110-65-6Relevant articles and documents
Walter Reppe Revival – Identification and Genesis of Copper Acetylides Cu2C2 as Active Species in Ethynylation Reactions
Bruhm, Tobias,Abram, Andrea,H?usler, Johannes,Thomys, Oliver,K?hler, Klaus
, p. 16834 - 16839 (2021)
More than six decades after proposing copper acetylide, Cu2C2, as catalytically active species in ethynylation reactions by Walter Reppe, the explosive species have been experimentally identified and investigated during catalysis in detail now. Taking into account specific safety precautions, unequivocal qualitative characterization was achieved by Raman spectroscopy and X-ray powder diffraction of supported copper catalysts Cu/Bi/SiO2 during and after activation and catalysis in comparison to bulk Cu2C2 materials. Quantification of Cu2C2 succeeded by thermal analysis and Raman spectroscopy. Its formation in aqueous suspension is studied starting from copper(II) oxide catalysts including dissolution, reduction and precipitation steps. Copper acetylide formation can be correlated with catalytic performance in the ethynylation of formaldehyde to 1,4-butynediol.
Syntheses of 7-Substituted Anthra[2,3- b]thiophene Derivatives and Naphtho[2,3- b:6,7- b']dithiophene
Al-Jumaili, Mustafa A.,Woodward, Simon
, p. 11437 - 11445 (2018)
7-R-Anthra[2,3-b]thiophene derivatives (1, R = H, Me, i-Pr, or MeO) are prepared in three steps (in average overall yield >50%) starting from (E)-4-RC6H4CH2(HOCH2)C=CI(CH2OH). The latter are commercial or readily prepared from 2-butyne-1,4-diol and ArCH2Cl (both costing 1 cent/mmol) at 10 g scales. These allow for the selective formation of (otherwise unattainable) higher solubility 7-derivatives. Similar methods allow for the preparation of naphtho[2,3-b:6,7-b']dithiophene 2 using equally low-cost starting materials.
Room-temperature carbonization of poly(diiododiacetylene) by reaction with Lewis bases
Luo, Liang,Resch, Daniel,Wilhelm, Christopher,Young, Christopher N.,Halada, Gary P.,Gambino, Richard J.,Grey, Clare P.,Goroff, Nancy S.
, p. 19274 - 19277 (2011)
Poly(diiododiacetylene) (PIDA) is a conjugated polymer containing an all-carbon backbone and only iodine atom substituents. Adding a Lewis base to the blue PIDA suspension at room temperature leads first to rapid disappearance of the absorption peaks attributed to PIDA, followed more slowly by release of free iodine. The resulting solid material gives a Raman scattering spectrum consistent with graphitic carbon, and it has a much higher conductivity than PIDA itself. Further investigation has led to the discovery of a previously unreported transformation, the reaction of a Lewis base such as pyrrolidine with a trans-diiodoalkene to form the corresponding alkyne. The generality of this iodine elimination further suggests that reaction of PIDA with Lewis bases dehalogenates the polymer, presenting a new method to prepare carbon nanomaterials at room temperature under very mild conditions.
Method for preparing 1,4-butynediol
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Paragraph 0009, (2017/03/14)
The invention discloses a method for preparing 1,4-butynediol. The method comprises the steps that firstly, a copper catalyst is activated to obtain a copper acetylide/bismuth catalyst, acetylene and formaldehyde are subjected to a reaction under the effect of the copper acetylide/bismuth catalyst to obtain a 1,4-butynediol and copper acetylide/bismuth catalyst mixed solution, and in a reaction kettle, the mixed solution is filtered through a metal film filter to obtain a 1,4-butynediol clear solution which is fed outside the reaction kettle to be subjected to follow-up technological treatment to obtain a finished product. In the reaction process, copper acetylide/bismuth catalyst turbid liquid is extracted periodically, then, an equimolar copper acetylide/bismuth catalyst or a copper catalyst is supplemented, a clear solution obtained after the extracted copper acetylide/bismuth catalyst turbid liquid is filtered is subjected to the follow-up technological treatment to obtain a finished product finally, and copper acetylide/bismuth catalyst cakes are subjected to a regeneration procedure to be recycled; the 1,4-butynediol clear solution is adopted for performing back flushing on the metal film filter periodically. Due to periodic extraction and supplementing of the catalyst, production losses caused by frequent stopping are avoided, and the product yield and output are improved.
