Reaction Of Dimethyl Acetylenedicarboxylate Research Articles

Synthesis of Highly Functionalized Spirocycles and Pentafulvene-Containing Dyes Involving 2-(2'-ketoalkyl)-1,3-indandiones.

Synthesis of highly functionalized spiro[4.4]nonane and spiro[4.5]decane motifs by the reaction of dimethylacetylenedicarboxylate (DMAD) with 2-(2'-ketoalkyl)-1,3-indandiones and 2-(3'-ketoalkyl)-1,3-indandiones, respectively, has been developed by utilizing a catalytic amount of DABCO. The tertiary hydroxy-containing spiro[4.4]nonane products were converted into fully conjugated pentafulvene π-systems in an acidic medium through dehydration and unprecedented C-C bond rearrangement.

“On Water” Effect for Green Click Reaction: Spontaneous Polymerization of Activated Alkyne with “Inert” Aromatic Amine in Aqueous Media

“On Water” Effect for Green Click Reaction: Spontaneous Polymerization of Activated Alkyne with “Inert” Aromatic Amine in Aqueous Media

Extremely Rapid Polythioether Synthesis in the Presence of TBD

A straightforward, novel, and extremely rapid method is developed for the synthesis of polythioether based on the reaction of dimethyl acetylenedicarboxylate with electron-deficient triple bond and 1,6-hexanedithiol in CHCl3 using an organobase 1,5,7-triazabicyclo[4.4.0]dec-5-ene at room temperature. The influence of various parameters, such as concentration of monomers, solvent, catalyst, and reaction time, on the polymerization was investigated through kinetic studies. Polythioether with molecular weight up to ∼50 kDa was quantitatively achieved in 1 min, under the optimum experimental conditions. Various dithiol compounds were then reacted with dimethyl acetylenedicarboxylate to enhance polymer diversity. Following, three propiolate compounds were reacted with 1,6-hexanedithiol to explore their ability for polythioether synthesis, but low to moderate molecular weights were achieved compared to those with dimethyl acetylenedicarboxylate. The versatility of these polythioethers was shown by postpolymeriz...

Generation and Trapping of Terminal Phosphinidene Complex [CF3P‐W(CO)5

AbstractThe LUMO of [CF3P−W(CO)5] is lower in energy than the LUMO of [ClP−W(CO)5] by 0.30 eV and [CF3P−W(CO)5] is the most electrophilic phosphinidene tungstenpentacarbonyl complex described so far. It is generated by reaction of dimethyl acetylenedicarboxylate with the appropriate 1‐trifluoromethylphosphole complex at 80 oC in toluene. It reacts normally with alkynes to give 1‐trifluoromethylphosphirene complexes. The reaction with alkenes works only with electron‐rich species. The phosphirane complexes appear to be unstable when electron‐poor C=C double bonds are used such as with trans‐stilbene. This highlights the importance of the P to C=C backbonding in the stability of the phosphirane adducts.

Dimethyl Acetylenedicarboxylate in Reactions with Substituted 3‐(2‐aminophenyl)‐6‐R1‐1,2,4‐triazin‐5‐(2H)‐ones: Structure and Properties of the Products

The article describes unusual [5 + 1]‐cyclocondensations of dimethyl acetylenedicarboxylate (DMAD), in which this reagent uncharacteristically acts as a 1,1‐biselelectrophilic agent. Reactions of DMAD with 1,5‐bisnucleophilic 3‐(2‐aminophenyl)‐6‐R1‐1,2,4‐triazin‐5(2H)‐ones yielded triazinoquinazoline‐derived diesters. The latter was shown to react with nucleophiles: hydrazine cleaved the pyrimidine ring of the diesters to give anilines, while ester hydrolysis furnished corresponding carboxylic acids.

ZnO‐NR as the efficient catalyst for the synthesis of new thiazole and cyclopentadienone phosphonate derivatives in water

AbstractFunctionalized thiazoles are generated from the reaction of dimethyl acetylenedicarboxylate, benzoylisothiocyanates, and primary amines and trialkyl phosphite in the presence of ZnO‐nanorods as the catalyst in water. Also, a series of polysubstituted cyclopentadienone phosphonate derivatives were synthesized via one‐pot multicomponent reactions of primary amines and phosphites with activated acetylenic compounds in water as the solvent at room temperature. Particularly valuable features of this method include high yields of products, broad substrate scope, short reaction time, and straightforward procedure.

Utility of Acetylenedicarboxylate in Organic Synthesis

Although, recent reviews demonstrated intensively on the reactivity of dimethyl acetylenedicarboxylate (DMAD) in organic synthesis, its reactions have still get importance addition in that field. Moreover, and due to the huge amount of published literatures dealing with the reactions of DMAD, we are trying to give more focus on the important missed reactions in addition to give more light to updated publications. DMAD is an organic compound with the formula (C6H6O4), and it is a diester in which the ester groups are conjugated with a triple bond. As such, DMAD is highly electrophilic and a widely employed as a dienophile in cycloaddition reactions, like the Diels–Alder reaction. Many organic compounds specially the heterocyclic ones were prepared via its reactions.

ChemInform Abstract: Reactions of Dimethyl Acetylenedicarboxylate with 2,5‐Dithiobiurea Derivatives.

ChemInform Abstract: Reactions of Dimethyl Acetylenedicarboxylate with 2,5‐Dithiobiurea Derivatives.

Reactions of Dimethyl Acetylenedicarboxylate with 2,5-Dithiobiurea Derivatives

Symmetrically and unsymmetrically N 1 ,N 2 -disubstituted hydrazine-1,2-dicarbothioamides (2,5-dithiobiureas) react with dimethyl acetylenedicarboxylate in refluxing ethanol to give dimethyl 2,2′-[2,2′-(hydrazine-1,2-diylidene)bis(3-aryl/alkyl-4-oxothiazolidine-5,2-diylidene)diacetate and methyl 2-(2-{[5-(2-methoxy-2-oxoethylidene)-4-oxothiazolidin-2-ylidene]hydrazono}-4-oxothiazolidin-5-ylidene)acetate derivatives and N 2 ,N 5 -disubstituted 1,3,4-thiadiazole-2,5-diamines. The structure of one product has been confirmed by a single-crystal X-ray structure analysis. A rationale for the formation of the products is presented.

ChemInform Abstract: Ceric (IV) Ammonium Nitrate (CAN) Mediated Synthesis of Pyrrole‐2,3,4,5‐tetracarboxylates by Reaction of Dimethyl Acetylenedicarboxylate with an Amine.

Abstract A simple one-step method for efficient synthesis of pyrrole-2,3,4,5-tetracarboxylates by reaction of dimethyl acetylenedicarboxylate with an amine using ceric (IV) ammonium nitrate as one electron oxidant is described.

Ceric (IV) ammonium nitrate (CAN) mediated synthesis of pyrrole-2,3,4,5-tetracarboxylates by reaction of dimethyl acetylenedicarboxylate with an amine

A simple one-step method for efficient synthesis of pyrrole-2,3,4,5-tetracarboxylates by reaction of dimethyl acetylenedicarboxylate with an amine using ceric (IV) ammonium nitrate as one electron oxidant is described.

Mechanisms by which Alkynes React with CpCr(CO)3H. Application to Radical Cyclization

The reaction of CpCr(CO)(3)H with activated alkynes in benzene has been examined. The kinetics of these reactions have been studied with various alkynes, along with the stereochemistry with which the alkynes are hydrogenated. The hydrogenation of phenyl acetylene and diphenyl acetylene with CpCr(CO)(3)H has been shown to occur by a hydrogen atom transfer (HAT) mechanism. The reaction of CpCr(CO)(3)H with dimethyl acetylenedicarboxylate (DMAD) produced hydrogenated products as well as phenyl substitution from reaction with solvent. On the basis of kinetic data, it is thought that the reaction of DMAD may proceed via a single electron transfer (SET) as the rate-determining step. The radical anion of dimethylfumarate was observed by EPR spectroscopy during the course of the reaction, supporting this claim. The aromatic 1,6 eneyne (8) gave cyclized products in 78% yield under catalytic conditions (35 psi H(2)), presumably by the 5-exo-trig cyclization of the vinyl radical arising from H• transfer. Using a cobaloxime catalyst (12) hydrogenation was completely eliminated to yield 100% cyclized products.

Chemical Properties of Tetragermaplatinacyclopentane. Insertion of an Alkyne into a Pt–Ge Bond and Silylation Caused by H2SiPh2

A platinum complex having dibutylgermyl ligands, [Pt(GeHBu2)2(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane), reacted with excess H2GeBu2 at 90 °C to yield a five-membered tetragermaplatinacycle, [Pt(GeBu2GeBu2GeBu2GeBu2)(dmpe)] (6). The direct reaction of H2GeBu2 with [Pt(dmpe)2] in 5:1 ratio also gave 6 in 67% yield. The reaction of dimethyl acetylenedicarboxylate with 6 caused insertion of a C≡C bond into a Pt–Ge bond to form a seven-membered germaplatinacycloheptene, which was characterized by X-ray crystallography. Complex 6 reacted with H2GePh2 and H2SiPh2 in 1:2 ratio to produce a mixture of tetragermane dihydride H(GeBu2)4H and bis(silyl)- or bis(germyl)platinum complexes [Pt(EHPh2)2(dmpe)] (E = Si, Ge).

ChemInform Abstract: Triphenylphosphine‐Catalyzed One‐Pot Synthesis of γ‐Butyrolactone Derivatives and Highly Substituted Enones via Reaction of Dimethyl Acetylenedicarboxylate and Aryl Aldehydes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Triphenylphosphine-catalysed one-pot synthesis of γ-butyrolactone derivatives and highly substituted enones via reaction of dimethyl acetylenedicarboxylate and aryl aldehydes

Abstract The reaction between dimethyl acetylenedicarboxylate and various aryl aldehydes in the presence of triphenylphosphine leads to unsaturated γ-butyrolactone derivatives and highly substituted enones in fairly good yields at room temperature.

A thorough study on the reaction of DMAD with 1-arylaminoimidazole-2-thiones. Expeditious synthesis of imidazo[2,1-b][1,3]thiazoles through a novel arylamino rearrangement

Upon reaction of 1-arylamino-imidazole-2-thiones 1 with dimethyl acetylenedicarboxylate (DMAD) in the presence of 2.2equiv of sodium hydride, imidazothiazoles 4 were exclusively formed (71–82% yield). However, from the reaction of 1 with DMAD in the absence of base, only the S-substituted products 5 were formed as an E/Z mixture (53–55%), which could also be converted to 4 with 2.0equiv of sodium hydride (65–68%). Furthermore, 5a-E/Z was converted to arylamino-substituted derivatives 8a upon reaction with 1.1equiv of sodium hydride in 78% yield. Formation of 8a (75% yield) was also possible by reaction of thione 1a with DMAD in the presence of sodium methoxide in methanol. Substitution on the imidazole 3-NH of thione 1a leading to 6a-Z was observed either by heating 1a with DMAD (91%) or by heating the 5a-E/Z mixture in benzene (90% yield). Finally, when 5a-E reacted with acetic anhydride the acetylated derivative 7a-Z was the only isolated product (58%). Full assignment of all 1H and 13C NMR chemical shifts has been unambiguously achieved.

Fullerene Derivatives Incorporating Phosphoramidous Ylide and Phosphoramidate: Synthesis and Property

The reaction of dimethyl acetylenedicarboxylate (DMAD) with C(60) in the presence of hexamethylphosphorous triamide (HMPT) or hexaethylphosphorus triamide (HEPT) results in fullerene derivatives incorporating HMPT or HEPT ylides. The ylide derivatives exhibit unusual electronic absorptions in the visible region (435-660 nm), likely due to the presence of the ylide moiety. Electrochemical studies revealed that the first reductive potential of these compounds was more negative relative to those of both C(60) (DeltaE = 130 mV) and a simple Bingel adduct (DeltaE = 90 mV). A phosphoramidate side product, which resulted from the addition of HMPT or HEPT to C(60) followed by hydrolysis, exhibited a featureless absorption spectrum in the visible region and a more negative first reductive potential (DeltaE = 70 mV) relative to that of C(60).

Concerted and Diradical Stepwise Mechanisms in the Diels-Alder Reactions of Phosphinine and Phosphinine Sulfide: A DFT Investigation

Computations of the concerted and diradical stepwise mechanisms of the Diels-Alder (DA) reactions on the >C=P− functionality of phosphinine and phosphinine sulfide with 1,3-butadiene at the density functional theory level B3LYP/6-311++G**//B3LYP/6-31G** give the values of energy of concert as 10.7 and 2.6 kcal mol−1, respectively. Similarly, the DA reaction of dimethyl acetylenedicarboxylate (DMAD) with the −CH=CH−CH=P− moiety of phosphinine or its sulfide has been investigated theoretically at the same level of theory. The results reveal that in the DA reaction of phosphinine, the role of sulfur is to oxidize phosphorus to generate a phosphinine sulfide intermediate, which subsequently undergoes DA reaction with 2,3-dimethylbutadiene or DMAD by a concerted mechanism to afford the respective cycloadducts.

ChemInform Abstract: Product Structure in the Reaction of Dimethyl Acetylenedicarboxylate with 2‐Furyl‐1,2,3,4‐tetrahydroquinolines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Product structure in the reaction of dimethyl acetylenedicarboxylate with 2-furyl-1,2,3,4-tetrahydroquinolines

Dimethyl acetylenedicarboxylate reacts with 4-substituted and 3,4-fused 2-furyl-1,2,3,4-tetrahydroquinoline derivatives at the furan fragment according to the [4 + 2]-cycloaddition pattern. The reaction is not stereoselective, and it yields two diastereoisomeric 7-oxabicyclo[2.2.1]hepta-2,5-dienes whose structure was determined by X-ray analysis and NMR spectroscopy.