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Cycloadditions dimer

The reaction of o-xylene showed the formation of dimethylphenols in about 63% yield together with 21% of the dimer of 6,6-dimethyl-2,4-cyclohexadien-l-one, which involves ipso attack followed by a methyl shift and cycloadditive dimerization of the intermediate 6,6-dimethyl-2,4-cyclohexadien-l-one catalyzed by the acid (Scheme 5). [Pg.794]

Photolysis of 3-methylbenzo[6]thiophene 1-oxide in benzene results in [2+2] cycloaddition-dimerization. Both products (Scheme 191) result from head-to-head dimerization. The yield is increased on using benzophenone sensitization (78TL999). The photodimerization proceeds from a triplet state precursor (81JOC4258). [Pg.841]

Similar results are reported by Jishi et al. (II IR and 16 Raman) [1560] and Gallagher et al. (25 Raman) [1561]. These observations may suggest that some vibrations are inherently weak and/or that serious band overlaps occur in these spectra. Vibrational frequencies of 50 and C70 were calculated by the quantum mechanical method (AMI) [1562]. The IR spectra of M3C70 and M4C70 (M = K,Rb) salts show that the 1430 cm band of C70 is, downshifted by 13 cm per electron added to the carbon cage [1563]. Similar to dimeric C60, C70 forms a [2+ 2] cycloadditional dimer of C2/ symmetry, and its IR and Raman spectra are reported [1564]. Table 2.14 summarizes structural and spectroscopic data of C28, C32, C50, and C70 [1539]. [Pg.265]

It is of interest to consider at this point some of the specific molecules in Scheme 8.2 and compare their chemical properties with the calculated stabilization energies. Benzocyclobutadiene has been generated in a number of ways, including dehalogenation of dibromobenzocyclobutene. " Chemically, benzocyclobutadiene reacts as a polyene having a quinodimethane stmcture and is a reactive diene in Diels-Alder cycloadditions, dimerizing or polymerizing readily. ... [Pg.751]

Simple olefins do not usually add well to ketenes except to ketoketenes and halogenated ketenes. Mild Lewis acids as well as bases often increase the rate of the cyclo addition. The cycloaddition of ketenes to acetylenes yields cyclobutenones. The cycloaddition of ketenes to aldehydes and ketones yields oxetanones. The reaction can also be base-cataly2ed if the reactant contains electron-poor carbonyl bonds. Optically active bases lead to chiral lactones (41—43). The dimerization of the ketene itself is the main competing reaction. This process precludes the parent compound ketene from many [2 + 2] cyclo additions. Intramolecular cycloaddition reactions of ketenes are known and have been reviewed (7). [Pg.474]

Most ozonolysis reaction products are postulated to form by the reaction of the 1,3-zwitterion with the extmded carbonyl compound in a 1,3-dipolar cycloaddition reaction to produce stable 1,2,4-trioxanes (ozonides) (17) as shown with itself (dimerization) to form cycHc diperoxides (4) or with protic solvents, such as alcohols, carboxyUc acids, etc, to form a-substituted alkyl hydroperoxides. The latter can form other peroxidic products, depending on reactants, reaction conditions, and solvent. [Pg.117]

The trans isomer is more reactive than the cis isomer ia 1,2-addition reactions (5). The cis and trans isomers also undergo ben2yne, C H, cycloaddition (6). The isomers dimerize to tetrachlorobutene ia the presence of organic peroxides. Photolysis of each isomer produces a different excited state (7,8). Oxidation of 1,2-dichloroethylene ia the presence of a free-radical iaitiator or concentrated sulfuric acid produces the corresponding epoxide [60336-63-2] which then rearranges to form chloroacetyl chloride [79-04-9] (9). [Pg.20]

Nitrile A-oxides, under reaction conditions used for the synthesis of isoxazoles, display four types of reactivity 1,3-cycloaddition 1,3-addition nucleophilic addition and dimerization. The first can give isoxazolines and isoxazoles directly. The second involves the nucleophilic addition of substrates to nitrile A-oxides and can give isoxazolines and isoxazoles indirectly. The third is the nucleophilic addition of undesirable nucleophiles to nitrile A-oxides and can be minimized or even eliminated by the proper selection of substrates and reaction conditions. The fourth is an undesirable side reaction which can often be avoided by generating the nitrile A-oxide in situ and by keeping its concentration low and by using a reactive acceptor (70E1169). [Pg.66]

Two extreme mechanisms can be envisaged (Scheme 12), concerted [2 + 2] cycloaddition or the more generally accepted formation of a dipolar intermediate (164) which closes to a /3-lactam or which can interact with a second molecule of ketene to give 2 1 adducts (165) and (166) which are sometimes found as side products. In some cases 2 1 adducts result from reaction of the imine with ketene dimer. [Pg.259]

The chemistry of benzazetidin-2-ones (251) can also be explained in terms of facile ring opening to the iminoketenes (252) which dimerize, rearrange or can be intercepted by nucleophiles or in cycloadditions depending on the conditions. Indeed, this ring opening precludes their isolation in all but exceptional cases (Section 5.09.4.3.5) (76AHC(19)215). [Pg.273]

Extrapolation from the known reactivity of cyclobutadiene would suggest that azetes should be highly reactive towards dimerization and as dienes and dienophiles in cycloaddition reactions and the presence of a polar C=N should impart additional reactivity towards attack by nucleophiles. Isolation of formal dimers of azetes has been claimed as evidence for the intermediacy of such species, but no clear reports of their interception in inter-molecular cycloaddition reactions or by nucleophiles have yet appeared. [Pg.279]

Schmidt reaction of ketones, 7, 530 from thienylnitrenes, 4, 820 tautomers, 7, 492 thermal reactions, 7, 503 transition metal complexes reactivity, 7, 28 tungsten complexes, 7, 523 UV spectra, 7, 501 X-ray analysis, 7, 494 1 H-Azepines conformation, 7, 492 cycloaddition reactions, 7, 520, 522 dimerization, 7, 508 H NMR, 7, 495 isomerization, 7, 519 metal complexes, 7, 512 photoaddition reactions with oxygen, 7, 523 protonation, 7, 509 ring contractions, 7, 506 sigmatropic rearrangements, 7, 506 stability, 7, 492 N-substituted mass spectra, 7, 501 rearrangements, 7, 504 synthesis, 7, 536-537... [Pg.524]

Indolizine, 1 -cyano-2-(methylthio)-synthesis, 4, 465 Indolizine, 3,5-dialkyl-synthesis, 4, 475 Indolizine, dihydrosynthesis, 4, 467, 468 Indolizine, dimethyl-mass spectrometry, 4, 187 Indolizine, 1,2-dimethyl-oxidative dimerization, 4, 458 Indolizine, 2,6-dimethyl-cycloaddition reaction, 4, 460 reduction, 4, 459... [Pg.672]

Oxazolium hydroxide, anhydro-5-hydroxy-aromaticity, 6, 184 cycloaddition reactions, 6, 209 dimerization, 6, 207 1,3-dipolar cycloaddition reactions with alkynes, 6, 210 electrophilic reactions, 6, 207 mesoionic reactions, 6, 188 reactions, 6, 206-211 synthesis, 6, 225-227... [Pg.729]

The behavior of strained,/Zuorimiret/ methylenecyelopropanes depends upon the position and level of fluorination [34], l-(Difluoromethylene)cyclopropane is much like tetrafluoroethylene in its preference for [2+2] cycloaddition (equation 37), but Its 2,2-difluoro isomer favors [4+2] cycloadditions (equation 38). Perfluoromethylenecyclopropane is an exceptionally reactive dienophile but does not undergo [2+2] cycloadditions, possibly because of stenc reasons [34, 45] Cycloadditions involving most possible combinations of simple fluoroalkenes and alkenes or alkynes have been tried [85], but kinetic activation enthalpies (A/f j for only the dimerizations of tetrafluoroethylene (22 6-23 5 kcal/mol), chlorotri-fluoroethylene (23 6 kcal/mol), and perfluoropropene (31.6 kcal/mol) and the cycloaddition between chlorotnfluoroethylene and perfluoropropene (25.5 kcal/mol) have been determined accurately [97, 98] Some cycloadditions involving more functionalized alkenes are listed in Table 5 [99. 100, 101, 102, 103]... [Pg.780]

The dimeric tellurium diimide 10.7 undergoes a cycloaddition reaction with BuNCO to generate the Ai,iV -ureatotellurium imide 10.11, which is converted to the corresponding telluroxide 10.12 by reaction with excess BuNCO. " By contrast, BuN=S=N Bu undergoes exchange reactions with isocyanates. [Pg.194]

Tile behavior of /3-moiiooxo derivatives of 4-chlomaiioiies (27) toward morpholine was rather complex (98JOC9840). Tlius, the proposed thio-ketoiie 5-sulhde intermediates 28 would dimerize into either 1,2,4,5-tetrathianes 29 in a two-step manner or to 1,3,4,5,6-oxatetrathiocins 30 by a [5 + 3] cycloaddition. Meanwhile, the formation of oxadithiins 31 and 1,2,4-trithiolanes 32 is suggestive of the disproportionation of 28 into the thioke-tones 33 and the thioketone 5 -disulhdes 34. Tlie oxadithiins 31 correspond to a Diels-Alder dimer of 33, and the 1,2,4-trithiolanes 32 correspond to cycloadducts of 33 and 34. [Pg.228]

UV irradiation. Indeed, thermal reaction of 1-phenyl-3,4-dimethylphosphole with (C5HloNH)Mo(CO)4 leads to 155 (M = Mo) and not to 154 (M = Mo, R = Ph). Complex 155 (M = Mo) converts into 154 (M = Mo, R = Ph) under UV irradiation. This route was confirmed by a photochemical reaction between 3,4-dimethyl-l-phenylphosphole and Mo(CO)6 when both 146 (M = Mo, R = Ph, R = R = H, R = R" = Me) and 155 (M = Mo) resulted (89IC4536). In excess phosphole, the product was 156. A similar chromium complex is known [82JCS(CC)667]. Complex 146 (M = Mo, R = Ph, r2 = R = H, R = R = Me) enters [4 -H 2] Diels-Alder cycloaddition with diphenylvinylphosphine to give 157. However, from the viewpoint of Woodward-Hoffmann rules and on the basis of the study of UV irradiation of 1,2,5-trimethylphosphole, it is highly probable that [2 - - 2] dimers are the initial products of dimerization, and [4 - - 2] dimers are the final results of thermally allowed intramolecular rearrangement of [2 - - 2] dimers. This hypothesis was confirmed by the data obtained from the reaction of 1-phenylphosphole with molybdenum hexacarbonyl under UV irradiation the head-to-tail structure of the complex 158. [Pg.144]

If the reaction temperature is raised to 430 K and the carbon monoxide pressure to 3 atm, coordination of the metal atom in the rearranged product occurs via the phosphorus site, as in 159 (M = Cr, Mo, W) [84JOM(263)55]. Along with this product (M = W) at 420 K, formation of the dimer of 5-phenyl-3,4-dimethyl-2//-phosphole, 160 (the a complex), is possible as a consequence of [4 - - 2] cycloaddition reactions. Chromium hexacarbonyl in turn forms phospholido-bridged TiyP)-coordinatedcomplex 161. At 420 K in excess 2,3-dimethylbutadiene, a transformation 162 163 takes place (82JA4484). [Pg.144]


See other pages where Cycloadditions dimer is mentioned: [Pg.37]    [Pg.247]    [Pg.36]    [Pg.129]    [Pg.389]    [Pg.37]    [Pg.247]    [Pg.36]    [Pg.129]    [Pg.389]    [Pg.333]    [Pg.482]    [Pg.397]    [Pg.4]    [Pg.279]    [Pg.528]    [Pg.538]    [Pg.561]    [Pg.575]    [Pg.616]    [Pg.670]    [Pg.678]    [Pg.774]    [Pg.789]    [Pg.815]    [Pg.68]    [Pg.122]    [Pg.318]    [Pg.343]    [Pg.781]    [Pg.188]    [Pg.731]   
See also in sourсe #XX -- [ Pg.521 , Pg.522 ]




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