Big Chemical Encyclopedia

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

Articles Figures Tables About

Mechanism addition-elimination, metal

Double-bond isomerization can also take place in other ways. Nucleophilic allylic rearrangements were discussed in Chapter 10 (p. 421). Electrocyclic and sigmatropic rearrangements are treated at 18-27-18-35. Double-bond migrations have also been accomplished photochemically, and by means of metallic ion (most often complex ions containing Pt, Rh, or Ru) or metal carbonyl catalysts. In the latter case there are at least two possible mechanisms. One of these, which requires external hydrogen, is called the nwtal hydride addition-elimination mechanism ... [Pg.772]

The MgX of Grignard reagents can migrate to terminal positions in the presence of small amounts of TiCU." The proposed mechanism consists of metal exchange (12-33), elimination-addition, and metal exchange ... [Pg.803]

Synthetically important substitutions of aromatic compounds can also be done by nucleophilic reagents. There are several general mechanism for substitution by nucleophiles. Unlike nucleophilic substitution at saturated carbon, aromatic nucleophilic substitution does not occur by a single-step mechanism. The broad mechanistic classes that can be recognized include addition-elimination, elimination-addition, and metal-catalyzed processes. (See Section 9.5 of Part A to review these mechanisms.) We first discuss diazonium ions, which can react by several mechanisms. Depending on the substitution pattern, aryl halides can react by either addition-elimination or elimination-addition. Aryl halides and sulfonates also react with nucleophiles by metal-catalyzed mechanisms and these are discussed in Section 11.3. [Pg.1027]

Although the high reactivity of metal-chalcogen double bonds of isolated heavy ketones is somewhat suppressed by the steric protecting groups, Tbt-substituted heavy ketones allow the examination of their intermolecular reactions with relatively small substrates. The most important feature in the reactivity of a carbonyl functionality is reversibility in reactions across its carbon-oxygen double bond (addition-elimination mechanism via a tetracoordinate intermediate) as is observed, for example, in reactions with water and alcohols. The energetic basis... [Pg.160]

The preparation of di-w-butyl ether is illustrative (Scheme 2.6). No reaction occurred with n-butanol alone for 2 h at 200 °C. However, in the presence of 10 mol % n-butyl bromide, 26% conversion of the alcohol to the ether was obtained after 1 h, without apparent depletion of the catalyst. It is known that addition of alkaline metal salts can accelerate solvolytic processes, including the rate of ionization of RX [41]. This was confirmed when the introduction of LiBr (10 mol %) along with n-butyl bromide, afforded a conversion of 54% after 1 h at 200 °C. Ethers incorporating a secondary butyl moiety were not detected, precluding mechanisms involving elimination followed by Markovnikov addition. [Pg.45]

Some experimental evidences are in agreement with this proposed mechanism. For example, coordinating solvents like diethyl ether show a deactivating effect certainly due to competition with a Lewis base (149). For the same reason, poor reactivity has been observed for the substrates carrying heteroatoms when an aluminum-based Lewis acid is used. Less efficient hydrovinylation of electron-deficient vinylarenes can be explained by their weaker coordination to the nickel hydride 144, hence metal hydride addition to form key intermediate 146. Isomerization of the final product can be catalyzed by metal hydride through sequential addition/elimination, affording the more stable compound. Finally, chelating phosphines inhibit the hydrovinylation reaction. [Pg.320]

The first mechanism appears to be the better basis for describing most of the results referred to by Cramer (56). It will, however, be noted that the addition-elimination mechanism requires that the metal catalyst be supplied as a metal hydride. Where the catalyst has not been supplied in this form, the reaction has usually been carried out in the presence of reagents known to convert transition metal compounds to hydrides (e.g. protonic acids, alcohols or hydrogen). These substances are known as co-catalysts and, where they have been used, induction periods have been encountered which are consistent with hydride formation as required in mechanism (a), but which would not be expected for (b). [Pg.44]

Mechanistic studies of the rearrangement activity of the ring-opening metathesis polymerization catalyst [Ru(H20)6]2+ were reported for unfunctionalized alkenes (112). The mechanism was found to be intermolecular, the alkene isomerization proceeding through an addition-elimination mechanism with a metal hydride catalytic species. This interpretation was... [Pg.493]

The two mechanisms may result in substantial and characteristic differences in deuterium distribution. The metal hydride addition-elimination mechanism usually leads to a complex mixture of labeled isomers.195 198 208-210 Hydride exchange between the catalyst and the solvent may further complicate deuterium distribution. Simple repeated intramolecular 1,3 shifts, in contrast, result in deuterium scram-bling in allylic positions when the ir-allyl mechanism is operative. ... [Pg.189]

There is wide diversity in the nature of organohalogen compounds but, of necessity, we have restricted this chapter to alkyl, cycloalkyl, alkenyl, alkynyl, and aryl halides. Some of the chemistry of the carbon-halogen bonds already will be familiar to you because it involves the addition, substitution, and elimination reactions discussed in previous chapters. To some extent, we will amplify these reactions and consider nucleophilic substitution by what are called the addition-elimination and elimination-addition mechanisms. Subsequently, we will discuss the formation of carbon-metal bonds from carbon-halogen bonds. The latter type of reaction is of special value because compounds that have carbon-metal bonds are potent reagents for the formation of carbon-carbon bonds, as we will show later in this chapter. [Pg.535]

A fairly general procedure, which has also been used on the industrial scale, involves heating the alkali metal sulphonate with either sodium or potassium hydroxide in the presence of a small amount of water to aid the fusion process. The reaction mechanism may be formulated as a bimolecular nucleophilic addition-elimination sequence. [Pg.970]

The mechanism of these displacement processes presumably involves a metal-assisted addition-elimination reaction, in which the metal ion stabilises the charge in the intermediate (Fig. 8-33). A number of useful synthetic applications of this methodology are... [Pg.254]

Reactions of alkynyliodonium salts 119 with nucleophiles proceed via an addition-elimination mechanism involving alkylidenecarbenes 120 as key intermediates. Depending on the structure of the alkynyliodonium salt, specific reaction conditions, and the nucleophile employed, this process can lead to a substituted alkyne 121 due to the carbene rearrangement, or to a cyclic product 122 via intramolecular 1,5-carbene insertion (Scheme 50). Both of these reaction pathways have been widely utilized as a synthetic tool for the formation of new C-C bonds. In addition, the transition metal mediated cross-coupling reactions of alkynyliodonium salts are increasingly used in organic synthesis. [Pg.120]

Depending on the nature of the catalyst, the transition-metal-catalysed isomerisation will proceed by an addition-elimination mechanism or by the formation of a it allyl complex followed by a 1,3-hydrogen shift (Scheme 2.7b). The equilibrium of the isomerisation lies strongly in favour of the propenyl ether because of resonance stabilisation between the oxygen lone pair and the it orbital of the double bond. Isomerisation can also be performed under strongly basic conditions by using potassium f-butoxide in dimethylsulfoxide (DMSO).18... [Pg.36]

The Tschitschibabin reaction285,266 of alkali metal amides with pyridine bases has been the subject of much recent discussion. While there is yet no agreement concerning the detailed mechanism (due to the lack of experimental information) there is no doubt that the overall reaction proceeds by an SN2 type addition-elimination pathway. [Pg.292]

Methyl-p-nitrophenyl phosphate coordinated to the two metal centers in 37 undergoes hydrolysis by a two-step addition-elimination mechanism [73]. The free phosphate hydrolyzes by a concerted mechanism. In both phosphate monoester and diester hydrolysis, the two Co(m) centers in 32 and 37 stabilize the five-coordinate phosphate species (transition state or intermediate) by bringing the phosphate and nucleophile together. This stabilization leads to a change in mechanism from dissociative to concerted for a phosphate monoester hydrolysis [96] and from concerted to stepwise for phosphate diester hydrolysis [73]. [Pg.151]

Several mechanisms for the catalytic action of Cu(I) and Ag(I) have been considered6. Among these, the metal-assisted addition-elimination sequence shown in equation 85 and illustrated with cuprous triflate was deemed most consistent with various control studies. A mechanism not discussed but equally plausible is the metal-assisted MC sequence depicted in equation 86. The greater separation of iodonium-sulfonate ion pairs in acetonitrile versus benzene should provide the tosylate (or mesylate) ions with sufficient mobility to add to the /7-carbon atom of the alkynyliodonium ion. [Pg.1205]

Isomerization of allylic alcohol to ketone has been extensively studied [13], and two different pathways have been established, including tt-allyl metal hydride and the metal hydride addition-elimination mechanisms [5,14]. McGrath and Grubbs [ 15] investigated the ruthenium-catalyzed isomerization of allyl alcohol in water and proposed a modified metal hydride addition-elimination mechanism through an oxygen-functionality-directed Markovnikov addition to the double bond. [Pg.323]

Now for some of the reactions you have seen in the last few chapters. Starting with carbonyl substitution reactions, the first example is the conversion of acid chlorides into esters. The simplest mechanism to understand is that involved when the anion of an alcohol (a metal alkoxide RO ) reacts with an acid chloride. The kinetics are bimolecular rate = fc[MeCOCl] [RO ]. The mechanism is the simple addition elimination process with a tetrahedral intermediate. [Pg.319]


See other pages where Mechanism addition-elimination, metal is mentioned: [Pg.208]    [Pg.394]    [Pg.410]    [Pg.53]    [Pg.246]    [Pg.42]    [Pg.44]    [Pg.126]    [Pg.187]    [Pg.61]    [Pg.171]    [Pg.791]    [Pg.2042]    [Pg.851]    [Pg.138]    [Pg.208]    [Pg.162]    [Pg.146]    [Pg.268]    [Pg.888]    [Pg.319]    [Pg.54]    [Pg.109]   


SEARCH



1,4 - Addition-eliminations 670 1,2-ADDITIONS

Addition-elimination

Additive mechanism

Elimination 1,6-addition, eliminative

Elimination addition mechanism

Mechanical metals

Mechanism elimination

Mechanisms addition

Mechanisms metal hydride addition-elimination

Metal additives

Metalation mechanism

Metals addition

© 2024 chempedia.info