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R-Butylated compounds

Cyclopropanations by carbenes from chlorodiazirines were observed in several cases, e.g. with the r-butyl compound. Cyclopropanation and stabilization by ring enlargement and by elimination compete in chlorocyclobutyldiazirine photolysis. [Pg.227]

Some benzylic mono- and di-cations have been studied by the NMR/DFT/IGLO technique. Of the stable dications, the trimethyl species (76 R = Me) was found to be the major resonance contributor to the structure of (75), and the same was found to be true for the trimethoxy derivative. In the related monocations, for (77) the major resonance contributor was (78), and this was also the case for the pentamethyl and 2,5-dimethyl-4-r-butyl compounds. The dication (79) and the trication (80),... [Pg.312]

Polynuclear aromatics fcis-phenols, triphenyl -r-butyl compounds Stabilizers... [Pg.93]

The carboxylation reaction (Scheme 13) nicely illustrates the advantage of using the hindered azobenzenes azobenzene is itself carboxylated under the reaction conditions used whereas the di-r-butyl compound is too hindered and acts only as a probase. Entry 8 is an example of both condensation (of ethyl acetate to ethyl acetoacetate) and subsequent alkylation. Yields are often high and the reaction conditions are usually convenient. The electrogenerated bases are effectively produced in either dimethylformamide or acetonitrile in the latter case the cyanomethyl anion must also be present but this does not seem to interfere with alkylation reactions. [Pg.142]

TI) (46) by pathway a. However, when protons are made available intra- or inter-molecularly, loss of urea from the TI (46) via pathway b also occurs to give a formami-dine (47) (Scheme 14). The proposed mechanism for the intramolecular pathway b is illustrated by the reaction between the r-butyl compound (48) and an ty-hydroxyamine (such as 5-aminopentanol) in Scheme 15.44... [Pg.59]

The enthalpies of activation of racemization amounted to 34.1 kcal mol -1 in the case of 2-methyl-3,3-diphenyloxaziridine, but only to 27.7 kcal mol-1 in the case of the JV-r-butyl compound 36 the entropies of activation were + 5 and +6 cal mol-1 deg-1, respectively. Further investigations into the dependence of racemization on N- and C-substituents of the oxaziridine ring were carried out by Bjorgo and Boyd.37... [Pg.67]

The higher alkyls are progressively less highly polymerized diethyl- and diisopropyl-beryllium are dimeric in benzene but the r-butyl compound is monomeric the same feature is found in aluminum alkyls. [Pg.214]

Butanes CC4Hio]r Butyl Compounds CC4H9X), and Conformational Analysis... [Pg.73]

Regioselectivity of C—C double bond formation can also be achieved in the reductiv or oxidative elimination of two functional groups from adjacent carbon atoms. Well estab llshed methods in synthesis include the reductive cleavage of cyclic thionocarbonates derivec from glycols (E.J. Corey, 1968 C W. Hartmann, 1972), the reduction of epoxides with Zn/Nal or of dihalides with metals, organometallic compounds, or Nal/acetone (seep.lS6f), and the oxidative decarboxylation of 1,2-dicarboxylic acids (C.A. Grob, 1958 S. Masamune, 1966 R.A. Sheldon, 1972) or their r-butyl peresters (E.N. Cain, 1969). [Pg.142]

Auto-association of A-4-thiazoline-2-thione and 4-alkyl derivatives has been deduced from infrared spectra of diluted solutions in carbon tetrachloride (58. 77). Results are interpretated (77) in terms of an equilibrium between monomer and cyclic dimer. The association constants are strongly dependent on the electronic and steric effects of the alkyl substituents in the 4- and 5-positions, respectively. This behavior is well shown if one compares the results for the unsubstituted compound (K - 1200 M" ,). 4-methyl-A-4-thiazoline-2-thione K = 2200 M ). and 5-methyl-4-r-butyl-A-4-thiazoline-2-thione K=120 M ) (58). [Pg.384]

The direct combination of selenium and acetylene provides the most convenient source of selenophene (76JHC1319). Lesser amounts of many other compounds are formed concurrently and include 2- and 3-alkylselenophenes, benzo[6]selenophene and isomeric selenoloselenophenes (76CS(10)159). The commercial availability of thiophene makes comparable reactions of little interest for the obtention of the parent heterocycle in the laboratory. However, the reaction of substituted acetylenes with morpholinyl disulfide is of some synthetic value. The process, which appears to entail the initial formation of thionitroxyl radicals, converts phenylacetylene into a 3 1 mixture of 2,4- and 2,5-diphenylthiophene, methyl propiolate into dimethyl thiophene-2,5-dicarboxylate, and ethyl phenylpropiolate into diethyl 3,4-diphenylthiophene-2,5-dicarboxylate (Scheme 83a) (77TL3413). Dimethyl thiophene-2,4-dicarboxylate is obtained from methyl propiolate by treatment with dimethyl sulfoxide and thionyl chloride (Scheme 83b) (66CB1558). The rhodium carbonyl catalyzed carbonylation of alkynes in alcohols provides 5-alkoxy-2(5//)-furanones (Scheme 83c) (81CL993). The inclusion of ethylene provides 5-ethyl-2(5//)-furanones instead (82NKK242). The nickel acetate catalyzed addition of r-butyl isocyanide to alkynes provides access to 2-aminopyrroles (Scheme 83d) (70S593). [Pg.135]

In comparison to N—S bond formation, O—N bond formation by essentially oxidative procedures has found few applications in the synthesis of five-membered heterocycles. The 1,2,4-oxadiazole system (278) was prepared by the action of sodium hypochlorite on A(-acylamidines (277) (76S268). The A -benzoylamidino compounds (279) were also converted into the 1,2,4-oxadiazoles (280) by the action of r-butyl hypochlorite followed by base. In both cyclizations A -chloro compounds are thought to be intermediates (76BCJ3607). [Pg.137]

Recently (79MI50500) Sharpless and coworkers have shown that r-butyl hydroperoxide (TBHP) epoxidations, catalyzed by molybdenum or vanadium compounds, offer advantages over peroxy acids with regard to safety, cost and, sometimes, selectivity, e.g. Scheme 73, although this is not always the case (Scheme 74). The oxidation of propene by 1-phenylethyl hydroperoxide is an important industrial route to methyloxirane (propylene oxide) (79MI5501). [Pg.116]

Peroxides. These are formed by aerial oxidation or by autoxidation of a wide range of organic compounds, including diethyl ether, allyl ethyl ether, allyl phenyl ether, dibenzyl ether, benzyl butyl ether, n-butyl ether, iso-butyl ether, r-butyl ether, dioxane, tetrahydrofuran, olefins, and aromatic and saturated aliphatic hydrocarbons. They accumulate during distillation and can detonate violently on evaporation or distillation when their concentration becomes high. If peroxides are likely to be present materials should be tested for peroxides before distillation (for tests see entry under "Ethers", in Chapter 2). Also, distillation should be discontinued when at least one quarter of the residue is left in the distilling flask. [Pg.5]

The compound was reasonably stable, reverting to the aromatic starting material only on heating. Part of the stability of this particular Dewar beii2ene derivative can be attributed to steric factors. The r-butyl groups are farther apart in the Dewar benzene stracture than in the aromatic structure. The unsubstituted Dewar benzene was successfully prepared in 1963. [Pg.615]

If Y is to be a valid measure of solvent ionizing power, presumably the defining reaction should proceed via the Lim (pure SnI) process. This was the basis for the original choice of r-butyl chloride. It is now believed that /-butyl chloride sol-volyzes with some solvent participation, and modern versions of Y are based on other compounds, of which 2-adamantyl tosylate (p-toluenesulfonate, OTs), 6, is the most favored." ... [Pg.431]

Cyclopropanes are now readily available and have become useful, through hydrogenolysis, for synthesis of compounds containing quaternary carbons, em-dialkyl, r-butyl, and angular-methyl substituents (779), compounds often available only with difficulty otherwise (.77,5i,55,750,756), Cyclopropanes can be formed in good yields by hydrogenation of cyclopropenes (26). [Pg.174]

An extensive survey has been carried out by McKervey and coworkers [7], who prepared the carbo-alkoxymethyl ethers of p-tert-h x y calix[4]arene, p-/< r/-butyl calix[6]arene, p-tert-bu y calix[8]arene, ca-lix[4]arene, calix[6Jarene, and calix[8]arene, and measured their abilities to extract cations from the aqueous phase into the nonaqueous phase. They concluded the following general aspects for the phase-transfer experiments (1) the calix[4]arene compounds show the greatest selectivity for Na (2) phase-transfer of Li is inefficient with all of the compounds (3) the calix[6]arene compounds show less affinity for Na than for K, with plateau selectivity for Rb" and Cs (4) the calix[8]ar-ene compounds are the least efficient of the cyclic oligomers, showing low levels of transport and low discrimination for all five cations (5) the calix[6]arene... [Pg.339]

Cyclodextrins, toroidal molecules composed of 6, 7 and 8 D-glucose units, are now commercially available at reasonable cost. They form inclusion compounds with a variety of molecules and often differentially include sulfoxide enantiomers29,30. This property has been used to partially resolve some benzyl alkyl, phenyl alkyl and p-tolyl alkyl sulfoxides. The enantiomeric purities after one inclusion process ranged from 1.1 % for t-butyl p-tolyl sulfoxide to 14.5% for benzyl r-butyl sulfoxide. Repeating the process on methyl p-tolyl sulfoxide (10) increased its enantiomeric purity from 8.1% to 11.4% four recrystallizations raised the value to 71.5%. The use of cyclodextrins in asymmetric oxidations is discussed in Section II.C.l and in the resolution of sulfmate esters in Section II.B.l. [Pg.59]

TABLE 22. Reaction of r-butyl p-toluenesulphinylacetate 298a with carbonyl compounds... [Pg.329]

All of the above high-volume organic chemicals are obtained from petroleum or natural gas. This is why the modern organic chemical industry is frequently referred to as the petrochemical industry. The high-volume status of some of these compounds is due to their use to make others lower on the list. For example, ethylene is used to make ethylene dichloride, which, in turn, is used to make vinyl chloride. Ethyl benzene, made from benzene and ethylene, is used to make styrene. Methyl r-butyl ether is made from methanol and butylene, a captive intermediate for which production data is not available. [Pg.119]


See other pages where R-Butylated compounds is mentioned: [Pg.122]    [Pg.42]    [Pg.122]    [Pg.346]    [Pg.407]    [Pg.45]    [Pg.122]    [Pg.548]    [Pg.1402]    [Pg.345]    [Pg.630]    [Pg.50]    [Pg.122]    [Pg.42]    [Pg.122]    [Pg.346]    [Pg.407]    [Pg.45]    [Pg.122]    [Pg.548]    [Pg.1402]    [Pg.345]    [Pg.630]    [Pg.50]    [Pg.162]    [Pg.122]    [Pg.180]    [Pg.49]    [Pg.23]    [Pg.24]    [Pg.42]    [Pg.12]    [Pg.99]    [Pg.214]    [Pg.59]    [Pg.320]   
See also in sourсe #XX -- [ Pg.89 ]




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GeR4 Compounds with R Larger than Butyl

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R-butyl

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