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Photochemical addition double bond

H-Pyrazoles Azo compounds of the 3 -pyrazole type are an interesting class of molecules. The basic mechanism for the photochemical decomposition of cyclic azo compounds becomes more complex for 3. ff-pyr azoles because of the additional double bond present. [Pg.76]

Irradiation of trienone 96a, which bears an additional double bond conjugated with the 4,5-double bond of the dienone, in glacial acetic acid yielded exclusively the azulene linearly conjugated dienone 97 in 54% yield (Scheme 17). Under similar conditions, trienone 96b yielded lactone 98 in 85% yield. Thus, it seems that the 6,7-double bond does not interfere in the photochemical rearrangement. [Pg.1640]

We will show here the classification procedure with a specific dataset [28]. A reaction center, the addition of a C-H bond to a C=C double bond, was chosen that comprised a variety of different reaction types such as Michael additions, Friedel-Crafts alkylation of aromatic compounds by alkenes, or photochemical reactions. We wanted to see whether these different reaction types can be discerned by this... [Pg.193]

The regioselectivity of addition of HBr to alkenes under normal (electrophilic addi tion) conditions is controlled by the tendency of a proton to add to the double bond so as to produce the more stable carbocatwn Under free radical conditions the regioselec tivity IS governed by addition of a bromine atom to give the more stable alkyl radical Free radical addition of hydrogen bromide to the double bond can also be initiated photochemically either with or without added peroxides... [Pg.244]

Hydrogen bromide is unique among the hydrogen halides m that it can add to alkenes either by electrophilic or free radical addition Under photochemical conditions or m the presence of peroxides free radical addition is observed and HBr adds to the double bond with a regio selectivity opposite to that of Markovmkov s rule... [Pg.274]

The a-methylene groups also add to double bonds eg, 1-decene at 160°C gives up to 80% of a-decylbutyrolactone (160). With photochemical initiation similar additions take place at room temperature (161). [Pg.111]

The reaction of (fluoroalkenyl)carboranes with potassium permanganate in acetone leads to formation of a-diketones [119. These compounds react by photochemical reaction in which the radical formation at boron is followed by addition to the double bond [120] (equation 92). [Pg.608]

Examples of perfluoroalkyl iodide addition to the triple bond include free radical addition of perfluoropropyl iodide to 1 -heptyne [28] (equation 21), thermal and free radical-initiated addition of lodoperfluoroalkanesulfonyl fluorides to acetylene [29] (equation 22), thermal addition of perfluoropropyl iodide to hexa-fluoro 2 butyne [30] (equation 23), and palladium-catalyzed addition of per-fluorobutyl iodide to phenylacetylene [31] (equation 24) The E isomers predominate in these reactions Photochemical addition of tnfluoromethyl iodide to vinylacetylene gives predominantly the 1 4 adduct by addition to the double bond [32] Platinum catalyzed addition of perfluorooctyl iodide to l-hexyne in the presence of potassium carbonate, carbon monoxide, and ethanol gives ethyl () per fluorooctyl-a-butylpropenoate [JJ] (equation 25)... [Pg.763]

Free-radical addition of hydrogen bromide to the double bond can also be initiated photochemically, either with or without added peroxides. [Pg.244]

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]

Photocycloaddition of Alkenes and Dienes. Photochemical cycloadditions provide a method that is often complementary to thermal cycloadditions with regard to the types of compounds that can be prepared. The theoretical basis for this complementary relationship between thermal and photochemical modes of reaction lies in orbital symmetry relationships, as discussed in Chapter 10 of Part A. The reaction types permitted by photochemical excitation that are particularly useful for synthesis are [2 + 2] additions between two carbon-carbon double bonds and [2+2] additions of alkenes and carbonyl groups to form oxetanes. Photochemical cycloadditions are often not concerted processes because in many cases the reactive excited state is a triplet. The initial adduct is a triplet 1,4-diradical that must undergo spin inversion before product formation is complete. Stereospecificity is lost if the intermediate 1,4-diradical undergoes bond rotation faster than ring closure. [Pg.544]

When similar photolysis of 11 in the presence of MeOD was carried out, again the product whose NMR reveals the resonance due to the Si-H proton was observed. The relative ratio of the Si-H and CH3-0 protons was identical with those of the products obtained in the presence of non-deuterated methanol. The formation of the methoxysilyl group can be understood by the addition of methanol across the silicon-carbon double bonds. H NMR spectra of all photoproducts obtained from the photolyses of 11 in the presence of methanol reveal no resonances attributed to the cyclohexadienyl ring protons. This indicates that the photochemical degradation of the polymer 11 gives no rearranged silene intermediates, but produces... [Pg.218]

In 1949 Sinsheimer and Hastings<64) reported the almost complete loss of the 260-nm absorption of the pyrimidines upon irradiation in aqueous solution. This effect is now known to be caused by the photochemical addition of water across the 5,6 double bond, as shown below for cytosine ... [Pg.590]

Several other types of photochemical reactions involving unsaturated carbohydrates have been reported. One of these is38 photochemical, E -Z isomerization of the groups attached to a double bond (see Scheme 5). A second is the internal cycloaddition between two double bonds connected by a carbohydrate chain.39-41 Although the carbohydrate portion of the molecule is not directly involved in this cycloaddition, its presence induces optical activity in the cyclobutane derivatives produced photochemically. Finally, a group of acid-catalyzed addition-reactions has been observed for which the catalyst appears to arise from photochemical decomposition of a noncarbohydrate reactant.42-44... [Pg.121]

In attempts to isolate the aforementioned irradiated products of thymine derivatives at lower temperature, the photochemical reactions were carried out in frozen aqueous solutions containing either thymine or 1,3-dimethylthymine. The resulting products were not hydrates, but had elementary analyses corresponding to the starting material. Molecular weight determination indicated that the products were dimers, and infrared and ultraviolet spectral data suggested cyclo addition across the 5,6-double bond to form a cyclobutane system... [Pg.314]

A new methodology for the construction of novel and uniquely shaped 3-azabicyclo[4.2.0]octan-4-one derivatives 166 by combining the Ugi multi-component reaction with [2 + 2] enone-olefin photochemical transformations was recently reported [132] (Fig. 32). The additional functional groups are in this case an enone (165) and a C=C double bond. Although the overall sequence is capable of creating up to five stereocentres, in most cases only two diastereomers are observed, which are epimeric at the exocyclic stereogenic centre. [Pg.27]

The most widely exploited photochemical cycloadditions involve irradiation of dienes in which the two double bonds are fairly close and result in formation of polycyclic cage compounds. Some examples are given in Scheme 6.7. Copper(I) triflate facilitates these intramolecular additions, as was the case for intermolecular reactions. [Pg.372]

The first step in the peroxide-induced reaction is the decomposition of the peroxide to form a free radical. The oxygen-induced reaction may involve the intermediate formation of a peroxide or a free radical olefin-oxygen addition product. (In the case of thermal and photochemical reactions, the free radical may be formed by the opening up of the double bond or, more probably, by dissociation of a carbon-hydrogen bond in metal alkyl-induced reactions, decomposition of the metal alkyl yields alkyl radicals.)... [Pg.25]


See other pages where Photochemical addition double bond is mentioned: [Pg.193]    [Pg.284]    [Pg.2213]    [Pg.2215]    [Pg.397]    [Pg.876]    [Pg.1081]    [Pg.185]    [Pg.876]    [Pg.10]    [Pg.314]    [Pg.315]    [Pg.118]    [Pg.431]    [Pg.473]    [Pg.188]    [Pg.141]    [Pg.314]    [Pg.315]    [Pg.88]    [Pg.313]    [Pg.212]    [Pg.41]    [Pg.183]    [Pg.101]    [Pg.220]    [Pg.350]    [Pg.194]    [Pg.163]   
See also in sourсe #XX -- [ Pg.78 ]

See also in sourсe #XX -- [ Pg.78 ]




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