Ethylenes nitroso

Reactions with Organic Compounds. Tetrafluoroethylene and OF2 react spontaneously to form C2F and COF2. Ethylene and OF2 may react explosively, but under controlled conditions monofluoroethane and 1,2-difluoroethane can be recovered (33). Benzene is oxidized to quinone and hydroquinone by OF2. Methanol and ethanol are oxidized at room temperature (4). Organic amines are extensively degraded by OF2 at room temperature, but primary aHphatic amines in a fluorocarbon solvent at —42°C are smoothly oxidized to the corresponding nitroso compounds (34). 

Treatment of the heterocycle, 38 (obtained from ethylene-diamine and carbon disulfide), with nitrous acid affords the N-nitroso compound, 39. Reduction with zinc leads to the corre-... 

N( 1 -Methyl-3-oxobutylidene)-N -( 1 -methyl-2-nitroso-3-oxobutylidene)ethylene-diaminecopperl ii)... 

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

There is a tendency toward alternation in the copolymerization of ethylene with carbon monoxide. Copolymerizations of carbon monoxide with tetrafluoroethylene, vinyl acetate, vinyl chloride, and acrylonitrile have been reported but with few details [Starkweather, 1987]. The reactions of alkenes with oxygen and quinones are not well defined in terms of the stoichiometry of the products. These reactions are better classified as retardation or inhibition reactions because of the very slow copolymerization rates (Sec. 3-7a). Other copolymerizations include the reaction of alkene monomers with sulfur and nitroso compounds [Green et al., 1967 Miyata and Sawada, 1988]. 

Octahydroazocine (1) behaves as a typical secondary amine and forms an azeotrope with water, b.p. 96 °C (52M386). It can be transformed into 1-nitroso and 1-amino derivatives in the usual way (74JMC948). The imine (1) can also be cyanoethylated, and adds ethylene oxide (59MI51900) to give the N- hydroxyethyl derivative. Attempts to convert (1) to an enamine by oxidation with silver acetate gave only a low yield of pyridine (52M386). 

Ethylenedioxybutyl)-3-trichloro-acetamido 1 cyclohexene, 58, 9, 11 Ethylene, 1,1-diphenyl-, 56, 32 Ethylene glycol, 56, 44 Ethylene glycol, phenyl-, 55, 116 Ethylene, tetramethyl-, 56, 35 Ethyl-or-fluoro-l-naphthaleneacetate, 57, 73 Ethyl 2-fluoropropanoate, 57, 73 3-Ethylhexane, 58, 3, 4 3-ETHYL-1-HEXYNE, 58,1, 2, 3, 4 Ethyl levuhnates, 5-substituted, 58, 81 Fthyl nitrite, 58, 113, 115 Ethyl V-nitroso-A-fp-tolylsulfonylmethyl)-carbamate, 57, 96 3-Ethyl-3-pentanol, 58, 25, 26, 31 3-Ethyl-3-pentyl alcohol, 58, 78 3-Ethyl-3-pentyl fluoride, 58, 78 Ethyl A -(p-tolylsulfonylmethyl)carbamate, 57, 95... 

N-Nitro-N -nitroso-N,N -dicylohexyl-ethylene-diamine or N,N -DicycIohexyl-N-nitro-N -nitroso-l,2-diaminoethane,... 

Oxazetidines have been obtained by [2 + 2] addition of nitroso compounds to appropriate alkenes. Trifluoronitrosomethane reacts with polyhalogenated ethylenes (69JCS(C)2ll9), with styrene (65JGU855) or with allenes (73JCS(Pi)l56l) to give oxazetidines (e.g. Scheme 7). 

Diethyizinc is changed to an active catalyst for the polymerization of ethylene oxide and propylen oxide by reacting it with an appropriate amount of water, alcohol, acetone, amine, nitro compound, or nitroso compound. This type of catalyst gives high molecular weight (over one million) polymers from ethylene oxide and propylene oxide. 

The interaction of aryldiazonium tetrachlorocuprates [Cu(II)] with olefins has been studied by ESR spectroscopy using the spin-trapping technique (Lyakhovich et al. 1991). The radicals ArCH2CH( )Ph and ArCH2CH( )CN have been detected in mixtures of the aryldiazonium tetrachlorocuprates [Cu(II)] with styrene and acrylonitrile using nitroso-durene as a spin adduct. However, aryl radical signals were not detected under those conditions. Obviously, aryl radicals react with the nearby ethylenic bond within the activated... 

Molecular orbital computational analysis by PM3 CI UHF semiempirical methods have been used to support the contention that preferable HSOMO-LUMO interactions produce a favored biradical and explain the site selectivity in the sensitized photochemical [2 + 2] cycloadduct formation of 2-pyrones with electron-deficient ethylenes <92BCJ354>. The lowest ionization energies, dipole moment, and dominant electronic configurations of a 5-methylidenated version of 7-nitroso-oxazolo[4,5- ]cyclopenta[e]pyrimidine of unknown origin were calculated by the ADC(3) ab initio method <92CPHii>. An extensive semiempirical and ab initio investigation into the mechanism of oxidation of methanol by PQQ is cited in Section 7.22.12.4. 

The hetero Diels-Alder reaction of nitrosoalkenes with electron-rich olefins has been known for a long time [363]. A detailed mechanistic study carried out by Reissig et al. has given evidence that this inverse electron demand cycloaddition is a concerted process [364]. Recent ab initio calculations dealing with the reaction between ethylene and nitroso ethylene strongly corrobate this view [365]. In this work, Jursic and Zdravkovski have also investigated the influence of BH3 as Lewis acid catalyst. However, cycloadditions of nitrosoalkenes already pro-... 

N-nilrosoaniline in fair yield. Bumgardner attempted to convert aziridine into the N-nitroso derivative by this method but isolated only ethylene and nitrous oxide. 

Allhtnigh the rate of reaction of olefins with nitrosyl chloride decreases with ilecreiising number of alkyl substituents, crystalline nitroso chlorides (dimeric) have been obtained even from ethylene and propylene. ... 

In conclusion, an illuminating insight of the reaction path is obtained by means of a rather naive, but inexpensive method of computation. Other reactions studied along these lines, include the addition of methylene to ethylene 76>, addition and insertion of sulfur to ethylene 77>, dimerization of methylenes and nitroso compounds 78> fragmentation of cyclo-butane to ethylenes 79>, the Cope rearrangement 80>, the interaction of tricycloalkanes with acids and bases 81>, and the polytopal rearrangements in (CH)s, (CH)i, and (CH CO systems 82). 

Another valuable approach to 1,2-oxazines makes use of the N=0 group as part of the diene. Thus, nitroso ethylene (5.10) is reactive to an enol ether in another case of cycloaddition with inverse electron demand (Scheme 5.12). 

Scheme 10.18. A cartoon representation of the decomposition of Af-nitroso-A,A.A-triethylamine by various pathways to A-nitroso-A -diethylamine [(CH3CH2)2N-NO] and then to (a) ethanol (CH3CH2OH), (b) ethanal (acetaldehyde, CH3CHO), and (c) ethene (ethylene, H2C=CH2) along with a variety of oxides of nitrogen.

As in the case of nitroso compounds, sometimes it is the metal itself which acts as a deoxygenating agent of the nitro group. The reaction of N,N -ethylene-bis(salicilideneiminato)iron(II), Fe(Salen), with RNO2 (R = alkyl, aryl) leads to deoxygenation at room temperature (eqs. 18 and 19) [68] ... 

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