- A contribution to the rational design of Ru(CO)3Cl2L complexes for in vivo delivery of CO
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A few ruthenium based metal carbonyl complexes, e.g. CORM-2 and CORM-3, have therapeutic activity attributed to their ability to deliver CO to biological targets. In this work, a series of related complexes with the formula [Ru(CO)3Cl2L] (L = DMSO (3), l-H3CSO(CH2)2CH(NH2)CO2H) (6a); d,l-H3CSO(CH2)2CH(NH2)CO2H (6b); 3-NC5H4(CH2)2SO3Na (7); 4-NC5H4(CH2)2SO3Na (8); PTA (9); DAPTA (10); H3CS(CH2)2CH(OH)CO2H (11); CNCMe2CO2Me (12); CNCMeEtCO2Me (13); CN(c-C3H4)CO2Et) (14)) were designed, synthesized and studied. The effects of L on their stability, CO release profile, cytotoxicity and anti-inflammatory properties are described. The stability in aqueous solution depends on the nature of L as shown using HPLC and LC-MS studies. The isocyanide derivatives are the least stable complexes, and the S-bound methionine oxide derivative is the more stable one. The complexes do not release CO gas to the headspace, but release CO2 instead. X-ray diffraction of crystals of the model protein Hen Egg White Lysozyme soaked with 6b (4UWN) and 8 (4UWV) shows the addition of RuII(CO)(H2O)4 at the His15 binding site. Soakings with 7 (4UWU) produced the metallacarboxylate [Ru(COOH)(CO)(H2O)3]+ bound to the His15 site. The aqueous chemistry of these complexes is governed by the water-gas shift reaction initiated with the nucleophilic attack of HO- on coordinated CO. DFT calculations show this addition to be essentially barrierless. The complexes have low cytotoxicity and low hemolytic indices. Following i.v. administration of CORM-3, the in vivo bio-distribution of CO differs from that obtained with CO inhalation or with heme oxygenase stimulation. A mechanism for CO transport and delivery from these complexes is proposed. This journal is
- Seixas, Jo?o D.,Santos, Marino F. A.,Mukhopadhyay, Abhik,Coelho, Ana C.,Reis, Patrícia M.,Veiros, Luís F.,Marques, Ana R.,Penacho, Nuno,Gon?alves, Ana M. L.,Rom?o, Maria J.,Bernardes, Gon?alo J. L.,Santos-Silva, Teresa,Rom?o, Carlos C.
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- METHOD FOR MANUFACTURING 2-HYDROXY-4-(METHYLTHIO)BUTYRIC ACID
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A method for manufacturing 2-hydroxy-4-(methylthio)butyric acid (HMTBA) from 2-hydroxy-4-methylthio-butyronitrile (HMTBN), where HMTBN is hydrolyzed into HMTBA in the presence of a mineral acid in an aqueous medium, the medium is neutralized by addition of a base, a first phase including at least HMTBA and salts and a second phase containing salts are separated, the method including the separation of the HMTBA from the salts of the first phase, by subjecting the latter to a chromatography.
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Paragraph 0050-0055
(2021/06/26)
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- METHOD AND DEVICE FOR PREPARING 2-HYDROXY-4-METHYLTHIOBUTYRIC ACID AND INTERMEDIATES THEREOF
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Provided by the present disclosure are a method and a device for preparing 2-hydroxy-4-methylthiobutyric acid and intermediates thereof; the intermediates for preparing 2-hydroxy-4-methylthiobutyric acid comprise 3-methylthiopropionaldehyde and 2-hydroxy-4-methylthiobutyronitrile. The method for preparing 2-hydroxy-4-methylthiobutyric acid provided by the present disclosure comprises: step (1), a step of reacting acrolein with methyl mercaptan to prepare 3-methylthiopropionaldehyde; step (2), a step of reacting 3-methylthiopropionaldehyde with hydrocyanic acid to prepare 2-hydroxy-4-methylthiobutyronitrile; and step (3), a step of hydrating 2-hydroxy-4-methylthiobutyronitrile by using sulfuric acid and then hydrolyzing to prepare 2-hydroxy-4-methylthiobutyric acid; wherein in steps (1), (2) and (3), the reaction status of the materials is detected online, and the proportions of the materials are controlled according to the detection results such that reactions are performed completely
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Paragraph 0166-0169; 0185-0188; 0204-0207
(2021/05/21)
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- Clean preparation method of high-purity methionine hydroxyl analogue calcium salt
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The invention discloses a clean preparation method of high-purity methionine hydroxyl analogue calcium salt. The clean preparation method comprises the following specific steps: adding water into 2-hydroxy-4-methylthiobutyronitrile serving as a raw material, carrying out a hydration reaction under the catalytic action of solid acid/solid alkali, adding strong acid or strong alkali for hydrolysis to obtain 2-hydroxy-4-methylthiobutyric acid, then adding CaO or Ca(OH)2, carrying out a salt forming reaction to obtain an aqueous solution of a mixture, carrying out chromatographic desalination treatment on the aqueous solution of the mixture to obtain an aqueous solution of a methionine hydroxyl analogue, and finally carrying out spray drying on the aqueous solution of the methionine hydroxyl analogue to obtain a target product. Compared with a traditional method, the method disclosed by the invention has the advantages that the step of neutralizing and alkali washing after the reaction is finished is avoided, the generation of a byproduct, namely inorganic ammonium salt is avoided, reaction is simple, conditions are mild, and the method is safe and environment-friendly; and in addition, a catalyst, namely the solid acid or solid alkali adopted in the method can be recycled, so production cost is reduced.
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Paragraph 0041-0049
(2021/07/14)
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- DEMETHYLATION OF METHYL ESTER OF METHIONINE AND ITS HYDROXY ANALOG
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The following invention regards a process of demethylating a methyl ester of methionine or its hydroxy analog and producing methane thiol as a side-product. The methionine and its hydroxy analog are suitable as an animal feed additive and as a food additive. The methane thiol may be consumed in a hydrothiolation step such as in a step of preparing the methyl ester of methio- nine or its hydroxy analog from from methyl vinyl glycolate.
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Page/Page column 14-15
(2019/12/04)
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- METHOD FOR PRODUCING METHIONINE AND/OR 2-HYDROXY-4-(METHYLTHIO) BUTANOIC ACID
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An object of the invention is to provide a simple method for producing methionine and/or 2-hydroxy-4-(methylthio)butanoic acid at a high yield using 3-(methylthio)propionaldehyde as a raw material. An oxide catalyst containing cerium, 3-(methylthio)propionaldehyde, a compound containing cyanide ion, ammonia or a compound containing ammonium ion, and water are contacted with each other to produce methionine and/or 2-hydroxy-4-(methylthio)butanoic acid.
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Paragraph 0051; 0052; 0055
(2019/03/30)
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- Method for manufacturing methylmercaptopropionaldehyde and methionine using renewable raw materials
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The present invention relates to a method for manufacturing methylmercaptopropionaldehyde (MMP) including at least the following steps: (a) dehydrating glycerol to acrolein from an aqueous solution of glycerol in the presence of an acid catalyst; (b) purifying the aqueous flux from step (a) to obtain a flux of acrolein containing at least 15 wt % of water relative to the acrolein; (c) causing a reaction of the acrolein flux obtained in step (b) with methylmercaptan in the presence of a catalyst; (d) optionally purifying the product obtained in step (c). The method of the invention can also include a reaction of the product obtained in step (c) or (d) with hydrocyanic acid, or sodium cyanide during a step (e) followed by a subsequent transformation to produce methionine or methionine hydroxyanalogue, which can then optionally be purified. The additional use of methylmercaptan and/or hydrocyanic acid derived from biomass as raw materials in the method according to the invention makes it possible to obtain MMP, methionine or methionine hydroxyanalogue made up of 100% organic carbon from renewable sources.
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Page/Page column 17
(2014/06/10)
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- Process for preparing 2-hydroxy-4-methylselenobutyric acid, alone or as a mixture with its sulphur-containing analogue, and uses thereof in nutrition, in particular animal nutrition
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The present invention relates to a novel process for preparing 2-hydroxy-4-methylselenobutyric acid from 3-methylselenoproprion-aldehyde. The 2-hydroxy-4-methylselenobutyric acid is obtained alone or as a mixture with its sulphur-containing analogue. The invention also relates to the compositions, in particular nutritional compositions, comprising a mixture of 2-hydroxy-4-methylselenobutyric acid and 2-hydroxy-4-methylthiobutyric acid, and a physiologically acceptable medium, and to the use of this mixture as a dietary ingredient.
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Page/Page column 7
(2012/12/13)
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- PROCESS FOR THE PREPARATION OF HYDROXYCARBOXYLIC ACID COMPOUND OR SALT THEREOF
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The present process can prepare a hydroxycarboxylic acid compound of Formula (1): or a salt thereof by reacting a ketocarboxylic acid compound of Formula (2): or a salt thereof and hydrogen in the presence of a transition metal catalyst, without using hydrogen cyanide.
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Page/Page column 20
(2012/06/30)
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- Reactive Extraction of Free Organic Acids from the Ammonium Salts Thereof
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The invention relates to a process for converting ammonium salts of organic acids to the particular free organic acid, wherein an aqueous solution of the ammonium salt is contacted with an organic extractant and the salt is dissociated at temperatures and pressures at which the aqueous solution and the extractant are in the liquid state, and a stripping medium or entraining gas is introduced in order to remove NH3 from the aqueous solution and transfer at least a portion of the free organic acid formed to the organic extractant. The invention described here thus provides an improved process for releasing an organic acid, preferably a carboxylic, sulphonic or phosphonic acid, especially an alpha-hydroxycarboxylic acid or beta-hydroxycarboxylic acid, from the ammonium salt thereof by release and removal of ammonia and simultaneous extraction of the acid released with a suitable extractant from the aqueous phase. This process corresponds to a reactive extraction. The reactive extraction of an organic acid from the aqueous ammonium salt solution thereof can be improved significantly by the use of a stripping medium or entraining gas, for example nitrogen, air, steam or inert gases, for example argon. The ammonia released is removed from the aqueous solution by the continuous gas stream and can be fed back into a production process. The free acid can be obtained from the extractant by a process such as distillation, rectification, crystallization, re-extraction, chromatography, adsorption, or by a membrane process.
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Page/Page column 10
(2010/08/22)
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- Method for the Production of D,L-2-Hydroxy-4-Alkylthio Butyric Acid
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The present invention relates to a process for preparing compounds of the formula (I) by reacting compounds of the formula (II) with thiolates (RS)nM. The present invention further relates to a process for preparing compounds of the formula (II) from γ-butyrolactone.
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Page/Page column 4
(2009/12/28)
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- PROCESS FOR PRODUCING 2-HYDROXY-4-(METHYLTHIO)BUTYRATE COMPOUNDS AND INTERMEDIATES THEREOF
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A process for producing a 2-hydroxy-4-(methylthio)butyrate compound represented by the formula (2): wherein A is a hydrogen atom or a group represented by R-CH2-, wherein R is a hydrogen atom or an alkyl group, which comprises the step of : reacting 4-(methylthio)-2-oxo-1-butanol with oxygen and a compound represented by the formula (1) : wherein A is as defined above, in the presence of a copper compound.
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Page/Page column 32-33
(2008/06/13)
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- METHOD FOR PRODUCING 2-HYDROXY-4-METHYLTHIOBUTANOIC ACID
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The present invention provides a process for producing 2-hydroxy-4-methylthiobutyric acid comprising the following steps (1) to (4); (1): hydrolyzing 2-hydroxy-4-methylthiobutyronitrile in the presence of sulfuric acid, (2): separating the reaction mixture obtained in the step (1) into an oil layer containing 2-hydroxy-4-methylthiobutyric acid and a water layer, (3): concentrating the oil layer obtained in the step (2), and (4): heating the concentrated product obtained in the step (3).
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Page/Page column 3; 4
(2008/06/13)
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- Process for purification and decolorization of 2-hydroxy-4-(methylthio)butanoic acid (HMTBA)-containing complexes
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Disclosed herein are processes for purifying a complex of 2-hydroxy-4-(methylthio)butanoic acid and a cation. The complex purified using the disclosed methods are substantially free of discoloration and can be suitable, for example, as a source of methionine and minerals for animals, including humans, companion animals and agricultural animals.
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Page/Page column 3
(2008/06/13)
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- Preparation of 2-hydroxy-4-methylthiobutyric acid
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A process for the preparation of 2-hydroxy-4-methylthiobutyric acid.
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Page/Page column 3
(2008/06/13)
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- Palatability of aquaculture feed
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A method for enhancing the palatability of aquaculture food, the method comprising treating the food with a compound of Formula I: wherein R1, R2, R3, and n are as defined herein, are disclosed.
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- Process for the production of 3-methylthiopropanal
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Process for the Production of 3-methylthiopropanal. A process for the production of 3-methylthiopropanal which reacting reaction medium comprising methyl mercaptan and acrolein in the presence of a catalyst comprising an organic base characterised in that the organic base is a N-alkyl morpholine compound.
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- Hydrolysis of nitriles using an immobilized nitrilase: Applications to the synthesis of methionine hydroxy analogue derivatives
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Mild and selective hydrolysis of a large range of nitriles leading to carboxylic acids was achieved under neutral conditions by an immobilized and genetically modified enzyme preparation from Alcaligenes faecalis ATCC8750. This immobilized nitrilase has been shown to be an effective catalyst for the stereoselective hydrolysis of mandelonitrile 1a to R-(-)-mandelic acid 1c. This method is particularly useful for the production of hydroxy analogues of methionine derivatives 2c-4c that could have an interest in cattle feeding and for the transformation of compounds containing other acid- or base-sensitive groups 3a-10a. A series of aliphatic dinitriles 11a-15a was hydrolyzed to the corresponding cyano acids. The suitability of the immobilized catalyst as a robust and versatile biocatalyst is discussed, and models to account for the stereoselectivity of the enzymic hydrolysis have been proposed.
- Rey, Patrick,Rossi, Jean-Christophe,Taillades, Jacques,Gros, Georges,Nore, Olivier
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p. 8155 - 8162
(2007/10/03)
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- Process for the preparation of hydroxymethylbutyric acid
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The invention relates to a new process for the preparation of hydroxymethylthiobutyric acid by sulphuric hydrolysis of hydroxymethylthiobutyronitrile.
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Page column 5-8
(2008/06/13)
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- Process for the production of a sulphur-containing organic compound
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A process for the production of an organic sulphur-containing product which comprises reacting a sulphur-containing compound with an unsaturated hydrocarbon in the presence of a boron compound at a temperature of less than or equal to 50°C.
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- Process for the preparation of 3-(methylthio)propanal
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A process for the continuous preparation of 3-(methylthio)propanal. A liquid reaction medium is contacted with a gaseous acrolein feed stream in a gas/liquid contact zone. The reaction medium contains 3-(methylthio)propanal, methyl mercaptan and a catalyst for the reaction between methyl mercaptan and acrolein. The gaseous acrolein feed stream comprises acrolein vapor and non-condensable gas. Acrolein is transferred from the acrolein feed stream to the reaction medium and reacts with methyl mercaptan in that medium to produce a liquid reaction product containing 3-(methylthio)propanal. The non-condensable gas is separated from the liquid reaction product. The reaction product is divided into a product fraction and a circulating fraction, and the circulating fraction is recycled to the gas/liquid contact zone.
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- Reaction of carboxylic acids with diethyl phosphorocyanidate; a novel synthesis of homologated α-hydroxycarboxylic acids from carboxylic acids
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Carboxylic acids react with 2 equivalents of diethyl phosphorocyanidate in the presence of triethylamine to give dicyanophosphates in good yields; these dicyanophosphates can be hydrolyzed easily to give homologated α- hydroxycarboxylic acids.
- Mizuno, Masanori,Shioiri, Takayuki
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p. 9209 - 9210
(2007/10/03)
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- Nonionic X-ray contrast agents, compositions and methods
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Triiodinated isophthalamide derivatives, useful as X-ray contrast agents, having at least one amide group derived from the amino-alcohol, 3-(N-2-hydroxyethyl)amino-1,2-propanediol, which provides high water solubility and low mammalian toxicity, and methods of preparing them. Methods of preparing 3-(N-2-hydroxyethyl)amino-1,2-propanediol are provided.
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- HYDRATION OF CYANOHYDRINS IN WEEKLY ALKALINE SOLUTIONS OF BORIC ACID SALTS
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α-Hydroxyamides and α-hydroxyacids were prepared in satisfactory yield by heating aldehyde-derived cyanohydrins in aqueous solution in the presence of borax or alkaline borates.
- Jammot, Jacqueline,Pascal, Robert,Commeyras, Auguste
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p. 563 - 564
(2007/10/02)
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- Method of making a diastereomeric mixture containing two diastereomeric α-acyloxy acid esters
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In the process of hydrocarboxylating an enol acylate with CO and an organic hydroxyl compound to produce an α-acyloxy acid ester, the improvement comprising using as the organic hydroxyl compound reactant, an organic hydroxyl compound which has a chiral center that is essentially all L or D, thereby producing a reaction mixture having essentially no enantiomeric pairs and containing diastereomeric α-acyloxy acid esters having two chiral centers.
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- Intramolecular S- to N-Nitrosation
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Diazotisation of L-methionine and of S-methyl-L-cycteine occurs ca. 100 times faster than that of alanine, suggesting that initial S-nitrosation occurs, followed by an internal S- to N-rearrangement of the nitroso group.
- Meyer, Thomas A.,Williams, D. Lyn H.
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p. 1067 - 1068
(2007/10/02)
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