534-07-6

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The kinetics of the reversible hydration of 1,3-dichloroacetone catalyzed by hydrochloric acid or by imidazole buffer solubilized by the reversed micelles of the nonionic surfactant Triton X-100 in carbon tetrachloride have been studied spectrophotometrically.Rate and equilibrium constants, kinetic isotope effects, and activation parameters have been determined as a function of the / molar ratio.The rate constants were found to be similar to those obtained in the presence of the reversed micelles of the anionic surfactant Aerosol-OT but higher (by factors from 4 to 327) than those for the same reaction in aqueous dioxane.On the basis of the obtained data, transition-state structures for the acid- or base-catalyzed reactions are suggested that clearly show the catalytic role (acid-base) played by the surfactant.The observed rate enhancement is attributed to this participation of the detergent which entails differences between the structures of the transition states for the micelle-mediated reactions and those in aqueous dioxane.

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The invention relates to 3-chloro-2-chloromethyl propene, a preparation method and application thereof. The preparation method comprises the step that 1, 3-dichloroacetone is subjected to a carbonization reaction under the action of a catalyst to obtain 3-chloro-2-chloromethyl propene. According to the invention, 1, 3-dichloroacetone serves as a raw material and is subjected to a carbonization reaction under the action of a catalyst to obtain a product 3-chloro-2-chloromethyl propene in one step, wherein the raw materials are easy to obtain, the steps are simple, a large amount of wastewater is not generated in the preparation process, the method is environment-friendly, the yield of the final product is high and can reach 51-65%, and the 3-chloro-2-chloromethyl propylene can be applied to the synthesis of bridged ring compounds.

Oxidation of secondary alcohols is an important part of synthetic organic chemistry. Various studies are carried out at different reaction conditions to determine the best mechanistic pathways. In our study, oxidation of different secondary alcohols was done by using Benzimidazolium Fluorochromate in dimethyl sulphoxide, which is a non-aqueous solvent. Oxidation resulted in the formation of ketonic compounds. The reaction showed first order kinetics both in BIFC and in the alcohols. Hydrogen ions were used to catalyze the reaction. We selected four different temperatures to carry out our study. The correlation within the activation parameters like enthalpies and entropies was in accordance with the Exner's criterion. The deuterated benzhydrol (PhCDOHPh) oxidation exhibited an important primary kinetic isotopic effect (kH/kD = 5.76) at 298 K. The solvent effect was studied using the multiparametric equations of Taft and Swain. There was no effect of addition of acrylonitrile on the oxidation rate. The mechanism involved sigmatropic rearrangement with the transfer of hydrogen ion taking place from alcohol to the oxidant via a cyclic chromate ester formation.

New efficient and reproductive routes to production of 1,3-dihydroxyacetone (1), 1,3-dichloroacetone (6), 1,3-dibromoacetone (7) and 1,3-diiodoacetone (8) from glycerol 1,3-dichlorohydrin (3) were developed. The synthesis of 1 was processed in three steps from glycerol 2 (1,3-selective chlorination of 2 to 3, oxidation of 3 to 6 and subsequent di-hydroxylation) in 51% overall yield. On the other hand, 7 and 8 were produced from 3, via a trans-bromination and trans-iodination, respectively, followed by oxidation and hydroxylation steps, in 38-52% overall yield. It was used homogeneous media with different reagents (HCl/AcOH, pyridinium chlorochromate (PCC), PCC-HIO4) and heterogeneous media with reagents supported on polymer resins such as Amberlyst A26-HCrO4– form, PV-PCC (polyvinyl-pyridinium chlorochromate) and Amberlyst A26-OH– form or reagents supported on alumina such as KI/Al2O3, KBr/Al2O3, in solvent free conditions.

The invention discloses a silicon dioxide load heteropoly acid catalytic synthesis of 1, 3 - dichloroacetone, comprises the following steps: (1) the two [...] acid sodium is dissolved in the water, under the mixing state, in the system dropwise phosphoric acid, after dripping flow back; (2) natural cooling crystallization, the crystal is dissolved into 80 °C in water, then adding ethyl ether extraction, in water recrystallization, get the heteropoly acid; (3) ethyl silicate, de-ionized water, anhydrous ethanol, heteropoly acid heteropoly acid mixing, stirring, to form a gel, then standing aging, drying, shall be silicon dioxide load heteropoly acid catalyst; (4) the 1, 3 - dichloropropanol with hydrogen peroxide solution, adding the silicon dioxide load heteropoly acid catalyst, constant temperature reaction 10 h, filtration, filtrate the product is 1, 3 - dichloroacetone. The method of the invention, the operation is simple, less pollution to the environment, 1, 3 - dichloroacetone high yield, purity is good. (by machine translation)

The invention relates to the technical field of organic synthesis, and discloses a preparation method of 1, 3-dihydroxyacetone. The preparation method of 1,3-dihydroxyacetone comprises the following steps: (1) carrying out contact reaction between glycerol and halogenated reagents in presence of a catalyst to prepare 1,3-dichloro-2-propanol; (2) carrying out oxidative dehydrogenation reaction on the 1,3-dichloro-2-propanol to obtain an intermediate product 1,3-dichloro-2 acetone; (3) contacting the 1,3-dichloro-2 acetone with alkali substances in a water-containing medium for hydrolysis reaction to obtain the 1,3-dihydroxyacetone, wherein a hydrolysis reaction temperature is 25 to 60 DEG C. According to the preparation method of the 1,3-dihydroxyacetone, the conversion rate of the glycerol and the yield of the 1,3-dihydroxyacetone are higher; by taking zirconium oxide as the catalyst, the preparation method disclosed by the invention is high-efficient, is low in cost and has industrial application prospect.

Industrial production of dichloropropanols through chlorohydrination of allyl chloride suffers from a series of disadvantages such as use of hazardous Cl2, low atom economy, low dichloropropanol concentration and serious pollution. In this work, a safer and greener route for chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate (HTS) at mild condition is developed. Unlike the traditional Cl2-based chlorohydrination, this novel method is initiated via synergistic effect of Lewis acidity (HTS) and Br?nsted acidity (HCl) to promote occurrence of oxidation, protonation and nucleophilic reaction of allyl chloride simultaneously and hence dichloropropanols are generated. Owing to a completely different reaction route, the formation of 1,2,3-trichloropropane by-product is depressed and the content of dichloropropanol exceeded 22?wt%, which increase by about 4 times compared with traditional Cl2-based chlorohydrination (the content of dichloropropanol is below 4?wt%). At the optimized conditions, both of the allyl chloride conversion and dichloropropanol selectivity could approach 99% simultaneously and the waste is minimized. What's more, the HTS was reusable. Concentrated HCl solution treatment was adopted to test HTS's stability. The characterization and catalytic evaluation results reveal that, although parts of the framework Ti species have transformed into non-framework Ti and then leached into the solution, HTS remains structural stable, and the allyl chloride conversion and dichloropropanol selectivity didn't decrease obviously during the treatment.

The invention relates to a preparing method for 1,1,3-trichloroacetone. The preparing method comprises the following process steps that firstly, acetone and methyl alcohol serve as raw materials, an intermediate product 1,3-dichloroacetone dimethyl carbinol is obtained through chlorine chlorination preparation, a crude 1,1,3-trichloroacetone product is obtained through methyl alcohol stripping and deep chlorination, and a pure product is obtained through rectification. According to an improvement of the preparing mehtod, 1,3-dichloroacetone dimethyl carbinol easy to separate is prepared firstly from acetone, by-products 1,1-dichloroacetone and 1,1,1-trichloroacetone are separated out, then carbonyl is reduced through the method of introducing chlorine, new substances cannot be introduced, the purity of the end product1,1,3-trichloroacetone is high, and the total yield through the three-step reaction is high.

Electrochemical oxidation technology is a powerful method in the degradation of recalcitrant organics, due to the high oxidizing ability of active chlorine and reactive oxygen species generated in the cell. However, influencing factor analysis and intermediates detection during the electrochemical removal of organics has not been extensively studied in the chloride electrolyte. In this study, an orthogonal test array design of L16(4)3 was carried on with Pt anode in NaCl electrolyte, using the typical endocrine disruptor bisphenol A (BPA) as the model pollutant. The influencing order of the three main factors for BPA degradation rate was current density?>?initial organic concentration?>?chloride concentration, based on the analysis of variance in this experiment. This emphasized the very significance of the active chlorine and hydroxyl radicals which were closely related with the potential of the system and the applied current density. Then both organic and inorganic Cl-byproducts were determined. The concentration of chloride decreased to 9.88?mM with an initial of 10?mM in the 480-min electrolysis and extremely low concentration of active chlorine was produced in this system (maximized at 0.037?mM) for the first set. Neither chlorate nor perchlorate was detected with the Pt anode. The factor of current density influenced greatest on the formation of chloroform due to the amount of active chlorine affected by the current density. Finally, intermediates generated in the electrolysis cell were concretely investigated. Compared with traditional chlorination, the amount of chlorinated-BPA (2, 2′-D2CBPA and T4CBPA) generated was relatively less (2.46 and 10.00?μM equiv BPA), which might be due to their fast simultaneously transformation in the electrochemical system. With the isopropylidene bridge cleavage of chlorinated-BPA, one-ring aromatic compounds (2,6-dichlorophenol, 2,6-dichloro-2,5-cyclohexadiene, 2,4,6-trichlorophenol) occurred at the same time. Finally, chlorinated-BPA was totally transformed and low molecular chlorinated compounds were detected to the end of the experiment. This is one of the very few studies dealing with chlorinated organic intermediates formed in chloride electrolyte, and thus these findings may have significant technical implications for electrochemical treatment of wastewater containing BPA.

Oxidation of several secondary alcohols by benzyltrimethylammonium chlorobromate (BTMACB) in aqueous acetic acid leads to the formation of corresponding ketones. The reaction is first order with respect to BTMACB and the alcohols. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The proposed reactive oxidizing species is chlorobromate ion. The oxidation of benzhydrol-α-d (PhCDOHPh) exhibited a substantial primary kinetic isotope effect (kH/kD = 5.61 at 298 K). The effect of solvent composition indicated that the rate increases with an increase in the polarity of the solvent. The reaction is susceptible to both the polar and steric effects of the substituents. A mechanism involving transfer of a hydride ion in the ratedetermining step has been proposed.

Oxidation of several aliphatic secondary alcohols by benzyltriethylammonium chlorochromate in dimethylsulfoxide leads to the formation of corresponding ketones. The reaction is first order each in benzyltriethylammonium chlorochromate and the alcohols. The reaction is catalysed by hydrogen ions. Hydrogen-ion dependence has the form: kobs = a + b [H+]. The oxidation of benzhydrol-α-d exhibits a substantial primary kinetic isotope effect (kH/kD = 6.12 at 288 K). Oxidation of 2-propanol has been studied in nineteen different organic solvents. The solvent effect has been analysed using Taft's and Swain's multiparametric equations. The reaction has been subjected to both polar and steric effects of the substituents. A mechanism involving transfer of hydride ion from alcohol to the oxidant via a chromate ester is also proposed.

2-Propanol is oxidized by tetrapropylammonium perruthenate (TPAP) in a reaction that is second order in TPAP and first order in 2-propanol. One of the products, believed to be ruthenium dioxide, is an effective catalyst for the reaction, making it an autocatalytic process. The rate of oxidation is relatively insensitive to the presence of substituents. Primary kinetic deuterium isotope effects are observed when either the hydroxyl or the α hydrogen is replaced by deuterium. The only product obtained from the oxidation of cyclobutanol is cyclobutanone, indicating that the reaction is a two-electron process. Tetrahydrofuran is oxidized at a rate that is several orders of magnitude slower than that observed for 2-propanol, suggesting that the reaction of TPAP with alcohols may be initiated by formation of perruthenate esters. A tentative mechanism consistent with these observations is proposed.

A process for preparing 1,3-dibromoacetone, 1-3-dichloroacetone and epichlorohydrin which comprises: (a) reacting acetone with 2 moles of bromine to make a mixture of brominated acetone derivatives and byproduct hydrogen bromide; (b) equilibrating the mixture of brominated acetone derivatives and hydrogen bromide to produce 1,3-dibromoacetone as the major product; (c) crystallizing the 1,3-dibromoacetone; and (d) isolating the 1,3-dibromoacetone. The process may further include the steps of (e) reacting the 1,3-dibromoacetone with a chloride source to produce 1,3-dichloroacetone; (f) hydrogenating the isolated 1,3-dichloroacetone to produce 1,3-dichlorohydrin; and (g) cyclizing the 1,3-dichlorohydrin with a base to produce epichlorohydrin.

Epichlorohydrin is produced from acetone by (1) chlorinating acetone to form monochloroacetone; (2) disproportionating the monochloroacetone in the presence of a platinum catalyst, a strong acid and preferably a chloride source (for example, added as a salt or from hydrolysis of monochloroacetone) and some water to produce acetone and 1,3-dichloroacetone; (3) hydrogenating the 1,3-dichloroacetone in the presence of a catalyst to produce 1,3-dichlorohydrin; and (4) cyclizing the 1,3-dichlorohydrin with a base to produce epichlorohydrin.

Piperazine derivatives and pharmaceutically acceptable derivatives thereof useful in methods of treatment of bacterial infections in mammals, particularly in man.

Piperazine derivatives, containing a quinoline analog moiety, of formula (I) and pharmaceutically acceptable derivatives thereof useful in methods of treatment of bacterial infections in mammal, particularly in man.

Aminopiperidine derivatives and pharmaceutically acceptable derivatives thereof useful in methods of treatment of bacterial infections in mammals, particularly in man.

Aminopiperidine derivatives of formula (I) and pharmaceutically acceptable derivatives thereof useful in methods of treatment of bacterial infections in mammals, particularly in man.

One aspect of the present invention relates to novel heterocyclic compounds. A second aspect of the present invention relates to the use of the novel heterocyclic compounds as ligands for various mammalian cellular receptors, including G-protein coupled receptors. A third aspect of the present invention relates to the use of the novel heterocyclic compounds as ligands for mammalian dopamine, muscarinic or serotonin receptors or transporters. Another aspect of the present invention relates to the use of the novel heterocyclic compounds as ligands for mammalian dopamine, muscarinic or serotonin receptors. The compounds of the present invention will also find use in the treatment of numerous ailments, conditions and diseases which afflict mammals, including but not limited to addiction, anxiety, depression, sexual dysfunction, hypertension, migraine, Alzheimer's disease, obesity, emesis, psychosis, analgesia, schizophrenia, Parkinson's disease, restless leg syndrome, sleeping disorders, attention deficit hyperactivity disorder, irritable bowel syndrome, premature ejaculation, menstrual dysphoria syndrome, urinary incontinence, inflammatory pain, neuropathic pain, Lesche-Nyhane disease, Wilson's disease, Tourette's syndrome, psychiatric disorders, stroke, senile dementia, peptic ulcers, pulmonary obstruction disorders, and asthma.

A method of modulating the activity of a aberrant cell topoisomerase enzyme involving contacting the enzyme with a compound that inhibits enzyme-mediated cleavage of a polynucleotide substrate with which the enzyme is in complex. Pharmaceutical compositions containing such compounds may be used to treat neoplasias or to inhibit the growth of certain cancer cells. Screening methods can be employed to identify other compounds for these uses.

Oxidation of several secondary alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of corresponding ketones. The reaction is first order with respect to TBATB and the alcohols. The reaction failed to induce polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The proposed reactive oxidizing species is tribromide ion. The oxidation of benzhydrol-α-d (PhCDOHPh) exhibited a substantial primary kinetic isotope effect (k H/kd = 5.15 at 298 K). The effect of solvent composition indicates that the rate increases with an increase in polarity of the solvent. The reaction is susceptible to both polar and steric effects of the substituents. A mechanism involving transfer of a hydride ion in the rate-determining step has been proposed.

The present invention relates to a chemical compound of the formula (I): in which R1 is: R2 is H, alkyl, which may optionally be substituted by halogen or N2, or NH2; m and o are 0 to 3 and n is 0 or 1; ap, bq and cr are amino acid chains and p, q and r denote the number of amino acids, where a and/or b and/or c may likewise comprise at least one side chain represented by (CH2)mYn(CH2)oC(Z)R2 where Y, Z, R2, m, n, and o have the same meanings as in formula (I), and p, q and r may be identical or different and are an integer from 0 to 1000; R3 and R4 are, independently of one another, H, alkyl, aryl, a heterocycle, an amino protective group or a carboxyl protective group; R5 and R6 are, independently of one another, alkyl which may comprise at least one heteroatom selected from N, O and S, aryl or a heterocycle; X is a methine group, a nitrogen or phosphorus atom; Y is an oxygen atom, sulfur atom or an NH group; and Z is an oxygen atom, sulfur atom or an NR7 group, where R7 is H, alkyl, aryl, a heterocycle, O-alkyl, O-aryl, O-heterocycle, NR2 or NHCONR2, where R is H, alkyl, aryl or a heterocycle, and to the use thereof as inhibitor of transglutaminases.

The kinetics and products of the Cl atom initiated oxidation of 1,2,3-trichloropropane were studied using FTIR-smog chamber systems at (295 ± 2) K in 700-760 torr of air. The major oxidation product in terms of carbon balance was 1,3-dichloroacetone with smaller amounts of HC(O)Cl and CH2ClC(O)Cl. Chemical activation effects played a significant role in the atmospheric fate of CH2ClCHClO(·) and CH2ClCO(·)ClCH2Cl radicals. The UV-visible spectrum of CH2ClC(O)CH2Cl was measured at 270-385 nm and has a maximum at 305 nm where σ = (1.6 ± 0.2) × 10-19 sq cm/molecule (base e). Assuming a photolysis quantum yield of 1-0.04, the lifetime of CH2ClC(O)CH2Cl with respect to photolysis on a summer day of 40° latitude was 0.5-12 hr. Photolysis was likely to be the dominant atmospheric loss mechanism of CH2ClC(O)CH2Cl. The results were discussed in the context of the atmospheric chemistry of 1,2,3-trichloropropane.

A process of synthesizing a compound of formula I is described: wherein P and P' independently represent H or a protecting group, R1 represents H or C1-4 alkyl, and Hal represents a halogen characterized by reacting a compound of formula 2: with R2OH, wherein R2 is C1-4 alkyl, C6-10 aryl or C5-10 heteroaryl in the presence of an acid catalyst or carbodiimide reagent to produce a compound of formula 3: and reacting a compound of formula 3 in the presence of a base and a haloalkylating agent to produce a compound of formula 1.

The kinetics of oxidation of a series of monoalomic alcohols (methanol, 2-propanol, 2-butanol, 2-methyl-1-propanol, 2-chloroethanol, 1,3-dichloro-2-propanol, benzyl alcohol), hydroxyacetic acid, and 1,3-butandiol (ROH) by dimethyldioxirane (1) was studied. The reaction kinetics obeys the second order equation w = k[ROH][1]. The rate constants were measured in the range of 7 - 50 C, and the activation parameters were found. To describe the reaction rate constants as a function of the ROH structure, the two-parametric Taft equation was used, which takes into account both the polar and resonance substituent effects. Alcohol oxidation produces the corresponding carbonyl compounds, viz., ketones from secondary alcohols and aldehydes from primary alcohols, in yields of at least 80%. The results were explained by the competition of the molecular (oxenoid) and radical mechanisms. The introduction of electron-withdrawing substituents into the alcohol molecule increases the contribution of the radical channel of the reaction.

Methods of use of compounds and compounds for the treatment of disorders characterized by the cerebral deposition of amyloid are provided. Among the compounds are those of formulae (I), (II) and (III): STR1 in which R. sub.1 is preferably 2-methyl propene, 2-butene, norleucine; R 2, R 4, and R 8 are each independently methyl or ethyl; R 3 is preferably iso-butyl or phenyl; R 5 is preferably iso-butyl; R 6 is H or methyl; R 7--(Q) n is preferably benzyloxycarbonyl or acetyl; Q is preferably--C(O)--; R B is preferbly iso-butyl; R A =--(T) m--(D) m--R 1, is which T is preferably oxygen or carbon, and D is preferably a mono-unsaturated C 3-4 alkenyl being more preferred; and X is an alcohol, particularly a secondary alcohol.

Methods of use of compounds and compounds for the treatment of disorders characterized by the cerebral deposition of amyloid are provided. Among the compounds are those of formulae I and II: STR1 in which R 1 is preferably 2-methyl propene, 2-butene, cyclohexyl or cyclohexylmethyl; R. sub.2, R 4, and R 8 are each independently methyl or ethyl; R 3 is preferably iso-butyl or phenyl; R 5 is preferably iso-butyl; R 6 is H or methyl; R 7--(Q) n is preferably benzyloxycarbonyl or acetyl; Q is preferably--C(O)--; R 8 is preferbly iso-butyl; R A =--(T) m--(D) m--R 1, is which T is preferably oxygen or carbon, and D is preferably a mono-unsaturated C 3-4 alkenyl being more preferred; and X is preferably an α-ketoester or α-ketoamide.

This invention relates to 4-substituted catechol diether compounds which are selective inhibitors of phosphodiesterase (PDE) type IV. The compounds of the present invention are useful in inhibiting PDE IV and in the treatment of AIDS, asthma, bronchitis, chronic obstructive airways disease, psoriasis, allergic rhinitis, dermatitis and other inflammatory diseases. This invention also relates to pharmaceutical compositions comprising the compounds hereof

Efficient routes are developed for the synthesis of variously labelled 2H- and 13C- labelled epichlorohydrins prepared from appropriately labelled acetic acids and sodium borodeuteride. The route is versatile and can be used for strategic location of isotopes at C-I, C-2 and C-3 of epichlorohydrin. By way of demonstration [2-13C]-, [2-2H]-, [3-2H2] and [2-2H, 3-2H2]-epithlorohydrins have been prepared. In addition the syntheses can be adapted for the preparation of enantiomerically pure and isotopically labelled epichlorohydrins.

A convenient method for the unambiguous preparation of α,α'-dihalogeno ketones 3 from in situ-generated chloromethyllithium and α-chloro or α-bromo carboxylic acid esters 1 at -78 deg C, is described.The unambiguous prparation of α,α-dihalogeno ketones 7 by using in situ-generated dihalogenomethyllithium and carboxylic acid esters 5 at -78 deg C is also reported.

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The reaction of α-chloro or α-bromo carboxylic acid esters (1) with in situ-generated chloromethyllithium (1: 1.5 molar ratio) at -78 deg C in the presence of lithium bromide leads, after hydrolysis, to the corresponding α,α'-dichloro or α-chloro-α'-bromo ketones (2), respectively.

A process for preparing N"-[4-[[(2-cyanoethyl)thiol]methyl]-2-thiazolyl]guanidine which comprises reacting a dihaloacetone with an β-cyanoethylthiol in a two phase solvent system at a pH of 4.5-6.0 to produce a 1-halo-3-(2-cyanoethylthio)propanone and reacting the 1-halo-3-(2-cyanoethylthio) with an amidinothiourea.

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(Chloroacetyl)cobalt tetracarbonyl, ClCH2C(O)Co(CO)4 (1), was prepared by the reaction of ClCH2C(O)Cl with Na[Co(CO)4]. 1 readily decarbonylates to (chloromethyl)cobalt tetracarbonyl (2). 1 is formed from 2 at ～5 bar of CO pressure and room temperature or at 1 bar of CO by cooling to ～-10°C in a reversible reaction. 2 gives with PPh3 the CO-substituted acyl derivative ClCH2C(O)Co(CO)3PPh3 (3) that can be decarbonylated at 50°C to the corresponding alkyl complex ClCH2Co(CO)3PPh3 (4). 4 takes up CO even under 1 bar of pressure at room temperature. The 3 ? 4 equilibrium is reversible. 1 was characterized by IR spectra, 2-4 could be isolated, and the structures of 3 and 4 were determined by X-ray diffraction. 2 reacts with the methoxide ion to yield CH2(COOMe)2. These results represent the first examples of (a) the carbonylation/decarbonylation reaction couple of an XCH2M vs. XCH2C(O)M (X = Cl, Br, I; M = transition metal) pair, (b) a ligand substitution reaction of a chloromethyl complex with a tertiary phosphine, and (c) the structure determination of a chloromethyl complex as well as (d) the structural study of an alkyl-/acylcobalt carbonyl pair with the same organic group. 3 crystallizes with monoclinic symmetry in the space group P21/c with Z = 4 and cell dimensions of a = 1212.3 (2) pm, b = 928.9 (3) pm, c = 2029.9 (4) pm, and β = 104.15 (2)°. Structure solution by Patterson methods and refinement with 3305 unique observed reflections led to a final R value of 0.057. The crystals of 4 are tetragonal of space group P43, with Z = 4 in a unit cell of dimensions a = b = 1086.3 (1) pm and c = 1815.5 (4) pm. The structure was determined by direct methods and refined with 4358 unique observed reflections to a final R value of 0.033.

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The title compound 1 is threefold substituted by sodium phenolate in dioxane at 70 deg C or by sec. aliphatic amines in ether at room temperature, yielding the merocyanine-like compounds 3 or 2a - d.The structure 2 is based on UV spectroscopic investigations and degradation with hydrochloric acid to 6.Ring closure of 2 occurs under amine elimination to the 2(1H)-pyridinones 7 with sulfuric acid and to the pyridine 8a with dry hydrogen chloride.

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The chlorination of aliphatic ketones in methanol has been examined.The product distributions in methanol differ substantially from those obtained by chlorination in carbon tetrachloride.The reaction in methanol favors addition of chlorine to the least substituted carbon α to the carbonyl group.The effect is especially pronounced if an α carbon bearing two substituents is present.The distribution of products is determined by the relative stability of the enol ethers formed from the ketone under the reaction conditions.

The substituted crotonitrile 1a formed by dimerization of chloroacetonitrile is reacted with primary, secondary and tertiary amines.With primary amines the pyrrolines 3a-c result which contain the partial structure of a vinylogous guanidine.Compound 3a is hydrolized by hydrochloric acid to yield the lactam 4 of β,γ-diaminocrotonic acid.

The anomalous temperature dependence of the β-deuterium (β-D) secondary isotope effect reported by Halevi and Margolin for the hydroxide-promoted hydrolysis of ethyl acetate has been observed also with methyl acetate 3H/k3D = 1.01 +/- 0.02 (0 deg C), 0.90 +/- 0.02 (25 deg C), 1.03 +/- 0.10 (50 deg C)>.In contrast, the β-D effects for the rates of acidic hydrolysis of methyl acetate (0.93 +/- 0.02, 0-42 deg C), basic hydrolysis of phenyl acetate (0.98 +/- 0.02, 5-45 deg C), basic methanolysis of phenyl acetate (0.98 +/- 0.02, 5-40 deg C), basic methanolysis of p-methoxyphenyl acetate (0.96 +/- 0.02, 5-45 deg C), and the equilibrium hydration of 1,3-dichloroacetone (ClCH2COCH2Cl vs.ClCD2COCD2Cl: K4H/K4D = 0.83 +/- 0.02, 15-46 deg C) over the indicated temperature ranges were statistically indistinguishable from the mean values cited.This constitutes "regular", expected behavior.Both kinds of cases are consistent with a cascade model for acyl-transfer reactions in which solvent-reorganization and heavy-atom-reorganization transition states along parallel reaction paths alternate in dominating rate limitation in the 0-70 deg C temperature range.Such a model also explains anomalous temperature dependences of solvent isotope effects for anhydride hydrolyses, reported by Rossall and Robertson.Observed transition-state properties would refer to a virtual, weighted-average, transition-state structure, according to the cascade model.

1,3-dichloroacetone oxime is prepared from 1,3-dichloropropanone by reaction with a hydroxylamine salt in a strongly acidic medium in the presence of a base selected from the group consisting of tertiary amines, lower alkyl amides, alkali metal bicarbonates, alkali metal carbonates and alkaline earth metal carbonates. 1,3-dichloroacetone oxime acetate is advantageously prepared by reaction of the oxime with acetic anhydride. The acetate is obtained in high purity.