81290-20-2Relevant articles and documents
TETRAKIS(DIMETHYLAMINO)ETHYLENE/TRIFLUOROIODOMETHANE, A SPECIFIC NOVEL TETRAFLUOROMETHYLATING AGENT
Pawelke, G.
, p. 429 - 434 (1989)
At low temperatures tetrakis(dimethylamino)ethylene (I) and CF3I form a charge transfer complex, which can act as a nucleophilic trifluoromethylating agent in polar solvents according to eqn. (1): The applicability of eqn.(1) to various silicon and boron halides R-X was tested and the following trifluoromethyl-silicon and boron derivatives were obtained in resonable yields: Me3SiCF3 (II), Me2Si(CF3)2 (III), (F3C)3BNHEt2 (IV).
SYNTHESIS AND PROPERTIES OF (TRIFLUOROMETHYL)TRICHLOROSILANE, A VERSATILE PRECURSORFOR CF3Si COMPOUNDS
Beckers, H.,Buerger, H.,Bursch, P.,Ruppert, I.
, p. 41 - 50 (1986)
(Trifluoromethyl)trichlorosilane (I) has been prepared for the first time by the reaction of CF3SiH(NMe2)2 (III) with HCl in dibutyl ether and, as a solution in CH2Cl2, by nucleophilic trifluoromethylation of SiCl4 with CF3Br/P(NEt2)3.From this solution, I mey be isolated by HCl cleavage of its insoluble bis(pyridine) adduct (II).The aminosilane III was obtained from the reaction of HSi(Cl)(NMe2)2 with CF3Br/P(NEt2)3.Selective substitution of I without attack on the CF3Si moiety was achieved in high yields with SbF3 (-> CF3SiF3), Ag(OCN) (-> CF3Si(NCO)3 (IV)), MeOH (-> CF3Si(OMe)3 (V)), HNMe2 (CF3Si(NMe2)3 (VI)), LiAlH4 (-> CF3SiH3), MeMgBr (-> CF3SiMe3) and LiPh (-> CF3SiPh3 (VII)).With 2,2'-bipyridyl a 1/1complex (VIII) was formed.The novel compounds I to VIII have been characterized by their IR, NMR and mass spectra, and for I a vibrational analysis including a normal coordinate treatment has been performed.
Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2)3]?, Stabilized by a Weakly Coordinating Cation
Weitkamp, Robin F.,Neumann, Beate,Stammler, Hans-Georg,Hoge, Berthold
supporting information, p. 14633 - 14638 (2019/11/05)
The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH2)3]? salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water-stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene-base-catalyzed preparation of the Ruppert–Prakash reagent Me3SiCF3 using fluoroform (HCF3) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.
Recyclable Trifluoromethylation Reagents from Fluoroform
Geri, Jacob B.,Szymczak, Nathaniel K.
supporting information, p. 9811 - 9814 (2017/08/03)
We present a strategy to rationally prepare CF3- transfer reagents at ambient temperature from HCF3. We demonstrate that a highly reactive CF3- adduct can be synthesized from alkali metal hydride, HCF3, and borazine Lewis acids in quantitative yield at room temperature. These nucleophilic reagents transfer CF3- to substrates without additional chemical activation, and after CF3 transfer, the free borazine is quantitatively regenerated. These features enable syntheses of popular nucleophilic, radical, and electrophilic trifluoromethylation reagents with complete recycling of the borazine Lewis acid.
