- Bifunctional Fe(ii) spin crossover-complexes based on ω-(1: H -tetrazol-1-yl) carboxylic acids
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To increase the supramolecular cooperativity in Fe(ii) spin crossover materials based on N1-substituted tetrazoles, a series of ω-(1H-tetrazol-1-yl) carboxylic acids with chain-lengths of C2-C4 were synthesized. Structural characterization confirmed the formation of a strong hydrogen-bond network, responsible for enhanced cooperativity in the materials and thus largely complete spin-state transitions for the ligands with chain lenghts of C2 and C4. To complement the structural and magnetic investigation, electronic spectroscopy was used to investigate the spin-state transition. An initial attempt to utilize the bifunctional coordination ability of the ω-(1H-tetrazol-1-yl) carboxylic acids for preparation of mixed-metallic 3d-4f coordination polymers resulted in a novel one-dimensional gadolinium-oxo chain system with the ω-(1H-tetrazol-1-yl) carboxylic acid acting as μ2-η2:η1 chelating-bridging ligand.
- Zeni, Willi,Seifried, Marco,Knoll, Christian,Welch, Jan M.,Giester, Gerald,St?ger, Berthold,Artner, Werner,Reissner, Michael,Müller, Danny,Weinberger, Peter
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- One-pot chemoenzymatic synthesis of 3'-functionalized cephalosphorines (cefazolin) by three consecutive biotransformations in fully aqueous medium
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We illustrate a new chemoenzymatic synthesis of cefazolin from cephalosporin C, involving three consecutive biotransformations in full aqueous medium. This one-pot three-step synthesis includes the D-amino acid oxidase catalyzed oxidative deamination of the cephalosporin C side chain, hydrolysis of the resulting glutaryl derivative catalyzed by glutaryl acylase, and the final penicillin G acylase (PGA)-catalyzed acylation of 7- aminocephalosporanic acid (1, 7-ACA). The product, 7-[(1H-tetrazol-1- yl)acetamido]-3-(acetoxymethyl)-Δ3-cephem-4-carboxylic acid (5), was used as an intermediate for cefazolin synthesis by 3'-acetoxy group displacement with 2-mercapto-5-methyl-1,3,4-thiadiazole. Very high yields have been achieved with all the enzymatic reactions performed; high product concentrations were obtained in short reaction times. This synthetic approach presents several advantages when compared with the conventional chemical processes. The use of the toxic reagents and chlorinated solvents is avoided, while the substrate specificity and chemoselectivity of the enzymes makes reactive group protection and intermediate purification unnecessary. The enzymatic deacylation of cephalosporin C was performed by the simultaneous use of D-amino acid oxidase and glutaryl acyclase. The substrate specificity of PGA allowed the acylation of 7-ACA (1) to be performed without purification from the glutaric acid produced during the enzymatic deacylation. These results were achieved by optimization and correct assembly of the different biotransformations involved. Special attention has been applied to the kinetically controlled acylation reaction. High yields were obtained through a careful selection of the enzyme catalyst, experimental conditions, and synthetic strategy.
- Justiz,Fernandez-Lafuente,Guisan
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- Energetic salts based on nitroiminotetrazole-containing acetic acid
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2-(5-Nitroiminotetrazol-1-yl)acetic acid (4) was synthesized from 100% nitric acid and ethyl 2-(5-aminotetrazol-1-yl)acetate (2), which was easily obtained by reaction of ethyl aminoacetate hydrochloride, sodium hydroxide, and cyanogen azide. Compound 4 was also formed with 100% nitric acid and 2-(5-aminotetrazol-1-yl)acetic acid which was prepared from sodium 5-aminotetrazolate and 2-chloroacetic acid. New energetic materials comprised of nitroiminotetrazolate salts with nitroiminotetrazolate and carboxylate anions have been characterized spectroscopically as well as with single crystal X-ray diffraction and elemental analyses. In addition, the heats of formation (ΔHf), and detonation pressures (P) and velocities (D) were calculated. All compounds were insensitive (>40 J) for impact with BAM Fallhammer. The Royal Society of Chemistry 2012.
- Joo, Young-Hyuk,Gao, Haixiang,Parrish, Damon A.,Cho, Soo Gyeong,Goh, Eun Mee,Shreeve, Jean'Ne M.
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- Synthesis, Structure, and Biological Activity of Palladium(II) Complexes with Some 1- and 2-Substituted Tetrazole Ligands
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Abstract: A series of palladium(II) complexes with 1H- and 2H-tetrazole ligands (2-isopropyl-5-R-2H-tetrazoles and 1H-tetrazol-1-ylcarboxylic acids) was synthesized. Structure of the obtained compounds was confirmed by 1H and 13C NMR spectroscopy, high-resolution mass spectrometry, and single crystal X-ray diffraction analysis. According to the spectrophotometry data, the complexes are weakly bound to DNA. The cytotoxic activity of the obtained palladium complexes was studied in vitro.
- Batyrenko,Mikolaichuk,Ovsepyan,Protas,Kornyakov,Lider,Eremina, Yu. A.,Khlebnikova,Lakhvich,Trifonov
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p. 666 - 671
(2021/06/02)
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- Process for synthesizing 1H-tetrazoleacetic acid
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The invention discloses a novel process for synthesizing 1H-tetrazoleacetic acid. According to the invention, glycine ester hydrochloride, triethyl orthoformate, sodium azide and the like are used asraw materials to synthesize 1H-tetrazoleacetic acid in an ethanol solution by a one-pot method; alkali is dropwise added into an ethanol solution of glycine ester hydrochloride, triethyl orthoformateand sodium azide, generated glycine ester reacts with triethyl orthoformate and sodium azide in a system, concentrated sulfuric acid and purified water are dropwise added into reaction liquid after the reaction is completed, and ring closing and hydrolysis are carried out to prepare 1H-tetrazoleacetic acid; the solvent ethanol used in the process can be repeatedly recycled, hydrolysis of triethylorthoformate can be inhibited, reaction progress is accelerated, cost is effectively reduced; and the synthesis process is simple in route, wide in application range, low in production cost, improvedin safety, free of pollution, capable of completely meeting the production requirements of modern green chemical engineering, high in yield, good in operability and repeatability and convenient for industrial production.
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Paragraph 0008; 0029-0030
(2020/11/12)
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- Method for catalytic synthesis of tetrazoleacetic acid and derivatives thereof
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The invention discloses a method for catalytic synthesis of tetrazoleacetic acid and derivatives thereof. According to the method, Click reaction of ethyl azide acetate and a cyano compound is realized to prepare tetrazoleacetic acid and derivatives thereof. The method comprises the following steps: by taking superparamagnetic nanoparticle supported ionic liquid as a catalyst, carrying out Click reaction on ethyl azide acetate and a cyano compound in a solvent at 60-100 DEG C and normal pressure for 8-14 hours, and then carrying out hydrolytic decarboxylation to obtain corresponding tetrazoleacetic acid and derivatives thereof. Tests prove that after the reaction is finished, the catalyst is simply recycled through an external magnetic field and can be repeatedly used, and the activity isnot obviously reduced. The catalytic system is simple to operate, high in yield and good in reusability, and has a good industrial prospect.
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Paragraph 0018-0024; 0027-0037
(2020/09/30)
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- Preparation method of 1-tetrazole acetate
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The invention relates to the field of organic synthesis, and discloses a preparation method of 1-tetrazole acetate, which comprises the following steps: 1) taking aminoguanidine carbonate as a raw material, regulating to acidity with an acid solution, cooling, dropwisely adding a sodium nitrite water solution, regulating the pH value to alkalinity, and carrying out reflux cyclization to generate 5-aminotetrazole; 2) reacting 5-aminotetrazole with chloroacetic acid under an alkaline condition to synthesize 1-acetic acid-5-aminotetrazole, and 3) finally reducing with a reducing agent to remove amino to obtain 1-tetrazole acetate. Compared with the prior art, the method provided by the invention is safer and more environment-friendly, and the obtained product has high yield and purity.
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Paragraph 0027; 0029; 0030; 0032
(2020/07/21)
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- Method for synthesis of tetrazolylacetic acid using hydrazine hydrate method
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The invention discloses a method for synthesis of tetrazolylacetic acid using a hydrazine hydrate method. The tetrazolylacetic acid is prepared from the raw materials of triethylorthoformate, glycine,hydrazine hydrate, sodium nitrite and the like. According to the method for synthesis of tetrazolylacetic acid using the hydrazine hydrate method, the processing route of a traditional azide ester method that sodium azide is adopted as a raw material to prepare the tetrazolylacetic acid is abandoned, the safety of the production technology is improved, the production cost is low, no waste water or waste gas is generated in the whole technology, the method accords with the production requirement of green chemical, co-produced salt sodium sulfate can be sold out directly, and the production cost is further lowered. According to the method for synthesis of tetrazolylacetic acid using the hydrazine hydrate method, the synthetic route is simple, the product purity is high, the maneuverabilityand the repeatability are high, and industrial production is facilitated.
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Paragraph 0028-0037
(2019/10/17)
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- A tetrazole acetic acid synthesis process (by machine translation)
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The invention discloses a tetrazole of acetic acid synthesis process, first of all by the formic acid and glycine heating reflux reaction preparation N - formyl glycine, then to acetic anhydride as the dehydrating agent preparation 5 - oxazolidone, finally, it with sodium azide in the zinc bromide under the catalytic action of the four nitrogen zuozuo ethanoic acid prepared. This invention relates to a new synthetic process of the reaction carried out in the aqueous phase, avoids the organic solvent and the use of large quantities of waste, can effectively reduce the cost, and without the generation of "three wastes", in accordance with the requirements of the production of the green, and the synthesis method is simple, easy control of reaction conditions, post-processing process is simple, has very strong operability and repeatability, and high product purity, can effectively reduce the cost, convenient for industrial production. (by machine translation)
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Paragraph 0011; 0032; 0034-0035; 0038; 0043; 0048
(2017/08/29)
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- 7-OXO -6-(SULFOOXY)- 1,6-DIAZABICYCLO [3.2.1] OCTANE CONTAINING COMPOUNDS AND THEIR USE IN TREATMENT OF BACTERIAL INFECTIONS
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Compounds of Formula (I) or a stereoisomer or a pharmaceutically acceptable salt thereof, their preparation, and use in treating a bacterial infection are disclosed.
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Page/Page column 53
(2017/06/19)
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- Microwave alkylation of lithium tetrazolate
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Abstract: N1-substituted tetrazoles are interesting ligands in transition metal coordination chemistry, especially in the field of spin crossover. Their synthesis is performed in most cases according to the Franke-synthesis, using a primary amine as reagent introducing the substitution pattern. To enhance flexibility in means of substrate scope, we developed a new protocol based on alkylation of lithium tetrazolate with alkyl bromides. The N1–N2 isomerism of the tetrazole during the alkylation was successfully suppressed by use of highly pure lithium tetrazolate and 30?vol.% aqueous ethanol as solvent, leading to pure N1-substituted products. The feasibility of this reaction was demonstrated by a selection of different substrates. Graphical abstract: [Figure not available: see fulltext.]
- Müller, Danny,Knoll, Christian,Weinberger, Peter
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p. 131 - 137
(2017/01/17)
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- A pharmaceutical intermediates to a [...] rhzomorph 2 - (1H-1-tetrazolyl) method for the synthesis of acetic acid (by machine translation)
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A pharmaceutical intermediates to a [...] rhzomorph 2 - (1H-1-tetrazolyl) method for the synthesis of acetic acid, comprising the following steps: adding the reaction container 2 - (5-nitro -1H-1-tetrazolyl) acetic acid 0.51mol, solution O-bromophenol the 0.56 [...] 0.59mol, control the stirring speed of the 130 [...] 150rpm, adding cuprous chloride 0.26mol, potassium chloride solution 310 ml, control the temperature of the solution is 10 - - 15°C, reaction of the 7 [...] 9h, reducing the temperature of the solution to 5 - - 8°C, adding ammonium nitrite solution to adjust the pH in the 6 [...] 7, dimethyl sulfoxide for extracting the 5 [...] 7 time, combined with the organic layer, cyclohexanol washing, dehydrating agent dehydration, dimethyl sulfoxide is distilled under reduced pressure, the residue is added to the N-methyl formamide, solid precipitation, filtration, recrystallization in the acetamide, to obtain crystal 2 - (1H-1-tetrazolyl) acetic acid. (by machine translation)
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Paragraph 0014; 0015
(2016/12/01)
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- Influence of substrate structure on PGA-catalyzed acylations. Evaluation of different approaches for the enzymatic synthesis of cefonicid
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The influence of the substrate structure on the catalytic properties of penicillin G acylase (PGA) from Escherichia coli in kinetically controlled acylations has been studied. In particular, the affinity of different β-lactam nuclei towards the active site has been evaluated considering the ratio between the rate of synthesis (vs) and the rate of hydrolysis of the acylating ester (vhl). 7-Aminocephalosporanic acid (7-ACA) and 7-amino-3-(1-sulfomethyl-1,2,3,4-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (7-SACA) showed a good affinity for the active centre of PGA. The enzymatic acylation of these nuclei with R-methyl mandelate has been studied in order to evaluate different approaches for the enzymatic synthesis of cefonicid. The best results have been obtained in the acylation of 7-SACA. Cefonicid (8) was recovered from the reaction mixture as the disodium salt in 65% yield and about 95% of purity. Furthermore, through acylation of 7-ACA, a "one-pot" chemo-enzymatic synthesis was carried out starting from cephalosporin C using three enzymes in sequence: D-amino acid oxidase (DAO), glutaryl acylase (GA) and PGA. Cefonicid disodium salt was obtained in three steps, avoiding any intermediate purification, in 35% overall yield and about 94% purity. This approach presents several advantages compared with the classical chemical processes.
- Terreni, Marco,Tchamkam, Joseph Gapesie,Sarnataro, Umberto,Rocchietti, Silvia,Fernandez-Lafuente, Roberto,Guisan, Jose M.
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p. 121 - 128
(2007/10/03)
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- SYNTHESIS AND PROPERTIES OF 1-(2-HYDROXYETHYL)TETRAZOLE
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The heterocyclization of monoethanolamine with ethyl orthoformate and sodium azide in acetic acid was studied.It was shown that the reaction proceeds through a step involving the formation of a disubstituted formamidine and leads to the production of 1-(2-hydroxyethyl)tetrazole in high yield.A method for the purification of 1-(2-hydroxyethyl)tetrazole by complexing with cupric chloride was developed, and its physicochemical properties and some chemical transformations were investigated.
- Gaponik, P. N.,Karavai, V. P.
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p. 1172 - 1174
(2007/10/02)
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- Methods and intermediates for preparing cis-4-oxoazetidine intermediates
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The stereospecific cycloaddition of nitrogen containing acetic acid halides or anhydrides with Schiff bases having a carbalkoxy group substituted on the methine carbon atom offers new intermediates and methods for preparing synthetic cephalosporin congeners having antibacterial activity.
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- 1H-Tetrazole-1-acetate esters and acids and process therefor
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Novel 1H-tetrazole-1-acetate esters and acids are prepared by reacting azidoacetate esters and acids with certain acyl cyanides or cyanoformates. The products of the process are useful as intermediates in the preparation of 1H-tetrazole-1-acetic acids which have utility in preparing certain cephalosporin and penicillin antibiotics.
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