites, significantly retarding O2 adsorption and slowing the photooxidation reaction.

The oxidation of trichloroethene by molecular oxygen in presence of CF3OF has been studied at 293.8, 313.8 and 333.5 K.The initial pressure of CF3OF was varied between 0.8 and 9.5 Torr, that of CHClCCl2 between 5.4 and 54.6 Torr and that of O2 between 19.9 and 603.5 Torr.Several runs were made adding N2 at pressures varying from 96.4 to 663.2 Torr.The major product was CHCl2C(O)Cl, COCl2, HCl and CO were formed in minor amounts.Traces of CF3OCHClC(O)Cl, CHClFC(O)Cl, CF3OCHClCCl2F and CHClFCCl2F were detected.The oxidation is a chain reaction, whose rate increases with total pressure.The following mechanism, where E = CHClCCl2, R = CHClFCCl2, CF3OCHClCCl2 or CHCl2CCl2, R' = CHClF, CF3OCHCl or CHCl2 and M = effective pressure, explains the experimental results: (1) CF3OF + E = R + CF3O, (2) CF3O + E = R, (3,7) R + O2 + M = RO2 + M, (4,8) 2RO2 = 2RO + O2, (5,9) RO = R'C(O)Cl + Cl, (6) Cl + E = R, (10) 2R = recombination products, (11) R + CF3OF = RF + CF3O, (12) RO2 + E = RO2(E), (13) RO2(E) = products (e.g., R, HCl, CO, COCl2), k9 = 1.1 +/- 1E14 exp(-39.5 +/- 10 kJ mol-1/RT) s-1, k12 = 9.4 +/- 8E8 exp(-27.0 +/- 11 kJ mol-1/RT) dm3 mol-1 s-1. - Keywords: Gas-phase, Oxidation, Trichloroethene, Trifluoromethylhypofluorite, Chlorine atoms

Trichloroethylene in solution with air is oxidized rapidly in the presence of irradiated titanium dioxide.Dichloroacetyl chloride (DCAC), which is formed as an intermediate during the trichloroethylene reaction, also undergoes photocatalytic oxidation.This paper describes the kinetics of these reactions and how operating conditions influence the observed reaction rates.Annular photocatalytic reactors with thin films of titanium dioxide catalyst were used to make kinetic measurements.Observations of the reaction rate of trichloroethylene were made while varying parameters such as catalyst loading, feed flow rate, feed composition, and ultraviolet light energy.The observed reaction rates are higher by several orders of magnitude than those previously reported in the literature, and an expression for the prediction of rate as a function of reactant partial pressure is provided.The rate of reaction of the DCAC intermediate is also discussed.Air is shown to be an optimum oxidant, and an optimum humidity is established.The reaction is shown to proceed indefinitely under dry conditions, supporting the existence of a chlorine radical propagated surface reaction.

The photochemical decomposition and oxidation of the chloroethenes C2H4-XClX (x=1-4) was investigated in the gas phase by irradiation with a low pressure mercury lamp in an oxygen atmosphere. Degradation efficiencies directly depend on the number of chlorine atoms both at 185 and 254 nm. The quantum yields for degradation increase from 2-3 for vinyl chloride to > 100 for tri- and tetrachloroethene at 185 nm in the 10-3 bar concentration range. At 254 nm we measured nearly time independent quantum yields of around 10 for tri- and 40 for tetrachloroethene. The photooxidation products and their mechanism of formation are discussed in detail.

Ozonolyses of acyclic olefins containing 1,2-dichloro-substituted (4a,b) and monochloro-substituted double bonds (7a, b, 12) as well as two (4a, b, 7a, b) or one halomethyl group (12) attached to the double bond afford the corresponding ozonides as the first representatives of monocyclic chlorinated ozonides.Their stability decreases in order 5a, 5b > 8a, 8b > 13. - Key Words: Ozonides/ 1,2,4-Trioxolanes, 3-chloro-, 3,5-dichloro- / Polyethylene

Reaction of N-aryl-2,4,6-cycloheptatrien-1-imine with hydrazine afforded tropone azine, which reacted with chloroketenes to give 1,1'-biazaazulanones via -type cycloadducts followed by elimination of hydrochloride.The similar reaction using phenyl isocyanate afforded a -type 1:2 cycloadduct, while the reaction with phenyl isocyanate yielded only a 1:1 cycloadduct. 15N and 13C nmr spectra on C=N bond of tropone azine showed a minor contribution of a dipolar structure compared with the case of N-aryl-2,4,6-cycloheptatrien-1-imines.

The kinetics and product formation of the homogeneous gas-phase reactions of the OH radical with 1,1-di-, tri- and tetrachloroethylene were investigated at temperatures between 298-459 K, in the pressure range of 0.5-5.6 mbar. Measurements were made in a discharge-flow apparatus, using helium as the carrier gas. The OH radical and the reaction products were detected by mass spectrometry. The rate constants were observed to be pressure independent in the case of 1,1-di- and tetrachloroethylene but slightly pressure dependent in the case of trichloroethylene. The temperature dependencies are expressed by Arrhenius equation. The major products are: CH2OH-CCl2 for 1,1-dichloroethylene; 2,2-dichloroethenol and Cl for trichloroethylene; trichloroethenol, dichloracetyl chloride, Cl, CHCl2 and phosgene for tetrachloroethylene.

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A series of 4-hydroxy-3-quinolinecarboxamides has been synthesized and evaluated by the oral route as antiinflammatory agents in carrageenin-induced foot edema and adjuvant-induced arthritis and as analgesic agents in the acetic acid induced writhing test. Among the most active molecules, some have shown both analgesic and acute antiinflammatory activities. Others, such as compounds 24, 37, and 52, were only powerful peripherally acting analgesics. Compound 52, being active at 1 mg/kg (ED50), is the most potent compound in the series. Some analogues, substituted in the 2-position by an alcohol, ester, or amine function, displayed potent antiarthritic activity in the same range as that of piroxicam and were also active in acute tests of inflammation and nociception. They inhibited the activity of both cyclooxygenase and 5-lipoxygenase at micromolar concentrations. Compound 102 (RU 43526) showed potent antiarthritic activity (adjuvant-induced arthritis, ED50 = 0.7 mg/kg, po), and gastrointestinal tolerance (ED100 250 mg/kg, po) and thus it is presently undergoing an extensive pharmacological evaluation.

Ultraviolet initiated liquid phase oxidation of neat trans-1,2-dichloroethene (1a) with oxigen at 30 deg C afforded ca. 45percent of the combined Cl-products CO, CO2, and phosgene as well as nine oxygenated and nine non-oxygenated chlorinated organic products.Major oxigenated products were cis- and trans-2,3-dichlorooxirane (6a, b) and 1,2,2-trichloroethyl formate (13); minor products were e.g., meso and rac bis(1,2,2-trichloroethyl)ether (11c, d) and dichloromethyl 1,2,2,-trichloroethyl ether (12).The mode of formation of all products is rationalized by a unified reaction scheme.

The mono-, di- and trichloroacetylorganylphenylphosphanes X1X2CClC(O)PPhR (3av-cz) are obtained by reaction of Me3SiPPhR (2v-z) with the azid chlorides X1X2CClC(O)Cl (1a-c).Increasing content of chlorine results in a shift of the >C=O band and the 31P signal to higher wavelengths and fields, respectively, in the IR and 31P NMR spectra of 3av-cz.Due to the centre of chirality at the phosphorus atom in the 1H NMR spectra one observes diastereotopic protons in the chloroacetyl moiety of 3av-az and of the P-adjacent CH2 protons of 3aw-cw and 3ay-cy.The magnetic inequivalence of both methyl substituents in the isopropyl groups of 3ax-cx is observable also in the 13C and 1H NMR spectra.Because of steric reasons the free rotation about the P-isopropyl axis is hindered up to 355 K.From the coalescence temperature the free activation energy ΔG* is calculated to give 74.7 kJ/mole.The degradation of the thermolabile compounds 3av-cz results in the formation of the chlorophosphanes 5v-z.Individual investigations on 3bv, 3bw and 3by indicate the formation of mono- and dichloroacetyl chloride.The appearance of ClCH2C(O)Cl proceeds via the chloroketene 4b.

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The purpose of this work is to study the causes of decomposition of trichloroethylene under production conditions, and to investigate the products formed. Experimental results show that among the high-boiling impurities in technical trichloroethylene, dichloroacetic acid, dichloroacetyl chloride, and hexachlorobutene were isolated. Formation of hexachlorobutene in trichloroethylene on heating is initiated by peroxides present as impurities in trichloroethylene. Decrease of pH of the aqueous extract when trichloroethylene is heated presumably occurs mainly as the result of hydrolysis of dichloroacetyl chloride present in trichloroethylene or formed from intermediate products of trichloroethylene oxidation.

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During the thermal and catalytic isomerization of chlorine-substituted epoxyethanes to the corresponding carbonyl compounds the reaction rate increases with increase in the number of chlorine atoms in the molecule.Active catalysts are amines, Lewis acids, and sulfuric acid but not hydrochloric acid and carboxylic acids) the type of catalyst (acid or base) affects the direction of isomerization in the unsymmetrical chloroepeoxyethanes.

Process for the production of chloroacetyl chloride. In the process ketene is reacted with sulfuryl chloride in a solvent at a temperature of -40° to +40° C. to produce chloroacetyl chloride. Up to, and including, one mole of ketene is used per mole of sulfuryl chloride. The product contains very low levels of dichloroacetyl chloride as a contaminant.