- Method for preparing diacid diester compound under catalysis of deep eutectic solvent
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The invention belongs to the technical field of organic synthesis, and discloses a method for preparing a diacid diester compound through catalysis of a deep eutectic solvent, wherein the deep eutectic solvent takes ammonium salt and ferric salt as hydrogen acceptors, takes p-toluenesulfonic acid as a hydrogen donor, takes diacid or anhydride of the diacid and an alcohol compound as raw materials, and adopts a one-pot method to prepare the diacid diester compound; and under the catalysis of the deep eutectic solvent, the esterification reaction is performed to generate the diester product. The selected deep eutectic solvent has characteristics of environmental protection, easy preparation, cheap components and easy recovery; the preparation method has characteristics of simple operation, simple separation, no water-carrying agent, repeated use of the deep eutectic solvent, and high diester yield.
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Paragraph 0055-0058
(2021/05/19)
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- Dichloro Butenediamides as Irreversible Site-Selective Protein Conjugation Reagent
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We describe maleic-acid derivatives as robust cysteine-selective reagents for protein labelling with comparable kinetics and superior stability relative to maleimides. Diamide and amido-ester derivatives proved to be efficient protein-labelling species with a common mechanism in which a spontaneous cyclization occurs upon addition to cysteine. Introduction of chlorine atoms in their structures triggers ring hydrolysis or further conjugation with adjacent residues, which results in conjugates that are completely resistant to retro-Michael reactions in the presence of biological thiols and human plasma. By controlling the microenvironment of the reactive site, we can control selectivity towards the hydrolytic pathway, forming homogeneous conjugates. The method is applicable to several scaffolds and enables conjugation of different payloads. The synthetic accessibility of these reagents and the mild conditions required for fast and complete conjugation together with the superior stability of the conjugates make this strategy an important alternative to maleimides in bioconjugation.
- Abegg, Daniel,Adibekian, Alexander,Afonso, Cláudia F.,Bernardes, Gon?alo J. L.,Corzana, Francisco,Laserna, Victor,Martin, Esther M.,Ravn, Peter
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supporting information
p. 23750 - 23755
(2021/10/01)
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- A Br?nsted acidic, ionic liquid containing, heteropolyacid functionalized polysiloxane network as a highly selective catalyst for the esterification of dicarboxylic acids
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A Br?nsted acidic, ionic liquid containing, heteropolyanion functionalized polysiloxane network was formed by self-condensation of dodecatungstophosphoric acid and a zwitterionic organosilane precursor containing both imidazolinium and sulfonate groups. The resulting hybrid material POS-HPA-IL was investigated as a catalyst for the selective esterification of dicarboxylic acids.
- Rajabi, Fatemeh,Wilhelm, Christian,Thiel, Werner R.
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supporting information
p. 4438 - 4444
(2020/08/10)
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- An empirical model for stereochemical control in the cyclization of cyclopropanetricarboxylic acid esters
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Here, we report an empirical model for diastereoselective cyclopropanation of fumarate/maleate diesters with chloroacetate, sulfonium ylide, or ammonium ylide. With symmetrical fumarate/maleate diesters, cyclopropanation was found to proceed with a high level of diastereoselectivity in favor of the chiral isomer. In contrast, production of the meso isomer was observed in 3848% diastereoselectivity when unsymmetrical fumarate/maleate was employed. An improved synthesis of (N-desmethy)dysibetaine CPa in both racemic and enantiomeri-cally pure forms was furthermore achieved. Configurational analysis by experimental and calculated 13C NMR data is also reported.
- Tanaka, Kento,Manabe, Hitomi,Irie, Raku,Oikawa, Masato
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p. 1314 - 1323
(2019/09/18)
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- Preparation method of chlorantraniliprole
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The invention relates to the technical field of synthesis processes of insecticides, and discloses a preparation method of chlorantraniliprole, which comprises the following steps: 1) adding 4-8 partsof maleic anhydride and 4-8 parts of methanol into a single-necked bottle, stirring the mixture, heating to 50 DEG C, and carrying out heat preservation reaction for 0.5-1.5 hours to obtain monomethyl maleate; and 2) cooling 80-120 parts of a hydrogen bromide-glacial acetic acid solution to 0 DEG C, then dropwise adding 3-5 parts of the monomethyl maleate, after addition is completed, carrying out heat preservation and stirring for 3-7 min, so that a large amount of a yellow viscous substance appears, and the monomethyl 3-bromomaleate can be prepared. The invention discloses a preparation method of chlorantraniliprole. The maleic anhydride, 2,3-dichloropyridine and 2-amino-3-methylbenzoic acid are adopted as starting materials to synthesize the target compound chlorantraniliprole througha convergent reaction. The structure is determined through HNMR, the route is mild in reaction condition, easy and convenient to operate and separate, raw materials are easy to obtain, special equipment is not needed, industrial production is easy to achieve, the action mechanism is novel and unique, and wide application and development prospects are achieved.
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Paragraph 0028-0030; 0041-0043; 0054-0056
(2020/01/08)
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- Synthesis of α,β-unsaturated esters of perfluoropolyalkylethers (PFPAEs) based on hexafluoropropylene oxide units for photopolymerization
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α,β-unsaturated esters are usually synthesized for polymer applications. However, the addition of maleate (cis-configuration) to a fluorinated moiety is challenging due to its potential isomerization during esterification. Various synthetic routes were attempted and led to very low conversion or side-products. The immiscibility of both reagents combined with an easy isomerization or attack on the double bond were potential explanations. In this paper, the synthesis of maleates oligo(hexafluoropropylene oxide) is reported by Steglich esterification and the reaction conditions are discussed depending on the molecular weight of the fluorinated moieties. After UV-curing, hydrophobic polymers were obtained by copolymerization with vinyl ethers by electron acceptor-donor systems.
- Bonneaud, Céline,Decostanzi, Mélanie,Burgess, Julia,Trusiano, Giuseppe,Burgess, Trevor,Bongiovanni, Roberta,Joly-Duhamel, Christine,Friesen, Chadron M.
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p. 32664 - 32671
(2018/10/15)
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- AN IMPROVED PROCESS FOR THE SYNTHESIS OF DIMETHYL FUMARATE
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The present invention describes an improved process for the industrial scale production of dimethyl fumarate. The process involves a one-pot ring opening reaction of maleic anhydride to monomethyl maleate and isomerization into the corresponding monomethyl fumarate in presence of a Lewis acid. Finally the mono methyl fumarate was converted into the dimethyl fumarate by an acid catalyzed esterification reaction.
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Paragraph 0027
(2017/05/10)
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- Synthesis process of dimethyl maleate
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The invention discloses a synthesis process of dimethyl maleate. The synthesis process comprises steps as follows: maleic anhydride and methanol are subjected to a reaction in a mono-esterification reaction kettle at the temperature of 70-100 DEG C, and monomethyl maleate is generated; monomethyl maleate enters a catalytic esterification tower from a tower, methanol steam enters the catalytic esterification tower from the position below upper liquid level of each layer of tower plate and is contacted with monomethyl maleate and a solid catalyst on the tower plate, and dimethyl maleate is generated. With the adoption of continuous production, energy utilization rate is increased by full use of waste heat of the esterification reaction; with the adoption of multiple methanol steam inputs, methanol steam is distributed on each tower plate, each tower plate forms one small reactor in a boiling state, the contact area of monomethyl maleate and methyl alcohol is increased, the contact time of monomethyl maleate and methyl alcohol is prolonged, the problem of uneven distribution of methanol in the tower due to liquefied reflow of the methyl alcohol steam in a rising process is solved, the reaction efficiency and the esterification rate are increased, the methanol utilization rate is increased, the production cost is reduced while the yield is increased, and the synthesis process is suitable for industrial application.
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Paragraph 0010
(2017/07/01)
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- PROCESS FOR CARRYING OUT A REACTION IN A REACTION COLUMN
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A process for carrying out a reaction in a reaction column, said process comprising: providing a first reactant to the reaction column in the liquid phase; contacting said first reactant with an excess of a second reactant such that reaction takes place within the reaction column to form a low boiling product and a high boiling product, at least a portion of said second reactant being provided to the reaction column in the vapour phase; recovering an overhead stream from at, or near, the top of the reaction column, said overhead stream comprising unreacted second reactant and the low boiling product; and recovering a bottoms stream from at, or near, the bottom of the reaction column comprising the high boiling product; wherein at least a portion of the heat required to vaporise the second reactant provided to the reaction column in the vapour phase is provided by heat exchange in a heat exchanger with a hot stream generated within the process other than a hot stream generated within the reaction column.
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Page/Page column 14-15
(2016/10/11)
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- PROCESS FOR THE PREPARATION OF DIALKYL SUCCINATE FROM MALEIC ANHYDRIDE
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A process for the production of dialkyl succinate from a feedstock comprising maleic anhydride, said process comprising the steps of providing the feed in the liquid phase to a reactor operated at a temperature of at least about 150°C; contacting said feed with hydrogen at a pressure of at least about 300 psig in the presence of an acid tolerant catalyst and an alkanol wherein at least some of the carbon carbon double bonds of the maleic anhydride are hydrogenated to form succinic acid and that the heat generated promotes esterification to dialkyl succinate acid in situ; and recovering a stream comprising dialkyl succinate from the reactor.
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Page/Page column 11; 12
(2015/05/05)
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- Promoted role of Cu(NO3)2 on aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over VOSO4
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The promoted effect of Cu(NO3)2 on aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) catalyzed by VOSO4 in acetonitrile was intensively investigated. It was revealed that Cu(NO3)2 facilitated the activation of VOSO 4 to generate active V5+ species via the generation of NOx gas. The high DFF selectivity is ascribed to Cu2+ cation which can effectively prohibit oxidative CC bond cleavage reaction of HMF and prevent radical reaction of DFF to humins. In addition, the polarity of solvent plays a great role on high selectivity of DFF.
- Jia, Xiuquan,Ma, Jiping,Wang, Min,Du, Zhongtian,Lu, Fang,Wang, Feng,Xu, Jie
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p. 231 - 236
(2014/07/08)
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- Synthesis, DFT and antimicrobial activity assays in vitro for novel cis/trans-but-2-enedioic acid esters
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Six novel cis/trans-but-2-enedioic acid esters had been synthesized to discover the new bioactive molecules that could kill food-related bacteria and fungi. Their structures were analyzed by melting point, LC-MS, 1H NMR and 13C NMR. 4-(Methoxycarbonyl) phenyl ethyl fumarate (6b) was also characterized by single-crystal X-ray diffraction. Their antimicrobial activities were evaluated in vitro by measuring the minimal inhibitory concentration (MIC). Compared with the single monomethyl fumarate and methyl 4-hydroxybenzoate, these compounds had stronger antimicrobial activity against all the eight microorganisms. Among the antibacterial and antifungal compounds, 4-(methoxycarbonyl) phenyl methyl fumarate (6a) showed the best antimicrobial activity. The electronic properties of these compounds were calculated by the density functional theory (DFT) method with 6-31G (d, p) basis set. DFT studies indicated that molecular electrostatic potential (MEP) map, ELUMO, energy gap, electronegativity and electrophilicity index could be helpful to understand the various antimicrobial activities among these compounds. The antimicrobial activity of compound 6a was evaluated in vitro against Salmonella choleraesuis subsp. choleraesuis, Lactococcus lactis subsp. lactis and Saccharomyces cerevisiae by time-kill, and it was found that compound 6a exhibited significant microbiocidal activity against the three microorganisms.
- Ma, Yan-Long,Zhou, Ru-Jin,Zeng, Xing-Ye,An, Ya-Xiong,Qiu, Song-Shan,Nie, Li-Jun
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p. 226 - 234
(2014/03/21)
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- An expeditious synthesis of imides from phthalic, maleic and succinic anhydrides and chemoselective C=C reduction of maleic amide esters
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Phthalic, maleic and succinic anhydrides have been reacted with aromatic amines to obtain the corresponding monoacid monoamides. The latter have been each transformed into the corresponding cyclic imide derivatives by treating with SOCl2. Alternatively, anhydrides have been reacted with methanolic KOH to obtain monomethyl ester derivatives which on reaction with aromatic amines in the presence of EDC. HCl and HOBt give cyclic imide derivatives. Reaction of monoacid monoamides independently, with SOCl 2 at 0-5°C give the monoamide monoester derivatives. Treatment of monoamide monoester of malic anhydride with NaBH4 leads to the unusual reduction of C=C grouping as well as the carbonyl group of the ester group to from monoamide monoalcohol of succinic anhydride. Preparation of monoamide monoalcohol of succinic anhydride can also be achieved by chemoselective reduction of monoamide monoester of malic anhydride with Mg turnings yielding monoamide monoester of succinic anhydride followed by reduction of the latter with NaBH4.
- Kumar, Padam Praveen,Reddy, Y. Dathu,Kumari, Y. Bharathi,Devi, B. Rama,Dubey
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p. 392 - 398
(2014/05/06)
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- METHOD OF MAKING MONOMETHYL FUMARATE
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Methods of making monomethyl fumarate, which can then also be used in methods of making prodrugs of monomethyl fumarate, are disclosed. Monomethyl fumarate and prodrugs of monomethyl fumarate are useful for treating neurodegenerative, inflammatory, and autoimmune diseases including multiple sclerosis, psoriasis, irritable bowel disorder, ulcerative colitis, arthritis, chronic obstructive pulmonary disease, asthma, Parkinson's disease, Huntington's disease, and amyotrophic lateral sclerosis.
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Paragraph 0204
(2015/01/06)
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- Ring-opening of cyclic anhydrides using ionic liquids
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Four novel Bronsted acidic ionic liquids with two different acid sites on the imidazolium cations were synthesised and employed as catalysts and solvents for the ring-opening of cyclic anhydrides to synthesise half-esters. The results showed that these novel Bronsted acidic ionic liquids were efficient and recyclable. Good yields, short reaction times and mild reaction conditions were achieved.
- Jiang, Dong,Wang, Yuan Yuan,Xu, Yan Nan,Dai, Li Yi
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experimental part
p. 167 - 169
(2009/10/15)
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- Selective monoesterification of malonic acid catalyzed by boric acid
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Boric acid catalyzes the monoesterification of malonic acid, likely through a chelation mechanism that is not available to the monoester product. Under more forcing conditions, diesters form to some extent, but conditions can be optimized to favour the monoester product (56?80%). With the easily handled solid acid catalyst, these reactions can be run with excess alcohol as solvent or with stoichiometric amounts of alcohol in acetonitrile with moderate heating. CSIRO 2007.
- Levonis, Stephan M.,Bornaghi, Laurent F.,Houston, Todd A.
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p. 821 - 823
(2008/03/12)
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- Microwave-assisted solvent-free intramolecular 1,3-dipolar cycloaddition reactions leading to hexahydrochromeno[4,3-b]pyrroles: scope and limitations
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We report the microwave-assisted solvent-free synthesis of hexahydrochromeno[4,3-b]pyrroles. Intramolecular 1,3-dipolar cycloadditions proceed under these conditions within 15-40 min in 16-84% yields. An influence of the microwave irradiation upon various [3+2] cycloaddition reaction intermediates was studied. Additionally, a scope and limitations of these reactions including an influence of the dipolarophile geometry upon the cycloaddition selectivity and steric demands of the dipole upon its reactivity were also disclosed. These observations led us to postulate a preferable transition state of the reaction. Finally, an influence of the microwave irradiation to the isomerization of activated olefins was also described.
- Pospí?il, Ji?í,Potá?ek, Milan
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p. 337 - 346
(2007/10/03)
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- PROCESS FOR THE PRODUCTION OF ESTERS OF MONO-,DI-OR POLYCARBOXYLIC ACIDS
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A process for the production of carboxylic acid esters by reaction of a carboxylic acid selected from mono-, di- and polycarboxylic acids, with an alcohol in the presence of water of solution comprising the steps of: (a) providing a solution comprising the carboxylic acid and the water of solution; (b) reacting the solution of the carboxylic acid in an esterification zone with an alcohol to form an ester and water of esterification; (c) removing the water of solution and the water of esterification; and (d) recovering the ester.
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Page/Page column 21-24
(2008/06/13)
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- Novel α-amino-acid phenolic ester derivatives with intravenous anaesthetic activity
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A novel series of α-amino-acid phenolic ester derivatives containing sulphide, sulphoxide, sulphone, ester and amide side chains were prepared and shown to display potent intravenous anaesthetic activity.
- Cooke, Andrew,Anderson, Alison,Bennett, Jonathan,Buchanan, Kirsteen,Gemmell, David,Hamilton, Niall,Maidment, Maurice,McPhail, Petula,Stevenson, Donald,Sundaram, Hardy
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p. 1107 - 1110
(2007/10/03)
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- Total synthesis of (-)-rosmarinecine by intramolecular cycloaddition of (S)-malic acid derived pyrroline N-oxide
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(equation presented) Straightforward total syntheses of (-)-rosmarinecine have been achieved from L-malic acid derived pyrroline N-oxides by two novel useful cascade processes, which join the family of domino reactions. Both strategies, which furnished the target alkaloid in enantioenriched and enantiopure forms, respectively, allow complete control of configuration at all the three newly created contiguous stereogenic centers.
- Goti, Andrea,Cacciarini, Martina,Cardona, Francesca,Cordero, Franca M.,Brandi, Alberto
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p. 1367 - 1369
(2007/10/03)
-
- Ring opening of cyclic anhydrides: Synthesis of achiral half-esters using Lewis acids
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A rapid and high yield preparation of half-esters from cyclic anhydrides using alcohols and Lewis acids is described.
- Sabitha, Gowravaram,Srividya,Yadav
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p. 4015 - 4018
(2007/10/03)
-
- Intermediates for pyrazolyl acetic acid derivatives
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The invention discloses a novel process for the preparation of a compound of formula II STR1 wherein R1 is C1-5 alkyl, R2 is hydrogen or C1-5 alkyl, and R3 is optionally substituted phenyl, comprising the reaction of a 4-hydroxypyrazole of formula III STR2 wherein R1 and R2 are as defined for formula II, with a benzylhalide of formula IV wherein Hal is halogen, preferably bromine or chlorine, and R3 is as defined for formula II, in the presence of a base. The invention further comprises a novel process for the preparation of the 4-hydroxypyrazole of formula III. The compounds of formulae II and III are intermediates for highly effective systemic fungicides of the class of pyrazolyl acetic acid derivatives.
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- Stereocontrol in cyclisation of dioxolanyl radicals
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Appropriate nitrate esters are cleaved under photolytic or thermal (tributyltin radical) conditions to yield dioxolanyl radicals which undergo stereoselective cyclisation to heterocyclic products.The X-ray crystallographic structures for compounds 30a and 35 are reported.
- Batsanov, Andrei S.,Begley, Michael J.,Fletcher, Rodney J.,Murphy, John A.,Sherburn, Michael S.
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p. 1281 - 1294
(2007/10/02)
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- Novel Three-component Coupling Reaction of Carbodiimide, Methyl Hydrogen Maleate, and an Alcohol or Amine: Synthesis of N-Carbamoylaspartic Acid Derivatives
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A novel three-component coupling reaction of methyl hydrogen maleate 1, a carbodiimide 2, and an alcohol or amine gave derivatives of N-carbamoylaspartic acid (3) in moderate to excellent yields.In the coupling, an intramolecular Michael addition of the acylisourea 6 subsequently occurs to give a new intermediate, 2-iminooxazolidin-5-one 7.The addition of alcohol or amine to the second intermediate 7 completes the three-component coupling.
- Kishikawa, Keiki,Sankhavasi, Wongsiri,Yoshizaki, Kazumi,Kohmoto, Shigeo,Yamamoto, Makoto,Yamada, Kazutoshi
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p. 1205 - 1210
(2007/10/02)
-
- Asymmetric Diels-Alder reaction of unsymmetrical maleates. A chemical access to chiral, unsymmetrical cis-cyclohexene-1,2-dicarboxylates
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A new route to optically active, unsymmetrical cis-cyclohexene-1,2-dicarboxylate derivatives has been developed on the basis of the asymmetric Diels-Alder reaction of chiral, unsymmetrical maleates catalyzed by certain Lewis acids. A notably high level of asymmetric induction has been observed in the asymmetric Diels-Alder reaction of unsymmetrical maleates possessing chiral auxiliaries such as α-phenethyl and trans-2-phenylcyclohexyl groups. The origin of the chiral outcome using these dienophiles has been elucidated.
- Maruoka, Keiji,Akakura, Matsujiro,Saito, Susumu,Ooi, Takashi,Yamamoto, Hisashi
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p. 6153 - 6158
(2007/10/02)
-
- Ionization Shifts in 1H-NMR Spectra of α,β-Unsaturated Carboxylic Acids
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Changes in chemical shifts of olefinic protons in a number of α,β- and α,β,γ,δ-unsaturated carboxylic acids caused by ionization of the COOH group were investigated.The ionization shifts of α-H-atoms are -0.09 to 0.07 ppm, those of β-H-atoms are 0.32-0.47 ppm.The ionization shifts of δ-H-atoms are substantially larger than those of γ-H-atoms.The ionization shifts can be used for immediate determination of the esterification site in monoesters of (2E,4Z)-2,4-hexadienedioic (muconic) acid, which are of interest in connection with synthetic studies on verrucarins.Thus, isomerization by heating in aqueous solution of monoesters of (2Z,4Z)-2,4-hexadienedioic acid yields 1-monoesters rather than 6-monoesters of (2E,4Z)-2,4-hexadienedioic acid, in accordance with the isomerization mechanism involving anchimeric assistance of the free COOH group.Solutions of the ABXY spectra of olefinic protons of monomethyl (2E,4E)- and (2Z,4Z)-2,4-hexadienedioate are reported.
- Jaroszewski, Jerzy W.,Grossen, Peter,Mohr, Peter,Tamm, Christoph
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p. 718 - 725
(2007/10/02)
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- 1-(4-Aminobenzyl)- and 1-(4-aminophenyl)isoquinoline derivatives: Synthesis and evaluation as potential irreversible cyclic nucleotide phosphodiesterase inhibitors
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In an effort to increase the specificity of the potent phosphodiesterase inhibitor papaverine, we synthesized two series of novel 1-(4-aminobenzyl)- and 1-(4-aminophenyl)isoquinoline derivatives, incorporating alkylating moieties on the amine substituents. These compounds were evaluated for their inhibitory action on phosphodiesterase preparations from bovine heart and rat cerebral cortex. Studies were also conducted to determine whether these compounds were reacting with the enzymes in an irreversible manner. The compounds were potent inhibitors of the phosphodiesterases; however, no evidence was found for an irreversible inhibition.
- Walker,Boots,Stubbins,Rogers,Davis
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p. 174 - 181
(2007/10/02)
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- Derivatives of pyrazole-5-acetic acid
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Compounds having anti-inflammatory and antipyretic action have the general formula SPC1 In which each of R1 and R2 is a phenyl group which may be substituted by a halogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms or a trifluoromethyl group, R3 is a straight or branched chain saturated or unsaturated aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group having 3 to 7 carbon atoms, or a benzyl or phenyl group which benzyl or phenyl groups may be substituted in the benzene ring by a halogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms or a trifluoromethyl group or by any two of these substituents, R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and A is a group having one of the formulae --COOH, --COOR5 and --CONR6 R7 in which R5 is an alkyl group having 1 to 4 carbon atoms or a benzyl group and each of R6 and R7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or R6 and R7 taken together with the nitrogen atom to which they are attached represents a pyrrolidino, a piperidino or a morpholino group.
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