- Effect of some parameters on the synthesis and the physico-chemical properties of new amphiphilic starch-g-copolymers
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The detailed studies on the graft copolymerization of phenyl methacrylate onto gelatinized potato starch in water using potassium persulfate as radical initiator were presented. The different reaction parameters such as effect of initiator concentration, starch to monomer ratio, reaction temperature and reaction time were studied in terms of grafting efficiency, grafting percent and percent homopolymer formation. It was found that grafting process of aromatic methacrylate monomer onto potato starch backbone allowed obtaining new amphiphilic copolymers with different physicochemical properties as compared to non-modified starch. The influence of the copolymer structure on the swelling behavior in polar and non-polar solvents, moisture absorbance, gelatinization properties, acid and base resistance, surface morphology and thermal properties was discussed.
- Worzakowska, Marta,Grochowicz, Marta
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Read Online
- Activation of stable polymeric esters by using organo-activated acyl transfer reactions
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In this study, we succeeded in the in situ activation of nonactivated ester moieties embedded in polymer structures. Although poly(pentafluorophenyl methacrylate) (PPFPMA) can react with 2-ethylhexylamine at 50 C in the presence of proton scavenger such as NEt3, such conditions were not suitable for poly(phenyl methacrylate) (PPhMA). Nevertheless, the combination of organo-activating agents, namely 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,2,4-triazole (TZ) led to a facile conversion from ester to amide for PPhMA. The reaction between PPhMA and 2-ethylhexylamine was conducted at 120 C in the presence of one equivalent of TZ and three equivalents of DBU and yielded >99% ester conversion to afford corresponding polymethacrylamide derivatives as confirmed by FT-IR and 1H NMR measurements. In addition, poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) and poly(methyl methacrylate) (PMMA) were also allowed to react with amines in the presence of the organo-activating agents with dramatically increased conversions (>70%).
- Kakuchi, Ryohei,Wongsanoh, Kwanjira,Hoven, Voravee P.,Theato, Patrick
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Read Online
- Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone
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Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield.
- Koyama, Minoru,Kawakami, Takafumi,Okazoe, Takashi,Nozaki, Kyoko
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p. 10913 - 10917
(2019/08/02)
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- PREPARATION OF PHENOLIC (METH)ACRYLATES
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A method for preparation of phenolic (meth)acrylates. The method comprises contacting acetic anyhydride, a phenolic compound and (meth)acrylic acid to form a reaction mixture.
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Page/Page column 3; 4
(2018/06/12)
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- CARBOXYLIC ACID ESTER PRODUCTION METHOD
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Provided is a production method whereby corresponding carboxylic acid esters can be obtained from a variety of carboxylic acids at a high yield, even under conditions using a simple reaction operation and little catalyst and even if the amount of substrate used is theoretical. A production method for carboxylic acid ester, whereby a prescribed diester dicarbonate, carboxylic acid, and alcohol are reacted in the presence of at least one type of magnesium compound and at least one type of alkali metal compound.
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Paragraph 0062; 0063; 0067; 0068; 0069; 0070; 0075; 0076
(2019/01/04)
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- METHOD FOR PRODUCING (METH) ACRYLATE
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PROBLEM TO BE SOLVED: To provide a production method for obtaining (meth) acrylate in high yields, by preventing a large amount of waste from produced from by-products, like the conventional art. SOLUTION: A method for producing (meth) acrylate includes the reaction between a compound represented by the following formula (I) and an aryl alcohol. Preferably, the reaction occurs in the presence of a catalyst of at least one metal compound selected from first Group metal compounds and second Group metal compounds. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0019-0024
(2018/12/05)
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- METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE AND METHOD FOR PRODUCING CARBOXYLIC ACID ESTER
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Provided is a production method whereby corresponding carboxylic acid anhydrides and carboxylic acid esters can be obtained at high yield from various carboxylic acids even without a solvent and near room temperature. A method for producing a carboxylic acid anhydride represented by formula (II), the method comprising reacting a compound represented by formula (I) and a carboxylic acid in the presence of a Group II metal compound having an ionic ligand containing an oxygen atom. A method for producing a carboxylic acid ester, the method comprising reacting a carboxylic acid anhydride produced by the aforementioned method and an alcohol. In formula (I), R1 represents a C1-20 hydrocarbon group. In formula (II), R2 represents a C1-20 hydrocarbon group.
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Paragraph 0082; 0083; 0085
(2017/04/18)
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- METHOD FOR PRODUCING CARBOXYLIC ESTER
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PROBLEM TO BE SOLVED: To provide a method that can efficiently produce carboxylic ester even with a small amount of use of catalysts at room temperature and normal pressure (25°C, 1 atm). SOLUTION: This invention relates to a method for producing carboxylic ester by the reaction between a compound represented by the following formula (I), carboxylic acid anhydride and alcohol, the reaction to occur in the presence of at least one Group I metal compound and at least one Group II metal compound [in formula (I), R1 and R2 are a C1-C20 hydrocarbon group]. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0059; 0060
(2018/04/18)
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- PHENYL (METH)ACRYLATE PRODUCTION METHOD AND PHENYL (METH)ACRYLATE COMPOSITION
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Provided is a method that can produce phenyl(meth)acrylate inexpensively and at high yields. The phenyl(meth)acrylate production method of the present invention reacts (meth)acrylic acid with carbonic acid diphenyl. Further, the phenyl(meth)acyrlate composition of the present invention contains 90-99.999 wt % phenyl(meth)acrylate and 0.001-10% carbonic acid diphenyl. Or, the phenyl(meth)acrylate composition of the present invention contains 90-99.999 wt % phenyl(meth)acrylate and 0.001-10 wt % of a specified compound.
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Paragraph 0114-0115
(2016/09/26)
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- PHENYL(META)ACRYLATE PRODUCTION METHOD AND PHENYL(META)ACRYLATE COMPOSITION
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Provided is a method that can produce phenyl(meth)acrylate inexpensively and at high yields. The phenyl(meth)acrylate production method of the present invention reacts (meth)acrylic acid with carbonic acid diphenyl. Further, the phenyl(meth)acyrlate composition of the present invention contains 90-99.999wt% phenyl(meth)acrylate and 0.001-10% carbonic acid diphenyl. Or, the phenyl(meth)acrylate composition of the present invention contains 90-99.999wt% phenyl(meth)acrylate and 0.001-10wt% of a specified compound.
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Paragraph 0128-0132
(2016/11/02)
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- Synthesis of Oxindoles by Bronsted Acid Catalyzed Radical Cascade Addition of Ketones
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Oxindoles bearing ketone side chains in the 3-position can be synthesized by Bronsted acid catalysis from N-aryl methacrylamides, ketones, and hydroperoxides. The cyclized products are presumably formed in a radical cascade reaction, initiated by decay of intermediate alkenyl peroxides. In the case of acrylic substrates that do not undergo cyclization, γ-peroxyketones were isolated instead, indicating that the final cyclization step of the cascade does not take place in these cases.
- Boess, Esther,Karanestora, Sofia,Bosnidou, Alexandra-Eleni,Schweitzer-Chaput, Bertrand,Hasenbeck, Max,Klussmann, Martin
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supporting information
p. 1973 - 1976
(2015/09/01)
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- Films based on new methacrylate monomers: Synthesis, characterisation and electro-optical properties
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A number of liquid crystal monomers based on methacrylate derivatives were synthesised by novel mild and solventless procedures under microwave irradiation. Their photo- and thermo assisted homo- and co-polymerizations with glycidyl methacrylate were investigated. The resulting polymers were characterised by NMR, GPC, DSC, and SEM to determine their structures and properties. The effects of the structures of the monomers on the electro-optical properties were correlated. Copyright Taylor & Francis Group, LLC.
- Mouquinho, Ana,Saavedra, Mara,Maiau, Alexandre,Petrova, Krasimira,Barros, M. Teresa,Figueirinhas,Sotomayor, Joao
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scheme or table
p. 132 - 140
(2012/01/06)
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- Fast synthesis employing a microwave assisted neat protocol of new monomers potentially useful for the preparation of PDLC films
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It has been repor ted that the length of the molecular chain and the rigidity of molecules influence the structure of the polymer network in PDLC films and hence the electro-optical proper ties of the composites. Herein, a series of new aromatic monomeric monomethacrylates, bismethacrylates and monovinylbenzene derivatives with a mesogenic core were successfully synthesized under microwave irradiation. The microwave assisted synthesis resulted in decreased reaction times, reduced solvent requirement, increased operational simplicity, and in most cases, improved yields and selectivity. Versita Sp. z o.o.
- Barros, M. Teresa,Mouquinho, Ana I.,Petrova, Krasimira T.,Saavedra, Mara D.,Sotomayor, Joao C.
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experimental part
p. 557 - 566
(2012/04/10)
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- METHOD FOR PRODUCING (METH)ACRYLIC ACID ANHYDRIDE, METHOD FOR STORING (METH)ACRYLIC ACID ANHYDRIDE, AND METHOD FOR PRODUCING (METH)ACRYLATE ESTER
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It is an object of the present invention to provide a method for producing (meth)acrylic anhydride that provides high yield and high efficiency and can suppress side reactions, in a method for reacting (meth)acrylic acid with a fatty acid anhydride to produce (meth)acrylic anhydride. The method for producing (meth)acrylic anhydride according to the present invention is a method for producing (meth)acrylic anhydride, including reacting a fatty acid anhydride with (meth)acrylic acid to produce (meth)acrylic anhydride, while extracting a fatty acid produced as a by-product, wherein the reaction is performed, while adjustment is performed so that a molar ratio of the (meth)acrylic acid to the (meth)acrylic anhydride in a reaction liquid is 0.3 or more.
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Page/Page column 22
(2011/04/25)
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- METHOD FOR PRODUCING (METH)ACRYLIC ANHYDRIDE, METHOD FOR STORING (METH)ACRYLIC ANHYDRIDE, AND METHOD FOR PRODUCING (METH)ACRYLATE
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It is an object of the present invention to provide a method for producing (meth)acrylic anhydride that provides high yield and high efficiency and can suppress side reactions, in a method for reacting (meth)acrylic acid with a fatty acid anhydride to produce (meth)acrylic anhydride. The method for producing (meth)acrylic anhydride according to the present invention is a method for producing (meth)acrylic anhydride, including reacting a fatty acid anhydride with (meth)acrylic acid to produce (meth)acrylic anhydride, while extracting a fatty acid produced as a by-product, wherein the reaction is performed, while adjustment is performed so that a molar ratio of the (meth)acrylic acid to the (meth)acrylic anhydride in a reaction liquid is 0.3 or more.
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Page/Page column 16
(2011/06/24)
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- METHOD FOR PRODUCING A (METH)ACRYLATE
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Disclosed is a method for producing a (meth)acrylate ester wherein a high purity (meth)acrylate ester is obtained with a high yield, with a reduced loss of (meth)acrylic acid anhydride. In the method, (meth)acrylic acid is recovered with a high yield, and the (meth)acrylate ester is purified easily. Specifically disclosed is a method for producing a (meth)acrylate ester which comprises: (1) a step of producing (meth)acrylic acid anhydride by reacting a specific fatty acid anhydride and (meth)acrylic acid, while removing a by-produced fatty acid; (2) a step of obtaining a (meth)acrylate ester by reacting an alcohol and unpurified (meth)acrylic acid anhydride obtained in step (1) preferably at a temperature not less than 90° C.; and (3) a step of recovering (meth)acrylic acid by distillation preferably at a temperature not less than 90° C. The method may also comprise a step of heating or distilling the reaction liquid obtained in step (2) at a temperature not less than 90° C.
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Page/Page column 11
(2011/12/14)
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- Process for the conversion of aldehydes to esters
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A process for the conversion of aldehydes to esters, specifically acrolein or methacrolein to methyl acrylate or methyl methacrylate, respectively. Essentially in the absence of water, an aldehyde is contacted with an oxidizing agent to form an intermediate and then the intermediate is contacted with a diol or an alcohol to form an ester or diester. Preferably, the oxidizing agent is also a chlorinating agent. Specifically, acrolein or methacrolein is contacted with an oxidizing/chlorinating agent, such as t-butyl hypochlorite, and the chlorinated compound is contacted with an alcohol, such as methanol, to form methyl acrylate or methyl methacrylate, respectively. Generally, the order of addition is for the oxidizing agent to be added to the aldehyde, specifically for t-butyl hypochlorite to be added to acrolein or methacrolein, and for the diol or alcohol to be added to the intermediate, specifically for the methanol to be added to the reaction product of acrolein or methacrolein and t-butyl hypochlorite. The process of the present invention can be carried out in the absence or in the presence of solvent. Generally, better methyl acrylate or methyl methacrylate yields are obtained at lower reaction temperatures.
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Page/Page column 4
(2010/01/31)
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- Pallidium catalysed reactions of allenes, carbon monoxide and nucleophiles
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Hydridopalladium(II) species generated in situ by oxidative addition of Pd(0) to acetic acid or acidic hydroxyl substrates (phenols, oximes) catalyse the termolecular assembly of allenes, CO and amines (primary, secondary) or oxygen nucleophiles to give methacrylamides or methacrylate esters and derivatives thereof in good to excellent yield.
- Grigg, Ronald,Monteith, Michael,Sridharan, Visuvanathar,Terrier, Catherine
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p. 3885 - 3894
(2007/10/03)
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- Bimetallic samarium(III) catalysts via electron transfer initiation: The facile synthesis of well-defined (meth)acrylate triblock copolymers
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A method for generating a bifunctional organolanthanide(III) initiator in situ from a (meth)acrylate monomer and a divalent samarium precursor. (C5Me5)2Sm (1) or (C5Me5)2Sm(THF)2 (2), is described. This process involves one-electron transfer from the Sm(II) species to monomer, forming radical anions which couple to give a bimetallic samarium(III) enolate that acts as a bisinitiator for living polymerization. Well-defined, highly syndiotactic ABA triblock copolymers containing both methacrylate and acrylate segments were prepared in two monomer addition steps with this methodology. Selective side chain deprotection may be carried out on copolymers containing poly(tert-butyl acrylate) or poly(benzyl methacrylate) blocks to give syndiotactic ester-acid copolymers.
- Boffa, Lisa S.,Novak, Bruce M.
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p. 15367 - 15396
(2007/10/03)
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- Diastereoselectivity and Enantioselectivity in the Addition of Chiral Imines of 2-Methylcyclohexanone to Crotonic and Methacrylic Acid Esters
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Additions of the chiral imine (reacting as its secondary enamine tautomer) obtained from (S)-1-phenylethylamine and 2-methylcyclohexanone were performed with the phenyl ester of crotonic and methacrylic acid as well as with their methyl ester.In each example, the stereochemical relationship of the substituents in the major adduct was shown to be the one predicted in a previous theoretical calculation which established that the reactants complex has a chairlike geometry.In all the examples, the diastereoselectivity is superior to 98percent.The enantioselectivity of the reactions is excellent as is usually the case with unsubstituted electrophilic olefins, the example with phenyl methacrylate being particularly remarkable (de and ee >99percent).In each case the favored diastereofacial selectivity is again in accordance with the rule elaborated previously.Relevant facts about the influence of the substituents upon the reactivity, the proportion of regioisomers, the stereoselectivity, and the enantioselectivity of the reaction are given.
- Jabin, Ivan,Revial, Gilbert,Tomas, Alain,Lemoine, Pascale,Pfau, Michel
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p. 1795 - 1812
(2007/10/02)
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- Synthesis of Functionalized Aryloxy 1,3-Butadienes and Their Transformation to Diaryl Ethers via Diels-Alder Cycloaddition Reactions
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The Diels-Alder reaction involving cycloaddition of aryloxy-substituted 1,3-butadienes with appropriate acetylenic electrophiles, followed by aromatization of the newly formed cyclohexadiene ring, has been used for the synthesis of diaryl ethers.The functionalized aryloxy 1,3-butadienes employed in this study were prepared by either of two methods: (1) methylenation of aryl esters via the Tebbe or related reagents, and (2) from 1-(aryloxy)-2-propanone by a sequence of formylation or alkylthio methylenation, and subsequent enolsilylation.A tetrasubstituted butadiene containing two phenoxy groups at the 1 and 3 positions also was prepared by the latter method.The cycloaddition reactions of 2,3-dioxy-substituted dienes occurred in high yield, but, as expected, with no regioselectivity to furnish nearly equal mixtures of regioisomeric cycloadducts.In contrast, application of 1,2,3-trihetero-substituted dienes resulted in regiospecific cycloaddition reactions.Transformation of the cyclohexadiene cycloadducts to an aromatic ring was accomplished by dehydrogenation with DDQ or by elimination during the cycloaddition process of a molecule of an alkyl mercaptan.A chiral acetylenic ketone derived from D- or L-serine underwent condensation, without racemization, with aryloxy dienes to provide diaryl ethers related to the isodityrosine antibiotics.
- Olsen, Richard K.,Feng, Xianqi,Campbell, Magnus,Shao, Rui-lian,Math, Shivanand K.
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p. 6025 - 6031
(2007/10/03)
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- Preparation and Reactivities of (η3-1- and 2-Trimethylsiloxyallyl)Fe(CO2)NO Complexes. Intermediates Functioning as Equivalents of β- and α-Acyl Carbocations and Acyl Carbanions
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(η3-1- and 2-Trimethylsiloxyallyl)Fe(CO)2NO complexes were prepared by the reaction of the corresponding siloxyallylic halides with Bu4N.These complexes reacted with both of carbon nucleophiles and carbon electrophiles preferentially at the less hindered sites of the allylic ligands.In these reactions, (η3-1-trimethylsiloxyallyl)Fe(CO)2NO complexes served as synthetically equivalent synthons for both of β-acyl carbocations and β-acyl carbanions and (η3-2-trimethylsiloxyallyl)Fe(CO)2NO complexes as both of α-acyl carbocations and α-acyl carbanions.The stereochemical courses of the reactions are described.
- Itoh, Keiji,Nakanishi, Saburo,Otsuji, Yoshio
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p. 2965 - 2977
(2007/10/02)
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