- Structural and IR-spectroscopic characterization of pyridinium acesulfamate, a monoclinic twin
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The crystal structure of pyridinium 6-methyl-1,2,3,-oxathiazine-4(3H)-one-2,2-dioxide [(C5NH6)(C4H4NO4S)], for short, pyH(ace), was determined by X-ray diffraction methods. It crystallizes as a twin in the monoclinic space group P21/c with a=6.9878(9), b=7.2211(7), c=21.740(2) ?, β=91.67(1)° and Z=4 molecules per unit cell. The structure was determined employing 1599 reflections with I>2 σ(I) from one of the twin domains and refined employing 2092 reflections from both crystal domains to an agreement R1 factor of 0.0466. Besides electrostatic attractions, intermolecular pyH···O=C(ace) hydrogen bonds stabilize the acesulfamate anion and the pyridinium cation into planar discrete units parallel to the (100) crystal plane. The units form stacks of alternating ace- and pyH+ ions along the a axis that favors inter-ring π-π interactions. The Fourier transform-infrared (FT-IR) spectrum of the compound was recorded and is briefly discussed. Some comparisons with related pyridinium saccharinate salts are also made.
- Baran, Enrique J.,Piro, Oscar E.,Echeverría, Gustavo A.,Parajón-Costa, Beatriz S.
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- A new acesulfamato complex: [Cu(acesulfamato)2(H2O)4]. Structural and spectroscopic characterization
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The crystal structure of tetraaqua-bis(6-methyl-1,2,3-oxathiazin-4(3H)-onato 2,2-dioxide) copper(II) complex, for short [Cu(ace)2(H2O)4], was determined by X-ray diffraction methods. The complex crystallizes in the monoclinic C2/c space group with a = 11.9838(4), b = 9.5240(3), c = 15.1686(6) ?, β = 102.975(4)° and Z = 4 molecules per unit cell. The structure was determined from 1609 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.0345. [Cu(ace)2(H2O)4] is a new member in the family of acesulfamate complexes of first row transition metals, namely [M(ace)2(H2O)4], M: Co, Ni, Zn. It differs from the other members in the bonding of acesulfamate to metal through one of its sulfoxide oxygen atoms. The new complex was further characterized by its infrared, Raman and electronic absorption spectra, which were discussed in comparison with those of other related species.
- Baran, Enrique J.,Echeverría, Gustavo A.,Parajón-Costa, Beatriz S.,Piro, Oscar E.
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- Structural and IR-spectroscopic characterization of cadmium and lead(II) acesulfamates
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Cadmium and lead(II) acesulfamate, Cd(C4H4NO4S)2 2H2O and Pb(C4H4NO4S)2, were prepared by the reaction of acesulfamic acid and the respective metal carbonates in aqueous solution, and characterized by elemental analysis. Their crystal structures were determined by single crystal X-ray diffraction methods. The Cd(II) compound crystallizes in the monoclinic space group P21/c with Z = 4 and the corresponding Pb(II) salt in the triclinic space group P1 with Z = 2. In both salts, acesulfamate acts both as a bi-dentate ligand through its nitrogen and carbonyl oxygen atoms and also as a mono-dentate ligand through this same oxygen atom, giving rise to polymeric structures; in the Pb(II) salt the ligand also binds the cation through its sulfoxido oxygen atoms. The FTIR spectra of the compounds were recorded and are briefly discussed. Some comparisons with other related acesulfamate and saccharinate complexes are made.
- Echeverría, Gustavo A.,Piro, Oscar E.,Parajón-Costa, Beatriz S.,Baran, Enrique J.
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- Pharmaceutical salts of biologically active hydrazone compound salinazid: Crystallographic, solubility, and thermodynamic aspects
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The crystal structures of salts of the active pharmaceutical ingredient (API) called salinazid with dicarboxylic acids and acesulfame were determined by single-crystal X-ray diffraction method. The crystals contain hydrogen bond motifs of different structure and complexity, the energies of which were estimated by using the quantum theory of atoms in molecules and crystals (QTAIMC) methodology. It was found that the driving force for facile the oxalate and malate salts formation is the bifurcated N+-H···O- and N+-H···O hydrogen bond synthon, while salinazid malonate is mainly stabilized via a "classic" pyridinium-carboxylate heterosynthon. The oxalate and acesulfame salts of salinazid were found to be stable during aqueous dissolution experiments, providing a substantial solubility improvement compared to pure API (33 and 18 times, respectively). However, the malonate and malate salts dissolved incongruently and rapidly underwent a solution-mediated transformation to form pure salinazid. Based on the solubility data of the stable salts and of the pure components, the Gibbs free energy of the salts formation were calculated to be -21.2 kJ·mol-1 for salinazid oxalate and -22.6 kJ·mol-1 for salinazid acesulfame.
- Surov, Artem O.,Voronin, Alexander P.,Simagina, Anna A.,Churakov, Andrei V.,Perlovich, German L.
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- Polymorphism in acesulfame sweetener: Structure-property and stability relationships of bending and brittle crystals
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Acesulfame is found to exist in two crystalline forms of which Form I (needles) shows bending upon mechanical stress. Crystal structures explain their mechanical response. This is the first case of aliphatic organic compounds featuring a bending phenomenon. Form I is physically more stable than Form II in ambient conditions.
- Velaga, Sitaram P.,Vangala, Venu R.,Basavoju, Srinivas,Bostr?m, Dan
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- Synthesis and characterization of ammonium acesulfamate
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Ammonium acesulfamate, (NH4)C4H4NO 4S, was prepared by the reaction of acesulfamic acid and ammonium carbonate in aqueous solution, and characterized by elemental analysis and 1H and 13C NM
- Echeverria, Gustavo A.,Piro, Oscar E.,Parajon-Costa, Beatriz S.,Baran, Enrique J.
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- Preparation method of acesulfame potassium
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The invention relates to a preparation method of acesulfame potassium. The preparation method comprises the following steps: (1) preparation of acetoacetamido-N-sulfonyl methyl ester: dissolving methyl sulfamate in a chlorinated hydrocarbon solvent, and reacting with diketene under the catalysis of strongly alkaline macroporous resin to generate an intermediate acetoacetamido-N-sulfonyl methyl ester; and (2) preparation of acesulfame potassium: carrying out cyclization reaction on acetoacetamido-N-sulfonyl methyl ester under the action of a copper pyridine complex catalyst, removing byproduct methanol through reactive distillation, and then performing KOH treatment to obtain acesulfame potassium. Compared with the existing production process, the copper pyridine complex is used for replacing a strong acid catalyst in the cyclization process, so that the polymerization side reaction of the intermediate is obviously reduced, and the product yield is increased. Meanwhile, triethylamine and SO3 are prevented from being used, and generation of waste acid and waste water is greatly reduced.
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Paragraph 0024; 0034; 0037-0039; 0042-0044; 0047; 0048; 0050
(2021/06/02)
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- Adapting decarbonylation chemistry for the development of prodrugs capable ofin vivodelivery of carbon monoxide utilizing sweeteners as carrier molecules
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Carbon monoxide as an endogenous signaling molecule exhibits pharmacological efficacy in various animal models of organ injury. To address the difficulty in using CO gas as a therapeutic agent for widespread applications, we are interested in developing CO prodrugs through bioreversible caging of CO in an organic compound. Specifically, we have explored the decarboxylation-decarbonylation chemistry of 1,2-dicarbonyl compounds. Examination and optimization of factors favorable for maximal CO release under physiological conditions led to organic CO prodrugs using non-calorific sweeteners as leaving groups attached to the 1,2-dicarbonyl core. Attaching a leaving group with appropriate properties promotes the desired hydrolysis-decarboxylation-decarbonylation sequence of reactions that leads to CO generation. One such CO prodrug was selected to recapitulate the anti-inflammatory effects of CO against LPS-induced TNF-α production in cell culture studies. Oral administration in mice elevated COHb levels to the safe and efficacious levels established in various preclinical and clinical studies. Furthermore, its pharmacological efficacy was demonstrated in mouse models of acute kidney injury. These studies demonstrate the potential of these prodrugs with benign carriers as orally active CO-based therapeutics. This represents the very first example of orally active organic CO prodrugs with a benign carrier that is an FDA-approved sweetener with demonstrated safety profilesin vivo.
- Brewer, Maya,Cachuela, Alyssa,De La Cruz, Ladie Kimberly,Gallo, David,Ji, Xingyue,Lu, Wen,Menshikh, Anna,Otterbein, Leo,Tan, Chalet,Wang, Binghe,Wang, Minjia,Wang, Siming,Yang, Haichun,Yang, Xiaoxiao,de Caestecker, Mark
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p. 10649 - 10654
(2021/08/20)
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- CARBON MONOXIDE PRODRUGS FOR THE TREATMENT OF MEDICAL DISORDERS
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The present invention provides new compounds and compositions thereof that release carbon monoxide for the treatment of medical disorders that are responsive to carbon monoxide, for example, inflammatory, pain, and dermatological disorders.
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Page/Page column 128-131
(2020/05/21)
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- PROCESS FOR THE PREPARATION OF AN ACESULFAME IN A SPRAY REACTOR HAVING A SPECIFIC VELOCITY OF FLOW
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In general, the invention relates to a process for the preparation of acesulfame or a derivative thereof. More specifically, the invention relates to a process, to a product obtainable by the process and the use of a specified velocity of flow for improving yield in the preparation of acesulfame or a derivative thereof. The invention relates to a process for the preparation of a product, the product being 6-methyl-3,4-dihydro1,2,3-oxathiazin-4-one 2,2-dioxide or a derivative thereof, the process comprising the following steps: a. Contacting SO3 and acetoacetamide-N-sulfonic acid or a derivative thereof in a reactor with a reactor pressure to obtain the product; b. The product exiting the reactor to a region outside the reactor through an aperture at a velocity of flow higher than 0.9 m/s, the region outside the reactor having an external pressure which is lower than the reactor pressure.
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Page/Page column 25
(2019/07/19)
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- PROCESS FOR THE PREPARATION OF AN ACESULFAME WITH SULPHURIC ACID PROCESSING
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The present invention generally relates to a process for the preparation of a product, the prod- uct being 6-methyl-3,4-dihydro1,2,3-oxathiazin-4-one 2,2-dioxide or a derivative thereof. The present invention also relates to the use of such a process for makingdiammonium sulphate. The present invention relates to a process for the preparation of a product, the product being 6- methyl-3,4-dihydro1,2,3-oxathiazin-4-one 2,2-dioxide or a derivative thereof, the process comprising the following steps: a.Contacting SO 3 and acetoacetamide-N-sulphonic acid or a derivative thereof in the presence of an amine, thereby obtaining a first stream comprising the amine and sul- phuric acid; b.Providing a second stream comprising ammonia; c.Providing a circuit; d.Introducing the second stream into the circuit at point A and the first stream into the circuit at point B to obtain a cyclestream cycling in the circuit; e.Removing a portion of the cycle stream at a point C to obtain a third stream; wherein the circulation ratio is in the range from 3 to 30, the circulation ratio being the value of the mass flow rate of the cycle stream immediately preceding point A F c divided by the val- ue of the mass flow rate of the first stream into the circuit at point B F according to the fol-20 lowing formula: circulation ratio = F c /F 2 Figure 130
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Page/Page column 24
(2019/08/08)
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- ACESULFAME POTASSIUM COMPOSITIONS AND PROCESSES FOR PRODUCING SAME
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A process for producing acesulfame potassium, the process comprising the steps of providing a cyclizing agent composition comprising a cyclizing agent and a solvent and having an initial temperature, cooling the cyclizing agent composition to form a cooled cyclizing agent composition having a cooled temperature less than 35° C., reacting an acetoacetamide salt with the cyclizing agent in the cooled cyclizing agent composition to form a cyclic sulfur trioxide adduct composition comprising cyclic sulfur trioxide adduct; and, forming from the cyclic sulfur trioxide adduct in the cyclic sulfur trioxide adduct composition the finished acesulfame potassium composition comprising non-chlorinated acesulfame potassium and less than 39 wppm 5-chloro-acesulfame potassium. The cooled temperature is at least 2° C. less than the initial temperature.
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Paragraph 0172; 0173; 0174; 0175; 0176
(2018/04/13)
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- METHOD FOR PRODUCING 3,4-DIHYDRO-1,2,3-OXATHIAZIN-4-ONE-2,2-DIOXIDE COMPOUND OR SALT THEREOF
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A high quality 3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide compound or a salt thereof is obtained easily and efficiently. When the compound represented by the following formula (2) (wherein, R1, R2, and R3 are hydrogen atom or an organic group inert to the reaction, and X is hydrogen atom) or a salt thereof is produced by cyclization of a mixture of β-ketoamide-N-sulfonic acid represented by the following formula (1) or a salt thereof and an inert solvent and a mixture of acid anhydride and an inert solvent, and by subsequent hydrolysis of the product, a step of (A) hydrolyzing the reaction product obtained by the cyclization by mixing with an aqueous solution of sulfuric acid so as a concentration of sulfuric acid in an aqueous phase after the hydrolysis would become 30% by weight or more, and then separating an organic phase and an aqueous phase, or a step of (B) washing the organic phase liquid after the hydrolysis with an aqueous solution of sulfuric acid with a concentration of 30% by weight or more is at least carried out.
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Page/Page column 6-7
(2009/12/28)
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- Method for producing 3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide compound or salt thereof
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A method produces a 3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide compound of following formula (2): wherein R1 and R2 are the same as or different from each other and are each hydrogen atom or an organic group inert to the reaction; and R3 is hydrogen atom or an organic group inert to the reaction, or a salt thereof, by subjecting a beta-ketoamide-N-sulfonic acid of following Formula (1): wherein R1, R2 and R3 are as defined above; and X is hydrogen atom, or a salt thereof, to cyclization in the presence of an acid anhydride with or without further subjecting the cyclized product to hydrolysis, in which the cyclization is continuously carried out using a continuous flow reactor.
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Page/Page column 5-7
(2008/06/13)
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- Composition comprising 6-methyl-3,4dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide, its salts, preparation thereof and uses therefor
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Acesulfame-K is a widely used sweetener in food and beverage. It is prepared by using the substituted sodium phenoxide or substituted phenol as the starting substance to synthesize the following three intermediates: a substituted phenoxide sulfonylchloride(I), a substituted phenoxide sulfonylamide(II) and an acetoacetamide-N-sulfonyl-substituted phenoxide(III). Particularly, II was prepared by using the liquid or gaseous ammonia to react with I under the action of some catalysts in a reaction column. III was prepared by using II to react with diketene. Acesulfame-K was prepared by ring-closure in III with methanol solution of KOH or K2CO3.
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- Process for the preparation of 6-methyl-3,4-dihydro-1,2,3-oxathiazin-4-one 2,2-dioxide and its non-toxic salts
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6-Methyl-3,4-dihydro-1,2,3-oxathiazin-4-one 2,2-dioxide and its non-toxic salts are prepared by reacting acetoacetamide with an S-O compound of the formula I wherein Y=F, Cl, --OSO2 F or --OSO2 Cl, preferably only F, in the presence of bases. The non-toxic salts--especially the potassium salt--are valuable synthetic sweeteners.
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- Process for the manufacture of 6-methyl-3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide
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6-Methyl-3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide or the nontoxic salts thereof is prepared by reacting 6-methyl-2,3-dihydro-1,3-oxazin-2,4-dione-3-sulfo-fluoride of the formula EQU1 with at least 1 mole water per mole of fluoride to obtain acetoacetamide-N-sulfo-fluoride with splitting off of CO2, treating the acetoacetamide-N-sulfofluoride with an aqueous and/or alcoholic base and isolating the oxathiazinone or the salts thereof.
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- Process for the manufacture of 6-methyl-3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide
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6-Methyl-3,4-dihydro-1,2,3-oxathiazin-4-one-2,2-dioxide and the nontoxic salts thereof are prepared by reacting acetoacetic acid with fluorosulfonyl isocyanate at a temperature of from -20°C to +50°C in the presence of from 0.5 to 2 moles, calculated on the FSI used, of an alkali methal fluoride or a tertiary amine of the formula in which R1, R2, R3 represent identical or different alkyl radicals having from 1 to 10 carbon atoms, two of the radicals R1 to R3 optionally form together an alkylene radical having from 4 to 5 carbon atoms which may contain N, O, or S as hetero atom, or one of the radicals R1 to R3 represents a phenyl radical, or of pyridine or quinoline, or of a mixture of the aforesaid compounds, and transforming the salt of acetoacetamide-N-sulfofluoride obtained into the oxathiazinone salt or the free oxathiazinone by a treatment with aqueous and/or alcoholic bases.
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