Olefins addition reactions, formed

There are also important differences in the nature of the polymer backbone formed by these processes. Olefin addition reactions lead to polymer chains containing aliphatic carbon as the backbone. Most step-growth reactions instead form polymer chains or rings containing heteroatoms (noncarbon atoms) in addition to aliphatic carbon in the backbone. The presence of heteratoms can provide remarkable enhancements in polymer performance and often leads to polymers with higher glass transition temperatures and thermal stability leading to such properties as conductivity or electroluminescence. 

Michael condensations are catalyzed by alkaU alkoxides, tertiary amines, and quaternary bases and salts. Active methylene compounds and aUphatic nitro compounds add to form P-substituted propionates. These addition reactions are frequendy reversible at high temperatures. Exceptions are the tertiary nitro adducts which are converted to olefins at elevated temperatures (24). 

Tetrafluoroethylene undergoes addition reactions typical of an olefin. It bums in air to form carbon tetrafluoride, carbonyl fluoride, and carbon dioxide (24). Under controlled conditions, oxygenation produces an epoxide (25) or an explosive polymeric peroxide (24). Trifluorovinyl ethers,... 

Chemical Properties. Higher a-olefins are exceedingly reactive because their double bond provides the reactive site for catalytic activation as well as numerous radical and ionic reactions. These olefins also participate in additional reactions, such as oxidations, hydrogenation, double-bond isomerization, complex formation with transition-metal derivatives, polymerization, and copolymerization with other olefins in the presence of Ziegler-Natta, metallocene, and cationic catalysts. All olefins readily form peroxides by exposure to air. 

Polymerization. Polymerization reactions, which are addition reactions, are used to produce the principal products formed direcdy from butlylenes butyl elastomers polybutylenes and polyisobutylene (see Elastomers, synthetic Olefin polymers). 

Addition reactions — The fullerenes Ceo and C70 react as electron-poor olefins with fairly localized double bonds. Addition occurs preferentially at a double bond common to two annelated 6-membered rings (a 6 6 bond) and a second addition, when it occurs is generally in the opposite hemisphere. The first characteriz-able mono adduct was [C6oOs04(NC5H4Bu )2]. formed by reacting Cgo with an excess of OSO4 in 4-butylpyridine. The structure is shown in... 

In addition there are certain other methods for the preparation such compounds. Upon heating of the thionocarbonate 2 with a trivalent phosphorus compound e.g. trimethyl phosphite, a -elimination reaction takes place to yield the olefin 3. A nucleophilic addition of the phosphorus to sulfur leads to the zwitterionic species 6, which is likely to react to the phosphorus ylide 7 via cyclization and subsequent desulfurization. An alternative pathway for the formation of 7 via a 2-carbena-l,3-dioxolane 8 has been formulated. From the ylide 7 the olefin 3 is formed stereospecifically by a concerted 1,3-dipolar cycloreversion (see 1,3-dipolar cycloaddition), together with the unstable phosphorus compound 9, which decomposes into carbon dioxide and R3P. The latter is finally obtained as R3PS ... 

The mechanism of the cyanide- and thioazolium ion-catalyzed conjugate addition reactions is considered to be analogous to the Lapworth mechanism for the cyanide-catalyzed benzoin condensation. Thus the cyano-stabilized carbanion resulting from deprotonation of the cyanohydrin of the aldehyde is presumed to be the actual Michael donor. After conjugate addition to the activated olefin, cyanide is eliminated to form the product and regenerate the catalyst. 

The addition of hydrogen halide to alkene is another classical electrophilic addition of alkene. Although normally such reactions are carried out under anhydrous conditions, occasionally aqueous conditions have been used.25 However, some difference in regioselectivity (Markovnikov and anti-Markovnikov addition) was observed. The addition product formed in an organic solvent with dry HBr gives exclusively the 1-Br derivative whereas with aq. HBr, 2-Br derivative is formed. The difference in the products formed by the two methods is believed to be due primarily to the difference in the solvents and not to the presence of any peroxide in the olefin.26... 

Mechanistic evidence indicates 450,451> that the triplet enone first approaches the olefinic partner to form an exciplex. The next step consists in the formation of one of the new C—C bonds to give a 1,4-diradical, which is now the immediate precursor of the cyclobutane. Both exciplex and 1,4-diradical can decay resp. disproportionate to afford ground state enone and alkene. Eventually oxetane formation, i.e. addition of the carbonyl group of the enone to an olefin is also observed452. Although at first view the photocycloaddition of an enone to an alkene would be expected to afford a variety of structurally related products, the knowledge of the influence of substituents on the stereochemical outcome of the reaction allows the selective synthesis of the desired annelation product in inter-molecular reactions 453,454a b). As for intramolecular reactions, the substituent effects are made up by structural limitations 449). 

The most characteristic and useful reaction is the dimerization with incorporation of certain nucleophiles. It is well-known that simple olefins coordinated by Pd2+ compounds undergo nucleophilic substitutions [Eq. (9)] or addition reactions [Eq. (10)] (16, 17). Water, alcohols, and carboxylic acids are typical nucleophiles which attack olefins to form aldehydes, ketones, vinyl ethers, and vinyl esters. 

Olefins dissolved in aqueous acid are in rapid reversible equilibrium with a carbonium ion formed by addition of a proton.288 This rapidly and reversibly formed carbonium ion has to be a non-classical one in view of the behavior of the isomeric pentenes XLVI and XLVII.28 Both pentenes react with dilute nitric acid to give the same tertiary carbinol. If the reaction is interrupted when half of the olefin has been converted to carbinol, the remaining olefin has its original structure in both cases. The first product of protonation of the olefin is therefore of such a structure that loss of a proton gives only the original olefin. The reversibly formed carbonium ion can not therefore be the classical one. 

A cyclic complex derivable by addition of positive bromine to a double bond has already been discussed as an example of the neighboring group effect. The same intermediate, except perhaps for the nature of the bonds to bromine, is formed in the addition of bromine to olefins and is responsible for the stereochemistry of the addition reaction and the nature of the by-products.232... 

The addition of a cation to an olefin to produce a carbonium ion or ion pair need not end there but may go through many cycles of olefin addition before the chain is eventually terminated by neutralization of the end carbonium ion. Simple addition to the double bond is essentially the same reaction stopped at the end of the first cycle. The addition of mineral acids to produce alkyl halides or sulfates, for example, may be prolonged into a polymerization reaction. However, simple addition or dimerization is the usual result with olefins and hydrogen acids. The polymerization which occurs with a-methyl-styrene and sulfuric acid or styrene and hydrochloric acid at low temperatures in polar solvents is exceptional.291 Polymerization may also be initiated by a carbonium ion formed by the dissociation of an alkyl halide as in the reaction of octyl vinyl ether with trityl chloride in ionizing solvents.292... 

The mechanism of this reaction has not been studied in detail. However, it can be represented as a sequence of reactions. The first reaction is, in fact, [3+ 2]-cycloaddition of olefin to furoxan (161). Under severe conditions, the resulting intermediate A undergoes fragmentation to give five-membered cyclic nitronate B. The latter is involved in the usual addition reaction with an excess of olefin to form isolable bicyclic product (162) (301, 378, 379). 

This observation may well explain the considerable difference between metal-olefin and metal-acetylene chemistry observed for the trinuclear metal carbonyl compounds of this group. As with iron, ruthenium and osmium have an extensive and rich chemistry, with acetylenic complexes involving in many instances polymerization reactions, and, as noted above for both ruthenium and osmium trinuclear carbonyl derivatives, olefin addition normally occurs with interaction at one olefin center. The main metal-ligand framework is often the same for both acetylene and olefin adducts, and differs in that, for the olefin complexes, two metal-hydrogen bonds are formed by transfer of hydrogen from the olefin. The steric requirements of these two edgebridging hydrogen atoms appear to be considerable and may reduce the tendency for the addition of the second olefin molecule to the metal cluster unit and hence restrict the equivalent chemistry to that observed for the acetylene derivatives. 

A stereoselective route to 2-(phenylthio)-l,3-butadienes such as 327 or 328 was developed by Pearson et al. [167] with allylboranes as crucial intermediates. Addition of 9-BBN to allenyl sulfide 324 gives the allylborane intermediate 325, which subsequently adds to aldehydes (Scheme 8.89). Typical of Peterson olefinations, this reaction can also be terminated by two different work-up procedures, either acidic conditions leading to anti-elimination, which affords Z-configuration of dienes 327, or basic work-up resulting in a syn-elimination to form (E)-dienes 328. 

The reaction was further applied to the synthesis of spiro heterocycles (Scheme 16.4) [8], The oxidative addition of an iodide to a Pd(0) species generates an ArPdl species, into which an internal olefin inserts to form an alkylpalladium complex otherwise difficult to access. Allene participates in the reaction at this stage to provide a jt-allylpalladium complex, which is attacked by the amine intramolecularly to afford the procuct. 

It is also called dissociative because one of the rate-determining steps is the dissociation of carbon monoxide. The cycle is started by the dissociation of a ligand, which results in the release of the planar 16 electron species (I). In analogy to the cobalt mechanism (see Wiese KD and Obst D, 2006, in this volume), the next step is the addition of an olefin molecule to form the r-complex (II). This complex undergoes a rearrangement reaction to the corresponding reaction steps decide whether a branched or a linear aldehyde is the product of the hydroformylation experiment. The next step is the addition of a carbon monoxide molecule to the 18 electron species (IV). Now, the insertion of carbon monoxide takes place and... 

Abstract Aldehydes obtained from olefins under hydroformylation conditions can be converted to more complex reaction products in one-pot reaction sequences. These involve heterofunctionalization of aldehydes to form acetals, aminals, imines and enamines, including reduction products of the latter in an overall hydroaminomethylation. Furthermore, numerous conversions of oxo aldehydes with additional C.C-bond formation are conceivable such as aldol reactions, allylations, carbonyl olefinations, ene reactions and electrophilic aromatic substitutions, including Fischer indole syntheses. 

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