H3PW12O40–[bmim][FeCl4]: A novel and green catalyst-medium system for microwave-promoted selective interconversion of alkoxymethyl ethers into their corresponding nitriles, bromides and iodides

In the present work, the catalytic activity of 12-tungstophosphoric acid immobilized on [bmim][FeCl₄] ionic liquid as a highly efficient and eco-friendly catalytic system for rapid and chemoselective direct conversion of MOM- or EOM-ethers into their corresponding nitriles, bromides and iodides under microwave irradiation is reported. In these reactions, the products are obtained in high yields. The catalyst exhibited remarkable reactivity and was reused several times.     

Ionic liquid-induced conversion of methoxymethyl-protected alcohols into nitriles and iodides using [Hmim][NO3]

This Letter reports a one-pot efficient conversion of methoxymethyl-ethers into their corresponding nitriles and iodides using the ionic liquid, 1-methyl-3H-imidazolium nitrate ([Hmim][NO₃]) under microwave irradiation. A variety of products were prepared in high yields using this method.     

Iodination of alcohols using triphenylphosphine/iodine under solvent-free conditions using microwave irradiation

A straightforward and effective procedure for the conversion of benzylic, allylic and aliphatic alcohols to the corresponding iodides using Ph₃P/I₂ under solvent-free conditions using microwave irradiation is reported.     

Silicaphosphine (Silphos): a filterable reagent for the conversion of alcohols and thiols to alkyl bromides and iodides

Silicaphosphine (Silphos), [P(Cl)_3−n(SiO₂)_n], as a new heterogeneous reagent is introduced. This reagent converts alcohols and thiols to their corresponding bromides and iodides in the presence of X₂ (X=Br, I) in refluxing CH₃CN in high to quantitative yields. Use of Silphos provides a highly practical method for the easy separation of the Silphos oxide byproduct by a simple filtration.     

Direct oxidative conversion of alcohols and amines to nitriles with molecular iodine and DIH in aq NH3

Simple and high-yield procedures for the direct oxidative conversion of various primary alcohols, and primary, secondary, and tertiary amines to the corresponding nitriles were successfully carried out with molecular iodine in aq ammonia and 1,3-diiodo-5,5-dimethylhydantoin in aq NH₃, respectively.     

One-pot conversion of aromatic bromides and aromatics into aromatic nitriles via aryllithiums and their DMF adduct

Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH₃. The same treatment of typical aromatics and heteroaromatics with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH₃ also provided the corresponding aromatic nitriles in good yields. Moreover, the same treatment of aromatic bromides and aromatics with half amount of DIH (1,3-diiodo-5,5-dimethylhydantoin) instead of molecular iodine worked effectively to give the corresponding aromatic nitriles, respectively, in good yields. These reactions are novel and environmentally benign one-pot methods for the preparation of aromatic nitriles from aromatic bromides and aromatics, respectively, through the formation of aryllithiums and their DMF adducts.     

Simple synthesis of fresh alkyl iodides using alcohols and hydriodic acid

A simple synthesis of fresh alkyl iodides using alcohols and hydriodic acid (HI) is reported. The alkyl iodides were obtained in quick and easy work-up with good to excellent yields (66-94%) and very high purities (97-99%). Freshly prepared iodomethane and 1-iodobutane were applied to synthesize biologically relevant 3,7-dimethyladenine and 9-butyladenine, which were characterized thoroughly using 1D and 2D NMR, individually.     

Acid‐Catalysed Selective Monoiodination of Electron‐Rich Arenes by Alkali Metal Iodides

Abstract

The reaction of electron‐rich arenes with alkali metal iodides such as sodium and potassium iodides in the presence of conc. H₂SO₄ gives p‐iodoarenes in high yields.     

Acetohydroxamic acid: a new reagent for efficient synthesis of nitriles directly from aldehydes using Bi(OTf)3 as the catalyst

An efficient method for the preparation of nitriles directly from aldehydes by reaction with AHA using Bi(OTf)₃ as the catalyst is described. Bi(OTf)₃ is shown to be an efficient catalyst also for the conversion of aldoximes into nitriles.     

Room temperature dehalogenation of (hetero)aryl halides with magnesium/methanol

Magnesium in methanol was found to be an effective and inexpensive reagent for the dehalogenation of (hetero)aryl chlorides, bromides and iodides under mild conditions. The halogen/hydrogen exchange proceeded at room temperature and tolerated functional groups such as esters, nitriles, alcohols, and alkenes.     

Reactifs de grignard vinyliques γ fonctionnels : II. Iodolyse,alkylation et arylation des iodo-alcools

Iodination of γ-functionally substituted vinylic Grignard reagents, prepared by addition of organomagnesium compounds to α-aactylenic or α-allenic alcohols gives vinyl iodides stereospecifically. Treatment of these iodides with Grignard reagents in the presence of (PPh₃)₂NiCl₂ gives allylic alcohols. This reaction proceeds with high stereoselectivity.     

CuFe2O4 nanoparticles: a magnetically recoverable and reusable catalyst for the synthesis of 5-substituted 1H-tetrazoles

An efficient and economical protocol for the synthesis of 5-substituted 1H-tetrazoles from various nitriles and sodium azide is described using magnetically recoverable and reusable CuFe₂O₄ nanoparticles. A wide variety of aryl nitriles underwent [2+3] cycloaddition under mild reaction conditions to afford tetrazoles in good to excellent yields. The catalyst was magnetically separated and reused five times without significant loss of catalytic activity.     

Synthesis of substituted imidazolines via [3+2]-cycloaddition of aziridines with nitriles

An efficient synthesis of 2,4-disubstituted 1H-imidazolines from aziridines and nitriles in the presence of BF₃-Et₂O or triethyloxonium tetrafluoroborate has been described. The reaction proceeds via a [3+2]-cycloaddition reaction. Most of the nitriles successfully underwent cycloaddition reactions with aziridines even at room temperature in a very short time.     

Antimony Trioxide as an Efficient Lewis Acid Catalyst for the Synthesis of 5-Substituted 1H-Tetrazoles

Sb₂O₃ was found to be effective as a catalyst for a smooth (2 + 3) cycloaddition of sodium azide with nitriles to afford 5-substituted 1H-tetrazoles in good yields.     

Palladium-catalyzed oxidation of lower aliphatic alcohols with oxygen in the presence of aromatic nitriles in aqueous medium

The kinetics of oxidation of lower aliphatic alcohols (C₁–C₄) to the corresponding carbonyl compounds with oxygen in the presence of palladium(II) tetraaqua complex and aromatic nitriles (benzonitrile, phenylacetonitrile, and o-tolunitrile) in aqueous medium (c = 0.01 M) at 65°C under atmospheric pressure were studied. A probable reaction mechanism and kinetic equation were proposed. Aromatic nitriles were found to stabilize decomposition of low-valence palladium species, ensuring activation of molecular oxygen and subsequent oxidation of alcohols.     

A Facile and Efficient Trimethylsilylation of Hydroxyl Groups Using Silica-Supported Zinc Chloride and Alumina-Supported Sodium Hydrogensulfate as Recyclable Heterogeneous Catalysts

Silica-supported zinc chloride (SiO₂-ZnCl₂) and novel alumina-supported sodium hydrogensulfate (NaHSO₄-Al₂O₃) as recyclable heterogeneous catalysts have been used for the mild trimethylsilylation of hydroxyl groups under ambient conditions. This procedure also allows for the selective protection of primary and secondary alcohols in the presence of tertiary alcohols.     

FeCl3-silica: A green approach for the synthesis of nitriles from oximes

A green and suitable protocol for the conversion of aldoximes into nitriles is described. The transformation is carried out under solvent-free conditions using FeCl₃-silica medium. The protocol offers a green, single-step facile procedure with the use of less toxic metal salt to isolate nitriles in good to excellent yields.     

Zn-promoted regio- and sequence-selective one-pot joining reactions of three components: vinylpyridines, alkyl iodides, and carbonyl compounds (or nitriles)

Addition of alkyl iodides (3) into the solution containing 2-(or 4-)vinylpyridine (1 or 2) and carbonyl compounds (6) in the presence of Zn-powder (99.9%) in acetonitrile under refluxing brought about regio- and sequence-selective joining reaction of three components to give the corresponding (2-hydroxyethyl)pyridines (7 or 8) in good to moderate yields. On the other hand, 2-(2- or 4-pyridyl)ethyl alkyl ketones (10 or 11) were obtained from the similar joining reaction of three components by addition of alkyl iodides (3) into the solution of 2-(or 4-)vinylpyridine (1 or 2), and nitriles (9) in toluene containing Zn-powder (99.9%) under the similar reaction conditions.     

Ritter Reaction with Cyclopropyl Ketones and Cyclopropyl Alcohols: Synthesis of N-Actyl- γ-Keto and N-Acyl Hohoallyl Amines

A variety of conjugated cyclopropyl ketones and cyclopropylcarbinyl alcohols were reacted with two nitriles viz. CH₃ CN and CH₂[dbnd]CH-CN in presence of cone. H₂ SO₄. It was found that with appropriate substitutions cyclopropyl ketones gave N-Acyl-γ-keto amines whereas cyclopropylcarbinyl alcohols gave the corresponding N-Acyl homoallylic amines in reasonably good yields. The olefins obtained had E-stereo-chemistry. With bicyclic cyclopropylcarbinyl alcohols the ring expanded products were formed. A plausible rationale is provided to account for these observations     

Highly efficient synthesis of amides via Ritter chemistry with ionic liquids

The utility of Brønsted-acidic imidazolium ionic liquid [BMIM(SO₃H)][OTf] as catalyst for the high yield synthesis of a wide variety of amides under mild conditions via the Ritter reaction of alcohols with nitriles has been demonstrated. As alternative methods for the carbocation generation step, NOPF₆ immobilized in [BMIM][PF₆] ionic liquid was used in the Ritter reaction of bromides with nitriles and for the synthesis of adamantyl amides from adamantane and nitriles.