Alkenes nitromethane

The telomer obtained from the nitromethane 65 is a good building block for civetonedicarboxylic acid. The nitro group was converted into a ketone, and the terminal alkenes into carboxylic acids. The acyloin condensation of protected dimethyl dvetonedicarboxylate (141) afforded the 17-membered acyloin 142, which was modified to introduce a triple bond 143. Finally, the triple bond was reduced to give civetone (144)[120). 

A nitromethane/aluminium chloride complex had been prepared. A gaseous alkene was added to the complex the pressure reached 5.6 bar and the temperature 2°C. The medium had been stirred at the beginning of the operation and then intemupted. A temperature rise caused the autoclave to detonate and the medium to carbonise entirely. 

The stereochemistry of addition of hydrogen halides to alkenes depends on the structure of the alkene and also on the reaction conditions. Addition of hydrogen bromide to cyclohexene and to E- and Z-2-butene is anti.6 The addition of hydrogen chloride to 1 -methylcyclopentene is entirely anti when carried out at 25° C in nitromethane.7... 

The Michael reaction of benzylidene acetophenone and benzylidene acetone with ethyl acetoacetate, nitromethane, and acetylacetone was studied by Musaliar and co-workers in the presence of a cetyltrimethy-lammonium bromide-containing aqueous micellar medium.50 The Michael reaction of various nitro alkanes with electrophilic alkenes is performed in NaOH (0.025-0.1 M) in the presence of cetyltrimethylam-monium chloride (CTACI) without any organic solvent (Eq. 10.23).51... 

Aluminium chloride, Nitromethane See Aluminium chloride-nitromethane An alkene... 

Primary nitro ketones, ethyl nitroacetate, and (phenylsulfony l)nitromethane react with alkenes in the presence of Lewis acids to give nitrile oxide cycloaddition.61a Similarly, the reaction of a-nitro ketones with TeCl4 generates the corresponding nitrile oxides, as shown in Eq. 6.36.61b... 

The addition to alkenes of radicals derived from an a-nitroketone is also catalysed by manganese(III) [30]. During the reaction between a-nitroacetophenone 8 and m-but-2-ene, the stereochemical relationship between the methyl substituents is not preserved. The process terminates with the formation of a nitrone. A related process will generate nitromethyl radicals from nitromethane and these add to benzene to give phenyinitromethane [31],... 

The direct electrochemical oxidation of phenols generates phenoxonium cations which are able to undergo [3-1-2] cycloaddition in the presence of unactivated alkenes to produce benzofurans <1999JOC7654>. Thus, electrolysis of methyl 2,5-dihydroxybenzoate in a solution of lithium perchlorate in nitromethane in the presence of acetic acid and 2-methyl-2-butene produces the dihydrobenzofuran in excellent yield (Equation 88). 

Some novel bicyclic pyrylium salts arise when a dicarboxylic acid derivative is used. For example, although decanedioyl chloride did not diacylate isobutene, possibly because of strain inherent in the expected product, 1,12-dodecanedioyl chloride gave a very low yield of the pyrylium salt (658) (62T1079). A dilute solution of the reactants in nitromethane was used in order to favour the intramolecular reaction. In a similar vein, a macrocyclic alkene, such as cyclododecene, undergoes diacylation to the bicyclic salt (659) (68TL4643), whilst... 

S,y-Unsaturated a-keto esters such as tnms -MeCH=CHCOCC>2Et undergo enan-tioselective reaction with nitromethane, using new catalytic auxiliaries based on cinchona alkaloids.145 Carried out at -20 °C in DCM, the organocatalysts give high conversion, predominantly reaction at ketone only (typically <5% of product involves simultaneous addition to the alkene), and up to 97% ee. 

A gaseous alkene was passed into a cooled autoclave containing the complex, initially with agitation, and later without. Later, when the alkene was admitted to a pressure of 5.6 bar at 2°C, a slight exotherm occurred, followed by an explosion. The autoclave contents were completely carbonised. Mixtures of ethylene, aluminium chloride and nitromethane had exploded previously, but at 75°C. 

Mixtures of ethylene and aluminium chloride, initially at 30—60 bar, rapidly heat and explode in presence of supported nickel catalysts, methyl chloride or nitromethane. See Aluminium chloride Alkenes... 

A Knoevenagel reaction is a condensation reaction between an active-methylene compound (or the comparably C,I I-acidic nitromethane) and a carbonyl compound. The product of a Knoevenagel reaction is an alkene that contains two geminal acceptor groups (B in Figure 13.52) or one nitro group (B in Figure 13.53). 

One-pot synthesis of ( )-alkenes has been directly performed from nitromethane by a radical process (Liu and Yao, 2001). In fact, the strategy is to react P-nitrostirene (3) as shown in Figure 2.1, in situ prepared from aromatic aldehydes (1) with nitromethane (2) in the acetic acid solution with a catalytic amount of ammonium acetate at 70-100°C, with triethylborane in the biphase of diethyl ether and aqueous solution in the presence of oxygen in air as radical initiator, to generate (4). 

Michaud, D., Texier-BouUet, F., and Hamelin, J. 1997a. Michael monoaddition of nitromethane on gem-diactivated alkenes in dry media coupled with microwave irradiation. Tetrahedron letters, 38 7563-64. 

The interaction of HC1 with an alkene in a non-polar medium results in a simple addition of the hydrogen halide. The centre generated from the proton and monomer is immediately deactivated by the strongly basic and mobile Cl-. In a solvating medium, e.g. nitromethane, styrene oligomerizes in the presence of HC1 [91 ]. Thus the combination of the solvated ions is relatively slow so that propagation can compete with it. 

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