Greener approach: Ionic liquid [Et3NH][HSO4]-catalyzed multicomponent synthesis of 4-arylidene-2-phenyl-5(4H)oxazolones under solvent-free condition

We have developed simple, greener, safer multicomponent synthesis series of 4-arylidene-2-phenyl-5(4H) oxazolones 4(a-r) catalyzed by Bronsted acid ionic liquid as triethylammonium hydrogen sulfate [Et₃NH][HSO₄] and catalytic amount of acetic anhydride and sodium acetate with excellent yields (90–99%). The protocol offers economical, environmentally benign, solvent-free conditions, and recycle–reuse of the catalyst and easily available starting as benzoyl chloride 1, amino acid 2 and a variety of aldehydes 3. The cyclization followed by condensation of benzoyl chloride, amino acid, and a variety of aldehydes catalyzed by ILs [Et₃NH][HSO₄] and catalytic amount of acetic anhydride and sodium acetate. The final products were confirmed by their characterization data such as FTIR, ¹H-NMR, ¹³C-NMR, Mass, high-resolution mass spectra and were compared with its reported method.     

EQUILIBRIA AND REACTION RATES OF PHOSPHORUS SUBSTITUTION REACTIONS IN 2-R-1,3,2-DISUBSTITUTED PHOSPHORINANES

Abstract

Equilibrium constants and reaction times were observed for six equilibria involving methanol, ethanol, dimethylamine, diethylamine and pyrrolidine with 2-R-1,3,2-dioxaphosphorinanes wherein R = MeO (1), EtO (2), Me₂N (3), Et₂N (4) and (CH₂)₄N (5), or 2-R-1,3-dimethyl-1,3,2-diazaphosphorinanes wherein R equalled the same five groups (6–10, respectively). Reaction times of amine substitutions were shorter for diaza compounds and for those reactions which contained pyrrolidine. Equilibrium constants were dependent not only upon the nucleophilicities of the exchanging groups, but also upon the steric interactions of the 2-substituents with the groups in the 1 and 3 positions. Thus, the values of K's for the equilibria 5 + Me₂NH → 3 + (CH₂)₄NH, and 10 + Me₂NH → 8 + (CH₂)₄NH were experimentally identical, whereas K for 9 + Me₂NH → 8 + Et₂NH was ca. eight times that for 4 + Me₂NH → 3 + Et₂NH. The reactions were acid catalyzed, and, for amine substitutions with 8–10, exchange could be rapid on the NMR time scale. Equilibrium positions of amine-containing reactions were [H⁺] dependent, where coordination of the less basic amine to phosphorus became increasingly favored by the addition of acid. These observations raise questions about a recent mechanistic proposal for catalyzed substitution reactions. Similar substitution reactions, such as Me₂NH with the isomeric 4-methyl analogues of 3, provide a procedure for the determination of cis-trans isomer equilibrium distributions.     

Novel ionic liquid N,N-diethyl-N-sulfoethanaminium hydrogen sulfate: Design,characterization, and application as a highly efficient catalyst for the production of triazolo[1,2-a]indazole-triones and 2H-indazolo[2,1-b]phthalazine-triones

A novel Brønsted acidic ionic liquid namely N,N-diethyl-N-sulfoethanamminium hydrogen sulfate ([Et₃N-SO₃H]HSO₄) was synthesized, and characterized using FT-IR, ¹H NMR, ¹³C NMR, and mass data. Then, its catalytic activity was examined for the preparation of triazolo[1,2-a]-indazole-triones and 2H-indazolo[2,1-b]phthalazine-triones by the one-pot multi-component condensation of arylaldehydes with dimedone and 4-phenylurazole/2,3-dihydrophthalazine-1,4-dione under solvent-free conditions. [Et₃N-SO₃H]HSO₄ efficiently promoted the reaction to afford the products in high yields and in short reaction times.     

Polymerization of phenylacetylene catalysed by RhTp(cod) and RhBp(cod) in ionic liquids: effect of alcohols and of tetraammonium halides

RhTp(cod) ( 1 ) and RhBp(cod) ( 2 ), almost inactive in CH₂Cl₂, became good catalysts of phenylacetylene polymerization in ionic liquids ([bmim]Cl, [bmim]BF₄: bmim = 1‐butyl‐3‐methylimidazolium, [mokt]BF₄: mokt = 1‐methyl‐3‐oktylimidazolium, [bumepy]BF₄: 1‐butyl‐4‐methylpyridinium) and in CH₂Cl₂ in the presence of tetraammonium halides ([R₄N]X, R = Bu, Et; X = Cl, Br). The highest yields of polyphenylacetylene with catalyst 1 were obtained in [bmim]Cl at 65°C (64% after 2 h) and in [mokt]BF₄ at 20°C (56% after 24 h). In alcohols (CH₃OH, (CH₃)₂CHOH, (CH₃)₃COH) as solvents, up to 100% of the polymer was produced. When a mixture of an ionic liquid and CH₃OH was used as the reaction medium, the polymer yield was similar to the yield achieved in an ionic liquid only, but the molecular weight increased remarkably. Tetraammonium salts, [R₄N]X, are co‐catalysts for 1 , and the yield of the polymer increased in the order [Et₄N]Br < [Bu₄N]Br < [Et₄N]Cl < [Bu₄N]Cl. Polymers with molecular weights from 6900 to 38 800 Da were obtained with catalyst 2 in [R₄N]Br or [R₄N]Cl, whereas in ionic liquids ([bmim]Cl, [bmim]BF₄) the corresponding molecular weights were higher, from 51 300 to 60 300 Da. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and Dehydrogenation of Organic Salts of a Five-Membered B/N Anionic Chain,a Novel Ionic Liquid

We have synthesized the tetrabutylammonium ([Bu₄N]⁺), tetraethylammonium ([Et₄N]⁺), guanidinium ([C(NH₂)₃]⁺), and methylguanidinium ([C(N₃H₅CH₃)]⁺) salts of the [BH₃(NH₂BH₂)₂H]⁻ anion, a five-membered B/N anionic chain, in high yields by the metathesis reactions of Na[BH₃(NH₂BH₂)₂H] with the corresponding halides and characterized them by NMR (¹¹B, ¹¹B{¹H}, ¹H, ¹H{¹¹B}, ¹³C), IR, elemental analysis, TGA-DSC, and TGA-MS. These complexes behave like ionic liquids (ILs), in which the melting point of the [Bu₄N][BH₃(NH₂BH₂)₂H] is the lowest (−51 °C). The dehydrogenation of these ILs have been studied through the thermal decomposition and catalytic hydrolysis in aqueous solution using the noble or non-noble metals or their salts as catalysts, and the results indicate that these ILs of five-membered B/N anionic chain are promising hydrogen storage materials.     

Front Cover: Reactivity of a Free Aluminylene towards Boron Lewis Acids: Accessing Aluminum-Boron-Bonded Species (Eur. J. Inorg. Chem. 25/2023)

The reactivity of the free aluminylene [N]-Al ( 1 ) ([N]=1,8-bis(3,5-di-tert-butylphenyl)-3,6-di-tert-butylcarbazolyl) towards boron Lewis acids is investigated. A facile oxidative addition reaction of 1 with Ph₂BOBPh₂ furnishes an exceedingly scarce example of the free alumaborane [N]-Al(BPh₂)(OBPh₂) ( 2 ) with an Al−B electron-sharing bond. By contrast, complexation of 1 with B(C₆F₅)₃ and HB(C₆F₅)₂ gives rise to the corresponding Lewis adducts [N]-Al→B(C₆F₅)₃ ( 3 ) and [N]-Al→BH(C₆F₅)₂ ( 4 ), respectively, with an Al→B dative bond. Crystallization of 4 in Et₂O produces the adduct [N]-Al(Et₂O)→BH(C₆F₅)₂ ( 5 ). Quantum chemical calculations are carried out to understand the formation of 2 as well as the bonding situation of 3 and 5 .     

A metallacage encapsulating chloride as a probe for a solvation scale in ionic liquids

With the purpose of assessing the reactivity of chloride ions dissolved in ionic liquids (ILs), a relative scale for the solvation of chloride is given for a series of ILs based on the bis(trifluoromethane)sulfonimide ([Tf(2)N]) anion and different cations, 1-butyl-3-methylimidazolium ([bmim]), 1-butyl-2,3-dimethylimidazolium ([bdmim]), 1-butyl-1-methylpyrrolidinium ([bmpy]), 1-butylpyridinium ([bpy]), 1-pentyl-1,1,1-triethylammonium ([C(5)e(3)am]), and 1-(2-hydroxy)ethyl-3-methylimidazolium ([mimeOH]). Insights into the solvation of chloride are achieved by the thermodynamic study of the reaction of dissociation of a chloride-templated nickel(II) metallacage performed at various temperatures by UV-visible spectroscopy in each IL. The order of chloride solvation [C(5)e(3)am][Tf(2)N] < [bmpy][Tf(2)N] < [bmim][Tf(2)N] 相似文献   

Simple ammonium ionic liquid catalyses the 1,5-benzodiazepine derivatives under mild conditions

Abstract

An incredibly elementary procedure for the effective synthesis of 1,5-benzodiazepine derivatives using triethyl ammonium acetate (TEAA) [Et₃NH][CH₃COO] ionic liquid has been developed. TEAA was found to be practical, inexpensive, reusable and has a simple work-up procedure, which is absent in other catalyst. The role of TEAA as the reaction medium as well as the catalyst has shown the benefits of the use of TEAA in organic synthesis. The effect of [Et₃NH][CH₃COO] on the synthesis of 1,5-benzodiazepine derivatives has been studied and results are provided herein.     

SYNTHESES AND STRUCTURES OF CLUSTER COMPOUNDS CONTAINING WSe4Cun (n = 3,4) CORES WITH DIALKYLDITHIOCARBAMATE LIGANDS

Abstract

The reactions of [Et₄N]₂[WSe₄] with three equivalents of CuCl in the presence of NaS₂CNR₂ (R = Me, Et) yielded two W-Cu-Se compounds, [Et₄N]₂[WCu₃Se₄(Et₂NCS₂)₃] (1) and [Et₄N]₂-[WCu₄Se₄(Me₂NCS₂)₄] (2). [Et₄N]₂[MoCu₃Se₄(Et₂NCS₂)₃] (1) crystallizes in the orthorhombic space group P2₁2₁2₁ with cell dimensions a = 12.976(3), b = 13.336(3) and c = 29.738(6)Å, V = 5153.8(13)ų, Z = 4. Full anisotropic refinement of the structure led to convergence at R = 0.061 (R_w = 0.070) for 453 variables and 5913 reflections with F>4.0σ(F). The [WCu₃-Se₄(Et₂NCS₂)₃]^2- anion in 1 comprises three Et₂NCS₂Cu fragments linked by a slightly distorted tetrahedral WSe₄ moiety. Compound 2 crystallizes in the orthorhombic space group Pbca with cell constants a = 14.698(3), b = 18.473(4), c = 37.182(5)Å, V = 10095.6(33) ų and Z = 8. Anisotropic refinement with 5839 reflections (F > 6.0σ(F)) and 460 parameters for all non-hydrogen atoms yielded the values R = 0.061 and R_w = 0.073. The [WCu₄Se₄(Me₂NCS₂)₄]^2- anion structure of 2 possesses pseudo D_2d symmetry for the WSe₄Cu₄ core and a nearly planar WCu₄ array and consists of four Me₂NCS₂Cu fragments coordinated across four edges of the tetrahedral [WSe₄]^2- group. IR and electronic spectroscopic data for the two compounds are reported.     

Syntheses,crystal structures,and electrochemical studies of diiron complexes from the reactions of [Et3NH][(μ-RS) Fe2(CO)6(μ-CO)] with isothiocyanates

Reactions of [Et₃NH][(μ-MeO₂CCH₂S)Fe₂(CO)₆(μ-CO)] in situ generated from the mixture of MeO₂CCH₂SH, Et₃N, and Fe₃(CO)₁₂ with 2-C₅H₄NNCS, 3-C₅H₄NNCS, and EtNCS in THF, form 1, (μ-MeO₂CCH₂S)Fe₂(CO)₅(μ-k²N,S:k²C-2-C₅H₄NNHCS), 2, (μ-MeO₂CCH₂S)Fe₂(CO)₆(μ-k²C,S-3-C₅H₄NNHCS), and 3, (μ-MeO₂CCH₂S)Fe₂(CO)₆(μ-k²C,S-EtNHCS). Reaction of [Et₃NH][(μ-PhS)Fe₂(CO)₆(μ-CO)] in situ formed from the mixture of PhSH, Et₃N, and Fe₃(CO)₁₂ with EtNCS affords 4, (μ-PhS)Fe₂(CO)₆(μ-k²C,S-EtNHCS). Reaction of [Et₃NH][(μ-EtS)Fe₂(CO)₆(μ-CO)] in situ produced from the mixture of EtSH, Et₃N, and Fe₃(CO)₁₂ with EtNCS offers 5, (μ-EtS)Fe₂(CO)₆(μ-k²C,S-EtNHCS). All new complexes have been fully characterized by EA, IR, ¹H NMR, and ¹³C NMR and structurally determined by X-ray crystallography. Electrochemical studies on 2 and 5 confirm that 2 shows high H₂-producing activity.     

Kinetics of Addition of Diethylamine to Oligo[(2-Acryloyloxy-5-Methyl-1,3-Phenylene)-Methylene] Catalyzed by Lithium Diethylamide

The kinetics of addition reaction of diethylamine to vinyl groups of oligo[(2-acryloyloxy-5-methyl-1,3-phenylene)methylene] in benzene with excess amine in the presence of lithium diethylamide as catalyst has been investigated. The reaction rate, was found to be expressed as: V = k [CH₂=CH-][Et₂NLi] with the ratio of [Et₂NH]o to [Et₂NLi]o being 5. Second-order rate constants for addition and the activation energy have been determined.     

Self-assembly of ionic triorganotin(IV) complexes of tetrafluorophthalic acid with a tetranuclear macrocyclic or polymeric structure: syntheses,characterization and crystal structures

Four triorganotin(IV) complexes constructed from tetrafluorophthalic acid (H₂tfp) with a 1?:?1?:?1 molar ratio of H₂tfp: Et₃N: R₃SnCl gave two of type {[R₃Sn (tfp)].Et₃NH}₄ (R?=?Me 1, R?=?n-Bu 2), and two of type [R₃Sn (tfp).Et₃NH] _n (R?=?PhCH₂ 3, Ph 4). All the complexes are characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR analyses. Complexes 1 and 4 were also confirmed by X-ray crystallography. Complex 1 is tetranuclear with a 28-membered C₁₆O₈Sn₄ macrocyclic ring system with a cavity. The supramolecular structure of 1 has been found to consist of a three-dimensional network built up by intermolecular N–H?···?O, C–H?···?O hydrogen bonds and C–F?···?F weak interactions. Complex 4 is an infinite polymeric structure. The salient feature of the supramolecular structure of 4 is that of a two-dimensional plane, in which intermolecular N–H?···?O and C–H?···?π hydrogen bonds are important.     

Non‐Ideal Mixing Behaviour of Hydrogen Bonding in Mixtures of Protic Ionic Liquids

Ionic liquids (ILs) attract interest in science and technology as a result of their unique properties. Binary and ternary mixtures of ILs significantly increase the number of possible cation/anion combinations, resulting in targeted physical and chemical properties. In this work, we study the mixing behaviour of two protic ILs: triethyl ammonium methylsulfonate [Et₃NH][CH₃SO₃] and triethylammonium triflate [Et₃NH][CF₃SO₃]. We find a characteristic deviation from ideal mixing by means of low‐frequency infrared spectroscopy. By using molecular dynamics simulations, we explain this behaviour as being the result of different strengths of anion/cation hydrogen bonding. This non‐ideality of non‐random H‐bond mixing is also reflected in macroscopic properties such as the viscosity. Mixing suitable ILs may, thus, result in new ILs with targeted physical properties.     

The physicochemical properties of some imidazolium-based ionic liquids and their binary mixtures

The density, viscosity and conductivity of ionic liquids (ILs), 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF4]), 1-octyl-3-methylimidazolium chloride ([omim][Cl]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim] BF4]), 1-hexyl- 3-methylimidazolium chloride ([hmim][Cl]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF6]), and the [omim][BF4] + [omim][Cl], [hmim][BF4] + [hmim][Cl], and [hmim][PF6] + [hmim][Cl] binary mixtures were studied at dif- ferent temperatures. It was demonstrated that the densities of both the neat ILs and their mixtures varied linearly with temper- ature. The density sensitivity of a binary mixture is between those of the two components. The excess molar volumes (VE) of [hmim][BF4] + [hmim][Cl] and [hmim][PF6] + [hmim][Cl] mixtures are positive in the whole composition range. For [omim][BF4] + [omim][Cl], the VE is also positive in the [omim][Cl]-rich region, but is negative in the [omim][BF4]-rich re- gion. The viscosity or conductivity of a mixture is in the intermediate of those of the two neat ILs. For all the neat ILs and the binary mixtures studied, the order of conductivity is opposite to that of the viscosity. The Vogel-Tammann-Fulcher (VTF) equations can be used to fit the viscosity and conductivity of all the neat ILs and the binary mixtures. The neat ILs and their mixtures obey the Fractional Walden Rule very well, and the values of the Walden slopes are all smaller than unit, indicating obvious ion associations in the neat ILs and the binary mixtures.     

An efficient and green protocol for synthesis of novel [1,3]oxazino[5,6-c]quinolin-5-one derivatives using [Et3NH]HSO4 as a reusable catalyst

A simple, efficient, and eco-friendly procedure has been developed using acidic ionic liquid [Et₃NH]HSO₄ as catalyst for the synthesis of novel [1,3]oxazino[5,6-c]quinolin-5-one derivatives via one-pot three-component condensation reaction of 4-hydroxyquinolin-2(1H)-one, amine and formaldehyde in aqueous ethanol at room temperature. Mild and environmentally benign reaction conditions, short reaction time, good to excellent yields, nontoxic, cheap and easily available catalyst, reusability of catalyst and reaction media, and easy work-up are the key features of this method.     

Difunctionalized {closo‐1‐CB11} Clusters: 1‐ and 2‐Amino‐12‐ethynylcarba‐closo‐dodecaborates

Carba‐closo‐dodecaborate anions with two functional groups have been synthesized via a simple two‐step procedure starting from monoamino‐functionalized {closo‐1‐CB₁₁} clusters. Iodination at the antipodal boron atom provided access to [1‐H₂N‐12‐I‐closo‐1‐CB₁₁H₁₀]^? ( 1 a ) and [2‐H₂N‐12‐I‐closo‐1‐CB₁₁H₁₀]^? ( 2 a ), which have been transformed into the anions [1‐H₂N‐12‐RC?C‐closo‐1‐CB₁₁H₁₀]^? (R=H ( 1 b ), Ph ( 1 c ), Et₃Si ( 1 d )) and [2‐H₂N‐12‐RC?C‐closo‐1‐CB₁₁H₁₀]^? (R=H ( 2 b ), Ph ( 2 c ), Et₃Si ( 2 d )) by microwave‐assisted Kumada‐type cross‐coupling reactions. The syntheses of the inner salts 1‐Me₃N‐12‐RC?C‐closo‐1‐CB₁₁H₁₀ (R=H ( 1 e ), Et₃Si ( 1 f )) and 2‐Me₃N‐12‐RC?C‐closo‐1‐CB₁₁H₁₀ (R=H ( 2 e ), Et₃Si ( 2 f )) are the first examples for a further derivatization of the new anions. All {closo‐1‐CB₁₁} clusters have been characterized by multinuclear NMR and vibrational spectroscopy as well as by mass spectrometry. The crystal structures of Cs 1 a , [Et₄N] 2 a , K 1 b , [Et₄N] 1 c , [Et₄N] 2 c , 1 e , and [Et₄N][1‐H₂N‐2‐F‐12‐I‐closo‐1‐CB₁₁H₉]?0.5 H₂O ([Et₄N ]4 a ?0.5 H₂O) have been determined. Experimental spectroscopic data and especially spectroscopic data and bond properties derived from DFT calculations provide some information on the importance of inductive and resonance‐type effects for the transfer of electronic effects through the {closo‐1‐CB₁₁} cage.     

Synthesis of sulphonated aminomethylphosphines and some nickel(II), palladium(II), platinum(II) and rhodium(I) complexes. Crystal structure of [Et3NH][(Ph2PCH2)2 N(CH2)2SO3]

Summary Aminoalkanesulphonic acids H₂N(CH₂) _n SO₃H, (n = 1, 2 or 3) react with phosphonium salts [R₂P(CH₂OH)₂]Cl (R = Ph or Cy, Cy = cyclohexyl) in the presence of Et₃N to give the sulphonated aminomethylphosphines [Et₃NH] [(R₂PCH₂)₂N(CH₂) _n SO₃] (R = Ph, n = 1, 2 or 3; R = Cy, n = 1). The single crystal X-ray structure of [Et₃NH] [(Ph₂PCH₂)₂N(CH₂)₂SO₃] has been determined. Some Ni^II, Pd^II, Pt^II and Rh^I complexes of the phosphines have been prepared.     

Synthesis and Crystal Structures of Four Novel Mo(W)/Cu/S Polymers Containing Thiolato Bridging Ligands

Four novel M/Cu/S polymers [Et₄N][MS₄Cu₃(S₂COEt)₂] (1a: M=Mo; 1b: M=W) and Et₄N][MS₄Cu₂SEt] (2a: M=Mo; 2b: M=W) have been prepared by reactions of [Et₄N]₂[MS₄] with CuS₂COEt and CuSEt. X-ray crystal structure determinations reveal that the polymeric anions of complexes 1a and 1b both consist of MS₄Cu₃ building blocks linked via bidentate [S₂COEt]⁻ bridging ligands to form 1D polymeric chains. The anion structures of the polymeric compounds 2a and 2b contain MS₄Cu₂ repeating units which are connected via μ-SEt⁻ ligands forming a zigzag chain running down the crystallographic b axis.     

Selenium-capped trimolybdenum and tritungsten carbonyl clusters [Se2M3(CO)10] (M = Mo, W)

A facile synthesis of the novel selenium-capped trimolybdenum and tritungsten ring carbonyl clusters [Se₂M₃(CO)₁₀]²⁻ (M = Mo, 1; W, 4) have been achieved. The selenium-capped trimolybdenum cluster compound [Et₄N]₂[Se₂Mo₃(CO)₁₀] ([Et₄N]₂[1]) can be obtained from the reaction of the trichromium cluster compound [Et₄N]₂[Se₂Cr₃(CO)₁₀] with 4 equiv. of Mo(CO)₆ in refluxing acetone. On the other hand, when [Et₄N]₂[Se₂Cr₃(CO)₁₀] reacted with 4 equiv. of W(CO)₆ in refluxing acetone, the planar cluster compound [Et₄N]₂[Se₂W₄(CO)₁₈] ([Et₄N]₂[3]) was isolated, which could further transform to the tritungsten cluster compound [Et₄N]₂[Se₂W₃(CO)₁₀] ([Et₄N]₂[4]) in good yield. Alternatively, clusters 1 and 4 could be formed from the reactions of the monosubstituted products [Et₄N]₂[Se₂Cr₂M(CO)₁₀] (M = Mo; W, [Et₄N]₂[2]) with 3 equiv. of M(CO)₆ in acetone, respectively. Complexes 1-4 are fully characterized by IR, ⁷⁷Se NMR spectroscopy, and single-crystal X-ray analysis. Clusters 1, 2, and 4 are isostructural and each display a trigonal bipyramidal structure with a homometallic M₃ ring (M = Mo, 1; W, 4) or a heterometallic Cr₂W ring that is further capped above and below by μ₃-Se atoms. Further, the intermediate planar complex 3 exhibits a Se₂W₂ square with each Se atom externally coordinated to one W(CO)₅ group. This paper describes a systematic route to a series of selenium-capped trimetallic carbonyl clusters and the formation and the structural features of the resultant clusters are discussed.     

Effect of Different Ionic Liquids on 5-Hydroxymethylfurfural Preparation from Glucose in DMA over AlCl3: Experimental and Theoretical Study

In this work, effect of different ionic liquids (ILs) on 5‐hydroxymethylfurfural (HMF) preparation from glucose in N,N‐dimethylacetamide (DMA) over AlCl₃ was revealed by a combined experimental and computational study. ILs used as cocatalysts in this work included N‐methyl‐2‐pyrrolidone hydrogen sulfate ([NMP]HSO₄), N‐methyl‐2‐pyrrolidone methyl sulfate ([NMP]CH₃SO₃), N‐methyl‐2‐pyrrolidone chlorine ([NMP]Cl) and N‐methyl‐2‐pyrrolidone bromide ([NMP]Br) which were endowed with the same cation but different anions. According to the conclusion that fructose was intermediate product from glucose to HMF, we found fructose was transformed to more by‐products by [NMP]HSO₄, making HMF yield decline significantly when glucose was treated as substrate. Neither glucose nor fructose could be converted by [NMP]CH₃SO₃ efficiently, leading to its no influence on glucose conversion to HMF. [NMP]Br had a higher selectivity for HMF from fructose than [NMP]Cl and AlCl₃. Besides, Al³⁺ preferred to combine with Br^?, slightly decreasing both the overall free energy barrier for glucose isomerization and activation barrier for H‐shift at 393.15 K. So a high HMF yield of 57% was obtained from glucose catalyzed by AlCl₃ together with [NMP]Br under mild conditions.