Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

In-situ reduction

The mechanism of the original Knorr pyrrole synthesis entails in situ reduction of the oxime moiety to an amine, condensation with the second carbonyl compound, and cyclization with loss of a second molecule of water to give a pyrrole for example, 10 + 11 to 12. Several studies have demonstrated that different pathways and pyrrole products obtain depending on the substrates. [Pg.80]

Because the Sonogashira coupling process outlined in Scheme 18 is initiated by the in situ reduction of palladium(n) to palladium(o), it would be expected that palladium(o) catalysts could be utilized directly. Indeed, a catalytic amount of tetrakis(triphenylphosphine)-... [Pg.584]

The ease of reduction of the Pu 4+ ions apparently can be affected by inclusion in the glass of additional additives. Whereas the addition of Ti02 apparently does not affect in-situ reduction, the addition of CaO, ZnO, or B2O3 appreciably accelerated reduction of the Pu 4+ ions. This effect is demonstrated with 4f core level spectra of glasses F, G, H, and I shown in Fig. 3. Each sample was subjected to the same X-ray exposure, i.e., the same number of scans at the same flux. [Pg.153]

The enantioselective 1,4-addition addition of organometaUic reagents to a,p-unsaturated carbonyl compounds, the so-called Michael reaction, provides a powerful method for the synthesis of optically active compounds by carbon-carbon bond formation [129]. Therefore, symmetrical and unsymmetrical MiniPHOS phosphines were used for in situ preparation of copper-catalysts, and employed in an optimization study on Cu(I)-catalyzed Michael reactions of di-ethylzinc to a, -unsaturated ketones (Scheme 31) [29,30]. In most cases, complete conversion and good enantioselectivity were obtained and no 1,2-addition product was detected, showing complete regioselectivity. Of interest, the enantioselectivity observed using Cu(I) directly in place of Cu(II) allowed enhanced enantioselectivity, implying that the chiral environment of the Cu(I) complex produced by in situ reduction of Cu(II) may be less selective than the one with preformed Cu(I). [Pg.36]

Enantiopure 3-phenyl-2-cyanoazetidines (S)-238 and (K)-238, which are epimeric at C2, are prepared in high yields from (K)-phenylglycinol. A one-pot sequence, including addition of organohthium or allyhnagne-sium bromide to the cyano group and in situ reduction of the resulting imine with sodium borohydride, allowed for the preparation of 2-(l-aminoalkyl)azetidines, which were then protected as N-Boc derivatives (R,S)-239 and (S,it)-239 [112] (Scheme 36). Complete anti diastereoselectivity (dr more than 95 5 by NMR) was observed in both cases. The same sequence... [Pg.42]

Maikov et al. [37] prepared a series of C2-symmetric bipyridine-type ligands, the chiral moieties arising from the isoprenoid chiral pool (/3-pinene, 3-carene, 2-carene, or a-pinene, for example). Some representative examples are drawn in Scheme 16 (see 25, 26, 27) and were used as copper ligands of a copper(I) species obtained by an in-situ reduction of Cu(OTf )2 with phenyl-hydrazine. The use of the resulting catalysts in enantioselective cyclopropana-tion proceeded with up to 76% ee (for ligand 27) and high diastereoselectivity (up to 99 1). [Pg.105]

Figure 6. Changes In Cu 2p and Cu(L3M cM j) electron spectra upon in situ reduction in H-. (Reproduced with permission from Ref, 7. Copyright 1984, Academic Press.)... Figure 6. Changes In Cu 2p and Cu(L3M cM j) electron spectra upon in situ reduction in H-. (Reproduced with permission from Ref, 7. Copyright 1984, Academic Press.)...
R. E. Campos and J. A. Hernandez. In-situ reduction of oil viscosity during steam injection process in EOR. Patent US 5209295, 1993. [Pg.367]

Formazans and their metal complexes are used as textile dyes by direct application. The in situ reduction of tetrazolium salts has not been used to introduce the dyes to their substrates. Treatment with triaryl mono and bis tetrazolium salts followed by a reducing agent such as ascorbic acid or thioglycolic acid has been claimed as a method of introducing formazans as permanent hair dyes.641 There are some references to their use as therapeutic agents.642 544... [Pg.278]

Pre-reduced catalyst (typically 2 g) was added with 300 ml of 2,2,4-trimethylpentane (Lancaster Synthesis Ltd) to the reactor vessel. An in-situ reduction of the catalyst was performed by sparging H2 (280 cm3 min 1) through this mixture for 30 minutes while stirring at 800 rpm. During this time the vessel was heated to 328 K. The stirrer was then turned off. [Pg.78]

The dispersion of the catalyst was measured by hydrogen chemisorption at 27 °C in the Coulter Omnisorp 100 CX equipment. The catalysts were subjected to an in situ reduction under hydrogen at 350 °C for 1 h before chemisorption... [Pg.527]

Tokunaga T.K., Wan J., Firestone M.K., Hazen T.C., Olson K.R., Herman D.J., Sutton S.R., Lanzirotti A. In situ reduction of chromium (VI) in heavily contaminated soils through organic carbon amendment. J Environ Qual 2003 32 1641-1649. [Pg.352]

In yet another example of an in situ reductive generation of an enolate, fi-amido esters are formed via the reaction of an o, /3-unsaturated ester with a silane in the presence of an isocyanate (Eq. 294).475 The yields obtained using methyl acrylate and methyl crotonate as substrates are generally excellent. [Pg.95]

Rh(bpy)2]+, obtained by the in-situ reduction of [Rh(bpy)2Cl2]Cl with hydrogen in methanolic sodium hydroxide [43], can reduce a series of simple ketones under 1 bar H2 and at 30 °C [44]. Yields of over 98% were obtained in all cases with a SCR of up to 680 1. When a mixture of ketones and aldehydes was placed under such conditions, the ketones were found to be reduced preferentially, although unsaturated ketones were generally reduced to saturated ketones. [Pg.428]

The synthesis of amines by the in-situ reductive amination of ketones is termed the Leuckart-Wallach reaction. Recently, an asymmetric transfer hydrogenation version of this reaction has been realized [85]. Whilst many catalysts tested give significant amounts of the alcohol, a few produced almost quantitative levels of the chiral amine, in high enantiomeric excess. [Pg.1234]

In the conjugate addition of diethylzinc to enones catalyzed by copper reagent CuOTf or Cu(OTf)2 in the presence of 90, an ee of over 60% has been obtained. Study also shows that the actual catalyst in the reaction may be a Cu(I) species formed via in situ reduction of Cu(II) complexes. [Pg.477]

Titanium catalysts have long been used in electron transfer reactions involving epoxides, mostly as stoichiometric reagents. Gansauer et al. have developed a catalytic version of these reactions using titanocenes along with zinc metal to generate the active catalyst (Scheme 60). In situ reduction of Ti(IV) with zinc metal provides Ti(III) species 231, which coordinates... [Pg.165]

The reaction starts with an oxidative addition of an allylic compound to palladium(O) and a Tt-allyl-palladium complex forms. Carboxylates, allyl halides, etc. can be used. In practice one often starts with divalent palladium sources, which require in situ reduction. This reduction can take place in several ways, it may involve the alkene, the nucleophile, or the phosphine ligand added. One can start from zerovalent palladium complexes, but very stable palladium(O) complexes may also require an incubation period. Good starting materials are the 7t-allyl-palladium intermediates ... [Pg.273]

For aromatic or heteroaromatic monoaldehydes, ArCHO, an efficient procedure has been developed for synthesis of 1,3-dinitro compounds [132]. Rather than in situ reduction of O2, the O2 reduction is carried out in a divided cell with the aliphatic nitro compound as the solvent. Charge corresponding to 0.5 F with respect to the aldehyde is passed through the cell, the current is switched off... [Pg.483]

Scheme 15.3 Preparation of soluble iridium nanoparticles from in situ reduction of the organometallic precursor [ir(COD)Cl]2 in imidazolium ionic liquids. Scheme 15.3 Preparation of soluble iridium nanoparticles from in situ reduction of the organometallic precursor [ir(COD)Cl]2 in imidazolium ionic liquids.
The typical in situ reduction of the precursor [lr(COD)Cl]2 by molecular hydrogen under the same reaction conditions have been also performed in 1-n-butyl-3-methylimidazolium trifluoromethanesulfonate (BMl-CFsSOs) and 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMl-BF [25]. The iridium nanoparticles prepared in BMTCF3SO3 and BM1-BF4 ILs, as previously observed with BM1-PF6, display irregular shapes with a monomodal size distribution (Figure 15.4). Mean diameters in the range of 2-3 nm were estimated with in situ TEM and small-angle X-ray scattering (SAXS) analyses of the lr(0) nanoparticles soluble in the ionic hquids, and by X-ray diffraction (XRD) of the isolated material. The mean diameters of iridium nanoparticles synthesized in the three ILs, as estimated by TEM, SAXS and XRD, are summarized in Table 15.1. [Pg.373]


See other pages where In-situ reduction is mentioned: [Pg.276]    [Pg.32]    [Pg.233]    [Pg.500]    [Pg.339]    [Pg.151]    [Pg.118]    [Pg.121]    [Pg.183]    [Pg.126]    [Pg.203]    [Pg.204]    [Pg.81]    [Pg.164]    [Pg.297]    [Pg.55]    [Pg.168]    [Pg.124]    [Pg.289]    [Pg.950]    [Pg.6]    [Pg.18]    [Pg.814]    [Pg.87]    [Pg.183]    [Pg.191]    [Pg.125]    [Pg.233]   
See also in sourсe #XX -- [ Pg.168 ]




SEARCH



© 2024 chempedia.info