Diamine Products Research Articles

Unraveling the Role of H2 and NH3 in the Amination of Isohexides over a Ru/C Catalyst

The direct amination of biomass-derived isohexides with NH3 over a Ru/C catalyst was systematically investigated to understand the role of H2 and NH3 in the production of isohexide diamines vs aminoalcohols, i.e., the transformation of one or both OH-groups in isohexides into NH2 groups. Only aminoalcohols with an exo-OH group were generated starting from isosorbide, which contains both an exo-OH and an endo-OH group, while a moderate yield of diamines was obtained from isomannide with two endo-OH groups due to the higher reactivity of the latter. The main byproducts were identified, including a variety of N- and O-containing cyclic compounds, such as 2,5-dimethylpyrrolidine, that arise from a decomposition path driven by hydrolysis/hydrodeoxygenation of a tricyclic amine intermediate. By combining density functional theory calculations with microkinetics, NH3 was found to adsorb strongly on the catalyst surface and generate adsorbed NH2 and NH species with variable coverage depending on the temperature and the nominal H2/NH3 ratio. Isomerization of isohexides was greatly suppressed by adsorbed NH3. Meanwhile, adsorbed NH3 discouraged the formation of byproducts driven by competing side reactions promoted by H2. The H2/NH3 ratio, which conditions the distribution of NH2 and NH species on the Ru surface, influences drastically the catalytic performance.

Recent Advances in the Catalytic Synthesis of 1,3‐Diamines

Abstract1,3‐Diamines are important for many biologically active molecules, but there have been fewer studies on the synthesis of 1,3‐diamines than those on the synthesis of 1,2‐diamines. Relatively speaking, there are not sufficient reports on non‐catalytic methods in this direction. Among various methods, the catalytic construction of diamine products from nitrogen‐containing substrates is the most straightforward, but it suffers from the need to pre‐synthesize nitrogen‐containing substrates and is therefore narrowly used. For non‐specialized substrates, the direct construction of C−N bonds by metal‐ or non‐metal‐catalyzed C−H functionalization is undoubtedly the most efficient approach. This method is currently focused on monofunctionalization, but less has been reported for the simultaneous construction of multiple C−N bonds. Here, we summarize some innovative methods for the synthesis of 1,3‐diamines that have been developed in the past five years, encompassing various directions such as non‐catalytic reaction and metal‐ or non‐metal catalyzed reaction.

Business Roundup

BUSINESS Business Roundup ShareShare onFacebookTwitterWechatLinked InRedditEmail C&EN, 2023, 101 (13), p 17April 24, 2023Cite this:C&EN 101, 13, 17AbstractDSM has agreed to acquire Adare Biome, a French maker of postbiotics, for about $300 million. Postbiotics are inanimate microorganisms thought to deliver health benefits to humans and animals. Celanese will supply VitalDose, its ethylene vinyl acetate–based drug delivery technology, for use in Glaukos’s intraocular implant. The implant, which is not yet approved, delivers the glaucoma treatment travoprost. RWDC Industries has signed an agreement with Lummus Technology to market technology to make the biodegradable polymer polyhydroxyalkanoate. RWDC has a process to make the PHAs from plant based oils. Evonik Industries and Siemens Energy are collaborating on a green hydrogen pilot program in Herne, Germany. Siemens will provide an 8 MW electrolyzer, which will make both H 2 and oxygen for Evonik’s production of isophorone diamine. Chemours and TC Energy plan to collaborate on electrolytic hydrogen production in West Virginia. The firms plan to use proton exchange membranes from Chemours inView: PDF | Full Text HTML

A study of the reactivity of cyclic aminomethylammonium mannich salts

A novel method for the preparation of aminoalkylaminomethyl products was developed utilising novel Mannich-type salts featuring a R2NCH2NR3+ moiety. This methodology showed good nucleophile scope and was successfully employed in reactions under basic, acidic, and neutral conditions. A wide range of diamine products was successfully synthesised, including a neuropeptide Y antagonist.

Direct Crystallization of Diamine Radical Cations: Carbon-Nitrogen Bond Formation from the Reaction of Triphenylamine with TiCl4 , TiBr4 , or SnCl4 versus Carbon-Carbon Bond Formation with SbCl5.

Direct synthesis of diamine radical cations in crystalline form proceeding through oxidation of triphenylamine followed by the formation of a new C-N bond is reported. Although the oxidative coupling of triphenylamine is well studied, diamine products are rarely captured in their radical cation state. The neutral diamine most frequently obtained from this reaction pathway is N,N,N',N'-tetraphenylbenzidine. Herein, the capture of radical cations of diamines in crystalline form in one step starting with neutral triphenylamine was demonstrated, and the formation of two products (the radical cations of N,N,N',N'-tetraphenyl-1,4-benzenediamine or N,N,N',N'-tetraphenylbenzidine) depending on the oxidizing agent used was observed. The radical species are characterized by single-crystal X-Ray diffraction, electron paramagnetic resonance spectroscopy, and optical spectroscopy.

Pd/Gorlos‐Phos‐Catalyzed Chemoselective Amination of Bromophenyl Chlorides with Primary Arylamines

AbstractWith the readily available Gorlos‐Phos as a ligand, halogenated diarylamines were prepared efficiently from Pd‐catalyzed monoamination of bromophenyl chlorides and primary arylamines, tolerating functional groups such as aldehyde, ketone, nitrile, fluorine, sulphonyl and trifluoromethyl groups. The formation of the amination of the C−Cl bond and diamination products were not observed.

Development of a Transcription Factor-Based Diamine Biosensor in Corynebacterium glutamicum.

Diamines serve as major platform chemicals that can be employed to a variety of industrial scenarios, particularly as monomers for polymer synthesis. High-throughput sensors for diamine biosynthesis can greatly improve the biological production of diamines. Here, we identified and characterized a transcription factor-driven biosensor for putrescine and cadaverine in Corynebacterium glutamicum. The transcriptional TetR-family regulatory protein CgmR (CGL2612) is used for the specific detection of diamine compounds. This study also improved the dynamic range and the sensitivity to putrescine by systematically optimizing genetic components of pSenPut. By a single cell-based screening strategy for a library of CgmR with random mutations, this study obtained the most sensitive variant CgmRI152T, which possessed an experimentally determined limit of detection (LoD) of ≤0.2 mM, a K of 11.4 mM, and a utility of 720. Using this highly sensitive putrescine biosensor pSenPutI152T, we demonstrated that CgmRI152T can be used as a sensor to detect putrescine produced biologically in a C. glutamicum system. This high sensitivity and the range of CgmR will be an influential tool for rewiring metabolic circuits and facilitating the directed evolution of recombinant strains toward the biological synthesis of diamine compounds.

Efficient catalytic amination of diols to diamines over Cu/ZnO/γ-Al2O3

Abstract Catalytic amination of diols with dimethylamine is a promising approach for the preparation of tetramethyl diamines. In this work, a series of Cu/ZnO/γ-Al2O3 catalysts were developed by co-precipitation and employed in the amination of 1,6-hexanediol (HDO) with dimethylamine (DMA) to N, N, N’, N’-tetramethyl-1,6-hexanediamine (TMHDA) in a fixed-bed reactor. Cu/ZnO/γ-Al2O3–20 exhibited remarkable catalytic performance. Nearly complete conversion of HDO was reached and 93% selectivity of TMHDA was obtained at 180 °C. The excellent catalytic performance was attributed to the highly dispersion of Cu, which was promoted by doped ZnO. The results of characterizations (TEM, H2-TPR, XRD, XPS, etc.) indicated that doped ZnO could efficiently decrease the average particle size and improve the dispersion of Cu. The promoting effect could be ascribed to strong interaction between Cu and ZnO. The availability and effectiveness of Cu/ZnO/γ-Al2O3 catalyst offer a prospective way for the industrial production of tertiary diamines through amination of diols.

Regioselective Three-Component Synthesis of Vicinal Diamines via 1,2-Diamination of Styrenes.

The vicinal diamine motif plays a significant role in natural products, drug design, and organic synthesis, and development of synthetic methods for the synthesis of diamines is a long-standing interest. Herein, we report a regioselective intermolecular three-component vicinal diamination of styrenes with acetonitrile and azodicarboxylates. The diamination products can be produced in moderate to excellent yields via the Ritter reaction. Synthetic applications and theoretical studies of this reaction have been conducted.

The production of biobased diamines from renewable carbon sources: Current advances and perspectives

Bio-based diamines are considered to be a promising alternative to traditional fossil-fuel-based diamines, the important platform chemical for the synthesis of polymer materials. In this review, the current status of the art of the synthesis of aliphatic and aromatic diamines from renewable biomass are considered. In the case of aliphatic diamines, we describe strategies for biologically producing diamines with different carbon numbers including 1,3-diaminopropane, 1,4-butanediamine, 1,5-pentanediamine, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. In addition, aromatic diamines produced from various kinds of renewable biomass, including lignin, cashew nut shell, and terpenoids, are reviewed here. Furthermore, the application of typical diamines in synthesis of polyurethane and polyamide are also reviewed.

Diamine Biosynthesis: Research Progress and Application Prospects.

Diamines are important monomers for polyamide plastics; they include 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane, among others. With increasing attention on environmental problems and green sustainable development, utilizing renewable raw materials for the synthesis of diamines is crucial for the establishment of a sustainable plastics industry. Recently, high-performance microbial factories, such as Escherichia coli and Corynebacterium glutamicum, have been widely used in the production of diamines. In particular, several synthetic pathways of 1,6-diaminohexane have been proposed based on glutamate or adipic acid. Here, we reviewed approaches for the biosynthesis of diamines, including metabolic engineering and biocatalysis, and the application of bio-based diamines in nylon materials. The related challenges and opportunities in the development of renewable bio-based diamines and nylon materials are also discussed.

Synthesis of Spirocyclic Amines by 1,3-Dipolar Cycloaddition of Azomethine Ylides and Azomethine Imines

Simple ketone starting materials with a halide leaving group and an alkene were prepared in one step and heated with glycine or glycine esters to promote a tandem imine formation, cyclization, and dipolar cycloaddition cascade. The chemistry was also feasible with acetylhydrazide. In each case a single stereoisomer of the tricyclic amine or pyrazolidine product was formed and the stereochemistry was verified by single crystal X-ray diffraction. When the reaction with glycine, which occurs with loss of CO2, was unsuccessful, the cascade process could be promoted by cross metathesis to give the vinyl sulfone starting material that provides a more reactive dipolarophile. Reductive cleavage of the pyrazolidine gave a spirocyclic diamine product.

Modulating trans-imination and hydrogenation towards the highly selective production of primary diamines from dialdehydes

A new strategy for the highly selective production of primary diamines from dialdehydes has been developed.

Practical and stereoselective electrocatalytic 1,2-diamination of alkenes

The 1,2-diamine motif is widely present in natural products, pharmaceutical compounds, and catalysts used in asymmetric synthesis. The simultaneous introduction of two amino groups across an alkene feedstock is an appealing yet challenging approach for the synthesis of 1,2-diamines, primarily due to the inhibitory effect of the diamine products to transition metal catalysts and the difficulty in controlling reaction diastereoselectivity and regioselectivity. Herein we report a scalable electrocatalytic 1,2-diamination reaction that can be used to convert stable, easily available aryl alkenes and sulfamides to 1,2-diamines with excellent diastereoselectivity. Monosubstituted sulfamides react in a regioselective manner to afford 1,2-diamines bearing different substituents on the two amino groups. The combination of an organic redox catalyst and electricity not only obviates the use of any transition metal catalyst and oxidizing reagent, but also ensures broad reaction compatibility with a variety of electronically and sterically diverse substrates.

Utilization of Cyclic Amides as Masked Aldehyde Equivalents in Reductive Amination Reactions.

An operationally simple protocol has been discovered that couples primary or secondary amines with N-aryl-substituted lactams to deliver differentiated diamines in moderate to high yields. The process allows for the partial reduction of a lactam in the presence of Cp2ZrHCl (Schwartz's reagent), followed by a reductive amination between the resulting hemiaminal and primary or secondary amine. These reactions can be telescoped in a one-pot fashion to significantly simplify the operation. The scope of amines and substituted lactams of various ring sizes was demonstrated through the formation of a range of differentiated diamine products. Furthermore, this methodology was expanded to include N-aryl pyrrolidinone substrates with an enantiopure ester group at the 5-position, and α-amino piperidinones were prepared with complete retention of stereochemical information. The development of this chemistry has enabled the consideration of lactams as useful synthons.

Separation and purification of three, four, and five carbon diamines from fermentation broth

1,3-diaminopropane (1,3-DAP), 1,4-diaminobutane (1,4-DAB), and 1,5-diaminopentane (1,5-DAP) are important chemicals due to their wide industrial use including agrochemicals, pharmaceuticals, surfactants, and building blocks for nylon synthesis. Over the last decade, several studies on bio-based production of diamines by metabolically engineered microorganisms have been published. However, development of efficient methods for the recovery of 1,3-DAP, 1,4-DAB, and 1,5-DAP from fermentation broth has not been reported. In this study, an efficient process for the separation and purification of 1,3-DAP, 1,4-DAB, and 1,5-DAP from fermentation broth without using highly flammable or toxic solvents was developed. The optimal process for the recovery and purification of these diamines from fermentation broth comprises several unit operations including removal of cell debris, decolorization of fermentation broth, product concentration, deprotonation of diamines, product separation, and final polishing to obtain pure 1,3-DAP, 1,4-DAB, and 1,5-DAP with yields of 87 ± 3%, 86 ± 4%, and 81 ± 2%, respectively. Process development for the recovery and purification of fermentatively produced diamines reported here is expected to facilitate synthesis of bio-based nylons. Furthermore, the strategy reported here could be similarly applicable in developing downstream processes to recover and purify other diamines and related chemicals from fermentation broth.

Graphene-modified nickel foam electrode for cathodic degradation of nitrofuranzone: Kinetics, transformation products and toxicity

Simple, efficient, and durable electrodes are highly demanded for practical electro­chemical process. In this study, a reduced graphene oxide modified nickel foam electrode (GR‑Ni foam) was facilely prepared via one-step cyclic voltammetry electrodeposition of gra­phene oxide suspension onto the Ni foam. The electrochemical degradation of nitrofuran­zone (NFZ, a kind of typical antibiotics) was studied on the GR-Ni foam cathode. The cyclic voltammetry and electrochemical impedance spectra analysis confirmed that presence of GR loading accelerated the electron transfer from the cathode surface to NFZ. With the applied cathode potential of −1.25 V (vs. Ag/AgCl), the removal efficiency of NFZ (C0 = 20 mg L−1) at the GR-Ni foam electrode reached up to 99 % within 30 min, showing a higher reaction rate constant (0.1297 min−1) than 0.0870 min−1 at the Pd-Ni foam and 0.0186 min−1 at the Ni foam electrode. It was also found that the pH, dissolved oxygen and NFZ initial concentration have slight effect on NFZ degradation at the GR-Ni foam electrode. The reactions first occurred at nitro groups (-NO2), unsaturated C=N bonds and N-N bonds to generate furan ring-containing products, and then these products were transformed into linear diamine products. The direct reduction by electrons was mainly responsible for NFZ reduction at the GR-Ni foam electrode. Even after 18 cycles, the removal efficiency of NFZ still reached up to 98 % within 1 h. In addition, the cathodic degradation process could eliminate the antibacterial activity of NFZ. The GR-Ni foam electrode would have a great potential in electrochemical process for treating wastewater containing furan antibiotics.

Construction of Recombinant Pdu Metabolosome Shells for Small Molecule Production in Corynebacterium glutamicum.

Bacterial microcompartments have significant potential in the area of industrial biotechnology for the production of small molecules, especially involving metabolic pathways with toxic or volatile intermediates. Corynebacterium glutamicum is an established industrial workhorse for the production of amino acids and has been investigated for the production of diamines, dicarboxylic acids, polymers and biobased fuels. Herein, we describe components for the establishment of bacterial microcompartments as production chambers in C.glutamicum. Within this study, we optimized genetic clusters for the expression of the shell components of the Citrobacter freundii propanediol utilization (Pdu) bacterial compartment, thereby facilitating heterologous compartment production in C.glutamicum. Upon induction, transmission electron microscopy images of thin sections from these strains revealed microcompartment-like structures within the cytosol. Furthermore, we demonstrate that it is possible to target eYFP to the empty microcompartments through C-terminal fusions with synthetic scaffold interaction partners (PDZ, SH3 and GBD) as well as with a non-native C-terminal targeting peptide from AdhDH (Klebsiella pneumonia). Thus, we show that it is possible to target proteins to compartments where N-terminal targeting is not possible. The overproduction of PduA alone leads to the construction of filamentous structures within the cytosol and eYFP molecules are localized to these structures when they are N-terminally fused to the P18 and D18 encapsulation peptides from PduP and PduD, respectively. In the future, these nanotube-like structures might be used as scaffolds for directed cellular organization and pathway enhancement.

The synthesis of unsymmetric diamides through Rh-catalyzed selective C–H bond activation of amides with isocyanates

Synthetic and mechanistic studies on Rh-catalyzed C–H activation of amides with isocyanates, resulting in one of the unsymmetric diamine products showing promising anti-cancer activity.

Cavitands as Reaction Vessels and Blocking Groups for Selective Reactions in Water.

The majority of reactions currently performed in the chemical industry take place in organic solvents, compounds that are generally derived from petrochemicals. To promote chemical processes in water, we examined the use of synthetic, deep water-soluble cavitands in the Staudinger reduction of long-chain aliphatic diazides (C8 , C10 , and C12 ). The diazide substrates are taken up by the cavitand in D2 O in folded, dynamic conformations. The reduction of one azide group to an amine gives a complex in which the substrate is fixed in an unsymmetrical conformation, with the amine terminal exposed and the azide terminal deep and inaccessible within the cavitand. Accordingly, the reduction of the second azide group is inhibited, even with excess phosphine, and good yields of the monofunctionalized products are obtained. In contrast, the reduction of the free diazides in bulk solution yields diamine products.