- Phase-Transfer Catalyzed Reactions. 5. Dramatic Effect of the Concentration of Base on the Dimerization of Crotonaldehyde
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Self-condensation of crotonaldehyde under base-catalyzed phase-transfer conditions leads to aldehydes 3 or 4, depending only on the concentration of aqueous hydroxide used.Quaternary ammonium fluorides in anhydrous THF is shown to be a useful system for conjugate additions involving base-sensitive aldehydes.
- McIntosh, John M.,Khalil, Hamdy,Pillon, David W.
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Read Online
- Palladium(II)-catalyzed oxidation of acrylate esters to acetals in supercritical carbon dioxide
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The development of a new palladium(II)-catalyzed oxidation of methyl acrylate, affording methyl 3,3-dimethoxypropanoate in excellent conversion and selectivity in supercritical CO2, is presented.
- Jia, Lanqi,Jiang, Huanfeng,Li, Jinheng
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Read Online
- Synthesis method of methyl 3-methoxypropionate
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The invention relates to a synthesis method of methyl 3-methoxypropionate, which comprises the following steps of carrying out addition reaction on absolute methanol and methyl acrylate under the condition of a catalyst which is a micromolecular tertiary amine catalyst, and after the reaction is finished, rectifying to remove excessive absolute methanol, unreacted methyl acrylate and the catalyst,collecting methyl 3-methoxypropionate with the purity of more than 99.8% as a product, and recycling the collected excessive absolute methanol, unreacted methyl acrylate and the catalyst in the nextreaction. The synthesis method has the advantages of simple synthesis, mild conditions, no need of acid neutralization, few side reactions, no three wastes, high conversion rate, long-term use of thecatalyst, repeated cyclic utilization, no damage, simplified separation process, good product quality, easy obtainment of 99.8% or above of purity, promotion of large-scale production, and facilitation of large-scale application to the photoelectric industry.
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Paragraph 0041-0068
(2021/03/13)
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- MANUFACTURING METHOD OF N-SUBSTITUTED (METH)ACRYLAMIDE
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To provide a method for industrially manufacturing high purity β-alkoxypropionic acid amide, β-aminopropionic acid amide and N-substituted (meth)acrylamide at high yield using (meth)acrylic acid ester as a starting material.SOLUTION: By conducting an amidation reaction with amine in the presence of a metal complex as a catalyst using β-substituted propionic acid ester which is a product material of a Michael addition reaction of (meth)acrylic acid ester and alcohol or amine, β-substituted propionic acid amide is obtained. Further by conducting a thermal decomposition reaction of the β-substituted propionic acid amide in the presence of the metal complex, and eliminating the alcohol or the amine, objective compound N-substituted (meth)acrylamide is obtained.SELECTED DRAWING: None
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Paragraph 0049; 0052
(2019/05/25)
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- Method for preparing 3-methyl methoxypropionate
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The invention relates to a method for preparing 3-methyl methoxypropionate. The method is characterized in that methyl acetate, formaldehyde and methanol are used as raw materials for reaction under the presence of a catalyst, and 3-methyl methoxypropionate is obtained. The catalyst is composed of an active component and a carrier. The active component includes a Cs metal salt, an alkali metal hydroxide and an IVB-group metal oxide. The method has the advantages in that the raw materials are low in cost, the production process is continuous and 3-methyl methoxypropionate is high in yield.
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Paragraph 0020; 0021; 0022; 0023; 0024; 0025; 0026-0029
(2018/04/03)
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- Manufacturing method of methyl 3-methoxypropionate with high purity and yield and manufacturing equipment therefor
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The present invention relates to a method for manufacturing methyl 3-methoxypropionate with high purity and yield, and a manufacturing device optimized therefor and, more specifically, to a process capable of inhibiting side reactions and obtaining products with high yield through a process of adjusting moisture or the like by passing through a reaction sampling process during a reaction process of methanol and methyl acrylate.COPYRIGHT KIPO 2018
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Paragraph 0043-0045
(2018/05/03)
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- MANUFACTURING METHOD OF β-SUBSTITUTED PROPIONIC ACID AMIDE AND N-SUBSTITUTED (METH)ACRYLAMIDE
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PROBLEM TO BE SOLVED: To provide a method for industrially manufacturing β-alkoxy propionic acid amide, β-amino propionic acid amide and N-substituted (meth)acryl amide using (meth)acrylic acid ester as starting material at high yield and high purity. SOLUTION: There is provided a method for obtaining N-substituted (meth)acryl amide represented by target compound formula (7) by conducting an amidation reaction with amine using β-substituted propionic acid ester represented by the formula (1) of a product of a Michael addition reaction of (meth)acrylic acid ester and alcohol or amine in presence of a metal complex as a catalyst to obtain β-substituted propionic acid amide represented by the formula (3) and conducting a thermal decomposition reaction of β-substituted propionic acid amide in presence of the metal complex as the catalyst to eliminate alcohol or amine. A-CH2-C(R1)H-C(=O)-OR2 (1), A-CH2-C(R1)H-C(=O)-N(R3)R4 (3), CH2=C(R1)-C(=O)-N(R3)R4 (7) SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0046; 0048; 0050
(2018/07/03)
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- Metal-Free Catalytic Reduction of α,β-Unsaturated Esters by 1,3,2-Diazaphospholene and Subsequent C-C Coupling with Nitriles
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1,3,2-Diazaphospholene 1 catalyzes the conjugate transfer hydrogenation as well as the 1,4-hydroboration of α,β-unsaturated esters. The initial step for both processes involves a 1,4-hydrophosphination of the α,β-unsaturated esters to afford a phosphinyl enol ether. Subsequent cleavage of the P-O bond in the phosphinyl enol ether by ammonia-borane (AB) generates an enol intermediate which tautomerizes to saturated esters, while the P-O bond cleavage by HBpin via a formal σ-bond metathesis affords boryl enolate intermediate. The latter could undergo a further coupling reaction with nitriles to form substituted amino diesters or 1,3-imino esters, depending on α,β-unsaturated ester substrates. These catalytic reactions can also be performed in a one-pot manner, illustrating a protocol for metal-free catalytic C-C bond construction.
- Chong, Che Chang,Rao, Bin,Kinjo, Rei
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p. 5814 - 5819
(2017/09/15)
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- Formation of a New, Strongly Basic Nitrogen Anion by Metal Oxide Modification
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Development of new hybrid materials having unique and unprecedented catalytic properties is a challenge for chemists, and heterogeneous-homogeneous hybrid catalysts have attracted much attention because of the preferable and exceptional properties that are highly expected to result from combination of the components. Base catalysts are widely used in organic synthesis as key materials, and a new class of base catalysts has made a large impact from academic and industrial viewpoints. Here, a principle for creating a new strong base by hybridization of homogeneous and heterogeneous components is presented. It is based on the modification of organic compounds with metal oxides by using the acid-base property of metal oxides. Based on kinetic and DFT studies, combination of CeO2 and 2-cyanopyridine drastically enhanced the basicity of 2-cyanopyridine by a factor of about 109 (~9 by pKa (in CH3CN)), and the pKa was estimated to be ~21, which locates it in the superbase category. 2-Cyanopyridine and CeO2 formed a unique adsorption complex via two interaction modes: (i) coordinative interaction between the Ce atom of CeO2 and the N atom of the pyridine ring in 2-cyanopyridine, and (ii) covalent interaction between the surface O atom of CeO2 and the C atom of the CN group in 2-cyanopyridine by addition of the lattice oxygen of CeO2 to the CN group of 2-cyanopyridine. These interactions established a new, strongly basic site of N- over the CeO2 surface.
- Tamura, Masazumi,Kishi, Ryota,Nakayama, Akira,Nakagawa, Yoshinao,Hasegawa, Jun-Ya,Tomishige, Keiichi
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supporting information
p. 11857 - 11867
(2017/09/08)
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- Preparation method of methyl 3-methoxypropionate
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The invention provides a preparation method of methyl 3-methoxypropionate. The preparation method comprises that methanol and methyl acrylate undergo an addition reaction under conditions of a mole ratio of methanol to methyl acrylate of 4-6: 1, a catalyst sodium methoxide use amount 2-3% of the total weight of methanol and methyl acrylate, a polymerization inhibitor use amount 0.2-0.3% of the total weight of methanol and methyl acrylate, an addition reaction temperature of 30-40 DEG C and methyl acrylate dropwise addition time of 1-3h, and after dropwise addition, thermal reaction time of 2-3h, the reaction solution is neutralized and then is subjected to normal pressure distillation so that unreacted methanol is distilled, and the residual reaction solution is subjected to reduced pressure distillation under pressure of -0.09MPa to -0.098MPa so that a methyl 3-methoxypropionate product is obtained. Under the above reaction conditions, methyl acrylate does not undergo a polymerization reaction so that reaction time is shortened. In the reaction, methyl acrylate is completely removed so that a reaction yield is improved, a product refining process is simple and a high purity product is obtained through simple distillation.
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Paragraph 0011-0016
(2017/04/11)
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- Free-solvent Michael addition of glycerol to acrylic compounds
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In this paper, we report the study of the free-solvent nucleophilic addition of alcohols and glycerol to acrylic compounds, in the presence of catalytic bases. With acrylates, Michael addition and transesterification are in competition: only the PTC reaction with t-butyl acrylate gave trifunctionalized glycerol. With acrylonitrile, the cyanoethylation of glycerol varies with catalysts, temperature, time of reactions and amounts of acrylonitrile. Mono functionalisation of glycerol can be obtained in 28% yield. The optimization of the free-solvent Michael addition of glycerol to acrylonitrile (3.4 equiv., 4 mol% NaOH, 5 h) leads to TCEG (tricyanoethylglycerol, 88% yield, 99% purity) without HCl neutralisation, chlorinated solvents or purification (chromatography or distillation). TCEG can be used as a prochiral core of G0.5 dendrimers.
- Nadeau, Frédéric,Sindt, Michèle,Oget, Nicolas
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p. 9155 - 9161
(2015/12/01)
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- Acid-catalyzed oxidation of levulinate derivatives to succinates under mild conditions
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Levulinate derivatives are an attractive platform for the production of renewable chemicals. Here we report on the oxidation of methyl levulinate into dimethyl succinate with peroxides under mild conditions using Br?nsted and Lewis acid catalysts. Selectivities to succinate and acetate derivatives of approximately 60 and 40 %, respectively, were obtained with strong Br?nsted acids in methanol. Although the molecular structure (i.e., carbon-chain length and branching around the C=O group) and the oxidant type affect the product distribution, solvent choice has the strongest impact on changing the location of oxygen insertion into the carbon backbone. Specifically, switching the solvent from methanol to heptane resulted in a decrease in the succinate/acetate ratio from 1.6 to 0.3. In contrast to Br?nsted acids, we demonstrate that the nature of the metal cation is responsible for changing the reaction selectivity of water-tolerant Lewis acidic triflate salts.
- Wang, Yuran,Vogelgsang, Ferdinand,Román-Leshkov, Yuriy
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p. 916 - 920
(2015/03/18)
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- Azide/oxygen photocatalysis with homogeneous and heterogeneous photocatalysts for 1,2-aminohydroxylation of acyclic/cyclic alkenes and Michael acceptors
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Homogeneous as well as heterogeneous photocatalysts that are able to oxidize the azide anion with low competitive singlet oxygen quantum yields are used to generate azidyl radicals. These radicals add to electron-rich as well as electron-poor (Michael acc
- Griesbeck, Axel G.,Steinwascher, Joerg,Reckenthaeler, Melissa,Uhlig, Johannes
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- Reaction of methyl acrylate with N,N-dimethylethanolamine in the presence of a titanium alkoxide
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The kinetic features were examined for transesterifi cation of methyl acrylate with N,N-dimethylethanolamine in the presence of tetra(N,N- dimethylaminoethyl) titanate at different molar ratios of the reactants and at temperatures within 50-80 C, as well as for side reactions of Michael addition at 95-125 C. The major parameters governing the selectivity of the synthesis of N,N-dimethylaminoethyl acrylate were determined.
- Demidov,Lavrent'Ev,Potekhin
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p. 1676 - 1680
(2013/04/10)
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- Organocatalytic head-to-tail dimerization of methacrolein via conjugate addition of methanol: An alcohol activation mechanism proved by electrospray ionization mass spectrometry
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The head-to-tail dimerization of methacrolein via the conjugate addition of methanol is catalyzed by various organic bases, such as an amine, phosphine, and N-heterocyclic carbene, to give 2,4-dimethyl-2-methoxymethylpentane-1,5-dial in moderate yields. Based on the interpretation of the key intermediates by electrospray ionization mass spectrometry, we propose a reaction mechanism involving the initial conjugate addition of the organic bases to methacrolein to generate a zwitterionic base followed by the activation of methanol.
- Matsuoka, Shin-Ichi,Shimakawa, Shintaro,Takagi, Koji,Suzuki, Masato
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supporting information; experimental part
p. 6835 - 6838
(2012/01/03)
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- Solid sodium stannate as a high-efficiency superbase catalyst for anti-Markovnikov hydroamination and hydroalkoxylation of electron-deficient olefins under mild conditions
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A solid superbase with H- above 26.5 has been obtained through thermal treatment of sodium stannate hydrate. It was found to be an efficient catalyst for anti-Markovnikov hydroamination and hydroalkoxylation of electron-deficient olefins under mild conditions.
- Zhang, Shuguo,Wei, Yudan,Yin, Shuangfeng,Au, Chak-Tong
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p. 712 - 716
(2013/01/09)
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- Aerobic oxidative esterification of alcohols catalyzed by polymer-incarcerated gold nanoclusters under ambient conditions
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Environmentally benign aerobic oxidation of alcohols to methyl esters catalyzed by polymer-incarcerated gold nanoclusters (PI-Au) was developed and reactions proceeded under very mild conditions. The catalyst could be recovered by simple operations without significant loss of activity.
- Miyamura, Hiroyuki,Yasukawa, Tomohiro,Kobayashi, Sh
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supporting information; experimental part
p. 776 - 778
(2010/09/05)
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- PROCESS FOR PREPARING 3-ALKOXYPROPAN-1-OLS
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The present invention relates to a process for preparing 3-alkoxypropan-1-ols of the general formula I by catalytic hydrogenation of esters of the general formula II, where the radicals R1 and R2 and R3, R4 and R5 are each, independently of one another, a straight-chain or branched C1-C20-alkyl radical which may optionally be substituted by one or more C1-C20-alkoxy radicals or interrupted by one or more oxygen atoms in the chain, C6-C20-aryl, C7-C20-arylalkyl which may optionally be substituted by one or more C1-C20-alkoxy radicals or interrupted by one or more oxygen atoms in the alkyl chain, C7-C20-alkylaryl which may optionally be substituted by one or more C1-C20-alkoxy radicals or interrupted by one or more oxygen atoms in the alkyl chain, a C1-C20-cycloalkyl radical which may optionally be substituted by one or more C1-C20-alkoxy radicals and R2, R3 and R4 can, independently of one another, also be hydrogen, over chromium- and nickel-free catalysts.
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Page/Page column 4-5
(2010/04/23)
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- PROCESS FOR PRODUCING -ALKOXYPROPIONAMIDE
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A method for producing a β-alkoxypropionamide shown by the following formula (I) including the step of reacting a β-alkoxypropionic acid ester with an amine in the presence of a basic catalyst or in the presence of a basic catalyst and a polyol: wherein R1 is an alkyl group having 1 to 8 carbon atoms, and R2 and R3 are independently hydrogen, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methoxymethyl group or a glycidyl group.
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Page/Page column 6
(2009/12/07)
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- Novel amine-catalysed hydroalkoxylation reactions of activated alkenes and alkynes
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Substoichiometric loadings of DBU catalyse the efficient 1,4-addition of alcohols and non-nucleophilic amines such as pyrrole to activated alkenes; the application of this methodology in a one-pot synthesis of a natural product, and as a novel strategy for the synthesis of mono-protected 1,3-carbonyl compounds is reported.
- Murtagh, Julie E.,McCooey, Seamus H.,Connon, Stephen J.
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p. 227 - 229
(2007/10/03)
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- Transesterification of alkoxyesters
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Method for the highly selective transesterification of alkyl 3-alkoxypropionates, as well as several novel alkoxypropionate compounds, are provided. Transesterification catalyzed by titanium alkoxides or tin compounds does not catalyze the Michael reaction, and therefore, provide highly selective transesterification reactions of these reactive materials.
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- Process for making an acrylamide containing a dialkyl acetal group
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A process is provided for making an N-substituted acrylamide dialkyl acetal, such as acrylamidobutyraldehyde dimethylacetal (ABDA), by blocking the double bond in an acrylic acid ester with a nucleophile, such as methanol, removing excess nucleophile from the blocked ester, aminating the blocked ester with an amino dialkyl acetal in the presence of an aminolysis catalyst but in the absence of any protic solvent, and deblocking the double bond in the product by pyrolysis.
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- KINETIC RELATIONSHIPS GOVERNING ADDITION OF METHANOL TO METHYL ACRYLATE
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The kinetic relationships governing the addition of methanol to methyl acrylate and the reverse reaction, i.e., the elimination of methanol from methyl β-methoxypropionate catalyzed by sulfuric and p-toluenesulfonic acids, were investigated.The rate of the forward reaction depends on the concentrations of methyl acrylate, methanol, and the catalyst, and the rate of the reverse reaction depends on the concentration of methyl β-methoxypropionate and of the catalyst.A kinetic expression which describes the process well was obtained.
- Chubarov, G. A.,Danov, S. M.,Kutnyaya, M. Yu.
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p. 1028 - 1030
(2007/10/02)
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- Chemical process involving ethers and amines
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A process for the production of (1) an ether or (2) a second amine comprises reacting an activated olefin with respectively an alcohol or first amine in the presence of a catalyst which is either (a) an amidine or (b) a Lewis base and epoxide. The same catalyst may also be used to carry out the reverse reaction in which an activated olefin and an alcohol or first amine are produced from the appropriate ether or second amine.
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- aIRON CATALYSIS OF GRIGNARD REDUCTIONS. MECHANISM OF 1,3-REDUCTIVE ELIMINATIONS FROM γ-PROPYL HALIDES
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The iron-catalyzed reduction of various 3-substituted propyl bromides by Grignard reagents affords propylene and cyclopropane.The reduction to propylene is particularly noteworthy since it formally represents a 1,2-hydrogen shift.Two key intermediates have been identified in propylene formation, in which 3-methoxypropyl bromide is first catalytically reduced to the magnesium derivative by Grignard reagent.The iron-catalyzed β-elimination of the 3-methoxypropylmagnesium intemediate affords allyl methyl ether, which is then reductively cleaved to propylene.Extensive studies of deuterium labeling in the reactants, as well as in both intermediates, allow the course of the hydrogen shift to be followed unequivocally.The mechanism of iron catalysis is proposed in Schemes 2 and 3, representing the first and second stages of the reduction to propylene.
- Rollick, K. L.,Nugent, W. A.,Kochi, J. K.
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p. 279 - 300
(2007/10/02)
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- KETTENVERLAENGERUNG DURCH CARBONYLINSERTION BEI DER REAKTION VON (TETRACARBONYL)-(OLEFIN)EISEN(O)-KOMPLEXEN MIT OXIDATIONSMITTELN
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On oxidation of (tetracarbonyl)(olefin)iron(O)-complexes in alcoholic solvents esters carrying a substituent in the 3-position are formed by a carbonylinsertion reaction.
- Schmidt, E. K. G.,Wiese, W.
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p. 4425 - 4428
(2007/10/02)
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- The preparation and oxidation of disulfides as a route to sulfone-sulfides
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Mercaptide/alkoxide competition in substitution and addition reactions is discussed as it applies to the preparation of disulfides.Oxidation of an asymmetric disulfide with H2O2 is shown to exhibit high regioselectivity which may be rationalized in the same terms employed for other sulfide oxidations, viz. substituent electron withdrawing ability (Xp) and steric effects.
- Ahern, Terence Patrick,Fong, Harvey Owen,Langler, Richard Francis,Mason, Peter Michael
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p. 878 - 883
(2007/10/02)
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- Preparation of β-alkoxy esters from olefins
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This invention discloses an improved process for the manufacture of α,β-unsaturated carboxylic acid esters from a β-alkoxycarboxylic acid ester prepared by contacting an olefin having 2 to about 15 carbon atoms with an alcohol and carbon monoxide, where this alkoxycarbonylation reaction is performed with mutually independent improvements which include (A) reacting the compounds in the presence of a catalyst having as the major catalytic agent a salt of a platinum group metal and as a co-catalyst a salt of a metal selected from the group consisting of mercury (II) and tin (II), with a reoxidizing agent which is a salt of a multivalent metal having an oxidation potential more positive than the platinum group metal salt, (B) performing the reaction in an improved solvent system comprising the monohydric alcohol, the β-alkoxycarboxylic acid ester and a solvent having a boiling point higher than that of the β-alkoxycarboxylic acid ester, (C) reoxidizing the catalyst prior to isolation of the β-alkoxycarboxylic acid ester from the reaction medium, and (D) cracking the β-alkoxycarboxylic acid ester to the corresponding α,β-unsaturated carboxylic acid ester.
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- Method for the oxycarbonylation of ethylene and propylene
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A process for the catalytic oxycarbonylation of ethylene and propylene by reaction with carbon monoxide and oxygen in a methanolic or ethanolic reaction medium employing a catalyst which contains a compound of vanadium, chromium, iron, cobalt, nickel or copper and chloride, bromide, or iodide ions.
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