- PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS
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Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.
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Paragraph 00182
(2019/02/15)
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- Transfer hydrogenation of cyclic carbonates and polycarbonate to methanol and diols by iron pincer catalysts
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Herein, we report the first example on the use of an earth-abundant metal complex as the catalyst for the transfer hydrogenation of cyclic carbonates to methanol and diols. The advantage of this method is the use of isopropanol as the hydrogen source, thus avoiding the handling of flammable hydrogen under high pressure. The reaction offers an indirect route for the reduction of CO2 to methanol. In addition, poly(propylene carbonate) was converted to methanol and propylene glycol. This methodology can be considered as an attractive opportunity for the chemical recycling of polycarbonates.
- Liu, Xin,De Vries, Johannes G.,Werner, Thomas
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p. 5248 - 5255
(2019/10/11)
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- IRON-CATALYZED CROSS-COUPLING OF METHHANOL WITH SECONDARY OR TERTIARY ALCOHOLS TO PRODUCE FORMATE ESTERS
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A process for preparing a variety of secondary and tertiary alkyl formate esters via the coupling of methanol and secondary (or tertiary) alcohols. Iron-based catalysts, supported by pincer ligands, are employed to produce these formate esters in high yields and unprecedentedly high selectivities (>99%). Remarkably, the coupling strategy is also applicable to bulkier tertiary alcohols, which afford corresponding tertiary formate esters in moderately high yields and high selectivities.
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Paragraph 0121; 0122
(2019/02/17)
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- Acidic ionic liquid based UiO-67 type MOFs: A stable and efficient heterogeneous catalyst for esterification
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A facile strategy for the synthesis of acidic ionic liquid based UiO-67 type MOFs was developed in this study. Br?nsted acids (H2SO4, CF3SO3H and hifpOSO3H (hexafluoroisopropyl sulfuric acid)) were introduced into UiO-67-bpy (bpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) frameworks by reacting with bipyridyl nitrogen to introduce the properties of an acidic ionic liquid into the frameworks. The prepared catalysts, denoted as UiO-67-HSO4, UiO-67-CF3SO3 and UiO-67-hifpOSO3, were characterized by XRD, SEM, FT-IR, EA, TGA and N2 adsorption-desorption studies. The relatively high surface area was still maintained and acidic active groups were uniformly dispersed in the frameworks. The catalytic performance of UiO-67-HSO4, UiO-67-CF3SO3 and UiO-67-hifpOSO3 was evaluated by the esterification of acetic acid with isooctyl alcohol. The prepared catalysts showed good catalytic activities in the esterification, of which UiO-67-CF3SO3 gave the maximum isooctyl alcohol conversion of 98.6% under optimized conditions. The catalyst could be reused five times without a significant decrease in the conversion of isooctyl alcohol, and almost no active species were leached, indicating the excellent stability and reusability of the catalyst. Our study provides one effective way to synthesize heterogeneous acidic ionic liquid catalysts consisting of isolated, well defined acidic groups that will probably attract interest in acid catalyst chemistry.
- Xu, Zichen,Zhao, Guoying,Ullah, Latif,Wang, Meng,Wang, Aoyun,Zhang, Yanqiang,Zhang, Suojiang
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p. 10009 - 10016
(2018/03/23)
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- Method for preparing formate-type compound
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The invention discloses a method for preparing a formate-type compound. The method comprises the following steps of: adopting an alcohol-type compound and 1,3-dihydroxyacetone as reaction raw materials, and under the existence of a composite catalyst and an oxidant, reacting for 2-48 hours in a reaction medium in a reactor at a reaction temperature of 25-100 DEG C so as to obtain the formate-typecompound. The method disclosed by the invention is simple, and is mild in reaction condition, and by the method, a target product can be obtained by low cost and high yield; the used catalyst has highcatalytic activity, and is easily separated from a reaction system to be repeatedly used; the whole process is environment-friendly, and the reaction raw material (1,3-dihydroxyacetone) is easily converted from a side product (glycerol) of biodiesel, so that the utilization of the glycerol is promoted.
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Paragraph 0039; 0047; 0048
(2018/07/30)
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- Purified mCPBA, a Useful Reagent for the Oxidation of Aldehydes
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Purified mCPBA is a useful reagent for the oxidation of several classes of aldehyde. Although linear unbranched aliphatic aldehydes are oxidized to the corresponding carboxylic acids, α-branched ones undergo Baeyer–Villiger oxidation to formates. α-Branched α,β-unsaturated aldehydes provide enolformates and/or epoxides, which can be saponified to α-hydroxy ketones with shortening of the carbon chain by 1 carbon. Unbranched α,β-unsaturated aldehydes undergo an interesting Baeyer–Villiger oxidation/epoxidation/formate migration/BV oxidation cascade, which results in formyl-protected hydrates with an overall loss of two carbon atoms.
- Horn, Alexander,Kazmaier, Uli
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p. 2531 - 2536
(2018/03/21)
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- Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers
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Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources.
- Schieweck, Benjamin G.,Klankermayer, Jürgen
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supporting information
p. 10854 - 10857
(2017/08/30)
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- Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen
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The synthesis of dimethoxymethane (DMM) by a multistep reaction of methanol with carbon dioxide and molecular hydrogen is reported. Using the molecular catalyst [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3resulted in a versatile catalytic system for the synthesis of various dialkoxymethane ethers. This new catalytic reaction provides the first synthetic example for the selective conversion of carbon dioxide and hydrogen into a formaldehyde oxidation level, thus opening access to new molecular structures using this important C1source.
- Thenert, Katharina,Beydoun, Kassem,Wiesenthal, Jan,Leitner, Walter,Klankermayer, Jürgen
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supporting information
p. 12266 - 12269
(2016/10/13)
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- PIFA-mediated esterification reaction of alkynes with alcohols via oxidative cleavage of carbon triple bonds
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A metal-free esterification of alkynes via C≡C triple bond cleavage has been developed. In the presence of phenyliodine bis(trifluoroacetate), a diverse range of alkyne and alcohol substrates undergoes triple bond cleavage to produce carboxylic ester motifs in moderate to good yields. The transformation is proposed to proceed via hydroxyethanones and ethanediones as intermediates on the basis of mechanistic studies and exhibits a broad substrate scope and good functional group tolerance.
- Jiang, Qing,Zhao, An,Xu, Bin,Jia, Jing,Liu, Xin,Guo, Cancheng
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supporting information
p. 2709 - 2715
(2014/04/17)
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- Effect of protecting agent concentration, catalyst (mol %) and temperature on the protection of 2-propanol catalyzed by dodeca-tungstophosphoric acid
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Protection of various alcohols with carboxylic acids catalyzed by heteropolyacids is realized as an efficient method among different familiar reaction pathways. Herein, effective reaction parameters such as temperature, alcohol:protecting agent mole ratio and catalyst (mol %) were investigated on the acetylation and formylation of 2-propanol with acetic acid, formic acid and ethyl formate, as acetylating agents, in the presence of dodeca- tungstophosphoric acid, H3PW12O40. Findings showed that efficiency of the protection system was increased by enhancing temperature, using higher amounts of catalyst and increasing concentration of the protecting agent. Obviously, enhancing concentration of the protecting agent was more effective than elevation of temperature on the reaction progress.
- Tayebee, Reza,Cheravi, Fatemeh
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scheme or table
p. 5567 - 5574
(2012/07/31)
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- Hypervalent λ3-bromane strategy for Baeyer-Villiger oxidation: Selective transformation of primary aliphatic and aromatic aldehydes to formates, which is missing in the classical Baeyer-Villiger oxidation
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A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.
- Ochiai, Masahito,Yoshimura, Akira,Miyamoto, Kazunori,Hayashi, Satoko,Nakanishi, Waro
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supporting information; experimental part
p. 9236 - 9239
(2010/11/02)
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- PROCESS FOR PREPARATION OF FORMATE ESTERS OR METHANOL AND CATALYST THEREFOR
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A production process and a catalyst are provided, which can be less decreased in activity of the catalyst even when CO2, water and the like are present in the starting material and/or the reaction system, and which can produce a formic ester or a methanol at a low temperature and a low pressure. The present invention relates to a process for producing methanol, comprising reacting carbon monoxide with an alcohol in the presence of an alkali metal-type catalyst, and/or an alkaline earth metal-type catalyst to produce a formic ester, wherein a hydrogenolysis catalyst of formic ester and hydrogen are allowed to be present together in the reaction system to hydrogenate the produced formic ester and thereby obtain a methanol.
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Page column 7
(2008/06/13)
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- Iso-propyl formate hydrolysis in water and the evaluation of rate constants
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Emphasis has been placed on the data for the hydrolysis of Iso-propyl formate in neutral medium over the temperature range 303-343 K to illustrate the method, employing numerical integration and the criteria of least squares, for the evaluation of the first and the second order rate constants in Kirmann's equation by the sum of trapezoids. The values obtained for the second order rate constant k1 (1 mol-1 sec-1) are compared with the values reported in the literature. The hydrolysis of iso-propyl formate involves alkyl-oxygen cleavage. A mini computer program on a 6502 12K, Acorn Atom computer has been designed for the evaluation of rate constants.
- Begum, Shakila,Zeb, Mohammad Aurang,Ilyas, Mohammad
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- Steel-promoted oxidation of olefins in supercritical carbon dioxide using dioxygen in the presence of aldehydes
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Oxidation of olefins occurs effectively in supercritical carbon dioxide as the reaction medium with dioxygen as the primary oxidant and aldehydes as sacrificial co-oxidants. No catalyst is required, but the reaction is promoted by the stainless steel of the reactor walls. Depending on the substrate, vinylic oxidation or epoxidation can be the prevailing pathway. Epoxidation is particularly effective for substrates with internal double bonds and for long-chain terminal olefins.
- Loeker, Frank,Leitner, Walter
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p. 2011 - 2015
(2007/10/03)
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- Hydroxyl-radical-initiated oxidation of isobutyl isopropyl ether under laboratory conditions related to the troposphere. Product studies and proposed mechanism
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The products formed by the hydroxyl-radical-initiated oxidation of the model ether, isobutyl isopropyl ether [(CH3)2CHCH2OCH(CH3)2], have been investigated by irradiating synthetic air mixtures containing the substrate, methyl nitrite, and nitric oxide at ppm levels in a Teflon bag reactor at room temperature. The decay of reactant and formation of products were monitored by gas chromatography, mass spectrometry and by HPLC. The molar yields of the major products (mol of product formed/mol of isobutyl isopropyl ether consumed) were as follows: acetone, 0.56 ± 0.04; isopropyl formate, 0.48 ± 0.03; isobutyl acetate, 0.28 ± 0.02; 2-hydroxy-2-methylpropyl acetate [CH3C(O)OCH2C(OH)(CH3)2], 0.25 ± 0.1. The molar yields of the minor products were as follows: isobutyraldehyde, 0.06 ± 0.05; isopropyl nitrate, 0.09 ± 0.06; 1,1,4-trimethyl-3-oxapentyl nitrate [(CH3)2CHOCH2C(CH3) 2(ONO2)], 0.07 ± 0.02; isopropyl isobutyrate [(CH3)2CHC(O)OCH(CH3)2] ca. 0.01; and isobutyl formate, ca. 0.01. The major products are explained by a mechanism involving initial OH attack at the -CH- and -CH2- groups in the alkyl side chains of the ether followed by the subsequent reactions of the resulting carbon-centred, organic peroxy, and organic oxy radicals. The observed products, in conjunction with the proposed reaction pathways, account for a total yield of about 1.15, indicating that all the main routes are accounted for in the degradation of this ether. The major reaction pathways of the three principal organic oxy radicals are summarised as follows (percentage of overall reaction in brackets): (CH3)2C(O)OCH2CH(CH3) 2 → CH3C(O)OCH2CH(CH3)2 + CH3 (28%) (CH3)2CHOCH(O)CH(CH3)2 → (CH3)2CHOC(O)H + CH(CH3)2 (≤48%) (CH3)2CHOCH2C(O)(CH3) 2 → (CH3)2COCH2C(OH)(CH3) 2 (25%) This study supports the finding that organic oxy radicals generated from ethers and containing the structure RCH(O.)OR undergo mainly decomposition by C-C bond cleavage, whereas those oxy radicals with the structure RCH(O.)CH2OR undergo preferential 1,5-H-atom transfer isomerisation reactions. The following rate coefficients (10-12 cm3 molecule-1 s-1) at room temperature for the reactions of OH radicals with the reactant and products have been determined by the relative rate technique: isobutyl isopropyl ether, 19.5 ± 0.4; isobutyl acetate, 6.0 ± 0.5; isobutyraldehyde, 25.8 ± 0.7; isopropyl formate, 2.1 ± 0.1; isopropyl isobutyrate, 6.5 ± 0.4; 1,1,4-trimethyl-3-oxapentyl nitrate, 16.5 ± 0.7; and 2-hydroxy-2-methylpropyl acetate, 9.5 ± 1.6.
- Stemmler, Konrad,Mengon, Wolfgang,Kerr, J. Alistair
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p. 2865 - 2875
(2007/10/03)
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- A convenient procedure for the formylation of amines and alcohols using cyanomethyl formate
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A simple metyod for the direct formylation of amines using cyanomethyl formate is described. The formylation succeeds in moderate to high yields under mild and neutral conditions. Thus, formamides 2a-f, 2i-m are obtained at room temperature. A chemoselective N-formylation is achieved in the case of ethanolamine. The formylation of nitroanilines and the O-formylation of alcohols only succeeds in the presence of a catalytic amount of imidazole leading to 2g,h and 3a-e, respectively.
- Deutsch,Niclas
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p. 1561 - 1568
(2007/10/02)
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- The Role of Catalysts in the Air Oxidation of Aliphatic Aldehydes
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Under preparative conditions, the liquid-phase air oxidation of 2-methylpropanal gives product profiles that differ with the catalyst.These distinctive profiles allow us to use this reaction to characterize the roles of some catalysts.The conversion of 2-methylpropanal to 2-methylpropanoic acid takes place in two stages.In stage 1 aldehyde is converted to peracid in a free radical chain reaction.In stage 2 peracid is converted to carboxylic acid.Paradoxically, noncatalyzed reactions give higher yields of 2-methylpropanoic acid than do reactions catalyzed by Mn or Co ions.The ions impove the efficiency of stage 2, but they also increase the rate of chain initiation in stage 1.Since these reactions are oxygen mass transfer limited, small increases in the reaction rate lead to oxygen starvation in the bulk liquid phase.This leads to increased formation of byproduct propane, propene, acetone, 2-propanol, CO and CO2.Increases in CO formation are due to decomposition of acyl radicals and are diagnostic of severe oxygen starvation.Obviously, increases in the reaction rate must also increase the amount of chain termination which is the sole source of CO2.It is shown that Cu ion can inhibit the chain reaction and thus alleviate both conditions.
- Larkin, Donald R.
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p. 1563 - 1568
(2007/10/02)
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- α,α-DICHLOROALDEHYDES AND α,α-DICHLOROCARBOXYLIC ACIDS FROM LONG CHAIN 1-ALKANOLS. IMPROVED CHLORINATION IN THE SYSTEM DMF-CHCl3-MgCl2
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Production of α,α-dichloroaldehydes by direct chlorination of 1-alkanols with chlorine gas, catalyzed by DMF and DMF*HCl, was extended to long chain compounds (CnH2n+1OH; n = 5, 6, 8, 10, 12, 14, 16, 18).Two problems specific to the longer chains were solved to obtain isolated yields in the range 70-85 percent; a) parasitic radical chlorination was largely controlled by shielding from light; b) alkyl alkanoate side product (8 percent for n = 8 but 25 percent for n = 16 or 18) was decreased to 0-2 percent in the presence of MgCl2*H2O.Homogeneity of the reaction medium was improved with chloroform as a cosolvent.Oxidation of the aldehydes to dichlorocarboxylic acids proceeded smoothly with aqueous KMnO4 up to the tetradecanal.For the longer chains 30 percent hydrogen peroxide-NaHCO3 in acetone (overnight at 48-52 deg C) was the preferred oxidant.
- Buyck, L. De,Casaert, F.,Lepeleire, C. De,Schamp, N.
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p. 525 - 534
(2007/10/02)
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- A STUDY OF THE CONVERSION OF ISOBUTYRALDEHYDE IN NONCATALYTIC OXIDATION BY OXYGEN IN THE LIQUID PHASE
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A specific effect was found for the isopropyl group at the carbonyl on the composition of the molecular products of the oxidation of isobutyraldehyde, which are largely formed in the early reaction steps.The mechanism for the conversion of isobutyraldehyde was discussed.
- Bondarenko, A. V.,Vasil'eva, I. A.,Gvozdovskii, G. N.,Srednev, S. S.,Gal'perina, A. I.,Kozlov, S. K.
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p. 1859 - 1863
(2007/10/02)
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- Process for preparing cyclooctene-4-ol-1 from cyclooctadiene-1,5
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A process for preparing cyclooctene-4-ol-1 with a content in excess of 70% by reacting cyclooctadiene-1,5 with formic acid and then saponifying or transesterifying the cyclooctenyl formate with an alcohol of low boiling point. In the absence of a catalyst, formic acid is reacted with cyclooctadiene-1,5 at 50° to 200° C., preferably 95° to 105° C. The reaction product without further processing is directly distilled, and the formic acid ester so obtained is transesterified with an alcohol of low boiling point into the formate of that alcohol and into cyclooctene-4-ol-1.
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- Preparation of N-Formylpyridones - Selective Esterification of Primary, Secondary and Tertiary Alcohols with N-Acylpyridones
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Formylation of monohydroxypyridines 1-3 with formic acid in the presence of dicyclohexylcarbodiimide in dichloromethylene yields N-formyl-4- (4), N-formyl-2-pyridone (5), and 3-(formyloxy)pyridine (6), resp.These acylpyridones react with prim., sec., and tert. alcohols with selectivity decreasing reactivity to give the formyl esters 7.
- Effenberger, Franz,Keil, Michael,Bessey, Eberhard
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p. 2110 - 2119
(2007/10/02)
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- Direct vs. Indirect Mechanisms in Organic Electrochemistry. Estimates of Activation Energies for Hydrogen Atom Transfer Processes of Relevance in Indirect Mechanisms Using the Bond Energy-Bond Order (BEBO) and Equibonding Methods
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Activation energies for a number of hydrogen abstraction reactions of interest in mechanistic organic electrochemistry have been calculated using the bond energy-bond-order (BEBO) and equibonding method.The main emphasis has been put on processes with bearing on the problem of deciding between direct and indirect mechanisms in anodic oxidation, viz. acyloxylation, hydroxylation, methoxylation, nitrooxylation, cyanation, carbomethoxylation and azidation.The results indicate that indirect mechanisms might play a more important role than presently assumed.
- Eberson, Lennart
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p. 481 - 492
(2007/10/02)
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