62675-22-3

Upstream product

• 3222-05-7 methyl tribromoacetate 
• 67-56-1 methanol 
• 44873-83-8 (2E)-dibromobut-2-enedioyl dichloride 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 7726-95-6 bromine 
• 64-19-7 acetic acid 

Downstream Products

• 142761-81-7 dimethyl 2,3-bis(phenylethynyl)fumarate 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 1071780-69-2 dimethyl 2,3-bis(N,N-di-4-methoxyphenyl-4-aminophenylethynyl)fumarate 
• 1203453-24-0 C₂₆H₂₆N₂O₄ 
• 144946-64-5 2-phenyl-oxazole-4,5-dicarboxylic acid dimethyl ester 
• 16377-51-8 dianilino-maleic acid dimethyl ester 
• 910468-02-9 dimethyl 2,3-bis(p-toluylethynyl)fumarate 

Relevant academic research and scientific papers

Photoisomerization of Enediynyl Linker Leads to Slipped Cofacial Hydroporphyrin Dyads with Strong Through-Bond and Through-Space Electronic Interactions

Photoisomerization of 3,4-di(methoxycarbonyl)-enediyne linker in hydroporphyrin (chlorin or bacteriochlorin) dyads leads to thermally stable cis isomers, where macrocycles adopt a slipped cofacial mutual geometry with an edge-to-edge distance of ～3.6 ? (d

Unlocking acyclic π–bond rich structure space with tetraethynylethylene–tetravinylethylene hybrids

Literature reports describe tetraethynylethylene (TEE) as unstable but tetravinylethylene (TVE) as stable. The stabilities of these two known compounds are reinvestigated, along with those of five unprecedented TEE-TVE hybrid compounds. The five new C10 hydrocarbons possess a core, tetrasubstituted C=C bond carrying all possible combinations of vinyl and ethynyl groups. A unified strategy is described for their synthesis, whereupon cross-conjugated ketones are dibromo-olefinated then cross-coupled. Due to an incorrect but nonetheless widely held belief that acyclic π-bond rich hydrocarbons are inherently unstable, a standardized set of robustness tests is introduced. Whereas only TVE survives storage in neat form, all seven hydrocarbons are remarkably robust in dilute solution, generally surviving exposure to moderate heat, light, air, and acid. The first X-ray crystal structure of TEE is reported. Subgroups of hybrids based upon conformational preferences are identified through electronic absorption spectra and associated computational studies. These new acyclic π-bond rich systems have extensive, untapped potential for the production of stable, conjugated carbon-rich materials.

The role of neat substrates in phase-vanishing and tandem phase-vanishing reactions

Phase-vanishing reactions are triphasic reactions, which involve a reagent, a liquid perfluoroalkane as a phase screen and a substrate. Aromatization, isomerization and halogenation of neat substrates under phase-vanishing conditions gave the expected products in good to excellent yields. In tandem single-phase-phase-vanishing reaction, two reactants, placed in the top phase, afforded the intermediate, which in a subsequent phase-vanishing reaction reacted with the reagent from the bottom phase to give the final product. The reaction worked well under solvent-free conditions on liquid substrates and intermediates. With solids, results were better if an additional solvent was employed.

A domino copper-catalyzed C-N and C-O cross-coupling for the conversion of primary amides into oxazoles

A variety of oxazoles can efficiently be prepared, in a single step and in good yield, from primary amides and 1,2-dihaloalkenes using copper-catalysis. This new method allows the regioselective formation of a range of substituted oxazoles. The required 1,2-dihaloalkenes can prepared by simple treatment of alkynes with elemental bromine or iodine. Georg Thieme Verlag Stuttgart.

Solvent incorporation in bromination of alkynes with tetrabutylammonium tribromide in methanol

The reaction of tetrabutylammonium tribromide (TBABr3) with mono and disubstituted alkynes in methanol at 20°C leads to the formation of mainly the corresponding α,α-dibromo, β,β-dimethoxyalkane and the E-(α,β)- dibromoalkene. The additions are faster using sonication.

Synthesis of acetylenedicarboxylic acid esters and asymmetric Diels-Alder reactions of the bis(methyl (S)-lactyl) ester

A general method has been developed for the preparation of acetylenedicarboxylic acid esters and applied to the synthesis of both achiral and chiral esters.Diels-Alder reactions of one of the chiral esters, the bis(methyl (S)-lactyl) ester, with various types of dienes, such as phenylbutadiene, orthoquinodimethanes, and isobenzofuran, have been investigated.Moderate asymmetric induction was observed in reactions with dienes bearing an α-hydroxyl group.In one case, an unusual solvent-induced reversal of asymmetric induction was observed.Key words: acetylenedicarboxylic acid esters, phenylbutadiene, orthoquinodimethanes, isobenzofurans, Diels-Alder , asymmetric.

Synthesis of Chiral Esters of Acetylenedicarboxylic Acid

A general method for the preparation of acetylenedicarboxylic acid esters has been investigated and several esters have been prepared in excellent yield.The bis-(methyl (S)-lactyl), bis-(methyl (R)-mandelyl), and bis-menthyl esters were prepared, as well as achiral diaryl and dialkyl esters.The esters were synthesized from the corresponding dibromofumarates by 2,3-dibromo elimination using zinc or zinc amalgam in THF at room temperature or at reflux.The dibromofumarates were prepared by the esterification of dibromofumaryl chloride with the corresponding alcohols.

Rates of Bromination of Dimethyl Fumarate and of Dimethyl Acetylenedicarboxylate

Rates of bromination of dimethyl fumarate and of dimethyl acetylenedicarboxylate were determined in 50percent aqueous acetic acid in the presence of varying amounts of sodium bromide.In the presence of bromide ions both substrates are believed to react by the termolecular AdE3 mechanism, and the acetylenic substrate reacts faster than the olefin.The acetylene also reacts faster in the reaction which involves a bimolecular attack by bromine (AdE2).Usually olefins react considerably faster than acetylenes in halogenation, and possible reasons for the reversal of the relative rates observed here are discussed.