Xi:Irritant;
106-30-9Relevant articles and documents
The Pd3(dppm)3 (CO)2+ cluster: An efficient electrochemically assisted Lewis acid catalyst for the fluorination and alcoholysis of acyl chlorides
Lemaitre, Frederic,Lucas, Dominique,Mugnier, Yves,Harvey, Pierre D.
, p. 7537 - 7540 (2002)
The dicationic palladium cluster Pd3(dppm)3-(CO)2+ (dppm = bis(diphenylphosphino)methane) reacts with acid chlorides RCOCl (R = n-C6H13, t-Bu, Ph) to afford quantitatively the chloride adduct Pd3(dppm)3(CO)(Cl)+ and the acyl cation RCO+ as the organic counterpart. The dicationic reactive cluster can be reformed by electrolyzing the chloride complex with a copper anode leaving CuCl as a byproduct. The combination of these two reactions provides an electrocatalytic way to form the acylium from the acid chloride. Indeed, in CH2Cl2, 0.2 M NBu4PF6, or NBu4BF4, the electrolysis of the acid chloride in the presence of a catalytic amount of the cluster (1%) gives in good yields the acid fluoride RCOF, arising from the coupling of the acylium with a F- issued from the fluorinated supporting electrolyte. Alternatively, in CH2Cl2 or 0.2 M NBu4ClO4, by operating with an alcohol R′OH as the nucleophile, the electrolysis gives the ester RC(O)OR′ as the only final product.
Immobilization of palladium acetate on ionic liquid copolymerized polystyrene: A way to eliminate inhibiting effect of imidazolium chloride and enhance catalytic performance
Sugimura, Rie,Kun, Qiao,Tomida, Daisuke,Kume, Yohei,Yokoyama, Chiaki
, p. 874 - 875 (2007)
Immobilization of palladium acetate on a novel polymeric support that is prepared by copolymerization of 3-butyl-1-vinylimidazolium chloride with styrene is demonstrated to be an effective way to eliminate inhibiting effect of imidazolium chloride and enhance catalytic performance. Copyright
Sulphonic Acid-induced Fragmentation of Dialkyl Acylphosphonates, Formation of Alkyl Carboxylates and Alkyl Sulphonates
Breuer, Eli,Karaman, Rafik,Goldblum, Amiram,Leader, Haim
, p. 2029 - 2034 (1988)
Heating of dialkyl acylphosphonates with sulphonic acids under anhydrous conditions leads to the formation of alkyl sulphonates and alkyl carboxylates. 31P N.m.r. spectroscopy revealed that the reaction of equimolar amounts of dimethyl benzoylphosphonate (1) and toluene-p-sulphonic acid at room temperature gives dimethyl phosphonate (6) in 50percent yield.It is proposed that the by-product of this reaction, benzoic toluene-p-sulphonic anhydride (8), reacts with the excess of toluene-p-sulphonic acid, to yield toluene-p-sulphonic anhydride (9) and benzoic acid.Heating of these two compounds with dimethyl phosphonate was shown to yield methyl toluene-p-sulphonate and methyl benzoate, respectively.A postulated by-product of these reactions is phosphenous acid (HPO2).Quantum mechanical calculations by the MNDO/H method carried out on dimethyl benzoylphosphonate and its protonation products show that the preferred site of protonation of dimethyl benzoylphosphonate is the P=O oxygen, and that protonation at this site is followed by C-P bond breaking, with zero energy of activation, leading to dimethyl phosphite and benzoylium cation.
Hydroalkoxycarbonylation of olefins in the presence of palladium phosphine complexes: High activity and regioselectivity
Chepaikin,Bezruchenko,Suerbaev,Shalmagambetov
, p. 117 - 121 (2006)
Several types of catalyst systems were examined in the olefin hydroalkoxycarbonylation reaction. The systems contained Pd(PPh 3)4, PdCl2(PPh3)2, or some other palladium compounds as a principal component. The second component (promoter) was p-toluenesulfonic acid or diphenyl(m-sulfophenyl)phosphine, which combines both the ligand and promoter functions. An important feature of these systems is their high activity in the hydroalkoxycarbonylation of ethylene and a high regioselectivity (83-100%) in the hydroalkoxycarbonylation of α-olefins with respect to linear products. Thus, it was unnecessary to introduce additional stabilizing ligands to augment the catalyst and promoter. The esters obtained can find application in the pharmaceutical industry and perfumery, as well as in other industries. Nauka/Interperiodica 2006.
Palladium complexes with N-heterocyclic carbene ligands as catalysts for the alkoxycarbonylation of olefins
Roberts, Gina M.,Pierce, Philip J.,Woo, L. Keith
, p. 2033 - 2036 (2013)
Palladium catalysts, generated from Pd(OAc)2 and 2 equiv of N,N-dialkylbenzimidazolium iodide, are effective for the alkoxycarbonylation of olefins in high yields (>90%). Alkoxycarbonylation of 1-hexene in dimethylacetamide is achieved within 24 h at 110 C using 1 mol % catalyst, 1000 psi CO, and ethanol. Reactions can be prepared in air, without the need of an acid additive to produce ethyl 2-methylhexanoate and ethyl heptanoate in approximately a 2:1 ratio.
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Rogic,M.M. et al.
, p. 3848 - 3850 (1975)
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Gold Complexes with ADAP Ligands: Effect of Bulkiness in Catalytic Carbene Transfer Reactions (ADAP = Alkoxydiaminophosphine)
Fructos, Manuel R.,Molina, Francisco,Pérez, Pedro J.,Pizarro, Juan Diego
supporting information, (2020/07/14)
A family of gold(I) complexes of composition AuCl(ADAP) (ADAP = alkoxydiaminophosphine) has been synthetized through a one-pot simple protocol in which the ADAP ligand is prepared in situ before reaction with the Au(I) source. Structural data demonstrate that these ADAP ligands exert a trans effect superior to those of phosphine or phosphite ligands. Evaluation of the buried volume (percentVBur) indicates a steric hindrance higher than those of several NHC, PR3, and P(OR3) ligands, in the context of AuCl(L) complexes. These complexes promote the catalytic transfer of a carbene group from ethyl diazoacetate to alkenes and alkanes. In the case of styrene, both the Csp2-H bonds and the Ca? C bond are functionalized, the relative ratio depending on the catalyst employed and correlating well with the percentVBur value. Data available allow proposing that these compounds display quite similar electronic properties but differ in steric properties, a variable that can be readily controlled upon modifying the alkoxy group at the ADAP ligand by simply replacing the starting alcohol employed in the synthesis.
Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
Allen, Benjamin D. W.,Hareram, Mishra Deepak,Seastram, Alex C.,McBride, Tom,Wirth, Thomas,Browne, Duncan L.,Morrill, Louis C.
supporting information, p. 9241 - 9246 (2019/11/19)
A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
