17953-97-8Relevant academic research and scientific papers
Carbene in Rigid Matrix. XI. Temperature and Matrix Effect on Phenylcarbene Processes in Ether and Amine
Tomioka, Hideo,Suzuki, Shinji,Izawa, Yasuji
, p. 492 - 495 (1982)
Product distributions from reactions of phenylcarbene with diethyl or diisopropyl ether or diethylamine were found to be highly dependent on reaction temperature.As temperature decreases, the C-O displacement reaction and N-H insertion are decreased.Concomitantly, primary C-H insertion products markedly increase especially at lower matrix temperatures.
Hydrodehalogenation of 1,1-dibromocyclopropanes by Grignard reagents promoted by titanium compounds
Dulayymi, Juma'a R. Al,Baird, Mark S.,Bolesov, Ivan G.,Nizovtsev, Alexey V.,Tverezovsky, Viacheslav V.
, p. 1603 - 1618 (2007/10/03)
1,1-Dibromocyclopropanes are converted into the corresponding monobromocyclopropanes (as mixtures of stereoisomers where appropriate) by reaction with 1.0-1.3 mol equiv. of ethylmagnesium bromide and 2-10 mol% titanium isopropoxide for 90%). With ethylmagnesium bromide, the reaction occurs very slowly in the absence of catalyst; with methylmagnesium bromide, the reaction does occur in the absence of catalyst, but is only slightly promoted in the presence of titanium isopropoxide. Reactions with a number of other Grignard reagents are also discussed. In the case of phenethylmagnesium bromide, the major product containing the phenethyl-group is ethylbenzene, together with small amounts of styrene and ethyl 4-phenyl-2-butyl ether, a product of trapping of the solvent, ether. In other cases, relatively large amounts of a diether, formally derived by hydrogen ion adjacent to the ether oxygen followed by dimerisation, are isolated. No products were identified incorporating the cyclopropane and either the Grignard alkyl group or the solvent. Labelling studies indicate that the hydrogen introduced into the cyclopropane is not derived from either the α- or β-positions of the Grignard reagent. When the reduction is carried out with phenethylmagnesium bromide in d8-tetrahydrofuran both monobromides contain deuterium.
FLUORINATION WITH XENON DIFLUORIDE, PART XXXV. REACTION WITH GRIGNARD REAGENTS
Bregar, Zvonko,Stavber, Stojan,Zupan, Marko
, p. 187 - 194 (2007/10/02)
Several Grignard reagents in diethyl ether solution readily react with xenon difluoride at room temperature, the complexity of the reaction course depending on the structure of the reagent.In all cases studied three main types of products, i.e. 1-ethoxy-1-substituted ethane (2), reduced product (3) and dimeric product (4) are formed.In the case of dodecyl magnesium bromide (1a), 2-ethoxydodecane (2a), decane (3a) and eicosane (4a) formed represent 98percent of products formed, with 2percent of the reaction mixture containing at least up to seven unidentified products, while with benzyl magnesium bromide (1b), the three main products 2b, 3b, and 4b represent 80percent of the reaction mixture, the remaining 20percent containing up to nine products with benzyl bromide being the main side product.The complexity of the reaction increases even more in the case of phenyl magnesium bromide, where 2c, 3c and 4c represent only 70percent of products formed, the remaining 30percent consisting of up to 21 products with the following being identified: bromobenzene, bromobiphenyl, 1,1-bromo-1-phenylethane, α-bromo and α,α-dibromoacetophenone, and 1,1-diphenyl-2-bromoethene.
Regiospecific Insertion of Benzylidene Ligands into α-C-H Bond of Ethers
Fischer, Helmut,Schmid, Johann,Maerkl, Robert
, p. 572 - 573 (2007/10/02)
The benzylidene complexes (CO)5W=CH(p-C6H4R) (R = H, Me) react with diethyl ether or tetrahydrofuran to give regiospecifically the products of the insertion of the benzylidene ligand into the α-C-H bond of the ethers; the insertion reaction follows an associative mechanism initiated by a nucleophilic attack of the ethers at the benzylidene ligand.
MODIFICATION OF SINGLET CARBENE REACTIVITIES BY SOLVENT
Tomoika, H.,Ozaki, Y.,Izawa, Y
, p. 4987 - 4994 (2007/10/02)
The solvent effect on the reactivity of singlet carbenes has been investigated.Competition reactions between pairs of alcohols for arylcarbenes in various solvents indicates that the O-H insertion selectivity is influenced only by 1,4-dioxane.Thus, phenylcarbene is some 33 times more reactive toward methanol relative to t-butyl alcohol in 90 molpercent dioxane than without solvent.Similar competition reactions between alcohol and olefin indicate that the O-H insertion-addition selectivities of arylcarbenes are considerably altered by dioxane.These results are interpreted as indicating that dioxane stabilizes singlet carbenes by complexing with its ione pairs of electrons.
MERCURY(II) OXIDE/TETRAFLUOROBORIC ACID. AN UNUSUAL BEHAVIOR IN THE OXIDATION OF ALKENES. SYNTHESIS OF trans-CINNAMYLETHERS
Barluenga, Jose,Alonso-Cires, Luisa,Asensio, Gregorio
, p. 2239 - 2240 (2007/10/02)
The synthesis of trans-cinnamylethers by oxidation of allylbenzene is described.The reaction cannot be explained by formation of an allylic mercurial.A new type of mechanism in the oxidation of alkenes by mercury(II) salts is proposed.
Reaction of Acetals with Grignard Reagents
Ishikawa, Hiroshi,Mukaiyama, Teruaki,Ikeda, Shigeru
, p. 776 - 780 (2007/10/02)
The reaction of dialkyl acetals derived from α,β-unsaturated aldehydes with Grignard reagents using TiCl4 in THF afforded the cross coupling products, allyl ethers, in high yields.The TiCl4-promoted reaction of alkyl 2,4-dichlorophenyl acetals, synthesized from 3,4-dihydro-2H-pyran or ethyl vinyl ether and 2,4-dichlorophenol, with Grignard reagents in THF at low temperature afforded the corresponding unsymmetrical ethers in high yields.When alkyl 2,4-dichlorophenyl acetals, synthesized from aromatic aldehyde or vinyl ethers and 2,4-dichlorophenol, were treated with Grignard reagents in benzene or toluene at room temperature in the absence of TiCl4, the cross coupling reaction took place and the corresponding ethers were isolated in good yields.
