- Vapor Pressures, Liquid Densities, Liquid Heat Capacities, and Ideal Gas Thermodynamic Properties for 3-Methylhexanal and 3,4-Dimethylpentanal
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Vapor pressures, liquid densities, and liquid heat capacities were measured for 3-methylhexanal and 3,4-dimethylpentanal which are two of several C7 aldehyde reaction products that can be obtained from the hydroformylation of hexenes using cobalt or rhodium homogeneous catalyst precursors.The vapor pressure data were fitted to the Miller and Antoine equations and also compared to predictions obtained form the Riedel-Plank-Miller equation.Values for the critical temperature and critical pressure were derived by group contribution methods and compared to independent values obtained by fitting the vapor pressure data to the Riedel-Plank-Miller equation and two corresponding-states-based equations.The liquid density data were compared to predictions obtained from the Yen-Woods equation and were also fitted to an empirical equation.Predictions from the Sternling-Brown, Yuan and Stiel, and the Rowlinson corresponding-state correlations were in good agreement with the liquid heat capacity data, although an empirical polynomial equation was also tested and had a lower mean deviation.Ideal gas thermodynamic properties were also derived and were used to calculate some of the predicted quantities.
- Mills, Patrick L.,Fenton, Ricky L.
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Read Online
- Phosphine ligand, preparation method and application thereof
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The invention provides a preparation method of a phosphine ligand and application of the phosphine ligand in catalyzing olefin hydroformylation reaction. A structural formula of the phosphine ligand is shown as the specification, wherein R, R1, R2 and R3 are selected from C1-C40 alkyl, alkenyl, alkynyl, and phenyl, substituted phenyl, naphthyl, anthryl, phenanthryl or other aromatic ring and aromatic heterocyclic substituents with higher carbon number. The preparation method of the phosphine ligand comprises the following step: carrying out one-step reaction on an isochroman salt and trisilylphosphine under the promotion of villiaumite. The phosphine ligand has strong stability and coordination ability, and can be well coordinated with cobalt, rhodium and other metals, the obtained complex can be used for hydroformylation reaction of terminal olefin, internal olefin, trisubstituted olefin and tetrasubstituted olefin, the catalyst dosage is small, the reaction conditions are mild, andthe yield and selectivity of aldehyde products are very high.
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Paragraph 0075-0077
(2020/07/13)
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- Dual Rh?Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols
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An active and selective dual catalytic system to promote domino hydroformylation–reduction reactions is described. Apart from terminal, di- and trisubstituted olefins, for the first time the less active internal C?C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3-dimethylbut-2-ene is converted into the corresponding n-alcohol with high yield (90 %) as well as regio- and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru-based Shvo's complex. A variety of aromatic and aliphatic alkenes can be directly used to obtain mainly linear alcohols.
- Rodrigues, Fábio M. S.,Kucmierczyk, Peter K.,Pineiro, Marta,Jackstell, Ralf,Franke, Robert,Pereira, Mariette M.,Beller, Matthias
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p. 2310 - 2314
(2018/07/31)
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- HIGH-COVERAGE, LOW ODOR MALODOR COUNTERACTANT COMPOUNDS AND METHODS OF USE
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The present invention relates to novel compounds and their use as malodor counteractant materials.
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Page/Page column 35
(2016/04/20)
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- Novel organoleptic compound
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The present invention is directed to a novel compound, but-2-enoic acid 1,2-dimethyl-butyl ester, and a method of improving, enhancing or modifying a fragrance formulation through the addition of an olfactory acceptable amount of but-2-enoic acid 1,2-dimethyl-butyl ester.
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Page/Page column
(2014/09/03)
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- Organoleptic compound
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The present invention is directed to a novel compound, but-2-enoic acid 1-ethyl-2-methyl-propyl ester, and a method of improving, enhancing or modifying a fragrance formulation through the addition of an olfactory acceptable amount of but-2-enoic acid 1-ethyl-2-methyl-propyl ester.
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Page/Page column 10
(2014/07/21)
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- Organoleptic compound
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The present invention is directed to a novel compound, but-2-enoic acid 1,2-dimethyl-butyl ester, and a method of improving, enhancing or modifying a fragrance formulation through the addition of an olfactory acceptable amount of but-2-enoic acid 1,2-dimethyl-butyl ester.
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Page/Page column 10
(2014/08/06)
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- Novel Organoleptic Compound
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The present invention is directed to a novel compound, but-2-enoic acid 1-ethyl-2-methyl-propyl ester, and a method of improving, enhancing or modifying a fragrance formulation through the addition of an olfactory acceptable amount of but-2-enoic acid 1-ethyl-2-methyl-propyl ester.
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Paragraph 0044
(2014/09/03)
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- A new type of phosphaferrocene-Pyrrole-phosphaferrocene P-N-P pincer ligand
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A 2-ethoxycarbonylphosphaferrocene was reduced to the corresponding 2-hydroxymethyl derivative, which was condensed with pyrrole in a 2:1 ratio in the presence of BF3 to give a phosphaferrocene-pyrrole- phosphaferrocene pincer ligand. This tridentate ligand, in turn, reacted with [Rh(acac)(CO)2] to yield a rhodium carbonyl pincer complex. This complex was characterized by X-ray crystal structure analysis and tested in the hydroformylation of internal olefins.
- Tian, Rongqiang,Ng, Yongxiang,Ganguly, Rakesh,Mathey, Francois
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scheme or table
p. 2486 - 2488
(2012/06/04)
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- Discovery of novel thieno[2,3-d]pyrimidin-4-yl hydrazone-based cyclin-dependent kinase 4 inhibitors: synthesis, biological evaluation and structure-activity relationships
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The design, synthesis, and evaluation of novel thieno[2,3-d]pyrimidin-4-yl hydrazone analogues as cyclin-dependent kinase 4 (CDK4) inhibitors are described. In continuing our program aim to search for potent CDK4 inhibitors, the introduction of a thiazole group at the hydrazone part has led to marked enhancement of chemical stability. Furthermore, by focusing on the optimization at the C-4′ position of the thiazole ring and the C-6 position of the thieno[2,3-d]pyrimidine moiety, compound 35 has been identified with efficacy in a xenograft model of HCT116 cells. In this paper, the potency, selectivity profile, and structure-activity relationships of our synthetic compounds are discussed.
- Horiuchi, Takao,Takeda, Yasuyuki,Haginoya, Noriyasu,Miyazaki, Masaki,Nagata, Motoko,Kitagawa, Mayumi,Akahane, Kouichi,Uoto, Kouichi
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experimental part
p. 991 - 1002
(2011/10/02)
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- Synthesis of novel rhodium phosphite catalysts for efficient and selective isomerization-hydroformylation reactions
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New modular H8-BINOL-based phosphite ligands have been synthesized. High activity and regioselectivity has been achieved in the rhodium-catalyzed isomerization-hydroformylation of internal olefins. The active catalysts have been characterized by in situ NMR studies.
- Piras, Irene,Jennerjahn, Reiko,Jackstell, Ralf,Baumann, Wolfgang,Spannenberg, Anke,Franke, Robert,Wiese, Klaus-Diether,Beller, Matthias
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experimental part
p. 479 - 486
(2010/04/05)
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- Iridium-catalyzed isomerization of primary allylic alcohols under mild reaction conditions
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The isomerization of primary allylic alcohols into the corresponding aldehydes has been accomplished using an analogue of Crabtree's iridium hydrogenation catalyst and by adequately tuning the experimental conditions. A wide range of substrates is converted quantitatively into the desired aldehyde at room temperature in expedient reaction times by using catalyst loading as low as 0.25 mol %.
- Mantilli, Luca,Mazet, Clément
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scheme or table
p. 4141 - 4144
(2009/12/01)
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- Iridium-catalyzed isomerization of primary allylic alcohols
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A readily accessible iridium hydrogenation catalyst displays high reactivity for the isomerization of primary allylic alcohols under mild reaction conditions. Key to the efficiency of the catalytic system is to deviate from the conventional hydrogenation route in favor of the desired isomerization pathway by adequately tuning the reaction conditions as indicated by preliminary mechanistic investigations. Schweizerische Chemische Gesellschaft.
- Mantilli, Luca,Mazet, Clement
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scheme or table
p. 35 - 37
(2010/03/30)
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- New hybrid bidentate ligands as precursors for smart catalysts
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1-Phosphanorbornadiene derivatives were grafted onto various periodically organized mesoporous powders, including a new zirconia/silica mixed oxide synthesized by aerosol techniques. After complexation with the [Rh(CO) 2]+ fragment, these materials were revealed to be more active in olefin hydrogenation than their homogeneous counterparts. The reasons for this higher activity are discussed in the light of theoretical modeling. Various surface treatments, such as esterification, drying, and functionalization with PhSi(OEt)3, provided insights into the nature and mechanism of formation of the active species. Zirconia-based materials were found to be active in internal olefin hydroformylation. Investigation of the mechanism of this reaction shows that the isomerization step is catalyzed by the Lewis acidic support, whereas the hydroformylation step is driven by the rhodium catalyst. Dissociation of these two steps leads to enhancement of activity.
- Goettmann, Frederic,Boissiere, Cedric,Grosso, David,Mercier, Francois,Le Floch, Pascal,Sanchez, Clement
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p. 7416 - 7426
(2008/02/02)
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- Rhodium-catalyzed hydroformylation of C6 alkenes and alkene mixtures - A comparative study in homogeneous and aqueous-biphasic media using PPh 3, TPPTS and TPPMS ligands
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The complexes RhH(CO)L3, where L = PPh3, P(m-C 6H4SO3Na)3 (TPPTS), and (C 6H5)2P(m-C6H4SO 3Na) (TPPMS) were used as catalyst precursors for a comparative study of the catalytic hydroformylation of several C6 alkenes and alkene mixtures under moderate reaction conditions in homogeneous (PPh3) and aqueous-biphasic (TPPTS, TPPMS) media. The biphasic systems are efficient for the hydroformylation of hex-1-ene, 2,3-dimethyl-1-butene, styrene, cyclohexene, and mixtures thereof, in water/n-heptane at 80 °C. The main problem associated with these catalysts is their tendency to promote alkene isomerization if the effective syngas concentration in the liquid phases is low, but this side-reaction can be suppressed by using higher CO/H2 pressures (54 atm). The selectivity of both water-soluble catalysts for linear products of hex-1-ene and for branched products of styrene is modest in comparison with the homogeneous system, which may limit their utility for classical oxo uses, but this is not a disadvantage for other interesting applications related to the hydroformylation of alkene mixtures and particularly to naphtha upgrading where linear and branched products are equally useful. The catalysts can be recycled without significant loss of activity and are resistant to the presence of benzothiophene in the mixture.
- Baricelli,Lujano,Modro?o,Marrero,García,Fuentes,Sánchez-Delgado
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p. 3782 - 3792
(2007/10/03)
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- Phosphabenzenes as monodentate π-acceptor ligands for rhodium-catalyzed hydroformylation
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A new class of phosphinine/rhodium catalysts for the hydroformylation of terminal and internal alkenes is presented in this study. A series of phosphabenzenes 1-14 has been prepared by condensation of phosphane or tris(trimethylsilyl)phosphane with the corresponding pyrylium salt. Trans[(phosphabenzene)2RhCl(CO)] complexes 21-25 have been prepared and studied spectroscopically and by X-ray crystal-structure analysis, The hydroformylation of oct-1-ene has been used to identify optimal catalyst preformation and reaction conditions. Hydroformylation studies with 15 monophosphabenzenes have been performed. The catalytic performance is dominated by steric influences, with the phosphabenzene 8/rhodium system being the most active catalyst. Turnover frequencies of up to 45370 h-1 for the hydroformylation of oct-1-ene have been determined. In further studies, hydroformylation activity toward more highly substituted alkenes was investigated and compared with the standard industrial triphenylphosphane/rhodium catalyst. The reactivity differences between the phosphabenzene and the triphenylphosphane catalyst increase on going to the more highly substituted alkenes. Even tetra substituted alkenes reacted with the phosphabenzene catalyst, whereas the triphenylphosphane system failed to give any product. In situ pressure NMR experiments have been performed to identify the resting state of the catalyst. A monophosphabenzene complex [(phosphinine 8)Ir(CO)3H] could be detected as the predominant catalyst resting state.
- Breit, Bernhard,Winde, Roland,Mackewitz, Thomas,Paciello, Rocco,Harms, Klaus
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p. 3106 - 3121
(2007/10/03)
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- Chiral Organometallic Reagents, IX On the Origins of the Diastereoselectivity in the Bromine/Lithium Exchange of 3-Alkoxy-1,1-dibromoalkanes
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The 3-alkoxy-1,1-dibromopentanes 5 are compounds, which according to MM2 calculations populate one conformation to >80percent at -110 deg C.On reaction with n-butyllithium the bromine atom which resides in the extended position is exchanged with selectivities around 80:20, irrespective of the nature of the oxy residue at C-3.The role of this substituent is solely to bias the conformational equilibria in favor of the conformer 17.Coordination of the butyllithium to the oxygen functionality plays an important role only in the carbamoyl derivative 5f, for which the sense of the asymmetric induction is reversed. Key words: Halogen/metal exchange / Stereoselectivity / Conformer populations / Calculations, MM2
- Hoffmann, Reinhard W.,Brumm, Karen,Bewersdorf, Martin,Mikolaiski, Wolfgang,Kusche, Andreas
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p. 2741 - 2748
(2007/10/02)
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- Studies on constituents of fruit body of Polyporus umbellatus and their cytotoxic activity
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From the crude drug Chorei, the fruit body of Polyporus umbellatus, seven new components named polyporusterone A. B, C, D, E, F and G, were isolated and their structures were determined on the basis of the spectral data. These compounds showed cytotoxic action on leukemia 1210 cell proliferation.
- Ohsawa,Yukawa,Takao,Murayama,Bando
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p. 143 - 147
(2007/10/02)
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- ADDITION D'ORGANOCUPRATES AUX OXAZOLIDINES CHIRALES α-β ETHYLENIQUES : I - RESULTATS - EFFETS DE SEL ET DE SOLVANT
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Organocuprates add quantitatively to oxazolidines I.The steric course of the reaction can be reversed and the diastereoselectivity enhanced by salt effect and (or) by solvent effect.
- Berlan, J.,Besace, Y.,Pourcelot, G.,Cresson, P.
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p. 4757 - 4766
(2007/10/02)
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- RHODIUM- AND PLATINUM-CATALYZED ASYMMETRIC HYDROFORMYLATION WITH (2S,3R)-2,3-BIS(DIPHENYLPHOSPHINO)BUTANE AS THE CHIRAL LIGAND
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Some mono- and disubstituted ethenes have been asymmetrically hydroformylated with rhodium and platinum catalysts using (2S,3S)-2,3-bis(diphenylphosphino)butane (Chiraphos) as the chiral ligand (maximum optical yield ca 45percent).The results are compared with those obtained when the chiral ligand is (4R,5R)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane (Diop).The Chiraphos ligand causes a decrease of the catalytic activity with respect to Diop.Optical yields for rhodium catalysts are always higher with Chiraphos, whereas scattered results were obtained with platinum catalysts.Since for the catalytic systems examined asymmetric induction takes place before or during the formation of the intermediate diastereomeric metal alkyl complexes, the results are tentatively rationalized on the basis of a stereochemical model for the transition state leading to the above metal alkyl complexes intermediate.
- Consiglio, Giambattista,Morandini, Franco,Scalone, Michelangelo,Pino, Piero
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p. 193 - 202
(2007/10/02)
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- Synthetic applications of α-hydroxydiazenes. III. Uncatalyzed and phenol catalyzed hydroalkylation of alkenes and of azobenzene with alkylazodiphenylmethanols
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Alkylazodiphenylmethanols (C6H5)2C(OH)N=NR, (R = CH(CH3)2, CH2CH3, CH3), when decomposed in the presence of olefinic substrates or in the presence of azobenzene, hydroalkylate those substrates.Addition of R and H across the double bond of an unsymmetric alkene occurs with the regiochemistry expected for a radical mechanism, in which the grooup R adds first.Radical intermediates from decomposition of alkylazodiphenylmethanols have been demonstrated earlier with spin trapping experiments.The fact that addition of phenol can enhance the yield of hydroalkylation product suggests that the process is a radical chain reaction, with chain carrying steps consisting of the reactions: (i) R. + CH2=CHY -> RCH2C.HY (ii) RCH2C.HY + (C6H5)2C(OH)N2R -> RCH2CH2Y + (C6H5)2CO + N2 + R..One deuterioalkylation and some yield-optimizing experiments are also reported.
- Yeung, Dominic W. K.,Warkentin, John
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p. 2386 - 2394
(2007/10/02)
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