110-65-6Relevant academic research and scientific papers
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.
Tetrabutylammonium tribromide (TBATB) - MeOH: An efficient chemoselective reagent for the cleavage of tert-butyldimethylsilyl (TBDMS) ethers
Gopinath, Rangam,Patel, Bhisma K.
, p. 4177 - 4180 (2000)
(equation presented) R = H, alkyl or aryl P = TBDMS, TBDPS, THP, DMT TBDMS THP and DMT ethers are efficiently deprotected with tetrabutylammonium tribromide in methanol. The apparent order of stability of different protecting group is phenolic TBDMS > 1° OTBDPS > 2° OTBDMS > 2° OTHP > 1° OTHP > 1° OTBDMS > 1° ODMT. TBDMS ether has been cleaved selectively in the presence of isopropylidine, Bn, Ac, Bz, THP, and TBDPS groups. This method is high yielding, fast, clean, safe, cost-effective, and therefore most suitable for practical organic synthesis.
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.
Mechanism and scope of the base-induced dehalogenation of (E)-diiodoalkenes
Resch, Daniel,Lee, Chang Heon,Tan, Siew Yoong,Luo, Liang,Goroff, Nancy S.
, p. 730 - 737 (2015)
A wide range of nucleophiles have induced the elimination of iodine from (E)-diiodoalkenes to form alkynes under surprisingly mild conditions. The iodide anion is particularly efficient, and can drive the reaction to completion in less than 1 hour at room temperature in a polar aprotic solvent. Detailed investigations have suggested the reaction has a bimolecular polar mechanism. The deiodination reaction can be driven to completion with 1 equiv. of nucleophile and is partially catalytic with substoichiometric amounts of deiodinating reagent. Kinetic analysis of the stoichiometric iodide-induced reaction indicated an overall pseudo-first-order behavior. The reaction exhibited strong solvent effects, with much slower reactions observed in protic solvents than in polar aprotic solvents. The substrate dimethyl (2E)-2,3-diiodo-butene-2-dioate demonstrated orthogonal reactivity for either elimination or hydrolysis, depending on the solvent and nucleophile used. This reaction is a major pathway for all the diiodoalkenes examined, and represents a challenge and an opportunity for using these substrates in organic synthesis.
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 synthesizing propargyl alcohol
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Paragraph 0040-0066, (2021/11/21)
The method comprises the following steps: taking potassium hydroxide or potassium alcoholate as a catalyst, and reacting with acetylene below 0.15 mpa pressure in an aromatic hydrocarbon or aliphatic hydrocarbon organic solvent to form propinyl alcohol. The reaction end point material is a 'liquid - liquid' two-phase system and is separated by sedimentation. The product is recovered by hydrolysis separation, extraction purification and rectification separation, and the yield of propargol in the product can reach 71% - 73%.
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.
Iodopropynyl a, 1,4-butyne diol and hexamine three cogeneration method for continuous production of
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Paragraph 0041-0052, (2017/06/19)
The invention discloses a trigeneration continuous production method for propiolic alcohol, 1,4-butinodiol and urotropine, and belongs to the technical field of chemical engineering. According to the method, a formaldehyde aqueous solution (10%-37% wt) and acetylene are taken as raw materials for synthesizing propiolic alcohol and co-producing 1,4-butinodiol and urotropine, the reaction temperature is 80-120 DEG C, the pressure is 1.0-2.5 MPa, and propiolic alcohol with the purity of 99.5% or more, a 1,4-butinodiol aqueous solution and a urotropine aqueous solution are obtained. The conversion rate of formaldehyde in the whole technology is 100%, and the method has the advantages of safety and environment friendliness.
METHODS OF PRODUCING DICARBONYL COMPOUNDS
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Paragraph 0036, (2015/05/06)
Dicarboxylic acids, such as adipic acid, and diesters, such as adipates, may be produced by hydrogenating alkynes that may be produced from raw materials salvaged from waste stream processes. The carbons of the dicarboxylic acids are provided by alkynes generated from biomass waste and carbon dioxide recovered from waste streams such as exhaust gases.
PROCESS FOR THE HYDROGENATION OF 1,4-BUTYNEDIOL TO TETRAHYDROFURAN IN THE GAS PHASE
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Page/Page column 9, (2012/07/28)
The present invention relates to a process for the catalytic hydrogenation of 1,4-butynediol to tetrahydrofuran at at least the decomposition temperature of 1,4-butynediol, wherein 1,4-butynediol is vaporized in a hydrogen-comprising gas stream and is hydrogenated in gaseous form over at least one catalyst, comprising at least one of the elements from groups 7 to 11 of the Periodic Table of the Elements.
