534-07-6Relevant articles and documents
Kinetics of the Acid-Base Catalyzed Hydration of 1,3-Dichloroacetone in the Presence of Triton X-100 Reversed Micelles in Carbon Tetrachloride
El Seoud, Omar A.,Vidotti, Gentil J.
, p. 5233 - 5236 (1984)
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.
3-chloro-2-chloromethyl propylene, preparation method and application thereof
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Paragraph 0052-0054; 0063; 0067, (2021/06/26)
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.
Kinetics and mechanism of oxidation of aliphatic secondary alcohols by benzimidazolium fluorochromate in dimethyl sulphoxide solvent
Arora, Bhawana,Ojha, Jitendra,Mishra, Pallavi
, p. 626 - 633 (2021/07/10)
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.
Expeditious Syntheses to Pharmochemicals 1,3-Dihydroxyacetone, 1,3-Dichloro-, 1,3-Dibromo- And 1,3-Diiodoacetone from Glycerol 1,3-Dichlorohydrin Using Homogenous and Heterogenous Medium
Pereira, Vera Lúcia P.,da Silva, Fernanda Priscila N. R.,da Silva, Sara R. B.,dos Santos, Priscila F.
, p. 1725 - 1731 (2020/10/09)
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.
Silicon dioxide load heteropoly acid catalytic synthesis of 1, 3 - dichloroacetone (by machine translation)
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Paragraph 0012; 0013; 0014, (2018/05/16)
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)
A safer and greener chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate zeolite
Peng, Xinxin,Xia, Changjiu,Lin, Min,Shu, Xingtian,Zhu, Bin,Wang, Baorong,Zhang, Yao,Luo, Yibin,Mu, Xuhong
, p. 17 - 25 (2017/06/23)
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.
Preparation method of 1,3-dihydroxyacetone
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Paragraph 0049, (2017/10/26)
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.
Preparing method for 1,1,3-trichloroacetone
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Paragraph 0012; 0021, (2017/03/08)
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 degradation of bisphenol A in chloride electrolyte—Factor analysis and mechanisms study
Li, Hongna,Long, Yujiao,Wang, Yu,Zhu, Changxiong,Ni, Jinren
, p. 1144 - 1152 (2017/01/06)
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.
Kinetics and mechanism of oxidation of aliphatic secondary alcohols by benzyltrimethylammonium chlorobromate
Sharma, Pradeep K.
, p. 2702 - 2706 (2014/06/09)
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.
