- Synthesis method of 3-hydroxypropionaldehyde
-
The invention relates to a synthesis method of 3-hydroxypropionaldehyde, which mainly solves the problem of difficulty in separation of a catalyst of a homogeneous system in the prior art. The synthesis method of 3-hydroxypropionaldehyde comprises the following steps: i, adding a cobalt catalyst and a cocatalyst into a solvent, and heating for pretreatment in a synthesis gas atmosphere; and ii, after the catalyst pretreatment is finished, cooling, releasing the pressure, adding ethylene oxide and synthesis gas, and reacting to obtain the 3-hydroxypropionaldehyde, so that the technical problemis better solved, and the method can be applied to industrial production of the 3-hydroxypropionaldehyde.
- -
-
Paragraph 0075; 0076; 0077
(2020/05/14)
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- Substrate inhibition in ruthenium(III) catalyzed oxidation of propane-1,3-diol by periodate in acidic medium: A kinetic study
-
Ruthenium(III) catalyzed oxidation of propane-1,3-diol by potassium periodate was studied in aqueous perchloric acid medium. Orders of reaction with respect to concentrations of oxidant, substrate, acid and catalyst were determined. First order in oxidant and catalyst concentrations, and inverse fractional order in acid medium were observed. In addition, substrate inhibition (i.e. a decrease in reaction rate with an increase in substrate concentration) was observed. Effect of addition of salt and solvent was studied. Based on the studies of temperature variation, Arrhenius parameters were calculated. Plausible mechanism was also proposed based on observed kinetics.
- Koteswara Rao,Nadh, R. Venkata,Ratnam, K. Venkata
-
p. 1569 - 1575
(2020/07/30)
-
- Method for preparing 3-hydroxypropionaldehyde by hydrating acrolein
-
The invention relates to a method for preparing 3-hydroxy propionaldehyde by hydrating acrolein. The acrolein is homogeneously catalyzed under the action of a N-heterocyclic carboxylic acid ionic liquid to prepare 3-hydroxy propionaldehyde, wherein the hydration reaction liquid is subjected to aqueous two-phase extraction to recover the ionic liquid catalyst for cyclic utilization. According to the invention, the method is simple to operate and stable in process, the catalyst has very high reaction activity and very good selectivity, and the problems of separation of a homogeneous catalyst andinstability and easy deactivation of a solid catalyst in the hydration process are effectively solved.
- -
-
Paragraph 0050-0059
(2020/12/31)
-
- 1. 3 - Propanediol (by machine translation)
-
The present invention provides a 1, 3 - propanediol, comprising the following steps: providing the mass concentration is 8% -13% of 3 - hydroxypropanal aqueous solution of; the hydrogen and 3 - hydroxypropionaldehyde mixed solution, sequentially for a period of hydrogenation reaction and secondary hydrogenation reaction, to obtain the secondary hydrogenation reaction product; part of the two-stage hydrogenation reaction product circulation to a hydrogenation reaction. The 1, 3 - propanediol, through a portion of a two-stage hydrogenation reaction product circulation to a hydrogenation reaction, the absorption of the reaction heat, reducing the temperature of the hydrogenation reaction of the 1st hot spots, can effectively reduce the acetal impurity content in the product, improve the selectivity of the hydrogenation reaction. (by machine translation)
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-
Paragraph 0044
(2018/09/08)
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- Catalytic glycerol hydrogenolysis to 1,3-propanediol in a gas-solid fluidized bed
-
Glycerol is a potential feedstock to produce 1,3-propanediol (1,3-PDO), which is a valuable commercial polyester monomer. Here, we report the gas-phase glycerol hydrogenolysis to 1,3-propanediol over Pt/WO3/Al2O3 in a fluidized bed operating above 240 °C and at ambient pressure. Fluidized beds are ideal contactors for this reaction because the heat transfer rates are sufficiently high to vaporize glycerol thereby minimizing its combustion and thermal degradation. The yield of 1,3-PDO approached 14% after 2 h at 260 °C. The major co-products were 1,2-PDO (18%), 1-propanol (28%) and 2-propanol (15%). In the first step, glycerol may dehydrate to acrolein, followed by rehydration to 3-hydroxypropanal and then hydrogenation to 1,3-PDO. The concentrations of the by-products including acrolein, ethylene glycol, propane, and acetone increased with increasing temperature.
- Edake, Mahesh,Dalil, Marjan,Darabi Mahboub, Mohammad Jaber,Dubois, Jean-Luc,Patience, Gregory S.
-
p. 3853 - 3860
(2017/02/05)
-
- Preparation method of 3-hydroxy-propionaldehyde
-
The invention relates to a preparation method of 3-hydroxy-propionaldehyde. The preparation method mainly solves the problem that a homogeneous system catalyst is difficult to recycle in the prior art. The preparation method of the 3-hydroxy-propionaldehyde comprises the following steps: a) performing a complexing reaction in a solvent on ligand and cobalt carbonyl so as to obtain a catalyst solution; and b) adding oxacyclopropane and synthesis gas, and reacting to obtain the 3-hydroxy-propionaldehyde, wherein the ligand is of a following structure, X is selected form one of an oxygen atom and a sulfur atom, and R is selected from one of a cyclo group, an aryl group or a substituted aryl group. Through the technical scheme, the technical problem is preferably solved, and the preparation method can be used in industrial production of the 3-hydroxy-propionaldehyde.
- -
-
Paragraph 0046; 0049
(2017/08/29)
-
- Micellar effect on hetero-aromatic nitrogen base promoted chromic acid oxidation of 1.3-propanediol in aqueous media at room temperature
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Surfactants are classified on the basis of the nature of the hydrophilic groups. Surfactant micelle represents a tiny template or nanoreactor which is generally used for preparing nano-structured materials of desired sizes and shapes with required functionalities. In this present investigation chromic acid oxidation of 1.3-propanediol (1.3-PDO) to 3-hydroxy propionaldehyde (3-HPA) was carried out by using four representative promoters: picolinic acid (PA), 2.3-pyridine dicarboxylic acid (2.3 diPA), 2.2′-bipyridine (bipy) and 1.10-phenanthroline (phen) in presence and absence of surfactants sodium dodecylsulphate (SDS), N-cetylpyridinium chloride (CPC) and Triton-X-100 (TX-100). Reactions were performed under pseudo-first-order condition: [1.3-PDO]T ? [Cr(VI)]T in aqueous media at 30 °C temperature. Different combinations were performed to select the suitable combination of promoter and micellar catalyst for this oxidation. Based on the kinetic results, combination of TX-100 and phen was found to be the most suitable one for this oxidation. The mechanisms of both unpromoted and promoted reaction paths were proposed. The product was confirmed by 2.4-DNP test followed by FTIR spectroscopy of the hydrazone derivative.
- Malik, Susanta,Saha, Debabrata,Mondal, Monohar Hossain,Sar, Pintu,Ghosh, Aniruddha,Mahali, Kalachand,Saha, Bidyut
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p. 207 - 216
(2016/12/06)
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- Syntheses and biological evaluation of 1,2,3-triazole and 1,3,4-oxadiazole derivatives of imatinib
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Three novel series of 1,2,3-triazole and 1,3,4-oxadiazole derivatives of imatinib were prepared and evaluated in vitro for their cytostatic effects against a human chronic myeloid leukemia (K562), acute myeloid leukemia (HL60), and human leukemia stem-like cell line (KG1a). The structure-activity relationship was analyzed by determining the inhibitory rate of each imatinib analog. Benzene and piperazine rings were necessary groups in these compounds for maintaining inhibitory activities against the K562 and HL60 cell lines. Introducing a trifluoromethyl group significantly enhanced the potency of the compounds against these two cell lines. Surprisingly, some compounds showed significant inhibitory activities against KG1a cells without inhibiting common leukemia cell lines (K562 and HL60). These findings suggest that these compounds are able to inhibit leukemia stem-like cells.
- Li, Yong-Tao,Wang, Jing-Han,Pan, Cheng-Wen,Meng, Fan-Fei,Chu, Xiao-Qian,Ding, Ya-Hui,Qu, Wen-Zheng,Li, Hui-Ying,Yang, Cheng,Zhang, Quan,Bai, Cui-Gai,Chen, Yue
-
p. 1419 - 1427
(2016/02/19)
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- Influence of acid-base sites on ZnO-ZnCr2O4 catalyst during dehydrocyclization of aqueous glycerol and ethylenediamine for the synthesis of 2-methylpyrazine: Kinetic and mechanism studies
-
The physicochemical characteristics of ZnO-ZnCr2O4 (Zn-Cr-O) mixed oxides were determined by adsorption and spectroscopic methods. The catalytic activities of Zn-Cr-O was investigated for dehydrocyclization of ethylenediamine and aqu
- Venugopal, Akula,Sarkari, Reema,Anjaneyulu, Chatla,Krishna, Vankudoth,Kumar, Mandari Kotesh,Narender, Nama,Padmasri, Aytam Hari
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p. 398 - 409
(2013/11/19)
-
- Unsymmetrical Bis Azainositol Hafnium Complexes for X-Ray Imaging
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The present invention describes a new class of trinuclear hafnium complexes comprising two hexadentate azainositol carboxylic acid ligands, methods for their preparation and their use as X-ray contrast agents.
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-
Paragraph 0128
(2014/11/11)
-
- Cu nanoclusters supported on nanocrystalline SiO2-MnO 2: A bifunctional catalyst for the one-step conversion of glycerol to acrylic acid
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A material consisting of highly dispersed Cu nanoclusters anchored on nanocrystalline SiO2-MnO2 has been prepared, and was found to act as a bifunctional catalyst for the one- step conversion of glycerol to acrylic acid using H2O2. Under optimized conditions a glycerol conversion of 77.1%, with 74.7% selectivity for acrylic acid, was achieved after 30 h reaction time. This journal is the Partner Organisations 2014.
- Sarkar, Bipul,Pendem, Chandrashekar,Sivakumar Konathala,Tiwari, Ritesh,Sasaki, Takehiko,Bal, Rajaram
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supporting information
p. 9707 - 9710
(2014/08/18)
-
- Coenzyme B12-dependent glycerol dehydratase deficiency in Klebsiella pneumoniae
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The physiology and fermentation properties of coenzyme B12-dependent glycerol dehydratase deficient mutant Klebsiella pneumoniae B1.9131 were investigated. Compared with that of wild type strain, glycerol dehydratase activity decreased by 80 %. Activities of dha regulon coded two enzymes are influenced by inactivation of GDHt. 1,3-Propanediol oxidoreductase activity decreased by 62 % while glycerol dehydrogenase activity increased by 36 %. Fed-batch fermentation showed that more of the metabolic flux of glycerol was directed to lactate and ethanol in the mutant. Instead, lactate other than 1,3-propanediol was the main product and its final concentration increased from 41 to 76 g L-1 with mutant isolate. The concentration of 1,3-propanediol decreased from 91 to 40 g L-1. The results demonstrate that GDHt is not indispensable in glycerol metabolism but is crucial for the efficient synthesis of 1,3-propanediol.
- Zheng, Zong-Ming,Wang, Ti-Peng,Xu, Yun-Zhen,Liu, De-Hua
-
p. 7323 - 7326
(2013/08/23)
-
- Characterization of a new enzyme oxidizing ω-amino group of aminocarboxyric acid, aminoalcohols and amines from Phialemonium sp. AIU 274
-
A new enzyme exhibiting oxidase activity for ω-aminocarboxylic acids, ω-aminoalcohols, monoamines and diamines was found from a newly isolated fungal strain, Phialemonium sp. AIU 274. The enzyme also oxidized aromatic amines, but not l- and d-amino acids. The Vmax/Km value for hexylamine was higher than those for 6-aminoalcohol and 6-aminhexanoic acid in the aliphatic C6 substrates. In the aliphatic amines, the higher Vmax/Km values were obtained by the longer carbon chain amines. Thus, the enzyme catalyzed oxidative deamination of the ω-amino group in a wide variety of the ω-amino compounds and preferred medium- and long-chain substrates. The oxidase with such broad substrate specificity was first reported here. The enzyme contained copper, and the enzyme activity was strongly inhibited by isoniazid, iproniazid and semicarbazide, but not by clorgyline and pargyline. The enzyme was composed of two identical subunits of 75 kDa.
- Isobe, Kimiyasu,Sasaki, Tomoko,Aigami, Yuusuke,Yamada, Miwa,Kishino, Shigenobu,Ogawa, Jun
-
-
- Perspectives on the kinetics of diol oxidation over supported platinum catalysts in aqueous solution
-
The catalytic oxidation of a variety of terminal alcohols was performed over Pt/C with 10 bar dioxygen at 343 K in aqueous solvent at low pH. The influences of Pt particle size, carbon support, alcohol structure, and start-up conditions were explored. Although the turnover frequency was not affected by particle size or the carbon support, the structure of the alcohols affected their initial rate of conversion. Both the rate of oxidation of α,ω-diols and selectivity of the diols to the diacids increased with increasing carbon chain length. The rate of 1,6-hexanediol oxidation was independent of dioxygen pressure and the order of reaction with respect to diol concentration depended on the start-up conditions. A kinetic model involving two types of metal sites was proposed to account for the experimental observations.
- Ide, Matthew S.,Davis, Robert J.
-
-
- METHOD AND DEVICE FOR SYNTHESIZING ACROLEIN
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An object of the present invention is to provide an industrially applicable method for producing acrolein via treatment with supercritical water from glycerin obtained as a by-product during the process of biodiesel fuel production from waste animal/plant fat or oil with the use of an alkali catalyst. The present invention provides a method for producing acrolein, which comprises: a determination step of determining the hydrogen ion concentration in glycerin obtained as a by-product; an acid addition step of adding to the glycerin an acid at an amount calculated based on the results of the determination step so as to make the glycerin acidic; and a supercritical water treatment step of allowing supercritical water to act on the glycerin after the acid addition so as to produce acrolein from the glycerin.
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Page/Page column 9
(2012/04/23)
-
- 2-Butoxyethanol and benzyl alcohol reactions with the nitrate radical: Rate coefficients and gas-phase products
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The bimolecular rate coefficients k NO 3 ? + 2-butoxyethanol and k NO 3 ? + benzyl alcohol were measured using the relative rate technique at (297 ± 3) K and 1 atmosphere total pressure. Values of (2.7 ± 0.7) and (4.0 ± 1.0) × 10-15 cm3/s
- Harrison, Joel C.,Wells
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p. 778 - 788
(2013/01/15)
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- Reactions of aminyl radicals during radiolysis and photolysis of aqueous solutions of amino alcohols and their derivatives
-
It has been found that the radiolysis of the aqueous solutions of a,a-amino alcohols leads to the formation of degradation products of the parent substances. The experimental data suggest that the degradation process includes the stage of the formation of aminyl radicals, which undergo decomposition with the simultaneous cleavage of -C-C- and -O-H bonds through a five-membered transition state. The radiation-induced degradation of amino alcohols is enhanced in an alkaline medium, in which the amino group is deprotonated, and is blocked via the etherification of the hydroxyl group in the parent substances or the introduction of reducing agents. Pleiades Publishing, Ltd., 2012.
- Lisovskaya,Sladkova,Sosnovskaya,Shadyro
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p. 241 - 246
(2012/11/13)
-
- Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals
-
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.
- Hasson, Alam S.,Tyndall, Geoffrey S.,Orlando, John J.,Singh, Sukhdeep,Hernandez, Samuel Q.,Campbell, Sean,Ibarra, Yesenia
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experimental part
p. 6264 - 6281
(2012/08/28)
-
- Kinetics and mechanism of the oxidation of diols by butyltriphenylphosphonium dichromate
-
The oxidation of four vicinal, four non-vicinal diols and one of their monoethers by butyltriphenylphosphonium dichromate (BTPPD), in dimethylsulfoxide (DMSO), resulted in the formation of corresponding hydroxyaldehyde as a main product of the oxidation. The reactions are of first order with respect to BTPPD, however, second order dependence is obtained with respect to each the diol and hydrogen ion. The oxidation of [1,1,2,2-2H 4]ethanediol exhibited primary kinetic isotope effect (k H/kD = 6.61 at 298 K). The temperature dependence of the kinetic isotope effect suggested the symmetrical transition state in the rate-determining step. The rate constants of oxidation of four vicinal diols show excellent correlation with Taft's ∑ σ* values with negative reaction constant, ρz.ast;. The rate of oxidation of ethanediol has been determined in nineteen different solvents. An analysis of the solvent effect indicates the importance of the cation-solvating power of the solvents. A suitable mechanism has been postulated involving the formation of chromate ester in a pre-equilibrium.
- Panday, Dinesh,Kothari, Seema
-
experimental part
p. 918 - 925
(2011/09/19)
-
- Oxidation of some vicinal and non-vicinal diols by tetrakis(pyridine)silver dichromate: A kinetic and mechanistic study
-
The kinetics of oxidation of four vicinal, four non-vicinal diols and two of their monoethers by tetrakis(pyridine)-silver dichromate (TPSD) have been studied in dimethylsulphoxide (DMSO). The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order in TPSD. Michaelis-Menten type of kinetics is observed with respect to the diols. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence has the form : kobs = a + b (H+]. The oxidation of [1,1,2,2- 2H4] ethanediol exhibits a substantial primary kinetic isotope effect (kH/kD = 5.91 at 298 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft's and Swain's multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed.
- Meena,Daiya,Sharma,Banerji,Kotai,Sharma, Vinita
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experimental part
p. 1887 - 1893
(2012/04/04)
-
- Oxidation of some vicinal and non-vicinal diols by morpholinium chlorochromate: A kinetic and mechanistic study
-
The kinetics of oxidation of four vicinal, four non-vicinal diols and two of their monoethers by morpholinium chlorochromate (MCC) have been studied in dimethylsulphoxide (DMSO). The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order in MCC and the diols. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence is taking the form : kobs = a + b [H+]. The oxidation of [1,1,2,2-2H4]ethanediol exhibits a substantial primary kinetic isotope effect (kH/kD = 5.82 at 298 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft's and Swain's multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed.
- Barthora,Baghmar,Agarwal,Sharma, Vinita
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experimental part
p. 677 - 683
(2012/04/10)
-
- Regioselective hydroformylation of allylic alcohols
-
A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.
- Lightburn, Thomas E.,De Paolis, Omar A.,Cheng, Ka H.,Tan, Kian L.
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supporting information; experimental part
p. 2686 - 2689
(2011/06/28)
-
- Michael acceptor based antiplasmodial and antitrypanosomal cysteine protease inhibitors with unusual amino acids
-
New peptidic Michael acceptor based cysteine protease inhibitors displaying antiparasitic activity were identified by testing a broad series of 45 compounds in total, containing Asn, Gln, or Phe. As target enzymes, falcipain-2 and -3 from P. falciparum and rhodesain from T. b. rhodesiense were used. In the case of the Asn/Gln containing compounds, the trityl-protected, diastereomeric ?'-configured vinylogous dipeptide esters 16 (Boc-(S)-Phg-(R/S)-vGln(Trt) -OEt) were discovered as most active inhibitors concerning both protease inhibition and antiparasitic acitivity, with inhibition constants in the submicromolar range. The compounds were shown to display time-dependent and competitive inhibition. In the case of the Phe containing compounds, the maleic acid derivatives 42 and 43 (BnOPhe←Mal-Phe-OBn, BnO-Phe-Mal←Phe-Ala- OBn, Mal = maleic acid) displayed good inhibition of rhodesain as well as good antitrypanosomal activity, while the fumaric acid derived E-analogue 14 (BnO-Phe-Fum-Phe-OBn) only displayed inhibition of the target enzymes but no antiparasitic activity. Inhibition by these Phe derivatives was shown to be time-independent and competitive.
- Breuning, Alexander,Degel, Bj?rn,Schulz, Franziska,Büchold, Christian,Stempka, Martin,Machon, Uwe,Heppner, Saskia,Gelhaus, Christoph,Leippe, Matthias,Leyh, Matthias,Kisker, Caroline,Rath, Jennifer,Stich, August,Gut, Jiri,Rosenthal, Philip J.,Schmuck, Carsten,Schirmeister, Tanja
-
body text
p. 1951 - 1963
(2010/08/03)
-
- Production of 3-hydroxypropionaldehyde in silage inoculated with lactobacillus coryniformis plus glycerol
-
We examined the production of an antimicrobial component, 3-hydroxypropionaldehyde (3-HPA), in laboratory-scale silage inoculated with Lactobacillus coryniformis strain 394, which ferments glycerol to 3-HPA. A modified colorimetric method that used an NaOH-treated blank and determined the absorption spectrum of the samples was employed to detect a 3-HPA-like component (HLC) that was assumed to be 3-HPA. Inoculation with Lb. coryniformis 394 plus glycerol in ensiling produced HLC at 10-460 ppm and contributed to inhibition of butyric fermentation and retardation of aerobic spoilage. HLC was considered to be 3-HPA from its absorption spectrum. These results suggest that the production of 3-HPA by Lb. coryniformis 394 is useful in ensiling and that the modified colorimetric method is effective to detect 3-HPA in silage.
- Tanaka, Osamu,Komatsu, Tokushi,Oshibe, Akinori,Cai, Yimin,Miyazaki, Shigeru,Nakanishi, Kotoyoshi
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experimental part
p. 1494 - 1499
(2010/03/04)
-
- HETEROGENEOUS PROMOTION OF OXIRANE HYDROFORMYLATION
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A process for making betahydroxyaldehydes such as 3-hydroxypropanal which comprises intimately contacting (a) an oxirane, (b) carbon monoxide, (c) a reducing agent such as hydrogen, (d) from about 0.01 to about 1 weight percent, basis cobalt metal, of a cobalt hydroformylation catalyst which is optionally complexed with a tertiary phosphine ligand, and (e) a heterogeneous, preferably solid, metal promoter used at a molar ratio of 0.05, preferably 0.15, to 100 moles of heterogeneous metal relative to the moles of soluble cobalt hydroformylation catalyst.
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Page/Page column 4-5
(2009/07/10)
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- METHOD OF TREATING AN ALDEHYDE MIXTURE, USE OF THE TREATED ALDEHYDE, AND AN ALCOHOL
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A method of treating an aldehyde mixture comprising a carboxylic acid and a metal cation, which method comprises: contacting the aldehyde mixture with a basic separating medium, and subsequently or simultaneously contacting with an acidic separating medium; use of the treated aldehyde mixture to prepare an alcohol; and the alcohol.
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Page/Page column 7-8
(2008/06/13)
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- TREATMENT OF AN AQUEOUS MIXTURE CONTAINING AN ALKYLENE OXIDE WITH AN ION EXCHANGE RESIN
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A process for separating an alkylene oxide from an aqueous mixture is provided in which no detectable dioxane byproduct is formed. An aqueous mixture containing an alkylene oxide is contacted with a carboxylic acid ion exchange resin to separate the alkylene oxide from the aqueous mixture. The ion exchange capacity of the resin is regenerated with an acid wash at a temperature of at least 6O0C, wherein regeneration of the resin does not result in the formation of dioxane in the spent acid wash. The process is particularly useful in purifying an aqueous 3-hydroxypropionaldehyde solution derived from an aqueous extraction of a hydroformylation reaction mixture containing ethylene oxide.
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Page/Page column 16-17
(2008/06/13)
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- PROCESS FOR PRODUCING 3-HYDROXYPROPIONALDEHYDE
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A process in which 3-hydroxypropionaldehyde can be produced from glycerin at high conversion rate. This process is characterized by including the step of dehydrating glycerin with bacterial cells and/or bacterial cell treatment product containing diol dehydratase and/or glycerol dehydratase optionally together with a diol dehydratase reactivating factor and/or glycerol dehydratase reactivating factor under such conditions that the quotient of catalytic amount [X (U/g glycerin)] of diol dehydratase and/or glycerol dehydratase divided by square of glycerin concentration [Y (g/100 ml)], X/Y2, is in the range of 10 to 8,000 so as to obtain 3-hydroxypropionaldehyde.
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- Process for preparing dioxy-functionalized propane compounds
-
The present invention relates to a process for preparing, dioxy functionalised propane compounds using cobalt and/or rhodium catalysts. More particularly, the present invention relates to a process for the preparation of the dioxy functionalised propane compounds of the formula X—CH2—CH(Y)—CH2-Z, wherein X=R—C(=O)—O— or H or —OH, Y and Z=—H or —OH or —C(=O)H, and wherein at a time, only one of X, Y and Z is —H, in high yields from vinyl carboxylates of formula R—C(=O)—O—CH=CH2 wherein, R=substituted or unsubstituted alkyl or aryl group.
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Page/Page column 11
(2010/02/14)
-
- Kinetics and mechanism of oxidation of some vicinal and non-vicinal diols by quinolinium bromochromate
-
Kinetics of oxidation of four vicinal, four non-vicinal diols and two of their monoethers by quinolinium bromochromate (QBC) have been studied in dimethyl sulphoxide (DMSO). The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order each in QBC and the diols. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence is taking the form: kobs = a + b[H+]. The oxidation of [1,1,2,2-2H4] ethanediol exhibits a substantial primary kinetic isotope effect (kH/kD = 5.83 at 298 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft's and Swain's multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed.
- Vyas, Shweta,Sharma, Pradeep K.
-
p. 1219 - 1223
(2007/10/03)
-
- Process for producing 1, 3-propanediol
-
A process for producing 1,3-propanediol, comprising: hydrating acrolein in a liquid phase in the presence of a hydration catalyst to form 3-hydroxypropanal; separating any unreacted acrolein, if any is present; and carrying out catalytic hydrogenation of the 3-hydroxypropanal in a liquid or gas phase with a hydrogenation catalyst, wherein the hydration catalyst is a catalyst comprising at least one member selected from the group consisting of the following materials (a) to (c) and has a pH of 6 or less at 20° C., when made into a slurry by dispersing the catalyst in a quantity of water 5 times as much as the quantity of catalyst by weight: (a) a metalloaluminophosphate molecular sieve, (b) an FER type zeolite, and (c) an oxide or compound oxide, excluding crystalline aluminosilicate zeolites, which comprises one or more element(s) selected from the elements belonging to group 4, group 13 and group 14 of the periodic table.
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- Rate constants for the gas-phase reactions of OH radicals with a series of hydroxyaldehydes at 296 ± 2 K
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Using a relative rate method with in situ generation of the hydroxyaldehydes, rate constants for the reactions of the OH radical with 2-hydroxybutanal [CH3CH2CH(OH)CHO], 3-hydroxybutanal [CH3CH(OH)CH2CHO], 2-hydroxypropanal [CH 3CH(OH)CHO], 2-hydroxy-2-methylpropanal [(CH3) 2C(OH)CHO], and 3-hydroxy-propanal [HOCH2CH 2CHO] have been measured at atmospheric pressure and 296 ± 2 K. The hydroxy-aldehydes were generated in situ from the OH radical-initiated reactions of precursor compounds (1,2- and 1,3-butanediol, 2-methyl-2,4-pentanediol, 2-methyl-3-buten-2-ol, and cis-3-hexen-1-ol) and the rate constants for the reaction of OH radicals with the hydroxyaldehydes were determined relative to those for reaction of OH radicals with the precursor compound. The rate constants obtained (in units of 10-11 cm 3 molecule-1 s-1) were CH3CH 2CH(OH)CHO, 2.37 ± 0.23; CH3CH(OH)CH 2CHO, 2.95 ± 0.24; CH3CH(OH)CHO, 1.70 ± 0.20; (CH3)2C(OH)CHO, 1.40 ± 0.25; and HOCH 2CH2CHO, 1.99 ± 0.29.
- Baker, Jillian,Arey, Janet,Atkinson, Roger
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p. 7032 - 7037
(2007/10/03)
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- Purification and structural characterization of 3-hydroxypropionaldehyde and its derivatives
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The compound 3-hydroxypropionaldehyde (3-HPA), together with HPA hydrate and HPA dimer, in aqueous solution forms a system with interesting chemical properties. Therefore, 3-HPA has attracted attention by the chemical industry for use as a precursor in the production of plastics, acrylic acid, and 1,3-propanediol and by the food industry, in using 3-HPA-producing Lactobacillus reuteri as a probiotic. To produce 3-HPA in high yield from glycerol, L. reuteri was used as a biotransformation system. A convenient chromatographic purification method was developed, and purified 3-HPA was analyzed using electrospray ionization mass spectrometry and 13C NMR. Quantitative 13C NMR revealed a concentration-dependent distribution of the three compounds forming the HPA system. At concentrations above 1.4 M, the HPA dimer was predominant. However, at concentrations relevant for biological systems, HPA hydrate was the most abundant, followed by the aldehyde form. Our results indicate that the dimeric form with expected antibiotic properties should not be the active form.
- Vollenweider, Sabine,Grassi, Guido,Koenig, Iwo,Puhan, Zdenko
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p. 3287 - 3293
(2007/10/03)
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- Synthesis of taurospongin A: a potent inhibitor of DNA polymerase and HIV reverse transcriptase, using pi-allyltricarbonyliron lactone complexes.
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The synthesis of taurospongin A has been achieved using, as a key step, a pi-allyltricarbonyliron lactone complex to control a highly stereoselective addition of a methyl group to a carbonyl unit located in the side chain of the complex.
- Hollowood, Christopher J,Ley, Steven V,Yamanoi, Shigeo
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p. 1624 - 1625
(2007/10/03)
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- Kinetics and mechanism of oxidation of some diols by benzyltrimethylammonium chlorobromate
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Kinetics of oxidation of five vicinal, four non-vicinal diols, and one of their monoethers by benzyltrimethylammonium chlorobromate (BTMACB) have been studied. The vicinal diols yield the products arising out of the glycol-bond fission while the other diols afford the hydroxycarbonyl compounds. The reaction is first order with respect to diols and the BTMACB. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of benzyltrimethylammonium chloride or potassium bromide on the reaction rate. The proposed reactive oxidizing species is chlorobromate ion. The effect of solvent composition indicated that the rate increases with an increase in the polarity of the solvent. The oxidation of [1,1,2,2-2H4]ethanediol show an absence of primary kinetic isotope effect. The value of solvent isotope effect, k(H2O)/k(D2O), at 288 K for the oxidation of ethanediol, propane-1,3-diol and 3-methoxybutan-1-ol are 3.32, 1.04 and 1.01 respectively. A cyclic mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidised by a hydride-transfer mechanism, as are monohydric alcohols.
- Bhatt, Monica,Sharma, Pradeep K.,Banerji, Kalyan K.
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p. 826 - 831
(2007/10/03)
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- Interaction of 2,2,6,6-tetramethylpiperidine-1-oxyl chlorite with alcohols
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The kinetics of the oxidation of a series of alcohols (viz., ethanol, propan-2-ol, butan-1-ol, butan-2-ol, heptan-4-ol, decan-2-ol, propan-1,3-diol, butan-2,3-diol, cyclohexanol, benzyl alcohol, and borneol) with the oxoammonium salt 2,2,6,6-tetramethylpiperidine-1-oxyl chlorite in acetonitrile was studied by spectrophotometry. The products of oxidation of primary alcohols are the corresponding aldehydes and carboxylic acids, and the products of oxidation of secondary alcohols are ketones. The reaction rate is described by the second order equation. The rate constants and activation parameters were determined. The rate constant as a function of the alcohol nature is described by the one-parameter Taft equation.
- Ganiev,Suvorkina,Igoshina,Kabal'nova,Imashev,Tolstikov
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p. 982 - 985
(2007/10/03)
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- Kinetics of oxidation of 3-aminopropan-1-ol and related compounds by silver(III) species
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The oxidation of 3-aminopropan-1-ol (3-AP) and certain diamines by diperiodatoargentate(III) (DPA) has been studied by stopped-flow spectrophotometry at pH 8.0. The kinetics of the reaction of 3-AP consist of three steps - an induction period, then a fast decay, which is followed by a slower decay. The initial step involves the axial binding of the substrate to the silver(III) species; this rearranges during the induction period (0.2 s) and takes up another ligand in the following step with a second-order rate constant of 4 × 103 dm3 mol-1 s-1 to yield [AgIII(H2IO6)(3-AP)2]. The silver(III) centre in this complex is reduced by 3-AP in the rate-determining step with a rate constant of 0.50 × 102 dm3 mol-1 s-1. Both of these processes show inverse dependence on [IO4-] and [OH-]. The kinetics of the oxidation of diamines by silver(III) follow a different kinetic behaviour. The rates of their complexation and oxidation follow the order 1,2-diaminoethane > 1,3-diaminopropane > 1,4-diaminobutane. Separation of the two functional groups by an additional CH2 in the studied substrates reduces the rates of both the steps. In case of the diamines, the formation of a cyclic complex involving silver(III) and the substrate prior to its oxidation is suggested. The mechanisms of these reactions are being analysed.
- Kumar,Vaishali,Ramamurthy
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p. 1174 - 1179
(2007/10/03)
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- Kinetics and mechanism of silver (I) catalyzed oxidation of 1,3-propanediol by peroxodiphosphate in acetate buffers
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The kinetics of silver (I) catalysed oxidation of 1,3-propanediol by peroxodiphosphate (pdp) has been studied in acetate buffers. 3-Hydroxypropanal has been identified spectrally to be the oxidation product of 1,3-propanediol. However, the rate is independent of diol concentration but first order each in the catalyst and oxidant. Rate is significantly retarded by acetate ions. The kinetics of the reaction account for the rate law. Rate parameters have been evaluated under varied experimental conditions. The role of the catalyst has been suggested through AgII/AgI redox cycle.
- Singh,Bansal,Gupta,Sharma,Khandelwal,Sharma
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p. 714 - 719
(2007/10/03)
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- Kinetics and Mechanism of Ruthenium(III) Chloride Catalyzed Oxidation of Propane-1,3-diol by Ceric Sulphate in Aqueous Sulphuric Acid Medium.
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The kinetics of ruthenium(III) chloride catalyzed oxidation of propane-1,3-diol by ceric sulphate have been studied. 3-Hydroxypropanal is spectrally confirmed to be the oxidation product of the diol. The kinetic rate law (1) is based on the proposed reaction mechanism. Kinetic rate parameters have been evaluated.
- Agrawal, Anju,Sharma, Indu,Gupta, Divya,Khandelwal, C. L.,Sharma, P. D.
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p. 621 - 636
(2007/10/03)
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- N-dealkylation of an N-cyclopropylamine by horseradish peroxidase. Fate of the cyclopropyl group
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Cyclopropylamines inactivate cytochrome P450 enzymes which catalyze their oxidative N-dealkylation. A key intermediate in both processes is postulated to be a highly reactive aminium cation radical formed by single electron transfer (SET) oxidation of the nitrogen center, but direct evidence for this has remained elusive. To address this deficiency and identify the fate of the cyclopropyl group lost upon N-dealkylation, we have investigated the oxidation of N-cyclopropyl-N-methylaniline (3) by horseradish peroxidase, a well-known SET enzyme. For comparison, similar studies were carried out in parallel with N-isopropyl-N-methylaniline (9) and N,N-dimethylaniline (8). Under standard peroxidatic conditions (HRP, H2O2, air), HRP oxidizes 8 completely to N-methylaniline (4) plus formaldehyde within 15-30 min, whereas 9 is oxidized more slowly (14C]-3, [1′-13C]-3, and [2′,3′-13C]-3 as substrates, radiochemical and NMR analyses of incubation mixtures revealed that the complete oxidation of 3 by HRP yields 4 (0.2 mol), β-hydroxypropionic acid (17, 0.2 mol), and N-methylquinolinium (16, 0.8 mol). In buffer purged with pure O2, the complete oxidation of 3 yields 4 (0.7 mol), 17 (0.7 mol), and 16 (0.3 mol), while under anaerobic conditions, 16 is formed quantitatively from 3. These results indicate that the aminium ion formed by SET oxidation of 3 undergoes cyclopropyl ring fragmentation exclusively to generate a distonic cation radical (14+?) which then partitions between unimolecular cyclization (leading, after further oxidation, to 16) and bimolecular reaction with dissolved oxygen (leading to 4 and 17 in a 1:1 ratio). Neither β-hydroxypropionaldehyde, acrolein, nor cyclopropanone hydrate are formed as SET metabolites of 3. The synthetic and analytical methods developed in the course of these studies should facilitate the application of cyclopropylamine-containing probes to reactions catalyzed by cytochrome P450 enzymes.
- Shaffer,Morton,Hanzlik
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p. 8502 - 8508
(2007/10/03)
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- Hydration of terminal alkynes to aldehydes in aqueous micellar solutions by ruthenium(II) catalysis; first anti-Markovnikov addition of water to propargylic alcohols
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The hydration of terminal alkynes and of propargylic alcohols to the corresponding aldehyde derivatives is conveniently carried out at 60°C in an aqueous micellar environment, in the presence of 5 mol% of the indenyl ruthenium(II) complex [Ru(η5-C9H7)Cl(PPh3) 2]. Higher yields and improved regioselectivity of aldehyde versus ketone as well as reaction conditions, in particular temperature and catalyst load, are found with respect to a solvent mixture 2-propanol-water, due to the aggregating conditions of the micellar solution. The reactions of the propargylic alcohols indicate the tolerance of the hydroxy functionality by the ruthenium complex.
- Alvarez, Patricia,Bassetti, Mauro,Gimeno, José,Mancini, Giovanna
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p. 8467 - 8470
(2007/10/03)
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- Hydroformylation of epoxides catalyzed by cobalt and hemilabile P-O ligands
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Complexes of cobalt efficiently catalyze the hydroformylation of epoxides in the presence of hemilabile P-O chelating ligands to give β-hydroxyaldehydes in high selectivities and yields.
- Weber,Englert,Ganter,Keim,Moethrath
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p. 1419 - 1420
(2007/10/03)
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- Oxidation of olefins by palladium(II): Part 17. An asymmetric chlorohydrin synthesis catalyzed by a bimetallic palladium(II) complex
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Previous studies showed that oxidation of α-olefins with monometallic catalysts containing chiral diphosphines and diamines gave chlorohydrins with poor to good enantioselectivites (28-82% ee). The present studies demonstrate that bimetallic catalysts containing a β-triketone and bridging chiral diphosphine and diamines are excellent catalysts for this reaction giving enantioselectivites considerably higher than the monometallic catalysts. Enantioselectivities were more than 50% for most olefins tested. The highest optical purities were 94% ee for propene and 93% ee for allylphenyl ether. A useful feature of this asymmetric synthesis is the fact it is a net air oxidation.
- El-Qisairi, Arab,Henry, Patrick M.
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- Kinetics and mechanism of oxidation of diols by quinolinium fluorochromate
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The kinetics of oxidation of four vicinal diols, four non-vicinal diols and two of their monoethers by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order in QFC. Michaelis-Menten type kinetics have been observed with respect to the diols. The oxidation of [1,1,2,22H4] ethanediol exhibits a substantial primary kinetic isotope effect (k(H)/k(D) = 6.35 at 303 K). The reaction has been in nineteen different organic solvents and the solvent effect has been analysed using Taft's and Swain's multiparametric equation. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed.
- Choudhary, Kirti,Sharma, Pradeep K.,Banerji, Kalyan K.
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p. 325 - 330
(2007/10/03)
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- Kinetics and Mechanism of Oxidation of Diols by Hexamethylenetetramine-bromine
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Kinetics of oxidation of five vicinal, four non-vicinal diols, and one of their monoethers by hexamethylenetetramine-bromine (HABR) have been studied. The vicinal diols yielded the products arising out of the glycol bond fission while the other diols yielded the hydroxycarbonyl compounds. The reaction is first order with respect to HABR. Michaelis-Menten type kinetics were observed with respect to the diol. Addition of hexamethylenetetramine resulted in an increase in the rate of reaction. The oxidation of 2H4>ethanediol showed an absence of primary kinetic isotope effect. A mechanism involving a glycol bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidised by a hydride-transfer mechanism as are monohydric alcohols.
- Gangwani, Hemlata,Sharma, Pradeep K.,Banerji, Kalyan K.
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p. 854 - 871
(2007/10/03)
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- Cobalt-catalyzed process for preparing 1,3-propanidiol
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1,3-propanediol is prepared in a process which involves hydroformylating ethylene oxide: (a) in an essentially non-water-miscible solvent in the presence of a non-ligated cobalt catalyst and a catalyst promoter at a temperature within the range of about 50° to about 100° C. and a pressure within the range of about 500 to about 5000 psig, to produce an intermediate product mixture comprising less than about 15 wt % 3-hydroxypropanal; (b) adding an aqueous liquid and extracting at a temperature less than about 100° C. the 3-hydroxypropanal to provide an aqueous phase comprising 3-hydroxypropanal in greater concentration than the concentration of 3-hydroxypropanal in said intermediate product mixture, and an organic phase comprising the cobalt catalyst; (c) separating the aqueous phase from the organic phase; (d) hydrogenating the 3-hydroxypropanal to provide a hydrogenation product mixture comprising 1,3-propanediol; and (e) recovering 1,3-propanediol from said hydrogenation product mixture. The process enables the production of 1,3-propanediol in high yields and selectivity without the use of a phosphine ligand-modified cobalt catalyst.
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- Effect of phosphorylation on the reaction rate of unnatural electrophiles with 2-keto-3-deoxy-6-phosphogluconate aldolase
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D-Glyceraldehyde is accepted as an electrophile by 2-keto-3-deoxy-6-phosphogluconate (KDPG) aldolase (EC 4.1.2.14) at 1% the rate of natural substrate, D-glyceraldehyde 3-phosphate. Accordingly, it was expected that addition of a phosphate moiety at C3 or C4 of unnatural aldehydes would enhance their activity as electrophilic substrates. Furthermore, phosphate would act as a useful protecting group during synthetic manipulations of the aldol adduct. A variety of phosphorylated and non-phosphorylated aldehydes were synthesized and evaluated as substrates for KDPG aldolase. Although small variations in reaction rate were observed, phosphorylation failed to provide a universal rate enhancement. Evaluation of substrate kinetic parameters revealed that the high rate of reaction of D-glyceraldehyde 3-phosphate compared to related electrophiles is entirely due to the efficiency of turnover with little change in binding exhibited among various substrates.
- Cotterill, Ian C.,Shelton, Michael C.,Machemer, Daniel E. W.,Henderson, Darla P.,Toone, Eric J.
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p. 1335 - 1341
(2007/10/03)
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- Kinetics and Mechanism of the Oxidation of Diols by Pyridinium Bromochromate
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The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulfoxide.The main product of oxidation is the corresponding hydroxyaldehyde.The reaction is first-order with respect to each the diol and PBC.The reaction is acid-catalyzed and the acid dependence has the form: kobs = a + b+>.The oxidation of ethanediol exhibited a primary kinetic isotope effect (kH/kD = 6.70 at 298 K).The reaction has been studied in 19 organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using multiparametric equations.The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step.A suitable mechanism has been proposed.
- Rao, P. Surya Chandra,Suri, Deepa,Kothari, Seema,Banerji, Kalyan K.
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p. 285 - 290
(2007/10/03)
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