cas 820-71-3, Methallyl acetate | Articles data

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Method for preparing 2-methyl-1, 3-propylene glycol from isobutene
The invention discloses a method for preparing 2-methyl-1, 3-propylene glycol from isobutene. The method comprises the following steps: mixing isobutene with acetic acid and oxygen, and carrying out an oxyacetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylene propane-1, 3-diacetoxy, namely a compound (C); carrying out transesterification on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D); and carrying out hydrogenation reaction on the compound (D) to obtain the 2-methyl-1,3-propylene glycol. According to the method, the 2-methyl-1, 3-propylene glycol can be generated with high selectivity, and the whole process is high in atom utilization rate, environmentally friendly and suitable for large-scale industrial application.
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Paragraph 0054-0056; 0058; 0064-0065; 0067-0068; 0070-0071;

(2021/02/10)

METHOD FOR PRODUCING 1-ACYLOXY-2-METHYL-2-PROPENE
A method for producing a 1-acyloxy-2-methyl-2-propene represented by the following general formula (II), including reacting a carboxylic acid represented by the following general formula (I), isobutylene, and oxygen, in the presence of a catalyst, in a liquid phase, with an amount of the isobutylene used of more than 1 mol and 50 mol or less per 1 mol of the carboxylic acid.
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Paragraph 0101-0104; 0107-0112

(2021/09/26)

Method for preparing methallyl alcohol by using in-situ generated Cu (I) catalyst
The invention relates to a method for preparing methallyl alcohol by using an in-situ generated Cu (I) catalyst, which comprises the following steps: (1) dissolving a bivalent copper salt in water, adding a reducing organic matter, stirring, and dropwisely adding an obtained mixture into a methallyl alcohol preparation system; or (2) in themethallyl alcohol preparation system, adding thebivalent copper salt, then dropwise adding a reduced organic matter aqueous solution, and carrying out a catalytic reaction; or (3) in themethylallyl alcohol preparation system, adding a reduced organic matteraqueous solution, then dropwise adding a bivalent copper salt aqueous solution, and carrying out a catalytic reaction; or (4) mixing asolid bivalent copper salt with asolid reduced organic matter in proportion, adding an obtained mixture into themethallyl alcohol preparation system in batches, and carrying out catalytic reaction. The reaction system has the characteristics of high activity and high selectivity, can significantly improvethe conversion rate and selectivity of methylallyl alcohol, reducethe generation of by-product methylallyl ether, significantly reduces the synthesis cost by replacing monovalent copper with bivalent copper, and improve the market competitiveness.
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Paragraph 0026-0029

(2020/06/16)

Sequential Palladium-Catalyzed Allylic Alkylation/retro-Dieckmann Fragmentation Strategy for the Synthesis of α-Substituted Acrylonitriles
A straightforward synthesis of α-substituted acrylonitriles is described using 4-cyano-3-oxotetrahydro-thiophene (c-THT) as an acrylonitrile surrogate. This unprecedented two-step sequence featuring a palladium-catalyzed allylic alkylation (Pd-AA) and a retro-Dieckmann fragmentation provides a general entry into diversely substituted 1,4-dienes.
Katsina, Tania,Sharma, Sachi Prem,Buccafusca, Roberto,Quinn, Derek J.,Moody, Thomas S.,Arseniyadis, Stellios
supporting information
p. 9348 - 9352
(2019/11/20)

Palladium-Catalyzed Asymmetric Allylic Alkylation of 4-Substituted Isoxazolidin-5-ones: Straightforward Access to β2,2-Amino Acids
We report here an unprecedented and highly enantioselective palladium-catalyzed allylic alkylation applied to 4-substituted isoxazolidin-5-ones. Ultimately, the process provides a straightforward access to β2,2-amino acids bearing an all-carbon quaternary stereogenic center in great yields and a high degree of enantioselectivity.
Nascimento de Oliveira, Marllon,Arseniyadis, Stellios,Cossy, Janine
supporting information
p. 4810 - 4814
(2018/03/21)

Highly Enantioselective, Base-Free Synthesis of α-Quaternary Succinimides through Catalytic Asymmetric Allylic Alkylation
The synthesis of diversely substituted five-membered ring succinimide derivatives is reported featuring a direct, base-free, palladium-catalyzed asymmetric allylic alkylation. The method allows a straightforward access to the desired heterocyclic scaffold bearing an all-carbon α-quaternary stereogenic center in high yields and good to excellent enantioselectivities. To further demonstrate the synthetic utility of the method, the allylated products were further converted to various versatile chiral building blocks, including a chiral pyrrolidine and a spirocyclic derivative, using selective transformations.
Song, Tao,Arseniyadis, Stellios,Cossy, Janine
supporting information
p. 8076 - 8080
(2018/06/15)

Scalable Microwave-Assisted Johnson-Claisen Rearrangement with a Continuous Flow Microwave System
We demonstrated the rapid Johnson-Claisen rearrangement of allyl alcohol and triethyl orthoacetate with a continuous flow apparatus combined with a microwave reactor. The reaction could be carried out without solvent, and only a catalytic amount of acetic acid was sufficient to promote the reaction under microwave irradiation conditions. To confirm the optimal reaction conditions found experimentally, we performed Design of Experiments (DoE) by the Nelder-Mead method and a least-squares method regarding the amount of acetic acid and the flow rate. Consequently, the highest yield of the desired γ,δ-unsaturated ester was obtained, and the productivity at the reaction step of the continuous process was 89.5 g/h under the optimal conditions, suggesting that 2.1 kg of the product would be theoretically obtained in 1 day. We also investigated the Johnson-Claisen rearrangement using other allylic alcohols, and the corresponding products were obtained in good to high yields per unit of time.
Egami, Hiromichi,Tamaoki, Souma,Abe, Masato,Ohneda, Noriyuki,Yoshimura, Takeo,Okamoto, Tadashi,Odajima, Hiromichi,Mase, Nobuyuki,Takeda, Kazuhiro,Hamashima, Yoshitaka
supporting information
p. 1029 - 1033
(2018/08/03)

Method for preparing methallyl alcohol and amide simultaneously
A method for preparing methallyl alcohol and amide simultaneously is characterized in that methylallyl carboxylate taken as a raw material and an amine compound taken as an ammonolysis agent react under the action of a catalyst to produce methallyl alcohol and an amide compound. The methylallyl carboxylate and the amine compound taken as the ammonolysis agent are firstly adopted, and the methallyl alcohol and the amide compound are obtained under the action of the catalyst. The reaction process is a bulk reaction, no solvents are added, almost no wastewater or salt are produced, and byproduct methyl allyl ether is not produced; the defect that a large number of wastewater is produced through hydrolysis is overcome due to adoption of ammonolysis, the methallyl alcohol and the amide compound are coproduced directly by use of ammonoysis, coupling production is realized, and the cost is reduced.
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Paragraph 0022-0023

(2017/11/29)

Radical Cyclization of Epoxy Vinyl- and Allylsulfones Promoted by Titanocene Chloride
A titanocene-mediated intramolecular radical addition of different epoxy vinyl- and allylsulfones has been achieved. Five- and six-membered ring products were obtained in good to excellent yields in the presence of both 2.2 and 0.2 equiv of Cp2TiCl. A novel double-activation strategy allowed us to achieve small-size rings such as cyclobutanes and cyclopropanes. (Chemical Equation Presented).
Fernández-Mateos,Madrazo, S. Encinas,Teijón, P. Herrero,González, R. Rubio
p. 4378 - 4391
(2015/05/13)

Hydroxyl-directed stereoselective diboration of alkenes
An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.
Blaisdell, Thomas P.,Caya, Thomas C.,Zhang, Liang,Sanz-Marco, Amparo,Morken, James P.
supporting information
p. 9264 - 9267
(2014/07/21)

Ni- and pd-catalyzed synthesis of substituted and functionalized allylic boronates
Two highly efficient and convenient methods for the synthesis of functionalized and substituted allylic boronates are described. In one procedure, readily available allylic acetates are converted to allylic boronates catalyzed by Ni/PCy3 or Ni/PPh3 complexes with high levels of stereoselectivity and in good yields. Alternatively, the borylation can be accomplished with commercially available Pd catalysts [e.g., Pd 2(dba)3, PdCl2, Pd/C], starting with easily accessed allylic halides.
Zhang, Ping,Roundtree, Ian A.,Morken, James P.
supporting information; scheme or table
p. 1416 - 1419
(2012/06/01)

Cobalt-catalyzed reductive allylation of alkyl halides with allylic acetates or carbonates
An efficient method for the direct allylation of alkyl halides catalyzed by simple cobalt(II) bromide has been developed. This reaction, using a variety of substituted allylic acetates or carbonates, provides the linear product as the major product. It displays broad substrate scope and good functional group tolerance. Copyright
Qian, Xin,Auffrant, Audrey,Felouat, Abdellah,Gosmini, Corinne
supporting information; experimental part
p. 10402 - 10405
(2011/12/03)

Ruthenium(III) chloride catalyzed acylation of alcohols, phenols, and thiols in room temperature Ionic liquids
Ruthenium(III) chloride-catalyzed acylation of a variety of alcohols, phenols, and thiols was achieved in high yields under mild conditions (room temperature) in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]). The ionic liquid and ruthenium catalyst can be recycled at least 10 times. Our system not only solves the basic problem of ruthenium catalyst reuse, but also avoids the use of volatile acetonitrile as solvent.
Xi, Zhiwen,Hao, Wenyan,Wang, Pingping,Cai, Mingzhong
experimental part
p. 3528 - 3537
(2009/12/24)

Highly regioselective lipase-catalyzed acetylation and hydrolysis of acyclic α,ω-terpenediols and their diacetates
Highly regioselective transformations of the acyclic α,ω-terpenediols and their diacetates to the monoacetates using lipase were accomplished. The acetylation of the α,ω-terpenediols gave regioselectively the ω-monoacetates 3, whereas the α-monoacetates 2 were obtained by hydrolysis of the α,ω-diacetates.
Takabe, Kunihiko,Mase, Nobuyuki,Hisano, Takaya,Yoda, Hidemi
p. 3267 - 3269
(2007/10/03)

Selective, catalytic carbon-carbon bond activation and functionalization promoted by late transition metal catalysts
The selective catalytic activation and functionalization of carbon-carbon bonds in a series of substituted cyclopropane substrates has been developed using commercially available transition metal catalysts. Catalytic hydrogenation and olefination procedures, tolerant of a range of functional groups, have been discovered. Introduction of a chelate-assisting substituent such as [PPh2] is effective in altering the kinetic selectivity and lowering the activation barrier for the catalytic processes. Copyright
Bart, Suzanne C.,Chirik, Paul J.
p. 886 - 887
(2007/10/03)

Intermediates useful for the preparation of antihistaminic piperidine derivatives
The present invention is related to a novel intermediates and processes which are useful in the preparation of certain antihistaminic piperidine derivatives of the formula whereinW represents —C(=O)— or —CH(OH)—;R1 represents hydrogen or hydroxy;R2 represents hydrogen;R1 and R2 taken together form a second bond between the carbon atoms bearing R1 and R2;n is an integer of from 1 to 5;m is an integer 0 or 1;R3 is —COOH or —COOalkyl wherein the alkyl moiety has from 1 to 6 carbon atoms and is straight or branched each of A is hydrogen or hydroxy; and pharmaceutically acceptable salts and individual optical isomers thereof,with the proviso that where R1 and R2 are taken together to form a second bond between the carbon atoms bearing R1 and R2 or where R1 represented hydroxy, m is an integer 0.
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Page column 87

(2010/01/30)

Intermediates useful for the preparation of antihistaminic piperidine derivatives
The present invention is related to a novel intermediates and processes which are useful in the preparation of certain antihistaminic piperidine derivatives of the formula whereinW represents —C(=O)— or —CH(OH)—;R1 represents hydrogen or hydroxy;R2 represents hydrogen;R1 and R2 taken together form a second bond between the carbon atoms bearing R1 and R2;n is an integer of from 1 to 5;m is an integer 0 or 1;R3 is —COOH or —COOalkyl wherein the alkyl moiety has from 1 to 6 carbon atoms and is straight or branched each of A is hydrogen or hydroxy; andpharmaceutically acceptable salts and individual optical isomers thereof, with the proviso that where R1 and R2 are taken together to form a second bond between the carbon atoms bearing R1 and R2 or where R1 represented hydroxy, m is an integer 0.
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Page column 87

(2008/06/13)

An amino alcohol ligand for highly enantioselective addition of organozinc reagents to aldehydes: Serendipity rules
(matrix presented) Amino alcohol 4 (or its enantiomer) is prepared in two simple steps. Commercial (1R,2S)-2-amino-1,2-diphenylethanol is dialkylated with bis(2-bromoethyl) ether. Subsequent hydrogenation over 5% Rh on alumina in the presence of morpholine unexpectedly stops at the hexahydro derivative 4. Amino alcohol 4 promotes the enantioselective addition of diethylzinc to aldehydes at room temperature in up to 99% enantiomeric excess.
Nugent, William A.
p. 2133 - 2136
(2007/10/03)

Synthetic and kinetic aspects of nickel-catalysed amination of allylic alcohol derivatives
The design of efficient nickel-based catalytic systems for coupling of diethylamine (1) with esters and ether derivatives of allyl alcohol (2a-c) and related allyl-substituted compounds (4a-e) is reported. Special attention is paid to solvent and salt effects on catalytic activities and kinetic profiles for the formation of allyllamines. The results are discussed in terms of the influence of some reaction parameters (polarity, ion exchange processes, substrate) on the rate determining step of the catalytic cycle.
Bricout, Herve,Carpentier, Jean-Francois,Mortreux, Andre
p. 1073 - 1084
(2007/10/03)

Palladium-catalyzed allylation of α-hydroxy acids
Mandelic and lactic acids are converted to the 1,3-dioxolan-4-ones by treatment with acetone dimethyl acetal.Deprotonation followed by treatment with an allyl acetate and a catalytic amount (1 mol percent) of palladium catalyst afforded the allylated dioxolanones, which could be hydrolyzed to the corresponding α-allyl α-hydroxy acids.The lithium enolate of the dioxolanone of mandelic acid was also coupled with methallyl, cinnamyl, geranyl and (E)-1-methyl-2-butenyl acetates.The zinc enolate of the dioxolanone of lactic acid reacted smoothly with allyl acetate in a catalyzed reaction whereas no detectable reaction was observed when the lithium enolate was used.This appears to be the result of complications arising from the enhanced basicity of the lithium compared to zinc enolate.Various attempts were made to achieve enantioselectivity using chiral ligands on the palladium catalyst.The zinc enolates were found to provide better results although the enantioselectivity was only modest, about 30percent enantiomeric excess being the best result obtained.Chiraphos proved to be the best optically active ligand of a variety tested.
Moorlag, Henk,Vries, Johannes G. de,Kaptein, Bernard,Schoemaker, Hans E.,Kamphuis, Johan,Kellogg, Richard M.
p. 129 - 137
(2007/10/02)

THE NITROGENATED ALLYLIC SYSTEM AS AN INTRAMOLECULAR NUCLEOPHILE: A NEW ROUTE TO PYRAZOLES
A new route to pyrazoles via the cyclization of N-allyl-N-nitrosoamides is described.
Momose, Takefumi,Toyooka, Naoki,Ikuta, Takashi,Yanagino, Hironobu
p. 789 - 793
(2007/10/02)

REACTION OF CYCLOPROPENE COMPOUNDS WITH BENZENESULFENYL CHLORIDES AND HYDROGEN CHLORIDE
The reactions of 3,3-dimethylcyclopropene and 1-methylcyclopropene with 2,4-dinitrobenzene- and benzenesulfenyl chlorides and hydrogen chloride in acetic acid were investigated.It was shown that the reaction with benzenesulfenyl chlorides leads mainly to cyclic adducts, which are formed as a result of anti-addition of the reagent.Under the conditions of doping addition the predominant reaction path is the formation of the acyclic products.The addition of hydrogen chloride to the investigated hydrocarbons takes place entirely with ring opening.
Kartashov, V. R.,Skorobogatova, E. V.,Akimkina, N. F.,Zefirov, N. S.
p. 32 - 35
(2007/10/02)