Org. Process res. dev.: the new process can safely use azide to generate o-diamine

There are o-diamine in many small molecule drugs and functional materials Therefore, extensive research work is devoted to develop a general and selective method for the production of o-diamine compounds Although remarkable progress has been made, it is still challenging to directly convert the non functionalized olefins, especially the inner olefins, into o-diamines It is also difficult to control the stereochemistry of o-diamine reaction of non functionalized olefins As an alternative method, catalytic dinitriding of olefins has been demonstrated, which has unique value, because it provides a convenient method to produce important o-diamines which are difficult to be manufactured in large scale by synthetic methods in the past Various new methods have been reported, but the existing chemical azide methods are mainly for some limited types of olefins Recent electrochemical methods involve the use of excess Nan 3 in acid conditions, making large-scale processes difficult to achieve Representative azides (origin: org Process res dev.) obtained from iron catalyzed dinitriding of olefins, especially those with lower molecular weight, may bring potential safety risks in terms of thermal stability and mechanical stability An industrial academic cooperation team led by haoxu from Georgia State University and Marino Nebuloni from redox laboratory, an Italian specialty chemicals company, has developed a general and practical synthesis strategy for o-diamine generation in order to explore the feasibility of industrial scale iron catalyzed olefin diamine reaction, and evaluated the chemical hazard of olefin azide process This is a gram scale synthesis process of directly adding azides to olefins to prepare o-diamine Reactive chemical hazard assessment refers to the identification and possible quantification of hazardous energy release scenarios for certain chemical processes ready for mass production Differential scanning calorimetry (DSC) is one of the most commonly used methods to test the thermal stability of organic compounds, and drop weight test (DWT) has been used to detect the sensitivity of chemical substances to mechanical impact The team used DSC and DWT methods to analyze and study the chemical safety and potential hazard assessment of iron catalyzed direct generation of o-diazide In the end of 2015, the research team of iron catalyzed synthesis method of trans indene diammonium salt (source: org Process res dev.) haoxu reported for the first time that the non functionalized linear and cyclic alkenes were converted into Diamines by a mild method using benzodioxoleoxidizing reagent and iron catalyst with tridentate ligand Dr Xu said the reaction attracted the attention of industrial chemists, who thought it was a suitable way to produce diamine compounds So we have now such a cross ocean cooperation team to explore the possibility of large-scale application Mechanism analysis of iron catalyzed dinitriding of olefins (source: org Process res dev.) cooperation with redox laboratory involves safety assessment of reagents, dinitrogen intermediates and product diammonium salts The evaluation shows that the most problematic compound, the diazide intermediate, is thermally stable, but sensitive to moderate impact, and the diammonium salt made from them is more stable Under the guidance of these knowledge, the team optimized the process, developed gram level reaction, and directly produced diammonium salt without purification of azide DSC analysis involves the safety of reagents, diazo intermediates and product diammonium salts (source: org Process res dev.) 1,2-o-phenylenediamine represents a common scaffold in many small molecules and is a common building block for synthetic organic chemists However, due to the danger of treating azides and diazides, the alkene azides which are usually used to prepare them have to be abandoned in industry The new method is in line with industry best practices for the safe use of high-energy compounds In this case, the researchers proved the practicability of this iron catalyzed method of olefin dinitriding by process safety test This will be a fast, safe and scalable way to obtain such useful compounds No need to purify azide to get diammonium salt (source: org Process res dev.) paper link: http://pubs.acs.org/doi/abs/10.1021/acs.oprd.7b00312? Source = Cen corresponding author: http://chemistry.gsu.edu/profile/hxu/