78-95-5Relevant academic research and scientific papers
PHOTOINDUCED REACTIONS OF ORGANIC COMPOUNDS WITH TRANSITION METAL COMPLEXES. II. REACTION OF PtCl62- WITH ACETONE TO GIVE A ?-ACETONYL COMPLEX OF PLATINUM(IV). DETECTION OF PLATINUM(III) COMPOUNDS BY ESR
Nizova, G. V.,Serdobov, M. V.,Nikitaev, A. T.,Shul'Pin, G. B.
, p. 139 - 144 (1984)
Light irradiation of a PtCl62- solution in acetone affords a ?-acetonyl complex of platinum(IV), 2-.Prolonged irradiation yields CH3COCH2Cl and PtCl42-.The signals of a platinum(III) complex and CH3COCH2-radical are detected in the ESR spectrum of the frozen solution of PtCl62- in acetone irradiated at 77 K.The proposed mechanism of the reaction involves electron transfer from the enol tautomer of acetone to PtCl62-.
Gas-phase oxidation of CH2-=-C(CH3)CH2Cl initiated by OH radicals and Cl atoms: Kinetics and fate of the alcoxy radical formed
Rivela, Cynthia,Gibilisco, Rodrigo G.,Teruel, Mariano A.
, p. 480 - 484 (2015)
Relative kinetics of the reactions of OH radicals and Cl atoms with 3-chloro-2-methyl-1-propene has been studied for the first time at 298-K and 1-atm by GC-FID. Rate coefficients are found to be (in cm3-molecule-1-s-1): k1 (OH-+-CH2-=-C(CH3)CH2Cl)-=-(3.23-±-0.35)-×-10-11, k2 (Cl-+-CH2-=-C(CH3)CH2Cl)-=-(2.10-±-0.78)-×-10-10 with uncertainties representing-±-2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC-MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2-hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed.
A process for the preparation method of thiabendazole
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Paragraph 0057; 0070; 0081; 0082; 0083; 0096, (2018/04/01)
The invention relates to a new method for synthesizing thiabendazole. Acetone and chlorine are taken as starting materials to synthesize chloroacetone, chloroacetone not subjected to separation can directly react with thiocarbamide to obtain 2-Amino-4-methylthiazole which is subjected to diazotization to obtain 4-methylthiazole, and 4-methylthiazole is oxidized to produce 4-thiazolecarboxylic acid, and finally, 4-thiazolecarboxylic acid reacts with o-phenylenediamine to obtain the target object thiabendazole. The thiabendazole is a broad-spectrum anthelmintic, can repel roundworms, hookworms, whipworms, pinworms, strongyloises stercoralis and trichinization, is also a broad-spectrum efficient disinfectant and is widely used as a fruit fresh-keeping agent and a bactericidal mildew inhibitor in various fields over the past decade in China.
Towards sustainable manufacture of epichlorohydrin from glycerol using hydrotalcite-derived basic oxides
Lari, Giacomo M.,Pastore, Giorgio,Mondelli, Cecilia,Pérez-Ramírez, Javier
supporting information, p. 148 - 159 (2018/01/12)
Commercial two-step processes to convert glycerol into epichlorohydrin are more benign compared to the predominant industrial route starting from propene in terms of materials requirements and CO2 emissions. Still, the use of alkali hydroxides in stoichiometric amounts in the second reaction, i.e., the dehydrochlorination of the dichloropropanol intermediate, leads to the formation of large amounts of salt wastes, thus limiting the greenness of the technology. Here, we show for the first time that the latter transformation can be selectively conducted in the gas phase in the presence of a heterogeneous hydrotalcite-derived mixed oxide of Al and Mg. Upon reaction, the lamellar solid is rehydrated to a hydrotalcite-like compound, which can effectively activate the alcoholic group of dichloropropanol owing to its strong Br?nsted basic character and moderately high surface area. In-depth characterisation of the porous, compositional, structural and acid/base properties demonstrates that the HCl formed during the reaction causes the progressive exchange of interlayer OH groups by Cl atoms, thus gradually diminishing the reactivity of the material. Facile calcination restores the original mixed oxide structure and is shown to enable three equivalent consecutive reaction runs. Since the HCl evolved along with water upon regeneration can be recycled in the first step of the process, i.e., glycerol hydrochlorination, our approach paves the way for a waste-free and more atom efficient biobased epichlorohydrin production process.
Gas-phase reaction of two unsaturated ketones with atomic Cl and O3: Kinetics and products
Wang, Jing,Zhou, Li,Wang, Weigang,Ge, Maofa
, p. 12000 - 12012 (2015/05/26)
The rate constants and products for the reactions of atomic Cl and O3 molecule with 3-methyl-3-buten-2-one (MBO332) and 3-methyl-3-penten-2-one (MPO332) were determined in a 100 L Teflon chamber at 293 ± 1 K and atmospheric pressure. For MBO332 and MPO332, the rate constants measured with atomic Cl were (2.38 ± 0.26) × 10-10 and (3.00 ± 0.34) × 10-10 cm3 molecule-1 s-1 using the relative rate method. Using the absolute rate method, the rate constants with O3 measured were (1.18 ± 0.21) × 10-17 and (4.07 ± 0.45) × 10-17 cm3 molecule-1 s-1. The products of these reactions were investigated by the proton-transfer-reaction mass spectrum (PTR-MS). The results indicated that the major products observed in the atomic Cl reaction were formaldehyde together with chloroacetone for MBO332, and acetaldehyde and CH3C(O)C(O)Cl for MPO332. For O3 reactions, butanedione and formaldehyde were the main products of MBO332, while butanedione and acetaldehyde were the main products of MPO332. Possible reaction mechanisms were proposed and discussed and the atmospheric implications of these reactions were also discussed.
Reactions of diazo ketones with activated unsaturated compounds in the presence of gallium trichloride
Novikov,Tomilov,Nefedov
, p. 404 - 408 (2015/01/08)
Diazoacetone reacts with methyl acrylate in the presence of anhydrous GaCl3 to give isomeric methyl 2-acetylcyclopropanecarboxylates rather than pyrazolines obtained from diazo esters or by noncatalytic reactions. In a similar reaction, diazoacetophenone yields methyl 2-benzoylcyclopropanecarboxylates, benzoylmethyl acrylate, and benzoylmethyl 2-benzoylcyclopropanecarboxylate via partial transesterification. Addition of an equimolar amount of GaCl3 to diazoacetone in the system CH2Cl2-HCl-H2O unexpectedly produces 4,5-dimethylfuran-3(2H)-one and 1,1'-oxybis(propan-2-one).
Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals
Hasson, Alam S.,Tyndall, Geoffrey S.,Orlando, John J.,Singh, Sukhdeep,Hernandez, Samuel Q.,Campbell, Sean,Ibarra, Yesenia
experimental part, p. 6264 - 6281 (2012/08/28)
An important chemical sink for organic peroxy radicals (RO2) in the troposphere is reaction with hydroperoxy radicals (HO2). Although this reaction is typically assumed to form hydroperoxides as the major products (R1a), acetyl peroxy radicals and acetonyl peroxy radicals have been shown to undergo other reactions (R1b) and (R1c) with substantial branching ratios: RO2 + HO2 → ROOH + O2 (R1a), RO 2 + HO2 → ROH + O3 (R1b), RO2 + HO2 → RO + OH + O2 (R1c). Theoretical work suggests that reactions (R1b) and (R1c) may be a general feature of acyl peroxy and α-carbonyl peroxy radicals. In this work, branching ratios for R1a-R1c were derived for six carbonyl-containing peroxy radicals: C2H 5C(O)O2, C3H7C(O)O2, CH3C(O)CH2O2, CH3C(O)CH(O 2)CH3, CH2ClCH(O2)C(O)CH 3, and CH2ClC(CH3)(O2)CHO. Branching ratios for reactions of Cl-atoms with butanal, butanone, methacrolein, and methyl vinyl ketone were also measured as a part of this work. Product yields were determined using a combination of long path Fourier transform infrared spectroscopy, high performance liquid chromatography with fluorescence detection, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry. The following branching ratios were determined: C2H5C(O)O2, YR1a = 0.35 ± 0.1, YR1b = 0.25 ± 0.1, and YR1c = 0.4 ± 0.1; C3H7C(O)O2, YR1a = 0.24 ± 0.15, YR1b = 0.29 ± 0.1, and YR1c = 0.47 ± 0.15; CH3C(O)CH2O2, Y R1a = 0.75 ± 0.13, YR1b = 0, and YR1c = 0.25 ± 0.13; CH3C(O)CH(O2)CH3, Y R1a = 0.42 ± 0.1, YR1b = 0, and YR1c = 0.58 ± 0.1; CH2ClC(CH3)(O2)CHO, Y R1a = 0.2 ± 0.2, YR1b = 0, and YR1c = 0.8 ± 0.2; and CH2ClCH(O2)C(O)CH3, YR1a = 0.2 ± 0.1, YR1b = 0, and YR1c = 0.8 ± 0.2. The results give insights into possible mechanisms for cycling of OH radicals in the atmosphere.
Ketone-alcohol hydrogen-transfer equilibria: Is the biooxidation of halohydrins blocked?
Bisogno, Fabricio R.,Garcia-Urdiales, Eduardo,Valdes, Haydee,Lavandera, Ivan,Kroutil, Wolfgang,Suarez, Dimas,Gotor, Vicente
body text, p. 11012 - 11019 (2010/11/18)
To ensure the quasi-irreversibility of the oxidation of alcohols coupled with the reduction of ketones in a hydrogen-transfer (HT) fashion, stoichiometric amounts of a-halo carbonyl compounds have been employed as hydrogen acceptors. The reason that these substrates lead to quasi-quantitative conversions has been tacitly attributed to both thermodynamic and kinetic effects. To provide a clear rationale for this behavior, we investigate herein the redox equilibrium of a selected series of ketones and 2-propanol by undertaking a study that combines experimental and theoretical approaches. First, the activity of the (R)-specific alcohol dehydrogenase from Lactobacillus brevis (LBADH) with these substrates was studied. The docking of acetophenone/(R)-l-phenyethanol and a-chloroacetophenone/(S)-2-chloro- lphenylethanol in the active site of the enzyme confirms that there seems to be no structural reason for the lack of reactivity of halohydrins. This assumption is confirmed by the fact that the corresponding aluminum-catalyzed Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reactions afford similar conversions to those obtained with LBADH, showing that the observed reactivity is independent of the catalyst employed. While the initial rates of the enzymatic reductions and the IR v(C=0) values contradict the general belief that electron-withdrawing groups increase the electrophilicity of the carbonyl group, the calculated βG values of the isodesmic redox transformations of these series of ketones/alcohols with 2-propanol/acetone support the thermodynamic control of the reaction. As a result, a general method to predict the degree of conversion obtained in the HT-reduction process of a given ketone based on the IR absorption band of the carbonyl group is proposed, and a strategy to achieve the HT oxidation of halohydrins is also shown.
MANUFACTURE OF DICHLOROPROPANOL
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Page/Page column 19-21, (2009/03/07)
Manufacture of dichloropropanol Process for manufacturing dichloropropa nol wherein a glycerol-based product comprising at least one diol containi ng at least 3 carbon atoms other than 1,2- propanediol, is reacted with a chlorinati ng agent, and of products derived from dichloropropanol such as ep ichlorohydrin and epoxy resins. No figure.
Enantioselective synthesis of cyclic sulfamidates via Pd-catalyzed hydrogenation
Wang, You-Qing,Yu, Chang-Bin,Wang, Da-Wei,Wang, Xiao-Bing,Zhou, Yong-Gui
supporting information; experimental part, p. 2071 - 2074 (2009/04/18)
Using Pd(CF3;CO2)2/(S,S)-f-binaphane as the catalyst, an efficient enantioselective synthesis of cyclic sulfamidates was developed via asymmetric hydrogenation of the corresponding cyclic imines in 2,2,2-trifluoroethanol at room temperature with high enantioselectivities (up to 99% ee).
