Big Chemical Encyclopedia

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

Articles Figures Tables About

Subject olefinic acids

Cyclo-olefins are subject to structural isomerization in contact with acidic catalysts, as Bloch and Thomas (27) and Greensfelder and Voge (21) have shown. Therefore, such catalytic activity when intimately coupled to the aromatization reaction may direct the reaction path to products having five-carbon ring structures which cannot aromatize ... [Pg.170]

As already mentioned, neutral aluminum has strong Lewis acidity and high oxo-philicity. It has long been a concern of chemists whether cationic aluminum species would have unprecedented reactivity and even more Lewis acidity. Several aluminum cations were isolated and characterized by X-ray single-crystal analysis, as described in Section 6.1.2.2 most were, however, hexacoordinated aluminum that catalyzed bimolecular reactions. They were also useful in the polymerization of a-olefins, the subject of this section. [Pg.296]

Chlorine heptoxide is more stable than either chlorine monoxide or chlorine dioxide however, the CX C) detonates when heated or subjected to shock. It melts at —91.5°C, bods at 80°C, has a molecular weight of 182.914, a heat of vapori2ation of 34.7 kj/mol (8.29 kcal/mol), and, at 0°C, a vapor pressure of 3.2 kPa (23.7 mm Hg) and a density of 1.86 g/mL (14,15). The infrared spectmm is consistent with the stmcture O CIOCIO (16). Cl O decomposes to chlorine and oxygen at low (0.2—10.7 kPa (1.5—80 mm Hg)) pressures and in a temperature range of 100—120°C (17). It is soluble in ben2ene, slowly attacking the solvent with water to form perchloric acid it also reacts with iodine to form iodine pentoxide and explodes on contact with a flame or by percussion. Reaction with olefins yields the impact-sensitive alkyl perchlorates (18). [Pg.65]

The reactions of olefins with peracids to form epoxides allows for the selective oxidation of carbon-carbon double bonds in the presence of other functional groups which may be subject to oxidation (for example, hydroxyl groups). The epoxides that result are easily cleaved by strong acids to diols or half-esters of diols and are therefore useful intermediates in the synthesis of polyfunctional compounds. [Pg.8]

Aldol addition and related reactions of enolates and enolate equivalents are the subject of the first part of Chapter 2. These reactions provide powerful methods for controlling the stereochemistry in reactions that form hydroxyl- and methyl-substituted structures, such as those found in many antibiotics. We will see how the choice of the nucleophile, the other reagents (such as Lewis acids), and adjustment of reaction conditions can be used to control stereochemistry. We discuss the role of open, cyclic, and chelated transition structures in determining stereochemistry, and will also see how chiral auxiliaries and chiral catalysts can control the enantiose-lectivity of these reactions. Intramolecular aldol reactions, including the Robinson annulation are discussed. Other reactions included in Chapter 2 include Mannich, carbon acylation, and olefination reactions. The reactivity of other carbon nucleophiles including phosphonium ylides, phosphonate carbanions, sulfone anions, sulfonium ylides, and sulfoxonium ylides are also considered. [Pg.1334]

Under Lewis-acid-catalyzed conditions, electron-rich arenes can be added to alkenes to generate Friedel-Crafts reaction products. This subject will be discussed in detail in Chapter 7, on aromatic compounds. However, it is interesting to note that direct arylation of styrene with benzene in aqueous CF3CO2H containing H2PtCl6 yielded 30-5% zram-PhCH CHR via the intermediate PhPt(H20)Cl4.157 Hydropheny-lation of olefins can be catalyzed by an Ir(III) complex.158... [Pg.75]

Reduction of the ketone (147), followed by elimination gave the olefin (148). The olefin (148) was subjected again to a second annelation, and as expected, dichloroketene addition, ring expansion and zinc reduction gave the tricyclic compound (149). Compound (149) could be converted to ( )-hirsutic acid C (150) 52K... [Pg.106]

When the RelSi terminology (29) was introduced (28), its use was suggested also for describing the faces of double bonds. This was to be accomplished by citing the descriptors of their trigonal atoms when seen from the same side. Although this extension seems an obvious choice, it is subject to a possible misinterpretation. If one characterizes a face of the olefinic bond of 2-butenoic acid as Re-Re, one can deduce that the compound in question must be the Z and not the E isomer. It might be inferred from this that the cis-trans isomerism of these acids can be factored into two elements of prostereoisomerism. This... [Pg.223]

The Pirrung synthesis is notable for its brevity and clever amalgamation of [2 + 2] photocycloaddition and Wagner-Meerwein rearrangement chemistry Enol ether 757 was reacted with the Grignard rea nt from 5-bromo-2-methyl-l-pentene, subjected to acid hydrolysis, and irradiated to generate the tricycle 738. Wittig olefination of this ketone and treatment with p-toluenesulfonic acid provided racemic isocomene. [Pg.72]

Thiosemicarbazones, such as 331, and thiourea (333) give rise to sulfinic acids when subjected to photosensitized oxygenation reaction conditions.62,233 It was suggested that by analogy to olefin oxygenation the primary products may be of hydroperoxidic nature... [Pg.95]

Tropolone has been made from 1,2-cycloheptanedione by bromination and reduction, and by reaction with N-bromosuccinimide from cyclo-heptanone by bromination, hydrolysis, and reduction from diethyl pimelate by acyloin condensation and bromination from cyclo-heptatriene by permanganate oxidation from 3,5-dihydroxybenzoic acid by a multistep synthesis from 2,3-dimethoxybenzoic acid by a multistep synthesis from tropone by chlorination and hydrolysis, by amination with hydrazine and hydrolysis, or by photooxidation followed by reduction with thiourea from cyclopentadiene and tetra-fluoroethylene and from cyclopentadiene and dichloroketene. - The present procedure, based on the last method, is relatively simple and uses inexpensive starting materials. Step A exemplifies the 2 + 2 cycloaddition of dichloroketene to an olefin, " and the specific oycloadduot obtained has proved to be a useful intermediate in other syntheses. " Step B has been the subject of several mechanistic studies, " and its yield has been greatly improved by the isolation technique described above. This synthesis has also been extended to the preparation of various tropolone derivatives. - " ... [Pg.61]

In a study of the addition of nitrosyl chloride or nitrosyl bromide to norbor-nene and norbomadiene, it was observed that (a) there was no structural rearrangement during the reaction, (b) a cis addition had taken place, (c) nucleophilic solvents such as ethanol or acetic acid were not incorporated in the products. These facts seem to speak against an ionic addition mechanism, while a free radical initiated by NO radicals was considered unlikely since nitric oxide is inactive toward norbomadiene. Therefore a four-center mechanism has been suggested [70], However, when a relatively simple, unstrained olefin such as A9-octalin was subjected to the reaction, only blue, crystalline, monomeric 9-nitroso-10-chlorodecalin was produced. This product had a trans configuration. Thus it is evident that the structure of the olefin has a significant bearing on the steric course of the addition [71]. [Pg.457]


See other pages where Subject olefinic acids is mentioned: [Pg.329]    [Pg.45]    [Pg.472]    [Pg.445]    [Pg.128]    [Pg.98]    [Pg.176]    [Pg.179]    [Pg.149]    [Pg.303]    [Pg.147]    [Pg.118]    [Pg.327]    [Pg.328]    [Pg.247]    [Pg.256]    [Pg.144]    [Pg.131]    [Pg.1]    [Pg.1]    [Pg.40]    [Pg.68]    [Pg.527]    [Pg.468]    [Pg.195]    [Pg.198]    [Pg.388]    [Pg.324]    [Pg.156]    [Pg.121]    [Pg.239]    [Pg.239]    [Pg.70]    [Pg.302]    [Pg.133]    [Pg.27]    [Pg.74]    [Pg.742]    [Pg.1188]   
See also in sourсe #XX -- [ Pg.295 ]




SEARCH



Olefinic acids

Olefins acids

Subject acidity

Subject olefins

© 2024 chempedia.info