7181-87-5

Usage

Uses

Used in Organic Synthesis:
1,3-Dimethyl-1H-benzo[d]imidazol-3-ium iodide is used as a catalyst for a range of organic reactions, including:
1. Domino ring-opening redox amidation: It accelerates the process by acting as a catalyst, enabling the formation of amides through a series of reactions.
2. Knoevenagel condensation: This catalyst promotes the condensation of aldehydes or ketones with active methylene compounds, leading to the formation of α,β-unsaturated carbonyl compounds.
3. Intramolecular stereoselective protonation: It selectively directs the protonation process within a molecule, ensuring the desired stereochemistry is achieved.
4. Grignard allylic substitution: The catalyst aids in the substitution of allylic compounds with Grignard reagents, facilitating the formation of new carbon-carbon bonds.
5. Acylation of alcohols: It enhances the acylation process, where alcohols react with carboxylic acids or their derivatives to form esters.
6. Umpolung reactions: The catalyst supports umpolung, a reversal of polarity in reactions, allowing for the formation of products that would otherwise be difficult to obtain.

InChI:InChI=1/C9H11N2/c1-10-7-11(2)9-6-4-3-5-8(9)10/h3-7H,1-2H3/q+1

Upstream product

• 51-17-2 benzoimidazole 
• 67-56-1 methanol 
• 74-88-4 methyl iodide 
• 1632-83-3 1-Methylbenzimidazole 
• 85510-65-2 1-methyl-2-(1-methyl-3-benzoyl-1,2-dihydro-2-benzimidazolyl)benzimidazole 
• 5805-52-7 1H-benzo[d]imidazole-2-carboxamide 
• 1865-09-4 ethyl 1H-benzimidazole-2-carboxylate 
• 1591-31-7 4-iodo-biphenyl 
• 3204-31-7 1,3-Dimethyl-2,3-dihydro-1H-benzoimidazole 
• 121-44-8 triethylamine 

Downstream Products

• 54825-26-2 2-(4-methoxyphenyl)-1,3-dimethyl-benzimidazoline 
• 100672-38-6 2-(4-methylphenyl)-1,3-dimethyl-benzimidazoline 
• 92-94-4 [1,1';4',1'']terphenyl 
• 3204-31-7 1,3-Dimethyl-2,3-dihydro-1H-benzoimidazole 
• 3652-92-4 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole 
• 3652-98-0 2-(4-nitrophenyl)-1,3-dimethyl-benzimidazoline 
• 3652-96-8 2-(4-chloro-phenyl)-1,3-dimethyl-2,3-dihydro-1H-benzoimidazole 
• 4166-43-2 formic acid-(N-methyl-2-methylamino-anilide) 
• 3097-21-0 1,3-dimethyl-1,3-dihydrobenzimidazol-2-one 
• 3213-79-4 N,N'-dimethyl-1,2-phenylenediamine 
• 3653-05-2 N,N’-dimethyl-2-phenyl-benzo[d]imidazolium iodide 
• 1638885-90-1 C₁₇H₁₉N₂⁽¹⁺⁾*BF₄^(1-) 
• 1638885-91-2 C₁₇H₁₉N₂⁽¹⁺⁾*BF₄^(1-) 
• 1638885-92-3 1,3-dimethyl-2-phenethyl-1H-benzo[d]imidazolium hexafluorophosphate 

Relevant academic research and scientific papers

N,N-Dialkylbenzimidazol-2-ylidene platinum complexes-effects of alkyl residues and ancillary cis-ligands on anticancer activity

Eleven complexes of [(1,3-dialkylbenzimidazol-2-ylidene)LnCl3?n]Pt(n?1)+, with Ln = DMSO (8), Ph3P (9), (Ph3P)2 (10), and alkyl = Me (a), Et (b), Bu (c), octyl (d), were synthesised and tested for cellular accumulation, cytotoxicity, interference with the tumour cell cycle, and interaction with DNA. The delocalised lipophilic cationic bisphosphane complexes 10 were on average found to be more cytotoxic in MTT assays against a panel of seven cancer cell lines than the neutral DMSO and monophosphane complexes 8 and 9. The uptake of complexes 10, at least into HCT116 colon carcinoma cells, was also significantly greater than that of analogues 8 and 9. Their cytotoxicities did not differ significantly with the N-alkyl side chain length. The complexes that were most active, with sub-micromolar IC50 (72 h) values against HCT116wt cells, that is 8b, 9b, 10a-c, worked by a mode of action that was dependent on the functional p53, yet were still far more active than cisplatin in both of the HCT116wt and HCT116?/? variants. In detailed binding analyses 8c, 9c and 10a-c showed a lower affinity to DNA and different binding modes when compared to cisplatin, preferably forming mono-adducts with DNA and distorting it to a lower extent. Also, unlike cisplatin, they arrested the HCT116 cells of both variants predominantly in the G1 phase.

Reactivity of gold nanoparticles towards N-heterocyclic carbenes

The reaction of gold nanoparticles with benzimididazol-2-ylidene ligands leads to the formation of well-defined bis-carbene gold(i) complexes, as shown by characterization techniques such as powder XRD and solid state NMR. This journal is the Partner Organisations 2014.

Benzimidazol-2-ylidene gold(I) complexes are thioredoxin reductase inhibitors with multiple antitumor properties

Gold(I) complexes such as auranofin have been used for decades to treat symptoms of rheumatoid arthritis and have also demonstrated a considerable potential as new anticancer drugs. The enzyme thioredoxin reductase (TrxR) is considered as the most relevan

Synthesis and characterization of a layered aluminosilicate NUD-11 and its transformation to a 3D stable zeolite

Aluminosilicate zeolites are a well-known class of crystalline materials that have wide applications in various industrial fields due to their selective adsorption, acidic sites, and stable hydrothermal stability. Great efforts have been devoted to discovering new zeolite structures. As one of the effective methods, layered silicates have been used as precursors to produce stable zeolites through topotactic transformation. Herein, a new layered aluminosilicate, named NUD-11, was hydrothermally synthesized using N,N-dimethylbenzimidazolium as the structure directing agent (SDA). It was then converted into a stable crystalline zeolite by linking the interlayer Si-OH groups with a silylation agent, diethoxymethylsilane. Studies showed that the resulting NUD-11S consisted of alkylsilicate-O-Si(CH3)2-O-linkages between the adjacent layers to form interconnecting 10-and 12-membered ring channels. The calcined NUD-11S possessed micropores of 0.74 nm and 1.2 nm in diameter with a large specific surface area of 314 m2 g-1. The abundant microporosity would make NUD-11S useful as adsorbents or catalysts.

Formation and Stability of N-Heterocyclic Carbenes in Water: The Carbon Acid pKa of Imidazolium Cations in Aqueous Solution

We report second-order rate constants kDO (M-1 s -1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 °C and l = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 1011 s-1. The data were used to calculate reliable carbon acid pKas for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pK a = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 × 1016 for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes.

Ni(ii)-catalyzed C-H hydroarylation of diarylacetylenes with imidazolium salts

A simple Ni(ii)-catalyzed C-H hydroarylation of diarylacetylenes with imidazolium salts without adding any ligand was developed. It provides a facile and efficient access to (E)-2-(1,2-diarylvinyl)imidazolium salts. The preliminary results indicate a rare nonredox catalytic cycle of Ni(ii), complementary to the common redox catalytic cycle starting from Ni(0).

Kinetic analysis of the complete mechanochemical synthesis of a palladium(II) carbene complex

Benzimidazoline-2-ylidene complexes of palladium(II) were synthesized mechanochemically in a vibratory ball mill. Complete syntheses began with preparation of benzimidiazolium halides from commercially available starting materials. These “greener chemistr

Preventing Pd-NHC bond cleavage and switching from nano-scale to molecular catalytic systems: Amines and temperature as catalyst activators

Many reactions catalyzed by Pd complexes with N-heterocyclic carbene (NHC) ligands are performed in the presence of amines which usually act as coupling reagents or mild bases. However, amines can react with Pd/NHC complexes in a number of ways: enhancing molecular catalysis, causing the catalyst deactivation or triggering the ligandless modes of catalysis by producing NHC-free active palladium species. This study gains insight into conditions required for the efficient use of amines as activators of molecular Pd/NHC catalysis and preventing the undesirable reductive cleavage of the Pd-NHC bond in catalytic systems. Reactions of Pd/NHC complexes with various amines within a temperature range of 25-140 °C and thermal stability of the resulting amino-complexes are examined. The results indicate the major influence of the amine structure and reaction temperature on the catalyst transformation. In particular, thermal decomposition of Pd/NHC complexes with aliphatic amine ligands predominantly leads to reductive Pd-NHC bond cleavage, while deprotonation of the complexes with primary and secondary aliphatic amine ligands in the presence of strong bases at 25-60 °C promotes the activation of molecular Pd/NHC catalysis. Efficient Pd-PEPPSI complex-amine systems suitable for strong-base-promoted C-S cross-coupling reactions between aryl halides and thiols are suggested on the basis of these findings.

Neutral Organic Super Electron Donors Made Catalytic

Neutral organic super electron donors (SEDs) display impressive reducing power but, until now, it has not been possible to use them catalytically in radical chain reactions. This is because, following electron transfer, these donors form persistent radical cations that trap substrate-derived radicals. This paper unlocks a conceptually new approach to super electron donors that overcomes this issue, leading to the first catalytic neutral organic super electron donor.

Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate

We report a novel metal-free chemical reduction of CO2 by a recyclable benzimidazole-based organo-hydride, whose choice was guided by quantum chemical calculations. Notably, benzimidazole-based hydride donors rival the hydride-donating abilities of noble-metal-based hydrides such as [Ru(tpy)(bpy)H]+ and [Pt(depe)2H]+. Chemical CO2 reduction to the formate anion (HCOO-) was carried out in the absence of biological enzymes, a sacrificial Lewis acid, or a base to activate the substrate or reductant. 13CO2 experiments confirmed the formation of H13COO- by CO2 reduction with the formate product characterized by 1H NMR and 13C NMR spectroscopy and ESI-MS. The highest formate yield of 66% was obtained in the presence of potassium tetrafluoroborate under mild conditions. The likely role of exogenous salt additives in this reaction is to stabilize and shift the equilibrium toward the ionic products. After CO2 reduction, the benzimidazole-based hydride donor was quantitatively oxidized to its aromatic benzimidazolium cation, establishing its recyclability. In addition, we electrochemically reduced the benzimidazolium cation to its organo-hydride form in quantitative yield, demonstrating its potential for electrocatalytic CO2 reduction. These results serve as a proof of concept for the electrocatalytic reduction of CO2 by sustainable, recyclable, and metal-free organo-hydrides.