Why is dmf a good solvent

A plausible mechanism for this transformation is suggested through nucleophilic attack of DMF with enolate and pyrrolyl nitrogen followed by formation of C—N bond Scheme In , Nozaki and co-workers presented a novel and brief strategy to synthesize arylcarboxamides from aryl halides 99 and N , N -dimethylformamide both as an amide source in one step and as a solvent without the need for using carbon monoxide Scheme A mechanism for the synthesis of arylcarboxamides has been proposed.

It also is likely this reaction take place through oxidative addition of aryl halide to Pd 0 under reaction conditions to yield the arylpalladium halide Scheme Two other proposed mechanisms are shown in Scheme In the third mechanism, the reaction can be performed through oxidative addition of C—H bond of N , N -dimethylformamide and then by an exchange process and reductive elimination. It is important to note that in these three proposed mechanisms no base was used although in conventional examples, presence of a base for the regeneration of Pd 0 species from H—Pd—X is required.

The reaction of 2- or 4-chloropyridine with DMF as an amine source and solvent under refluxing conditions afforded aminopyridines Scheme In this reaction, the corresponding N , N -dimethyl amides were synthesized via treatment of aryl halides iodides, bromides, as well as chlorides with N , N -dimethylformamide, using PdCl 2 as a pre-catalyst without any phosphorous ligand under standard conditions Scheme Thioamides were produced in by Liu and co-workers from compounds , octasulfur and dimethylamine which was prepared in situ from DMF through a base-induced cleavage Scheme Bates's group presented a one-step method for the generation of alkyl E dimethylamino acrylates by reaction of ketene acetals with DMF Scheme Incorporation of all the atoms of a DMF molecule into the product was achieved by a formal stereoselective 1,2-insertion of rhodium II azavinyl carbenes, produced in situ from N -sulfonylated 1,2,3-triazoles using Rh 2 t -BuCO 2 4 , into the C O double bond of DMF to provide cis -diamino enones Scheme A plausible mechanism for the formation of a is illustrated in Scheme Rhodium—iminium zwitterionic B prepared by stereoselective 1,2-insertion of A into the C O bond of DMF resulted in the formation of 2-aminooxazoline C as a product.

The latter is rearranged to give aziridine D. At last, the synthesis of stable vinylogous enamino ketone a is completed by conversion of intermediate D by ring-opening and deprotonation. The reaction of the cationic intermediate with acetanilide furnished the 2-chloroquinolinecarbaldehydes Scheme As shown in Scheme 59 , by addition of alcohol to Vilsmeier—Haack VH complex 49 , an interaction occurs between the hydroxyl group of the alcohol and choloromethyleniminium species cationic species which is followed by nucleophilic attack of chloride ion to generate the desired chloride On the basis of observed stereochemical results, the reaction probably occurs through SN 2 reaction mechanism.

For years, the Vilsmeier reaction has been used to achieve a key transformation such as formylation. The mechanism of the formation of Z chloro-1,3-diarylpropenones could be explained by an initial reaction of BTC with DMF to generate halomethylene iminium salts 49 followed by coordination with 2,3-epoxy-l,3-diarylpropanones to furnish intermediates oxiranium A , as shown in Scheme Next, intermediates B produced by attack of previously released halide anion from the Vilsmeier reagent on the benzyl position of A led to obtain dichloride D.

At the end, one molecule of HCl from compound D is eliminated to yield the desired products As an example, the reaction did not occur in DMF. The main advantages of this present methodology are: i work-up procedure is simple; ii the products are prepared from readily available and economically cheap reagents; iii yields are excellent; and iv the reaction time is short.

A simple and efficient protocol was designed and reported by Moghanian's group in for synthesis of azlactone derivatives through a condensation reaction of aromatic aldehydes with hippuric acid using a TsCl and DMF system as condensing agent under microwave irradiation Scheme Among the bases, DMF gave the best result.

Scheme 66 shows a possible mechanism for synthesis of azlactone derivatives Then, the intermolecular cyclization of intermediate B , produced the azlactone based on good evidence via Erlenmeyer synthesis. A mechanistic scheme for a one-pot synthesis of benzimidazoles 61 is shown in Scheme The resulting compound is cyclized in the presence of DMF as a C1 source to afford benzimidazole.

Liu and co-workers reported the synthesis of heterocycles from 2-phenylenediamines and DMF using PhSiH 3 as the only promoter without the need for any other catalysts or additives under metal-free conditions Scheme Formation of 2-azetidinones via a unique reaction between Schiff bases, substituted acetic acids, and alkoxymethylene- N , N -dimethyliminium salts was reported by Jarrahpour and co-workers in Scheme As a proposal, the reaction just progressed through generation of an activated form of the carboxylic acid which in the following, the corresponding ketene is prepared under deprotonation and loss of DMF from A clean, facile and highly efficient pathway for synthesis of 1-aminoacetylanthraquinone Singh and co-workers in achieved and reported a very mild protocol for regioselective synthesis of the corresponding azepine a and 1,4-diazepine b through a Beckmann rearrangement of ketoximes of pyrazolo annulated oxocarbazole a and oxoazacarbazole b with an organocatalyst derived from DMF and TCTA Scheme Scheme 73 shows a rational mechanistic pathway for formation of a , b from a , b.

The reaction was carried out through preparation of a complex derived from TCT as a cheap reagent and DMF, that allowed the Beckmann rearrangement to be accomplished with a , b to yield a , b , respectively. Interestingly, DMF in a small amount interacted as a co-catalyst with CO 2 in the gas phase while in a large amount, served as activator and solvent of CO 2 in the liquid phase.

Propylene carbonate was produced in A probable catalytic cycle is proposed in Scheme 74 , part B. The reaction began through coordination of PO with ZnBr 2 to provide the adduct of zinc—epoxide complex , which simply gave a propylene oxide open ring; next, the oxy anion of complex was generated by attack of the carboxylate anion which is formed by CO 2 activated with DMF to the less hindered carbon atom of PO; at the late stage, the propylene carbonate is produced by attack of oxy anion to DMF bonded CO 2 and breaking of the bond Zn—O concurrently, followed by cyclic elimination, in an intermolecular fashion.

DMF is a simple, small molecule, and cost-effective organic catalyst which was used for the synthesis of cyclic carbonates via coupling reaction of epoxides with CO 2 under solvent-free conditions by Jiang and Hua in Scheme Scheme 76 displays a probable mechanism for this transformation.

The conversion of to imine salt and then its reaction with CO 2 afforded the intermediate In recent years, metal oxides as inexpensive and simple heterogeneous catalysts have been developed, while their big draw backs were noticeable. To solve problems of the metal oxides, they were loaded onto mesoporous SBA In this method, the surface of metal oxides enhanced the reaction and the amount of metal oxides used decreased.

In addition, a small amount of DMF was applied as a catalyst instead of a large amount of organic solvent. In the first step, the Lewis acid center of zinc on the SBA surface activated the propylene oxide. In the second step, the carboxylate anion, which was produced by coordination of nitrogen of DMF with CO 2 , attacked the less sterically hindered carbon atom of PO. As a result, the negative charge of the carboxylate anion was converted to the oxygen atom of PO.

The propylene carbonate was generated by intramolecular nucleophilic attack of the oxygen anion on the carbon atom of CO 2 bonding with DMF step III followed by ring-closure reaction step IV. Production of 1,2-diols was performed via hydrolysis of epoxides with H 2 O one equimolar using DMF.

This organocatalytic procedure offers remarkable advantages, such as low cost of the catalyst, mild reaction conditions, and easy separation of the product Scheme As shown in Scheme 79 , epoxide is treated with DMF to furnish N , N -dimethylformamide ethylene acetal derivative The ring of is opened in the presence of H 2 O to give the species The vicinal diol and regenerated DMF are obtained by C—O bond cleavage of intermediate which is, in turn, produced from A simple, brief, and efficient method was developed by Zhu and co-workers in to produce 4-chlorooxypyrazoles by treatment of 3-oxypyrazoles with SOCl 2 using catalytic amounts of DMF Scheme In this reaction, the catalyst DMF plays a vital role both as an electron-withdrawing group and as a leaving group upon protonation.

Nitriles were obtained by Varvounis and co-workers in through dehydration of aldoximes by employing DMF as catalyst and solvent Scheme It is mechanistically suggested that the reaction occurs by initial attack of the hydroxyl group of the oxime on the carbonyl group of dimethylformamide to yield the cyclic intermediate Scheme It can lose the proton of hydroxyl to convert to the nitrogen atom of intermediate species Next, the intramolecularly hydrogen bonded aldoxime formate as an intermediate is formed by removal of dimethylamine from which was transformed to the expected nitrile by subsequent thermal elimination of formic acid.

In , and for the first time, a novel and general pathway to synthesize 1,2-disubstituted E -vinyl bromides was performed by DMF-induced reaction of [ Z bromoalkenyl]dialkylboranes with a N -halogeno compound Scheme A mechanistic proposal for the synthesis of is displayed in Scheme It starts through electrophilic attack of the N -halogeno compound. Next, the latter under trans -elimination produces the 2-disubstituted E -vinyl bromides Syntheses of N -Boc and N -Cbz homoallylic amines was achieved and presented in by Wu and Sun through facile allylation of various N -Boc and N -Cbz imines with allyltrichorosilanes as an allylating agent using N , N -dimethylformamide dual roles, as an activator and solvent Scheme In , Teimouri and Tayyebi synthesized 5-[ alkyl or arylamino methylene]barbituric acids by DMF promoted condensation reactions of alkylisocyanides or arylisocyanides with barbituric acid derivatives Scheme Synthesis of syn- and anti- homoallylic alcohols was achieved by smooth treatment of aldehydes with Z - or E -allyltrichlorosilanes in DMF without any other catalyst, respectively Scheme As for the transition state, a six-membered molecule is suggested for the allylation of aldehydes Scheme The organosilicate as a hypervalent molecule has enough Lewis acidity and nucleophilicity, to enable the reaction to proceed smoothly and stereoselectively.

In order to gain appropriate conditions for this method, Jung's group used different polar and nonpolar solvents, such as cyclohexane, hexanes, petroleum ether, dichloromethane, etc. Among the solvents, cyclohexane was shown to give the best result. The reaction is carried out under conditions including minimal energy-consumption and minimal wastes. At the end of the reaction, catalyst and wastes are innocuous for the environment Scheme This catalyst exhibits a unique behavior in the Friedel—Crafts acylation of aromatic compounds bearing electron-donating groups.

The DMF-based ionic liquid was applied as a nucleophilic reagent and as a solvent for preparing a variety of 1,2 disubstituted-3,4-dihydronaphthalenes by cycloaddition of various vinylarenes with electron-deficient alkynes by Hullio and his group, recently Scheme Next, another zwitter ion intermediate B, which is constructed by nucleophilic attack of the anionic carbon to the acetylenic carbon of acetylene dicarboxylate , converted to product C and regenerated ionic liquid D under the indicated bonding arrangements.

The corresponding compound A undergoes aromatization to afford the expected product a Scheme 93 , Path A. The anionic carbon of E attacks the beta carbon of a with the production of another intermediate F that undergoes bond shuffling to obtain C with regeneration of a DMF-based ionic liquid.

Finally, the expected product a is provided by restoration of aromaticity Scheme 93 , Path B. In the second step, PNP penetrated onto the active surface of Au through diffusion. By changing reaction time and temperature, the size of the gold nanoparticles could be controlled.

Among different sizes of Au NPs, 2. Apart from DMF, this catalytic coupling reaction does not require any other organic ligand; DMF serves as a reductant, stabilizer, and solvent in the synthesis of metal NP Scheme Obora's group found that the reactions could be successfully performed with low loadings of the catalyst.

The Migitae—Kosugie—Stille cross-coupling reaction is based on organostannanes catalyzed by Pd complexes. In , synthesis of biaryls and vinylarenes was reported through the Migitae—Kosugie—Stille cross-coupling reaction using N , N -dimethylformamide-stabilized palladium nanoclusters.

It was reported that the palladium-catalyzed Migita—Kosugi—Stille reaction is promoted by addition of copper iodide as an additive. Product was provided in excellent yield by addition of CuI. Find more information about Crossref citation counts. The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online.

Clicking on the donut icon will load a page at altmetric. Find more information on the Altmetric Attention Score and how the score is calculated. Although the molecular weights of the polymers prepared in DMF were routinely lower than those prepared in THF, the polydispersities were as low as and in most cases lower than those obtained using THF.

Gel permeation chromatograms illustrating the molecular weight distributions of selected polymerization trials listed in Tables 1 and 2. Such files may be downloaded by article for research use if there is a public use license linked to the relevant article, that license may permit other uses. View Author Information. Cite this: Macromolecules , 37 , 24 , — Article Views Altmetric -. Citations Supporting Information Available. Cited By.

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Gnade, T. Randall Lee. ACS Omega , 4 27 , It can be used as a reagent, a catalyst, and a stabilizer. Majid M. Heravi, M. Ghavidel and L. Mohammadkhani, RSC Adv. This article is licensed under a Creative Commons Attribution 3.

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