- 1,1,1,3,3,3-Hexafluoroisopropanol as a Remarkable Medium for Atroposelective Sulfoxide-Directed Fujiwara-Moritani Reaction with Acrylates and Styrenes
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Axially chiral biaryls are ubiquitous structural motifs of biologically active molecules and privileged ligands for asymmetric catalysis. Their properties are due to their configurationally stable axis, and therefore, the control of their absolute configuration is essential. Efficient access to atropo-enantioenriched biaryl moieties through asymmetric direct C-H activation, by using enantiopure sulfoxide as both the directing group (DG) and chiral auxiliary, is reported. The stereoselective oxidative Heck reactions are performed in high yields and with excellent atropo-stereoselectivities. The pivotal role of 1,1,1,3,3,3-hexafluoropropanol (HFIP) solvent, which enables a drastic increase in yield and stereoselectivity of this transformation, is evidenced and investigated. Finally, the synthetic usefulness of the herein disclosed transformation is showcased because the traceless character of the sulfoxide DG allows straightforward conversions of the newly accessed, atropopure sulfoxide-biaryls into several differently substituted axially chiral scaffolds.
- Dherbassy, Quentin,Schwertz, Geoffrey,Chess, Matthieu,Hazra, Chinmoy Kumar,Wencel-Delord, Joanna,Colobert, Franoise
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Read Online
- Preparation method of hexafluoroisopropyl methyl ether
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The invention discloses a preparation method of 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. The preparation method includes reacting trifluoroacetate with formate to obtain 1,1,1,3,3,3-hexafluoroisopropanol, and applying a methylation reagent to the 1,1,1,3,3,3-hexafluoroisopropanol to obtain the 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. The preparation method has the advantages that raw materials are cheap and easy to obtain, the preparation process is mild and the method is simple to operate.
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Paragraph 0072; 0073
(2019/06/30)
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- Method for synthesizing hexafluoroacetone and method for synthesizing hexafluoroisopropanol
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The invention provides a method for synthesizing hexafluoroacetone and a method for synthesizing hexafluoroisopropanol. The method for synthesizing hexafluoroacetone comprises the following steps: generating first-step substitution reaction by virtue of hexachloroacetone and hydrogen fluoride under the effect of a first catalyst so as to generate a first product, wherein the temperature of the first-step substitution reaction is 70-80 DEG C, and the first catalyst is a trivalent chromium compound; and generating second-step substitution reaction by virtue of the first product and hydrogen fluoride under the effect of a second catalyst so as to generate hexafluoroacetone, wherein the temperature of the second-step substitution reaction is 350-400 DEG C, and the second catalyst is a trivalent chromium compound. The method for synthesizing hexafluoroisopropanol comprises the steps of carrying out all steps of the method for synthesizing hexafluoroacetone, and further carrying out reductive hydrogenation. According to the two methods, the problem that carbon is easily generated in a traditional process is solved.
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Paragraph 0059; 0060; 0061; 0062; 0063; 0064; 0065-0106
(2018/03/24)
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- Nickel N-heterocyclic carbene catalyzed C-C bond formation: A new route to aryl ketones
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A novel nickel N-heterocyclic carbene catalyzed cross-coupling reaction of aryl aldehydes with boronic esters for the synthesis of aryl ketones was developed. This reaction provides a mild, practical method toward aryl ketones, which are versatile intermediates and building blocks in organic synthesis.
- Gu, Li-Jun,Jin, Cheng,Zhang, Hong-Tao
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supporting information
p. 8741 - 8744
(2015/06/08)
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- Manufacture of hexafluoroisopropanol
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Hexafluoroisopropanol (CF3CHOHCF3) is manufactured in two steps from monochloromalonic acid or monochlomalonic acid esters by a reaction with a fluorinating agent, notably SF4, to form CF3CHClCF3 which is hydrolyzed to form CF3CHOHCF3. The hexafluoroisopropanol can be used as such, or, preferably, it is further reacted to form Sevoflurane, an anesthetic. Compounds of the formula CF3-CH(OY)-CF3 wherein Y is OTs, OMe, OTf or OTMS are also described.
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Paragraph 0086-0087
(2013/08/28)
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- HF-mediated equilibrium between fluorinated ketones and the corresponding α-fluoroalcohols
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We have successfully obtained the first unambiguous spectroscopic proof of the structure of heptafluoropropan-2-ol by 13C NMR, which has been assumed from early 70s but without unequivocal evidence. Equilibrating relationship between fluorinated ketones and the corresponding hydrates as well as α-fluoroalcohols in anhydrous HF was at least qualitatively supported by our ab initio computation, and moreover, anhydrous HF as a convenient solvent was found to offer an effective new route for production of 1,1,1,3,3,3-hexafluoropropan-2-ol in industrial scales.
- Hayasaka, Tatsuya,Katsuhara, Yutaka,Kume, Takashi,Yamazaki, Takashi
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experimental part
p. 2215 - 2219
(2011/04/22)
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- Hydrogen bonding between solutes in solvents octan-1-ol and water
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The 1:1 equilibrium constants, K, for the association of hydrogen bond bases and hydrogen bond acids have been determined by using octan-1-ol solvent at 298 K for 30 acid-base combinations. The values of K are much smaller than those found for aprotic, rather nonpolar solvents. It is shown that the log K values can satisfactorily be correlated against αH 2?βH2, where αH 2 and βH2 are the 1:1 hydrogen bond acidities and basicities of solutes. The slope of the plot, 2.938, is much smaller than those for log K values in the nonpolar organic solvents previously studied. An analysis of literature data on 1:1 hydrogen bonding in water yields a negative slope for a plot of log K against αH 2?βH2, thus showing how the use of very strong hydrogen bond acids and bases does not lead to larger values of log K for 1:1 hydrogen bonding in water. It is suggested that for simple 1:1 association between monofunctional solutes in water, log K cannot be larger than about -0.1 log units. Descriptors have been obtained for the complex between 2,2,2-trifluoroethanol and propanone, and used to analyze solvent effects on the two reactants, the complex, and the complexation constant.
- Abraham, Michael H.,Gola, Joelle M. R.,Cometto-Muniz, J. Enrique,Acree, William E.
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experimental part
p. 7651 - 7658
(2011/02/25)
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- METHOD FOR PRODUCING FLUOROALKYL ALCOHOL
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The present invention provides a method for producing a fluoroalkyl alcohol represented by general formula (6) wherein Rf1 and Rf2 are the same or different, each represents a CF3(CF2)n group (wherein n is an integer of 0 to 10) or a CH3(CH2)m group (wherein m is an integer of 0 to 10), and at least one of Rf1 and Rf2 represents a CF3(CF2)n group, the method comprising: decarboxylating a compound represented by general formula (1) wherein Rf1 and Rf2 are the same as above; and R1 represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an alkali metal, or M1/2 (wherein M represents an alkaline earth metal), in the presence of at least one member selected from the group consisting of pyridines, amines, quaternary ammonium salts, and quaternary phosphonium salts. According to the present invention, fluoroalkyl alcohol such as hexafluoroisopropyl alcohol can be easily produced with high selectivity, using an inexpensive starting material.
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Page/Page column 9-10
(2010/03/02)
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- Continuous process to produce hexafluoroisopropanol
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A continuous process for producing hexafluoroisopropanol is provided which comprises contacting hexafluoroacetone with hexafluoroisopropanol and hydrogen to produce a liquid feed stream; introducing the liquid feed stream to a reactor containing an immobilized hydrogenation catalyst to convert the hexafluoroacetone to hexafluoroisopropanol and provide a product stream; and recovering at least a portion of the hexafluoroisopropanol from the product stream. Preferably a portion of the product stream is recycled. The reactor can be a packed bed or stirred tank reactor.
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Page/Page column 9-12
(2009/05/29)
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- One-pot synthesis of 3-fluoro-4-(trifluoromethyl)quinolines from pentafluoropropen-2-ol and their molecular modification
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(Chemical Equation Presented) Pentafluoropropen-2-ol (PFP) was prepared by the reaction of hexafluoroacetone (HFA) with Mg/TMSCl. The one-pot tandem sequential reactions of PFP via Mannich addition with aldimines followed by Friedel-Crafts cyclization and aromatization afforded the title quinolines. A variety of corresponding 3-substituted quinolines were derived from the title quinoline by nucleophilic substitution of 3-fluorine with nucleophiles. A defluorinative transformation of the 4-trifluoromethyl group of the title quinoline with hydrazine afforded py razoloquinoline.
- Hosokawa, Tsuyoshi,Matsumura, Akemi,Katagiri, Toshimasa,Uneyama, Kenji
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p. 1468 - 1474
(2008/09/16)
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- Synthesis of perfluorinated ketones by utilizing liquid-phase direct fluorination
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A new synthetic procedure for the preparation of perfluorinated ketones from nonfiuorinated sec-alcohols was developed. A key step in the synthetic route was a liquid-phase direct fluorination reaction with elemental fluorine. Direct fluorination of a partially fluorinated ester, which was prepared from a nonfiuorinated sec-alcohols and a perfluorinated acyl fluoride, followed by thermal elimination, gave a perfluorinated ketone and the starting perfluorinated acyl fluoride, which could be recycled. Application to the synthesis of a precursor polyfluoroketone for fluoropolymer resists for 157nm microlithography was also established.
- Okazoe, Takashi,Watanabe, Kunio,Itoh, Masahiro,Shirakawa, Daisuke,Takagi, Hirokazu,Kawahara, Kengo,Tatematsu, Shin
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body text
p. 1611 - 1616
(2009/07/18)
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- METHOD FOR THE PREPARATION OF SEVOFLURANE
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A method for the preparation of (CF3)2CHOCH2F (Sevoflurane) is presented, which comprises providing a mixture of (CF3)2CHOCH2Cl, potassium fluoride, water, and a phase transfer catalyst and reacting the mixture to form (CF3)2CHOCH2F.
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Page/Page column 12
(2008/06/13)
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- Spectrokinetic study of the reaction system of 2NO2?N 2O4 with some fluorinated derivatives of ethanol and propanols between 293-358 K in the gas phase
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The gas phase kinetics of the reversible reactions between nitrogen tetroxide and some fluorinated alcohols in the reaction system 2NO 2?N2O4 (1, 2) N2O4 + ROH?RONO+ + HNO3 (3, 4) have been studied by UV-Vis spectrophotometry to follow the NO2 decay. The products - RONO (R = CH2FCH2, CHF2CH2, CF 3CH2, CHF2CF2CH2, CF 3CF2CH2, CF3CHCF3) - were identified by their UV spectra and the values of the maxima UV absorption cross sections were determined in the range 320-400 nm. The rate constants for the forward reaction are 10-19k3av/cm 3molec-1s-1 9.7±1.5; 2.5±0.4; 1.8±0.3; 23±3.5, 2.3±0.3, 0.2±0.03 and for the reverse reaction 10-19k4av/cm 3molec-1s-1 4.6±0.7; 5.5±0.8; 4.9±0.7; 9.1±1.4; 7.7±1.2; 23±3.5 at 298 K for the reaction with 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol and 1,1,1,3,3,3-hexafluoro-2-propanol, respectively, were derived by the computer simulation of monitored NO2 decay profiles. The temperature dependence of the bimolecular rate constants k3 and k4 were studied in the temperature range 293-358 K and the activation energy for the forward E3 and for the reverse E4 reaction were derived. From the observed temperature dependence of the equilibrium constants K3,4, expressed in terms of the van't Hoff equation, the thermochemical parameters for all reactions studied were estimated.
- Wojcik-Pastuszka,Golonka,Ratajczak
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p. 1559 - 1574
(2008/02/04)
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- β-Isocupreidine-hexafluoroisopropyl acrylate method for asymmetric Baylis-Hillman reactions
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Key features of the β-isocupreidine (β-ICD)-catalyzed asymmetric Baylis-Hillman reaction of aldehydes with 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) are presented. In addition, an improved method using azeotropically dried β-ICD is described.
- Nakano, Ayako,Kawahara, Sakie,Akamatsu, Saori,Morokuma, Kenji,Nakatani, Mari,Iwabuchi, Yoshiharu,Takahashi, Keisuke,Ishihara, Jun,Hatakeyama, Susumi
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p. 381 - 389
(2007/10/03)
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- STABLE PHARMACEUTICAL COMPOSITION OF FLUOROETHER COMPOUND FOR ANESTHETIC USE, METHOD FOR STABILIZING A FLUOROETHER COMPOUND, USE OF STABILIZER AGENT FOR PRECLUDING THE DEGRADATION OF A FLUOROETHER COMPOUND
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The present invention has as objective the stabilization of a fluoroether compound against degradation by acid substances. The stabilizers proposed are selected among appropriate pharmaceutical compounds and are used for preparing stable pharmaceutical compositions of a fluoroether compound. Method for stabilizing a fluoroether compound and use of stabilizers agents for precluding the degradation of a fluoroether are also described.
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Page/Page column 17-18; figure 1
(2008/06/13)
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- PURIFICATION OF 1,1,1,3,3,3-HEXAFLUOROISOPROPANOL
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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) substantially free of 1,1,1-trifluoroacetone (TFA) can be separated from a mixture containing both compounds by A) catalytic reduction with hydrogen followed by fractional distillation; B) cooling to a temperature at which HFIP freezes and TFA remains liquid; C) forming a high boiling complex comprising HF and TFA followed by fractional distillation; or D) producing HF-free conditions to yield a HFIP/TFA azeotrope followed by fractional distillation. It is emphasized that this abstract is provided to comply with the rules requiring an abstract, which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. 37 CFR § 1.72(b).
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Page/Page column 1
(2008/06/13)
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- Process for recovery of 1,1,1,3,3,3-hexafluoroisopropanol from the waste stream of sevoflurane synthesis
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Provided is a process of obtaining 1,1,1,3,3,3-hexafluoro-2-propanol (“HFIP”) from a composition comprising an HFIP hydrolyzable precursor. The HFIP hydrolyzable precursor is a compound, other than sevoflurane itself, that has an intact 1,1,1,3,3,3-hexafluoroisopropoxy moiety[(CF3)2CHO—], and contains one or more moieties susceptible to acidic hydrolysis, such that HFIP is released upon such treatment. The process is useful, among other things, for recovering HFIP from waste streams associated with the synthesis of the inhalation anesthetic, fluoromethyl 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ether (“sevoflurane”). The process includes heating the composition with a strong protic acid to a temperature effective to hydrolyze at least some of the HFIP hydrolyzable precursor to HFIP, and then isolating the HFIP from the heated composition.
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- A study of the IR and UV-Vis absorption cross-sections, photolysis and OH-initiated oxidation of CF3CHO and CF3CH2CHO
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Infrared and ultraviolet-visible absorption cross-sections, effective quantum yields of photolysis and OH reaction rate coefficients for CF 3CHO and CF3CH2CHO are reported. Relative rate measurements at 298(2) K and 1013(10) hPa, give k(OH + CF3CHO)/k(OH + CH3CH3) = 2.00(13), k(OH + CF3CH 2CHO)/ k(OH + CH3CH2OH) = 1.21(5) and k(OH + CF3CH2CHO)/k(OH + HC(O)OC2H5) = 3.51(9) (2σ). The effective quantum yield of photolysis was measured under pseudo-natural conditions in the European simulation chamber, Valencia, Spain (EUPHORE). Over the wavelength range 290-400 nm, the effective quantum yields of photolysis for CF3CHO and CF3CH2CHO are less than 2 × 10-2 and 4 × 10-2, respectively. The tropospheric lifetimes are estimated to be: τOH(CF3CHO) ～ 26 days; τ photol(CF3CHO) > 27 days; τOH(CF 3CH2CHO) ～ 4 days; τphotol(CF 3CH2CHO) > 15 days.
- Sellevag, Stig R.,Kelly, Tanya,Sidebottom, Howard,Nielsen, Claus J.
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p. 1243 - 1252
(2007/10/03)
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- Uncatalyzed Meerwein-Ponndorf-Verley reduction of trifluoromethyl carbonyl compounds by high-temperature secondary alcohols
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Noncatalytic Meerwein-Ponndorf-Verley (MPV) reduction of hexafluoroacetone and methyl ester of trifluoropyruvic acid into hexafluoroisopropanol (HFIP) and trifluorolactic esters, respectively can be achieved by heating with secondary alcohols at 210-250 °C without any catalyst.
- Lermontov, Sergei A.,Shkavrov, Sergei V.,Kuryleva, Nina V.
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p. 223 - 225
(2007/10/03)
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- The potential application of catalytic antibodies to protecting group removal: Catalytic antibodies with broad substrate tolerance
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A catalytic antibody was developed to selectively cleave the alcohol ester of 4-nitrophenylacetyl moiety while also tolerating a wide variety of structural variation on the alcohol portion of the molecule. The basis to the success of this study was that antibody epitope recognition was directed toward only key elements contained within the 4-nitrophenylacetyl group and not the entire haptenic molecule. This study offers the potential application of catalytic antibodies as practical reagents for the selective deprotection of complex multifunctionalized molecules possessing class similar protecting groups. Such a chemoabzymatic approach could eventually minimize synthetic complications which can arise from functional group protection in the synthesis of complex natural products.
- Li,Hilton,Janda
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p. 2123 - 2127
(2007/10/02)
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- Structure-Activity Relationships in the Esterase-catalysed Hydrolysis and Transesterification of Esters and Lactones
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The Broensted exponents for the alkaline hydrolysis of alkyl esters are 1.3 and 0.4 for substitution in the acyl and alcohol portions, respectively, which is indicative of a transition state which resembles the anionic tetrahedral intermediate with a localised negative charge.By contrast, the rate of the pig liver esterase (PLE)-catalysed hydrolysis shows little dependence upon the electron-withdrawing power of substituents.The values of kcat are independent of the pKa of the leaving group alcohol suggesting rate-limiting deacylation.There is a small steric effect of α-substitution in both the alcohol and carboxylic acid residues for the enzyme-catalysed reactions but the enzyme rate enhancement factor remains high for most esters.There is no substantial ee observed for the hydrolysis of racemic esters although the kinetic data can be used for determining the regioselective hydrolysis of diesters.Unsubstituted lactones are poor substrates for PLE but derivatives with hydrophobic substituents show kcat/Km values similar to those for acyclic esters.Dihydrocoumarin undergoes transesterification catalysed by PLE, kcat increases with increasing alcohol concentration indicative of rate-limiting deacylation.There is enantioselectivity in the PLE-catalysed hydrolysis of some racemic lactones but little or none in the transesterification of racemic alcohols with dihydrocoumarin.
- Barton, Patrick,Laws, Andrew P.,Page, Michael I.
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p. 2021 - 2030
(2007/10/02)
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- Evidence for a concerted mechanism in the solvolysis of phenyldimethylsilyl ethers
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The trifluoroethoxide-catalyzed trifluoroethanolysis and the hydroxide-catalyzed hydrolysis of a series of phenyldimethylsilyl ethers were examined. A Bronsted plot of the logarithm of the second-order rate constant KTFE for reaction with trifluoroethanol against the pKLG is not linear. The nonlinear plot might be taken as evidence for a change in rate-determining step of a reaction that proceeds through a pentavalent intermediate. However, the Bronsted plot for the hydroxide-catalyzed hydrolysis, where all the leaving groups are of lower pKa than hydroxide, has an identical shape as the Bronsted plot for the trifluoroethanolysis reaction. Therefore, the unusual shape of the Bronsted plots is not due to a change in rate-determining step. It is suggested that the results are most consistent with a one-step concerted mechanism and not with a mechanism involving a pentavalent intermediate.
- Xu, Yiying,Dietze, Paul E.
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p. 10722 - 10727
(2007/10/02)
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- Preparation and properties of new methyl(alkoxo)- and methyl(thiolato)nickel and methyl(alkoxo)- and methyl(thiolato)palladium complexes. CO and CS2 insertion into the alkoxo-palladium bond
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Reactions of fluorinated alcohols (HOCH(CF3)2, HOCH2CF3, and HOCH(CF3)C6H5) or aromatic thiols (HSC6H5 and HSC6H4-p-CH3) with dialkylnickel and -palladium complexes (NiMe2(bpy), NiEt2(bpy) (bpy = 2,2′-bipyridine), NiMe2(dpe), and PdMe2(dpe) (dpe = 1,2-bis(diphenylphosphino)ethane)) give the corresponding monoalkyl complexes with an alkoxo or a thiolato ligand (NiMe(OR)(bpy), NiEt(OR)(bpy), MMe(OR)(dpe), and MMe(SAr)(dpe) (M = Ni, Pd; R = CH(CF3)2, CH2CF3, CH(CF3)C6H5)). These complexes have been characterized by elemental analysis and NMR (1H, 31P{1H}, 19F, and 13C{1H}) spectroscopy. The methyl(alkoxo)nickel(II) and -palladium(II) complexes thus obtained react with carbon monoxide at normal pressure to give carboxylic esters in high yields. Reaction of carbon monoxide with NiMe(SAr)(dpe) (Ar = C6H5, C6H4-p-CH3) also gives the corresponding carbothioic esters in good yields, while PdMe(SPh)(dpe) is unreactive with carbon monoxide under similar conditions. The 31P{1H} and 13C{1H} NMR spectra of the reaction mixture of PdMe(OCH(CF3)2)(dpe) with an equimolar amount of 13CO at -60°C show the formation of PdMe (13COOCH(CF3)2)(dpe) produced through insertion of the carbon monoxide into the Pd-O bond. When the reaction temperature is raised to -20°C, this alkoxycarbonyl complex undergoes reductive elimination to give 1,1,1,3,3,3-hexafluoro-2-propyl acetate. The reaction is accompanied by simultaneous decarbonylation of the alkoxycarbonyl ligand to regenerate PdMe(OCH(CF3)2)(dpe). The reaction of PdMe(OCH(CF3)Ph)(dpe) with carbon disulfide gives an isolable palladium complex, PdMe(SCSOCH(CF3)Ph)(dpe), formed by insertion of CS2 into the Pd-O bond, while PdMe(SPh)(dpe) is unreactive with CS2.
- Kim, Yong-Joo,Osakada, Kohtaro,Sugita, Kouji,Yamamoto, Takakazu,Yamamoto, Akio
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p. 2182 - 2188
(2008/10/08)
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- Untersuchungen zur H-Brueckenassoziation von Azaaromaten mit OH-Bruecken-II. H-Brueckenassoziationgleichgewichte von 1,2,7,8-Dibenzacridin mit verschiedenen OH-Donatoren: Ein Vergleich ir-Spektroskopischer und uv-vis-Spektroskopischer Messungen
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The equilibrium of association of 1,2,7,8-dibenzacridine with 7 different OH-donors was investigated in CCl4 as solvent.The results show, that the values measured by infrared spectroscopy as well as by uv-vis-spectroscopy are identical within the respective accuracy limits.
- Juffernbruch, J.,Perkampus, H.-H.
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p. 1093 - 1096
(2007/10/02)
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- Untersuchungen zur H-Brueckenassoziation von Azaaromaten mit OH-Bruecken-III. Loesungsmittelabhaengigkeit der Assoziationsgleichgewichte zwischen 1,2,7,8-Dibenzacridin und OH-Donatoren
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The association equilibria of the H-bridges between dibenzacridine (DBA) and 7 different OH-donors were investigated in CCl4, n-heptane, toluene and benzene as solvents by uv-vis spectroscopic methods.The results show a significant dependence of the association constants and the thermodynamic data upon the solvents used.This solvent dependence is thoroughly discussed in connection with the spectroscopic data.
- Juffernbruch, J.,Perkampus, H.-H.
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p. 1097 - 1104
(2007/10/02)
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- Anionic metal hydride catalysts. 2. Application to the hydrogenation of ketones, aldehydes, carboxylic acid esters, and nitriles
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The application of the potassium hydrido(phosphine)ruthenate complexes K+[(Ph3P)2Ph2-PC6H 4RuH2]-·C10H 8·(C2H5)2O (1) and K2+[(Ph3P)3(Ph2P)Ru 2H4]2-·2C6H 14O3 (2) as catalysts for the homogeneous phase hydrogenation of a variety of unsaturated organic compounds is described. Ketones and aldehydes are catalytically hydrogenated with 1 and 2 typically at 85°C and under 620 kPa of hydrogen, to yield the corresponding alcohols as well as minor aldol condensation byproducts. The hydrogenation of acrolein, depending on conditions, can give either propionaldehyde or mixtures of propionaldehyde and allyl alcohol. Carboxylic acid esters, which are activated by adjacent electron-withdrawing groups, e.g., CF3CO2CH3, CF3CO2CH2CF3, (-CO2CH3)2, can be hydrogenated, with 1 and 2, to yield, respectively, CF3CH2OH and CH3OH, CF3CH2OH, and HOCH2CO2CH3. Methyl acetate diluted with toluene (1:10 (v/v)) in the presence of 2 is hydrogenated (at 90°C, under 620 kPa of H2) giving methanol, ethanol, and ethyl acetate (formed by trans-esterification with the ethanol product). This represents the first instance of a homogeneous catalytic hydrogenation of a simple aliphatic ester. Nitriles are hydrogenated with 1 and 2 (at 90°C, 620 kPa of H2) to give, selectively, primary amines. The rates and achievable conversions for these reactions are dependent upon the solvent medium used and on the nature of the cation associated with the hydridometalate catalysts.
- Grey, Roger A.,Pez, Guido P.,Wallo, Andrea
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p. 7536 - 7542
(2007/10/02)
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- Anionic group VIII metal hydride catalysts
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A novel class of compounds, anionic Group VIII metal hydrides containing phosphorus, arsenic and antimony organoligands is described, such as potassium tris and bis(triphenylphosphine) ruthenium hydride. The compounds are useful as homogeneous catalysts in the hydrogenation of aldehydes, ketones, olefins or alkynes. Processes for producing the compounds are also described.
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