- Cp? versus Bis-carbonyl iridium precursors as CH oxidation precatalysts
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We previously reported a dimeric IrIV-oxo species as the active water oxidation catalyst formed from a Cp?Ir(pyalc)Cl {pyalc = 2-(2′-pyridyl)-2-propanoate} precursor, where the Cp? is lost to oxidative degradation during catalyst activation; this system can also oxidize unactivated CH bonds. We now show that the same Cp?Ir(pyalc)Cl precursor leads to two distinct active catalysts for CH oxidation. In the presence of external CH substrate, the Cp? remains ligated to the Ir center during catalysis; the active species-likely a highvalent Cp?Ir(pyalc) species-will oxidize the substrate instead of its own Cp?. If there is no external CH substrate in the reaction mixture, the Cp? will be oxidized and lost, and the active species is then an iridium-μ-oxo dimer. Additionally, the recently reported Ir(CO)2(pyalc) water oxidation precatalyst is now found to be an efficient, stereoretentive CH oxidation precursor. We compare the reactivity of Ir(CO)2(pyalc) and Cp?Ir(pyalc)Cl precursors and show that both can lose their placeholder ligands, CO or Cp?, to form substantially similar dimeric IrIV-oxo catalyst resting states. The more efficient activation of the bis-carbonyl precursor makes it less inhibited by obligatory byproducts formed from Cp? degradation, and therefore the dicarbonyl is our preferred precatalyst for oxidation catalysis.
- Huang, Daria L.,Vinyard, David J.,Blakemore, James D.,Hashmi, Sara M.,Crabtree, Robert H.
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p. 199 - 206
(2017/11/27)
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- METHOD FOR CONVERSION OF DIAMMONIM SUCCINATE IN FERMENTATION BROTH TO 2-PYRROLIDONE AND N-METHYLPYRROLIDONE
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This invention relates to a process for preparing 2-pyrroiidone (also called 2- pyrrolidinone) and N-methylpyrrolidone (also called N-methylpyrrolidinone) from diammonium succinate in fermentation broth. In the first stage of this invention, renewable carbon resources are utilized to produce diammonium succinate through biological fermentation. In the second stage of this present invention, diammonium succinate is converted into 2-pyrroiidone and N-methylpyrrolidone through a two step reaction. Both the steps of the reaction leading to the production of 2-pyrroiidone and N-methylpyrrolidone are carried out in a solvent phase to prevent the loss of succinimide through hydrolysis.
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Paragraph 095
(2013/03/28)
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- PROCESSES FOR THE PRODUCTION OF HYDROGENATED PRODUCTS
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A process for making a hydrogenated product includes providing a clarified DAS-containing fermentation broth; distilling the broth under super atmospheric pressure at a temperature of >100° C. to about 300° C. to form an overhead that includes water and ammonia, and a liquid bottoms that includes SA, and at least about 20 wt % water; cooling the bottoms to a temperature sufficient to cause the bottoms to separate into a liquid portion in contact with a solid portion that is substantially pure SA; separating the solid portion from the liquid portion; recovering the solid portion; hydrogenating the solid portion in the presence of at least one hydrogenation catalyst to produce the hydrogenated product including at least one of THF, GBL or BDO; and recovering the hydrogenated product.
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Page/Page column 7
(2011/10/13)
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- Reaction of γ-dicarboxylic acids amides and imides with trifluoromethanesulfonamide and formaldehyde
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Three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and succinamide depending on the reaction conditions led alongside bis(trifluoromethanesulfonamido)methane to the formation of a substitution product, bis[(trifluoromethylsulfonyl)aminomethyl]succinamide, or to a cyclization product, N-[trifluoromethylsulfonyl)aminomethyl]succinimide. The attempt to obtain the latter by the reaction of the trifluoromethanesulfonamide sodium salt CF3SO2NHNa with N-chloromethylsuccinimide unexpectedly resulted in N,N-bis(succinimidomethyl)-trifluoromethanesulfonamide. Analogously the reaction of CF3SO2NHNa with N-chloromethyl-phthalimide gave N,N-bis(phthalimidomethyl)trifluoromethanesulfonamide. The reaction of CF3SO2NHNa with succinimide and phthalimide in water and alcohol solution resulted in the ring opening and further transformation of the formed monosubstituted N-(trifluoromethylsulfonyl)amides of succinic and phthalic acids.
- Moskalik,Meshcheryakov,Shainyan
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experimental part
p. 1644 - 1650
(2010/04/27)
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- METHOD FOR PRODUCING ORGANIC ACID
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A novel method is provided whereby a free organic acid can be produced particularly from an ammonium salt of an organic acid having a high melting point obtainable by bioconversion of a carbon source in the presence of a neutralizing agent, efficiently at a low cost, and the used material for reaction and a byproduct can be recycled for reuse without being disposed. An ammonium salt of organic acid A such as a dicarboxylic acid, a tricarboxylic acid or an amino acid is subjected to reactive crystallization by means of acid B such as a monocarboxylic acid satisfying the following formula (1), to separate free organic acid A in solid form:pKa(A) ≦ pKa(B) where pKa(A) and pKa(B) represent ionization indices of organic acid A and acid B, respectively, provided that when they have plural values, they represent the minimum pKa among them. The crystallization mother liquor after precipitating and separating organic acid A is, after separating acid B and then an ammonium salt of acid B, recycled for use in the reactive crystallization step. The ammonium salt of acid B is decomposed into acid B and ammonia, which are recycled for use in the reactive crystallization step and as a neutralizing agent in the bioconversion step, respectively.
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Page/Page column 35-36
(2008/06/13)
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- PROCESS FOR PRODUCING N-METHYL SUCCINIMIDE
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The invention includes methods of processing an initial di-carbonyl compound by conversion to a cyclic compound. The cyclic compound is reacted with an alkyating agent to form a derivative having an alkylated ring nitrogen. The invention encompasses a method of producing an N-alkyl product. Amonia content of a solution is adjusted to produce a ratio of ammonia to di-carboxylate compound of from about 1:1 to about 1.5:1. An alkylating agent is added and the initial compound is alkylated and cyclized. The invention includes methods of making N-methyl pyrrolidinone (NMP). Aqueous ammonia and succinate is introduced into a vessel and ammonia is adjusted to provide a ratio of ammonia to succinate of less than 2:1. A methylating agent is reacted with succinate at a temperature of from greater than 100 °C to about 400 °C to produce N-methyl succinimide which is purified and hydrogenated to form NMP.
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- Complex Formation of Calcium Ions and Monosubstituted Succinic Acid Derivatives in Aqueous Solutions
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Complex formation of calcium ions with succinic acid monoamide and methyl hydrogen succinate at 25°C and ionic strength I = 0.3 (KC1) was studied by pH-potentiometric titration. The stability constants of the complexes were determined.
- Mitrofanova
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- Ligands for α-7 nicotinic acetylcholine receptors based on methyllcaconitine
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Ligands for nAChRs are provided based on various derivatives of methyllycaconitine (MLA) such as radiolabeled MLA, and MLA containing a fluorimetric marker group and their use in imaging for detection of Alzheimer's and other CNS diseases, and combinatorial assays for detection of compounds having affinity for nAChRs, as well as injectable compositions containing the same and kits for performing the imaging studies.
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- Nitric acid esters of cyclohexanol derivatives
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The invention concerns nitric acid esters of cyclohexanol of formula I STR1 in which A signifies a valency bond or a C1 -C6 -alkylene chain and B the group --NR1 --CO--Z, --NR1 --SO2 --Z or --CO--NR2 --Z, whereby R1 signifies hydrogen or a C1 -C6 -alkyl alkyl group R2 hydrogen, a hydroxyl, hydroxy-C1 -C6 -alkyl, C1 -C6 -alkoxy, C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group and Z signifies hydrogen a C1 -C6 -alkyl, C2 -C6 -alkenyl or C2 -C6 -alkynyl group which may optionally be substituted for the case that B is an --NR1 --CO--Z group, Z can also signify a C1 -C6 -alkoxy group.
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- Polychromic tetracyclo-spiro-adamatylidene derivatives, and polychromic lens incorporating said compounds
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A series of photochromic compounds are disclosed which have the property of undergoing a reversible color change when exposed to unfiltered sunlight and reverting to their original color in the absence of U.V. light at room temperature. These compounds have the general formula: STR1 represents an adamantylidene or a substituted adamantylidene group; R1 represents hydrogen, alkyl, aryl, aralkyl or a heterocyclic group, X represents oxygen or > NR2, in which R2 is hydrogen, aryl, alkyl or aralkyl and STR2 represents an aromatic group, an unsaturated heterocyclic group or a benzannelated heterocyclic group. The photochromic compounds of the invention are useful in the manufacture of photoreactive lenses, particularly plastic lenses.
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- Intramolecular Influence of a Carboxylic Function on Platinium Blue Synthesis. A systematic Study of Complexes Originating from Acid Amides
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The use of acid amide as ligand for obtaining platinium blue has been investigated.While blue compounds are generally obtained by using the hydrolysis product of cis-dichlorodiammineplatinum(II) as platinum surce, with such ligands the reaction occurs very readily using potassium tetrachloroplatinate(II).The role of the carboxylic function which offers here a primary ligating site to platinum is evidenced.The compounds obtained have been characterized by UV-visible spectral measurments, Ce(IV) oxydative titration , ESR spectroscopy, and magnetic properties.Antitumoral activity toward leukemia L1210 and sarcoma 180 is reported for two of thesecompounds.As a first step for this antitumor study, these compounds have been found to be inactive toward Leukemia while they presnt intersting activity toward Sarcoma.
- Arrizabalaga, Philippe,Castan, Paule,Laurent, Jean-Pierre
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p. 4814 - 4818
(2007/10/02)
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- Organic compounds substituted heptadeca-5,9- and 5,10-dienoic acid
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The present invention provides novel substituted heptadeca-5,9- and 5,10-dienoic acid and similar fatty acid compounds which are derivatives of certain prostaglandins and are potent thromboxane A2 inhibitors. By virtue of this pharmacological property, they represent useful pharmacological agents for a wide variety of purposes.
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