51301-55-4

Usage

Uses

Used in Pharmaceutical Industry:
Formic acid, compound with 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (1:1) is used as a potential pharmaceutical agent for its possible unique properties and pharmacological activities. The combination of formic acid and the bicyclic organic compound may offer novel therapeutic applications, such as the development of new drugs or drug delivery systems, due to their distinct chemical interactions and potential synergistic effects.
Used in Material Science:
Further research is essential to uncover the full spectrum of applications and to optimize the synthesis and production methods of formic acid, compound with 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (1:1), ensuring its safety, efficacy, and potential for commercialization in various industries.

InChI:InChI=1/C9H16N2.CH2O2/c1-2-5-9-10-6-4-8-11(9)7-3-1;2-1-3/h1-8H2;1H,(H,2,3)

Upstream product

• 64-18-6 formic acid 
• 6674-22-2 1,8-diazabicyclo[5.4.0]undec-7-ene 
• 67-56-1 methanol 
• 124-38-9 carbon dioxide 

Downstream Products

• 124-38-9 carbon dioxide 
• 6674-22-2 1,8-diazabicyclo[5.4.0]undec-7-ene 
• 91-01-0 1,1-Diphenylmethanol 

Relevant academic research and scientific papers

Mechanism of CO2hydrogenation to formates by homogeneous Ru-PNP pincer catalyst: From a theoretical description to performance optimization

The reaction mechanism of CO2hydrogenation by pyridine-based Ru-PNP catalyst in the presence of DBU base promoter was studied by means of density functional theory calculations. Three alternative reaction channels promoted by the complexes potentially present under the reaction conditions, namely the dearomatized complex 2 and the products of cooperative CO2(3) and H2(4) addition, were analysed. It is shown that the bis-hydrido Ru-PNP complex 4 provides the unique lowest-energy reaction path involving a direct effectively barrierless hydrogenolysis of the polarized complex 5?. The reaction rate in this case is controlled by the CO2activation by Ru-H that proceeds with a very low barrier of ca. 20 kJ mol-1. The catalytic reaction can be hampered by the formation of a stable formato-complex 5. In this case, the rate is controlled by the H2insertion into the Ru-OCHO coordination bond, for which a barrier of 65 kJ mol-1is predicted. The DFT calculations suggest that the preference for the particular route can be controlled by varying the partial pressure of H2in the reaction mixture. Under H2-rich conditions, the former more facile catalytic path should be preferred. Dedicated kinetic experiments verify these theoretical predictions. The apparent activation energies measured at different H2/CO2molar ratios are in a perfect agreement with the calculated values. Ru-PNP is a highly active CO2hydrogenation catalyst allowing reaching turnover frequencies in the order of 106h-1at elevated temperatures. Moreover, a minor temperature dependency of the reaction rate attainable in excess H2points to the possibility of efficient CO2hydrogenation at near-ambient temperatures. This journal is

A highly active non-precious transition metal catalyst for the hydrogenation of carbon dioxide to formates

Herein a highly active non-precious transition metal catalyst system for homogeneous hydrogenation of carbon dioxide to formate is presented. The application of selected nickel(ii) salts in combination with tailored multidentate ligands enabled the effective transformation of carbon dioxide with an exceptional TON of up to 4.65 × 106. This unprecedented productivity based on the novel nickel catalyst not only outmatches that of existing systems containing first row transition metals, but also established catalysts based on precious transition metals.

Aperture-Opening Encapsulation of a Transition Metal Catalyst in a Metal-Organic Framework for CO2 Hydrogenation

The aperture-opening process resulting from dissociative linker exchange in zirconium-based metal-organic framework (MOF) UiO-66 was used to encapsulate the ruthenium complex (tBuPNP)Ru(CO)HCl in the framework (tBuPNP = 2,6-bis((di-tert-butyl-phosphino)methyl)pyridine). The resulting encapsulated complex, [Ru]@UiO-66, was a very active catalyst for the hydrogenation of CO2 to formate. Unlike the analogous homogeneous catalyst, [Ru]@UiO-66 could be recycled five times, showed no evidence for bimolecular catalyst decomposition, and was less prone to catalyst poisoning. These results demonstrated for the first time how the aperture-opening process in MOFs can be used to synthesize host-guest materials useful for chemical catalysis.

Bio-Inspired Mn(I) Complexes for the Hydrogenation of CO2 to Formate and Formamide

Developing new, efficient catalysts that contain Earth-abundant metals and simple, robust ligands for CO2 hydrogenation is important to create cost-effective processes of CO2 utilization. Inspired by nature, which utilizes an ortho-OH-substituted pyridine motif in Fe-containing hydrogenases, we developed a Mn complex with a simple N-donor ligand, 6,6′-dihydroxy-2,2′-bipyridine, that acts as an efficient catalyst for CO2 hydrogenation. Turnover numbers of 6250 for hydrogenation of CO2 to formate in the presence of DBU were achieved. Moreover, hydrogenation of CO2 to formamide was achieved in the presence of a secondary amine.

Amidines as effective ancillary ligands in copper-catalyzed hydrogenation of carbon dioxide

Mononuclear Cu(II) complexes bearing a bidentate bisamidine ligand were newly synthesized and characterized. The catalytic activity was evaluated in the hydrogenation of carbon dioxide to formate salts. A substantial enhancement of the catalyst turnover number was achieved by the imidazoline-based complex, indicating that amidines serve as effective ancillary ligands for homogeneous copper catalysis.

Cellulose-dissolving protic ionic liquids as low cost catalysts for direct transesterification reactions of cellulose

Cellulose acetate (CA) is a resin derived from biomass. In addition to its various superior properties, CA is preferable to existing petroleum-derived resins from the viewpoint of green chemistry. Therefore, the acetylation of cellulose is one of the most important subjects in cellulose research. In this study, we found that the acetylation of cellulose could proceed in some protic ionic liquids (PILs) composed of amidine and acetic acid with ΔpKa = ca. 8.4-8.7 under mild conditions without any catalyst. The degree of substitution (DS) of the produced CA was above 1.84, and the maximum DS was 2.87 when the ΔpKa of the PIL was about 8.5. In propionate-based PILs, cellulose was not only acetylated but also propionated; however, the cellulose acetylation did not occur in formate-based PILs. It was revealed that the esterification of cellulose proceeded through the anion exchange between carboxylic anhydride and anion species of the PIL.

Catalytic Formic Acid Dehydrogenation and CO2 Hydrogenation Using Iron PNRP Pincer Complexes with Isonitrile Ligands

It has previously been demonstrated that complexes of the form (iPrPNP)Fe(H)(C≡NR) (iPrPNP = N(CH2CH2P(iPr)2)2-, R = 2,6-dimethylphenyl or 4-methoxyphenyl), which contain a pincer ligand capable of metal-ligand cooperation (MLC), are active for CO2 hydrogenation. Herein, the synthesis and catalytic activity of a second-generation of precatalysts containing a tertiary amine ligand, which cannot participate in MLC, are presented. Specifically, the complexes (iPrPNMeP)Fe(H)(HBH3)(C≡NR) (iPrPNMeP = MeN(CH2CH2P(iPr)2)2, R = 2,6-dimethylphenyl (2a), tert-butyl (2b), or adamantyl (2c)) have been prepared and crystallographically characterized. These complexes are precatalysts for both formic acid dehydrogenation and CO2 hydrogenation to formate, and give improved activity compared to first-generation systems with isonitrile ligands. The second-generation systems 2a-c, however, give inferior activity compared to the related carbonyl complexes (iPrPNP)Fe(H)(CO) and (iPrPNMeP)Fe(H)(HBH3)(CO), which have been previously reported. This study demonstrates that a ligand which can participate in MLC is not universally advantageous for promoting the hydrogenation and dehydrogenation reactions studied in this work and provides guidance for the rational design of improved catalysts for reactions relevant to energy storage.

Hydrogenation of carbon dioxide to formate catalyzed by a copper/1,8-diazabicyclo[5.4.0]undec-7-ene system

Hydrogenation of carbon dioxide to formate was achieved using copper (Cu) catalysts in the presence of strong organic bases including amidines and guanidines. Specifically, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) proved to be effective for the transformation of a 1:1 mixture of hydrogen and carbon dioxide into its formate salt under increased pressure in the presence of various Cu(I) and Cu(II) salts at 100°C. A novel complex derived from copper iodide and DBU equally promoted the same reaction, indicating that DBU-Cu species are involved as real catalysts in this hydrogenation.

Cu(i) complex bearing a PNP-pincer-Type phosphaalkene ligand with a bulky fused-ring Eind group: Properties and applications to FLP-Type bond activation and catalytic CO2 reduction

Herein, we report the synthesis of [Cu(Eind2-BPEP)][PF6] (2) (Eind2-BPEP = 2,6-bis(2-Eind-2-phosphaethenyl)pyridine, Eind = 1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-yl), a three-coordinated Cu(i) complex bearing a PNP-pincer-Type phosphaalkene ligand with bulky fused-ring Eind groups. The Gutmann-Beckett test revealed that complex 2 is highly Lewis acidic and comparable in strength to B(C6F5)3, which is a relatively strong Lewis acid. In addition, 2 is more Lewis acidic than [Cu(Mes?2-BPEP)][PF6] (3), the analogous complex with less-bulky Mes? instead of Eind groups. DFT calculations using model compounds revealed that the higher Lewis acidity of 2 compared to 3 is not due to the electronic effects of the ligand, but due to a reduction in the LUMO energy caused by the steric effect of the bulky Eind groups. When combined with a tertiary amine, the highly Lewis acidic and bulky 2 exhibits the reactivity of a frustrated Lewis pair (FLP) and can activate hydrogen and phenylacetylene. Complexes 2 and 3 were found to catalyze the hydrogenation and hydrosilylation of CO2 in the presence of DBU under relatively mild conditions.

Carbon dioxide hydrogenation to formate catalyzed by a bench-stable, non-pincer-type Mn(I) alkylcarbonyl complex

The catalytic reduction of carbon dioxide is a process of growing interest for the use of this simple and abundant molecule as a renewable building block in C1-chemical synthesis and for hydrogen storage. The well-defined, bench-stable alkylcarbonyl Mn(I) bis(phosphine) complex fac-[Mn(CH2CH2CH3)(dippe)(CO)3] [dippe = 1,2-bis(diisopropylphosphino)-ethane] was tested as an efficient and selective non-precious-metal precatalyst for the hydrogenation of CO2 to formate under mild conditions (75 bar total pressure, 80 °C), in the presence of a Lewis acid co-catalyst (LiOTf) and a base (DBU). Mechanistic insight into the catalytic reaction is provided by means of density functional theory (DFT) calculations.