67-62-9Relevant articles and documents
High-density energetic mono- or bis(Oxy)-5-nitroiminotetrazoles
Joo, Young-Hyuk,Shreeve, Jean'ne M.
, p. 7320 - 7323 (2010)
Making an impact: Oxy-5-aminotetrazoles, which were obtained from the reaction of cyanogen azide and alkyl oxy-amine in 100% nitric acid (see scheme), give a series of highly energetic oxy-5-nitroiminotetrazolates in good yield. These compounds exhibit good physical and detonation properties, such as moderate thermal stabilities, high densities, high endothermy, good detonation pressures P, and good detonation velocities D.
The Reactions of Singlet NH Radicals with Methyl and Ethyl Alcohols in the Liquid Phase
Kawai, Jun,Tsunashima, Shigeru,Sato, Shin
, p. 3312 - 3316 (1982)
The reactions of the singlet NH(a1Δ) radicals with alcohols were studied by the photolyses of hydrogen azide in liquid methyl and ethyl alcohols at the temperature of Dry Ice-methyl alcohol and at 0 deg C.The main products were nitrogen, ammonia, and oxime ethers; acetaldehyde oxime O-ethyl ether from ethyl alcohol and formaldehyde oxime O-methyl ether from methyl alcohol.The relative yields of the products were independent of the changes in the reaction temperature and in the concentration of the hydrogen azide examined.Methoxyamine or ethoxyamine, a possible insertion product of the singlet NH into the O-H bond of alcohol, was detected as a form of oxime ether by the reactions with the aldehyde eventually formed.It was concluded that the singlet NH radicals can effectively insert into the O-H bond of the alcohol.
Synthetic Model Complex of the Key Intermediate in Cytochrome P450 Nitric Oxide Reductase
McQuarters, Ashley B.,Blaesi, Elizabeth J.,Kampf, Jeff W.,Alp, E. Ercan,Zhao, Jiyong,Hu, Michael,Krebs, Carsten,Lehnert, Nicolai
, p. 1398 - 1413 (2019)
Fungal denitrification plays a crucial role in the nitrogen cycle and contributes to the total N2O emission from agricultural soils. Here, cytochrome P450 NO reductase (P450nor) reduces two NO to N2O using a single heme site. Despite much research, the exact nature of the critical "Intermediate I" responsible for the key N-N coupling step in P450nor is unknown. This species likely corresponds to a Fe-NHOH-type intermediate with an unknown electronic structure. Here we report a new strategy to generate a model system for this intermediate, starting from the iron(III) methylhydroxylamide complex [Fe(3,5-Me-BAFP)(NHOMe)] (1), which was fully characterized by 1H NMR, UV-vis, electron paramagnetic resonance, and vibrational spectroscopy (rRaman and NRVS). Our data show that 1 is a high-spin ferric complex with an N-bound hydroxylamide ligand that is strongly coordinated (Fe-N distance, 1.918 ? Fe-NHOMe stretch, 558 cm-1). Simple one-electron oxidation of 1 at -80 °C then cleanly generates the first model system for Intermediate I, [Fe(3,5-Me-BAFP)(NHOMe)]+ (1+). UV-vis, resonance Raman, and M?ssbauer spectroscopies, in comparison to the chloro analogue [Fe(3,5-Me-BAFP)(Cl)]+, demonstrate that 1+ is best described as an FeIII-(NHOMe)? complex with a bound NHOMe radical. Further reactivity studies show that 1+ is highly reactive toward NO, a reaction that likely proceeds via N-N bond formation, following a radical-radical-type coupling mechanism. Our results therefore provide experimental evidence, for the first time, that an FeIII-(NHOMe)? electronic structure is indeed a reasonable electronic description for Intermediate I and that this electronic structure is advantageous for P450nor catalysis because it can greatly facilitate N-N bond formation and, ultimately, N2O generation.
Studies on the Chemistry of Isoindoles and Isoindolenines, XXXX [1,2] 3-Hydroximino-1-alkyl(aryl)-isoindolines and 3-Hydroxylamino-1-alkyl(aryl)-1H-isoindoles - Model Compounds for Investigations of Structure and Reactivity -
Clemens, Andrea,Kreher, Richard P.,Preut, Johannes
, p. 1791 - 1814 (1996)
3-Hydroximino-isoindolines and 3-hydroxylamino-1H-isoindoles with substituents at the five membered ring have been prepared by condensation of substituted 3-alkoxy-1H-isoindoles with hydroxylamine and O-/N-substituted hydroxylamines. Constitution and configuration of semi-cyclic amidoximes were derived from spectroscopic investigations and deduced on the basis of orientating chemical transformations. These results have been established by a crystal structure determination of a representative 3-hydroximino-isoindoline.
Vinylogous Aza-Michael Addition of Urea Derivatives with p-Quinone Methides Followed by Oxidative Dearomative Cyclization: Approach to Spiroimidazolidinone Derivatives
Kaur, Navpreet,Singh, Priyanka,Banerjee, Prabal
supporting information, p. 2813 - 2824 (2021/04/21)
Herein, we report an efficient protocol for the synthesis of spiro-imidazolidinone-cyclohexadienones from p-quinone methides (p-QMs) and dialkyloxy ureas under mild conditions. The strategy follows a two-step process involving an initial vinylogous conjugate addition of urea derivatives to p-QMs, followed by oxidative dearomative cyclization of open-chain product to the projected spiro-imidazolidinones. This protocol exhibits good functional group tolerance and provides a straightforward method to access spiro-imidazolidinone-cyclohexadienones. In follow-up chemistry, we have shown the debenzylation of spiroimidazolidinones to give N-hydroxycyclic ureas. (Figure presented.).
Tuning the exchange dynamics of boronic acid hydrazones and oximes with pH and redox control
Han, Gun Su,Domaille, Dylan W.
supporting information, p. 4986 - 4991 (2021/06/16)
Dynamic bonds continually form and dissociate at equilibrium. Carbonyl compounds with proximal boronic acids, including 2-formylphenylboronic acid (2-FPBA), have been reported to form highly dynamic covalent hydrazone and oxime bonds in physiological conditions, but strategies to tune the dynamics have not yet been reported. Here, we characterize the dynamics of 2-FPBA-derived hydrazones and oximes and account for both the rapid rate of formation (～102-103M?1s?1) and the relatively fast rate of hydrolysis (～10?4s?1) at physiological pH. We further show that these substrates undergo exchange with α-nucleophiles, which can be reversibly paused and restarted with pH control. Finally, we show that oxidation of the arylboronic acid effectively abolishes the rapid dynamics, which slows the forward reaction by more than 30?000 times and increases the hydrolytic half-life from 50 minutes to 6 months at physiological pH. These results set the stage to explore these linkages in dynamic combinatorial libraries, reversible bioconjugation, and self-healing materials.
One-pot method for preparing O-alkyl hydroxylamine hydrochloride and N,O-dialkyl hydroxylamine hydrochloride
-
Paragraph 0038-0039, (2020/10/20)
The invention relates to the field of organic synthesis, in particular to a one-pot method for preparing O-alkyl hydroxylamine hydrochloride and N,O-dialkyl hydroxylamine hydrochloride. The method comprises the following steps: S1, acetylation: mixing hydroxylamine hydrochloride with water and methyl acetate, and dropwise adding a sodium hydroxide solution while stirring at room temperature to obtain an intermediate acetyl hydroxylamine; S2, alkylation: dropwise adding an alkylation reagent into the reaction kettle at normal temperature, and then heating the reactants for reaction; S3, hydrolysis and purification: after the reaction is qualified, adding concentrated sulfuric acid, performing heating hydrolysis, after the reaction is qualified, adding caustic soda flakes or liquid caustic soda to adjust the pH value to 12, carrying out atmospheric distillation and hydrochloric acid acidification, cooling the product for crystallization, and centrifuging and drying the crystal to obtaina final product. According to the invention, methyl acetate is used as an acetyl protective agent, and compared with ethyl acetate, methyl acetate has the advantages of good water solubility, small reaction steric hindrance, sufficient protection, few impurities, low price and cost and the like; therefore, the method has the advantages of high product purity, simple process operation, accessible raw materials, simple wastewater components and environment friendliness, and is suitable for industrial production.
Methoxylamine preparation method and methoxylamine hydrochloride preparation method
-
Paragraph 0056-0061; 0077-0079, (2021/01/04)
The invention discloses a methoxylamine preparation method which at least comprises the following steps of enabling feed gas containing methyl nitrite and a reducing agent to be in contact with a reduction reaction catalyst in a reactor, and performing reduction reaction to obtain methoxylamine. According to the method, the important intermediate methyl nitrite in the technical process of preparing ethylene glycol from coal can be fully utilized, and the conversion rate of methyl nitrite is high. The invention also provides a method for preparing methoxylamine hydrochloride by taking methoxylamine obtained by the method as a raw material.
Tris(2-carboxyethyl)phosphine promotes hydrolysis of iminoboronates
Liu, Xiaoyu,Li, Zhihong,Xu, Hongtao,Zhan, Yuexiong,Ma, Peixiang,Chen, Hongli,Jiang, Biao
, p. 3101 - 3106 (2017/07/18)
Iminoboronates are stable and formed fast. Their B[sbnd]N bonds could be reverted by some endogenous biological molecules. The reversible characteristic attracts significant attention in biological and chemical fields. Although synthesis of iminoboronates is well-studied, less efforts have been devoted to disconnecting the units. Here, a series of selected compounds were screened to evaluate their hydrolytic capability of iminoboronates by 1H NMR or 11B NMR detection. Tris(2-carboxyethyl)phosphine (TCEP), was emerged as an excellent reagent, which decomposed most iminoboronates in short time with high yields. In addition, TCEP is also able to hydrolyze hydrazones and oximes with moderate yields.
Method for coproducing vasoxine hydrochloride and N,O-dimethylhydroxylamine hydrochloride
-
Paragraph 0042-0048, (2017/04/03)
The invention relates to the technical field of compound synthesis methods, particularly a method for coproducing vasoxine hydrochloride and N,O-dimethylhydroxylamine hydrochloride. The method comprises the following steps: carrying out methylation reaction on hydroxylamine salt under alkaline conditions by using a methylating agent to obtain a reaction solution containing vasoxine and N,O-dimethylhydroxylamine, rectifying to separate a vasoxine bottom solution and an N,O-dimethylhydroxylamine crude distillate, respectively adding hydrochloric acid for salification, concentrating and crystallizing under reduced pressure, cooling, carrying out vacuum filtration, recrystallizing with water or methanol, and drying to obtain the vasoxine hydrochloride product and N,O-dimethylhydroxylamine hydrochloride product. The method has the advantages of simple and reliable technique, high product quality, high total yield and low comprehensive cost, and is more friendly to the environment and suitable for industrial production.
