- Catalyst-free method for synthesizing 2, 2, 6, 6-tetramethyl-4-piperidylamine
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The invention provides a method for synthesizing 2, 2, 6, 6-tetramethyl-4-piperidylamine without a catalyst. Comprising the following steps: adding 2, 2, 6, 6-tetramethyl-4-piperidone and ammonium formate which is 1.25-1.6 times of the equivalent weight of the 2, 2, 6, 6-tetramethyl-4-piperidone into a reactor, and carrying out a Leuckart reaction, so as to obtain the 2, 2, 6, 6-tetramethyl-4-piperidylamine. According to the method, 2, 2, 6, 6-tetramethyl-4-piperidone and ammonium formate are adopted to react under the conditions of no catalyst, normal pressure or high pressure and no hydrogen; and the method provided by the invention has the advantages of high safety, high reaction selectivity, no generation of byproduct tetramethylpiperidinol, and effective increase of the yield. The method can be carried out without complex equipment, and is simple, convenient to operate, high in safety, high in repetition rate and low in cost.
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Paragraph 0023-0039
(2021/05/01)
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- 2,2,6,6-tetramethyl-4-piperidinamine preparation method
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The invention relates to a 2,2,6,6-tetramethyl-4-piperidinamine preparation method, which comprises: adding a raw material 2,2,6,6-tetramethylpiperidone, an amine reactant and a solvent into a reaction kettle, stirring and premixing at 10-50 DEG C to form an imine intermediate, reducing the imine intermediate by using a reducing agent at a certain temperature under a certain pressure, and reactingfor a certain time to finally synthesize the target product 2,2,6,6-tetramethyl-4-piperidinamine compound. According to the invention, 2,2,6,6-tetramethyl-4-carbonyl piperidone reacts with an amine compound to generate an imine intermediate, and a reducing agent is used for replacing catalytic hydrogenation to perform reduction, so the product yield can reach more than 92%, the generation of the2,2,6,6-tetramethylpiperidone hydrogenation byproduct tetramethylpiperidinol is avoided, the hydrogenation process with a high risk coefficient is avoided, and the method is an ideal process for achieving industrialization.
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Paragraph 0024-0028
(2020/03/09)
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- Synthetic method of amino-2,2,6,6-tetramentylniperidine with specific pH range
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The invention discloses a synthetic method of amino-2,2,6,6-tetramentylniperidine with a specific pH range, and the method comprises the following steps: taking 2,2,6, 6-tetramethyl piperidone as a raw material, adding the raw material and ammonia water into a high-pressure kettle, first adjusting the pH value to 12.0-13.0, adding framework nickel serving as a catalyst, carrying out hydrogenationreaction at temperature of 55-65 DEG C under a set pressure value of 1.5-2.5 mpa, stopping the reaction until the pressure in the kettle is always not lower than 2% of a set pressure value in one hour; and carrying out normal pressure distillation on the reaction liquid, and then carrying out reduced pressure rectification to obtain the product amino-2,2,6,6-tetramentylniperidine. According to themethod disclosed by the invention, the conversion rate of the tetramethyl piperidone is improved, and the product yield is improved.
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Paragraph 0025; 0038-0073
(2019/07/04)
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- Method for preparing intermediate 2,2,6,6-tetramethyl-4-piperidylamine
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The invention relates to a method for preparing intermediate 2,2,6,6-tetramethyl-4-piperidylamine. The method is characterized by comprising the following steps: step 1), in the presence of a catalyst1, reacting acetone with ammonia gas to produce 2,2,6,6-tetramethyl-4-piperidinone and water; and step 2), in the presence of a catalyst 2, reacting the 2,2,6,6-tetramethyl-4-piperidinone with ammonia gas to produce 2,2,6,6-tetramethyl-4-piperidylimine and water, and reacting the 2,2,6,6-tetramethyl-4-piperidylimine with hydrogen gas to produce the 2,2,6,6-tetramethyl-4-piperidylamine, wherein the catalyst 1 is ammonium nitrate, and the catalyst 2 is a sodium hydroxyphenyl phosphate modified framework nickel catalyst. The method provided by the invention has the advantages of short synthetictime, a high conversion rate of the acetone and a high repeating utilization rate of the raw materials.
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Paragraph 0039; 0042; 0044
(2019/12/25)
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- Synthesis and fluorescence properties of six fluorescein-nitroxide radical hybrid-compounds
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Six fluorescein-nitroxide radical hybrid-compounds (2ab, 3ab, 4, and 5) were synthesized by the condensation of 5- or 6-carboxy-fluorescein and 4-amino-TEMPO (2ab), 5- or 6-aminofluorescein and 4-carboxy-TEMPO (3ab), and fluorescein and 4-carboxy-TEMPO (4), or by reaction of the 3-hydroxyl group of fluorescein with DPROXYL-3-ylmethyl methanesulfonate (5). Fluorescence intensities (around 520 nm) after reduction of the radical increased to 1.43-, 1.38-, and 1.61-folds for 2a, 2b and 3b respectively; 3a alone exhibited a decrease in intensity on reduction. Since 4 was readily solvolyzed in PBS or even methanol to afford fluorescein and 4-carboxy-TEMPO, its fluorescence change could not be measured. Hybrid compound 5 containing an ether-linkage between the fluorescein phenol and 3-hydroxymethyl-DPROXYL hydroxyl centers, was stable and on reduction, showed a maximum increase (3.21-fold) in relative fluorescence intensity in PBS (pH 5.0), despite its remarkably low absolute fluorescence intensity.
- Sato, Shingo,Endo, Susumu,Kurokawa, Yusuke,Yamaguchi, Masaki,Nagai, Akio,Ito, Tomohiro,Ogata, Tateaki
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supporting information
p. 66 - 71
(2016/07/06)
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- A 2, 2, 6, 6-tetramethyl-4-PIPERIDYLAMINES method for the preparation of
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The invention discloses a method for preparing 2,2,6,6-tetramethyl-4-piperidinamine. The method comprises the following steps: synthesizing 2,2,6,6-tetramethyl-4-piperidone and carrying out a hydrogenation reaction of the 2,2,6,6-tetramethyl-4-piperidone. The key synthesis steps are controlled, the addition amount for acetone recovery is controlled, and the rectification purity and conversion rate of the product are improved through the optimized distillation, crystallization and hydrogenation reduction process.
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Paragraph 0028; 0037-0042
(2017/04/11)
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- MODIFIED ZNO NANOPARTICLES
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Process for the preparation of modified zinc oxide nanoparticles, which comprises reacting zinc oxide nanoparticles, which are dissolved in a solvent, in the presence of ammonia or amines with a tetraalkyl orthosilicate and optionally with an organosilane, with the proviso that the reaction takes place at a content of less than 5% by weight of water, based on the total amount of solvent and water. Modified zinc oxide nanoparticles which have Si—O-alkyl groups and are soluble in organic solvents, obtainable by this process for the preparation. Liquid or solid formulations which comprise modified ZnO nanoparticles. Inanimate organic materials, for example plastics or coatings, which comprise modified ZnO nanoparticles. Method of stabilizing inanimate organic materials against the effect of light, free radicals or heat, where modified ZnO nanoparticles, which optionally comprise UV absorbers and/or stabilizers as further additives, are added to the materials.
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- Reactions of nitroxides. Part X: Antifungal activity of selected sulfur and selenium derivatives of 2,2,6,6-tetramethylpiperidine
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The antifungal activity of nitroxyl radicals - derivatives of 2,2,6,6-tetramethylpiperidine-1-oxyl with reactive substituents 4-isothiocyanato-, 4-isocyano-, and 4-isoselenocyanato- and of N-formyl-, N-thioformyl-, N-selenoformyl-derivatives of 2,2,6,6-tetramethylpiperidine was investigated. Those of the above compounds, which contain a sulfur or selenium atom are the most active against four fungus plant patogens: Botrytis cinerea, Fusarium culmorum, Phytophthora cactorum, Rhizoctonia solani. 4-Isoselenocyanato-2,2,6,6-tetramethylpiperidine-1-oxyl proved to be the most active compound.
- Zakrzewski, Jerzy,Krawczyk, Maria
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scheme or table
p. 514 - 516
(2011/02/28)
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- Electron paramagnetic resonance (EPR) study of spin-labeled camptothecin derivatives: A different look of the ternary complex
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Camptothecin (CPT) derivatives are clinically effective poisons of DNA topoisomerase I (Top1) able to form a ternary complex with the Top1-DNA complex. The aim of this investigation was to examine the dynamic aspects of the ternary complex formation by means of site-directed spin labeling electron paramagnetic resonance (SDSL-EPR). Two semisynthetic CPT derivatives bearing the paramagnetic moiety were synthesized, and their biological activity was tested. A 22-mer DNA oligonucleotide sequence with high affinity cleavage site for Top1 was also synthesized. EPR experiments were carried out on modified CPT in the presence of DNA, of Top1, or of both. In the last case, a slow motion component in the EPR signal appeared, indicating the formation of the ternary complex. Deconvolution of the EPR spectrum allowed to obtain the relative drug amounts in the complex. It was also possible to demonstrate that the residence time of CPT "trapped" in the ternary complex is longer than hundreds of microseconds.
- Ricci, Antonio,Marinello, Jessica,Bortolus, Marco,Sánchez, Albert,Grandas, Anna,Pedroso, Enrique,Pommier, Yves,Capranico, Giovanni,Maniero, Anna Lisa,Zagotto, Giuseppe
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supporting information; experimental part
p. 1003 - 1009
(2011/04/25)
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- PROCESS FOR THE PREPARATION OF 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE
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4-amino-2,2,6,6-tetramethylpiperidine is prepared by reacting 2,2,6,6-tetramethylpiperidine-4-one with ammonia and hydrogen in the presence of nickel and/or cobalt catalyst and water. The main reaction is carried out at a pressure of at most 50 bar and a temperature of at most 120° C. up to a conversion of the 2,2,6,6-tetramethylpiperidine-4-one of at least 80%. Then, an after-reaction takes place at a higher temperature and at a higher pressure compared to the pressure and temperature of the main reaction.
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Page/Page column 3-4
(2009/09/05)
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- Tetracyclic benzimidazole derivatives and combinatorial libraries thereof
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The present invention relates to novel tetracyclic benzimidazole derivative compounds of the following formula: wherein R1to R10have the meanings described in here. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing tetracyclic benzimidazole derivative compounds.
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- 2-aminobenzoxazole derivatives and combinatorial libraries thereof
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The present invention relates to novel 2-aminobenzoxazole derivative compounds of the following formula: wherein R1 to R4 and Z have the meanings provided herein. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing 2-aminobenzoxazole derivative compounds.
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- 2-aminopyridine derivatives and combinatorial libraries thereof
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The present invention relates to novel 2-aminopyridine derivative compounds of the following formula: wherein R1to R5have the meanings provided herein. The invention further relates to combinatorial libraries containing two or more such compounds, as well as methods of preparing 2-aminopyridine derivative compounds.
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- Synthesis, electrosynthesis and electrochemical properties of substituted 2,2,6,6-tetramethylpiperidine and the respective stable nitroxyl radicals. XIV
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The various derivatives of 2,2,6,6-tetramethylpiperidine and their stable nitroxyl radicals were investigated by means of chemical, electrochemical and empirical calculation methods. The titration results were calculated by means of TURBO BASIC with PKAS and MINIGLASS algorithm, and the prototropic experimental data were obtained. The reaction ways were calculated on the basis of the formation enthalpie values which were calculated by means of AM 1 (MOPACK) method. On the basis of a voltammetry and an electrolysis under controlled potential the reaction products were analyzed and the yields of the investigated processes were received. The various quasireversible redox reactions of the type stable nitroxyl radical oxoannonium cation were investigated by means of a cyclic voltammetry and electrochemical impedance spectroscopy. The mechanisms of the investigated reactions have been discussed and the reaction schemes are presented. - Key words: derivatives of 2,2,6,6-tetramethylpiperidine; electrolysis; electrochemical impedance spectroscopy; formation enthalpy values; prototropic constants
- Avrutskaya, Inna A.,Novikov, Vasilii T.,Dziegiec, Jozef,Grzejdziak, Andrzej,Krzyczmonik, Pawel,Scholl, Henryk
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- Novel piperidine compounds containing a tetrahydrofuran ring for use as stabilisers for organic materials
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The present invention relates to novel tetramethylpiperidine compounds of the general formula (I) in which X and Y are e.g. a group of the formula (IIa) or (IIb) in which R1 and R2 are e.g. hydrogen or methyl. The said compounds are effective stabilisers for organic materials, in particular synthetic polymers, against the action of light, heat and oxidation.
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- Interaction of tert-Butylcalixarenes with Cyclic Amines
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p-tert Butylcalixarenes 1 and 2 react with the cyclic amines 3 - 8, 10 by proton transfer forming so -called "exo-complexes" between the ammonium and phenolate groups.As well endocyclic as exocyclic amino groups are reactive.The nitroxyl radical 9 does not react with 1 or 2 by the proton transfer reaction.These results demonstrate that an interaction between the nitrogen atom of HALS-compounds, esp. compound 10, with calixarene hydroxylgroups is possible, but an interaction between the corresponding nitroxyl radicals with calixarene hydroxylgroups does not occur.
- Goermar, Gerhard,Seiffarth, Klaus,Schulz, Manfred,Chachimbombo, Chitula Leopoldina
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p. 475 - 479
(2007/10/02)
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- Process for preparing 1-oxa-3,8-diaza-4-oxo-spiro-[4,5]-decanes
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1-Oxa-3,8-diaza-4-oxo-spiro-[4,5]-decane compounds of the formula STR1 are new light stabilizers for protecting polymers from the damaging effect of UV radiation.
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- PREPARATION OF 2,2,6,6-TETRAMETHYL-4-AMINOPIPERIDINE AND ITS SUBSTITUTED COMPOUNDS BY ELECTROREDUCTION OF AZOMETHINES OF 2,2,6,6-TETRAMETHYL-4-OXOPIPERIDINE (TRIACETONAMINE)
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Five methods have been developed for electrosynthesis of 2,2,6,6-tetramethyl-4-aminopiperidine in 95 - 98 percent yield via the lead-cathode reduction of 2,2,6,6-tetramethyl-4-oxiimino-piperidine, a mixture of triacetonamine with inorganic salts of hydroxylamine, and a mixture of triacetonamine with nitric acid in a solution of sulphuric acid, via the reduction of azine triacetonamine and of a mixture of triacetonamine with inorganic salts of hydrazine in a neutral solution.The corresponding saturated derivatives of 2,2,6,6-tetramethyl-4-aminopiperidine have been obtained in 60 - 80 percent yield by ele ctroreduction of phenylimine and ethylene diimine.
- Fioshin, M. Ya.,Avrutskaya, I. A.,Surov, I. I.,Novikov, V. T.
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p. 182 - 191
(2007/10/02)
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- Potential Anticancer Agents. XXVI. Spin Labelled Nitrosoureas
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In order to obtain more information about the in vivo mechanism of action of nitrosoureas, the synthesis of spin labelled nitrosoureas derived from 1-oxyl-2.2.6.6-tetramethyl-4-aminopiperidine was undertaken.The synthesis of four spin labelled ureas 4a-4d was reported as well as two spin labelled nitrosoureas: 1-methyl-3-(2'.2'.6'.6'-tetramethyl-piperidin-4'-yl-1'-oxyl)-1-nitrosourea (9a) and 1-(2'-chloroethyl)-3-(2".2".6".6"-tetramethyl-piperidin-4"-yl-1"-oxyl)-1-nitrosourea (9b).Their e.s.r. spectra were recorded.None of these compounds proved to be active against L1210.
- Baracu, Ileana,Dobre, V.,Niculescu-Duvaz, I.
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p. 667 - 674
(2007/10/02)
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- Poly-bis-triazinylimides, their preparation
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Poly-bis-triazinylimides of the formula STR1 are prepared from bis-(2,4-dichloro-1,3,5-triazin-6-yl)imides and polyalkylpiperidylamines. They are used as light stabilizers for polymers.
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- The Reaction of Diphenylcarbene with Nitroxides
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Diphenylcarbene reacts with 2,2,6,6-tetramethylpiperidine N-oxide with a rate constant of 2.7 x 108 M-1 s-1 in acetonitrile at room temperature.The reaction involves the thransfer of an oxygen atom, leading to benzophenone and 2,2,6,6-tetramethylpiperidinyl radical in essentially quantitative yields.In the case of 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxide insertion at the O-H bond competes with reaction at the nitroxide center, with rate constants of 1.9 x 107 and 2.8 x 108 M-1 s-1, respectively.The reaction of the OH site is not enhanced significantly by the presence of a paramagnetic center in the molecule.
- Casal, H. L.,Werstiuk, N. H.,Scaiano, J. C.
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p. 5214 - 5217
(2007/10/02)
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- Process for preparing 4-amino-2,2,6,6-tetramethyl piperidine
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4-AMINO-2,2,6,6-TETRAMETHYL PIPERIDINE IS PREPARED BY REACTING PHORONE WITH AMMONIA AND HYDROGEN IN THE PRESENCE OF A HYDROGENATION CATALYST. The reaction is generally carried out at a temperature in the range of from 80° to 200° C and under a pressure of from 80 to 250 atmospheres.
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