5333-87-9Relevant academic research and scientific papers
Structural information from OH stretching frequencies-XI. The orientation of the hydroxyl group in tertiary α-ethynyl alcohols
Visser, T.,Maas, J. H. Van der
, p. 241 - 244 (1983)
The presence of different OH-rotamers in 11 tertiary α-ethynyl alcohols dissolved in CCl4 has been studied by means of the i.r. absorption band.In all compounds the hydroxyl appears to be present only in a position next to the triple bond.It is demonstrated that this phenomenon arises from OH...? interactions.The existence of OH...? hydrogen bonding could not unambiguously be established.Like in saturated compounds the orientation of the OH proves to be influenced by β- and γ-CH3 groups.
Fluoride-assisted activation of calcium carbide: A simple method for the ethynylation of aldehydes and ketones
Hosseini, Abolfazl,Seidel, Daniel,Miska, Andreas,Schreiner, Peter R.
supporting information, p. 2808 - 2811 (2015/06/16)
The fluoride-assisted ethynylation of ketones and aldehydes is described using commercially available calcium carbide with typically 5 mol % of TBAF·3H2O as the catalyst in DMSO. Activation of calcium carbide by fluoride is thought to generate an acetylide "ate"-complex that readily adds to carbonyl groups. Aliphatic aldehydes and ketones generally provide high yields, whereas aromatic carbonyls afford propargylic alcohols with moderate to good yields. The use of calcium carbide as a safe acetylide ion source along with economic amounts of TBAF·3H2O make this procedure a cheap and operationally simple method for the preparation of propargylic alcohols.
Synthesis of acetylenic alcohols with calcium carbide as the acetylene source
Sum, Yin Ngai,Yu, Dingyi,Zhang, Yugen
supporting information, p. 2718 - 2721 (2013/10/08)
Propargyl alcohols containing a terminal alkyne group are highly important and versatile intermediates. Here, we report the synthesis of these compounds from an inexpensive and renewable resource, calcium carbide (CaC2). No metal catalysts are required in this new protocol and the reactions take place under very mild conditions.
Synthesis of alkyne derivatives of a novel triazolopyrazine as A 2A adenosine receptor antagonists
Yao, Gang,Haque, Serajul,Sha, Li,Kumaravel, Gnanasambandam,Wang, Joy,Engber, Thomas M.,Whalley, Eric T.,Conlon, Patrick R.,Chang, Hexi,Kiesman, William F.,Petter, Russell C.
, p. 511 - 515 (2007/10/03)
A novel [1,2,4]triazolo[1,5-a]pyrazine core was synthesized and coupled with terminal acetylenes. The structure-activity relationship of the alkynes from this novel template was studied for their in vitro and in vivo adenosine A2A receptor antagonism. Selected compounds from this series were shown to have potent in vitro and in vivo activities against adenosine A 2A receptor. Compound 12, in particular, was found to be orally active at 3 mg/kg in both a mouse catalepsy model and a 6-hydroxydopamine- lesioned rat model.
Rearrangements of bridged diallenes. A facile synthesis of novel condensed heterocycles by tandem [3,3]-sigmatropic rearrangement and double intramolecular michael addition of diallenyl disulfides and diselenides. Isolation of stable diallenyl diselenides
Braverman, Samuel,Freund, Meir
, p. 5759 - 5776 (2007/10/02)
Thienothiophene 14 and selenoloselenophene 16 have been synthesized by the action of lithium methoxide on τ,τ-dimethylallenyl thiocyanate and selenocyanate, respectively. A multistep mechanism involving bis-τ,τ-dimethylallenyl disulfide (20) or diselenide as key intermediates, is suggested. The latter are believed to undergo consecutive 3,3]-sigmatropic rearrangement and double Michael addition, to the observed products. This mechanism is supported by the isolation of bis-τ,τ- diisopropylallenyl and bis-τ-methyl-τ-isopropylallenyl diselenides, under the same reaction conditions, and the rearrangement of the latter to the expected selenoloseleophene 33. The synthesis of the novel mixed selenolothiophene 35 by treatment of a mixture of allenyl thiocyanate 13 and selenocyanate 15 with lithium methoxide, is also described.
The reaction of some propargyl alcohols with benzeneselenenyl chloride
Garratt, Dennis G.,Beaulieu, Pierre L.,Morisset, Veronique M.
, p. 927 - 934 (2007/10/02)
The reaction of benzeneselenenyl chloride with twenty-two propargyl alcohols in methylene chloride solution is reported.Products of both Markownikoff and anti-Markownikoff regiochemistry are formed in an anti stereospecific manner.The regioselectivity or specificity is found to be very dependent upon the nature of the substituents geminal to the alcoholic moiety.In general the presence of bulky substituents geminal to the alcoholic moiety tend to favour formation of the anti-Markownikoff adduct under conditions of kinetic control.The Markownikoff adducts are found to be favoured thermodynamically.
Preparation of a Series of Highly Hindered Secondary Amines, Including Bis(triethylcarbinyl)amine
Kopka, Ihor E.,Fataftah, Zacharia A.,Rathke, Michael W.
, p. 4616 - 4622 (2007/10/02)
A series of highly branched secondary amines was prepared by coupling propargylamines with propargyl chlorides.Hydrogenation of the resultant dipropargylamines was accomplished with Raney nickel in the presence of potassium hydroxide.The resultant amines, including bis(triethylcarbinyl)amine, are among the most hindered secondary amines reported to date.The pKa values of the conjugate acids of the series of secondary amines exhibit a regular decrease with increasing size of the amine.The bulkier members of the series are inert to methyl iodide.Bis(triethylcarbinyl)amine reacts with boron trifluoride etherate to give a primary amine adduct and 3-ethyl-2-pentene.
