Hydrocarbons reaction with acetonitrile

By analogy with their behavior in mass spectrometry, branched hydrocarbons are cleaved when oxidized in CH3 CN/TEABF4 at —45 °C. The resulting acetamides of the fragments (Table 6) are formed by cleavage of the initial radical cation at the C,C bond between the secondary and tertiary C atom, to afford after a second electron transfer, carbocations, which react in a Ritter reaction with acetonitrile [29]. 

Nitrobenzenes react with potassium cyanide in the presence of cetyltrimethylammo-nium bromide to yield benzonitriles [71], The reaction also requires the presence of chloro substituents on the ring and at least two nitro groups (Table 2.9). Diazosulphides, ArN=NSPh, are converted into the benzonitriles, ArCN, by a photochemically induced SRN1 reaction with tetra-n-butylammonium cyanide [72, 73], Yields vary from <20% to >70%. Photocyanation of aromatic hydrocarbons has been achieved using tetra-n-butylammonium cyanide in acetonitrile or dichloromethane [74, 75]. 

Reactions between aromatic hydrocarbon radicabcations and cyanide ions, with few exceptions, give low yields of nuclear substitution products [76], In some cases, better results have been obtained by anodic oxidation of the aromatic compound in an emulsion of aqueous sodium cyanide and dichloromethane with tetra-butylammonium hydrogen sulphate as a phase transfer agent [77, 78]. Methoxy-benzenes give exceptionally good yields from reactions in acetonitrile containing tetraethylammonium cyanide, sometimes with displacement of methoxide [79, 80]... 

Aliphatic ketones are oxidised in both acetonitrile [1,2] and trifluoracetic acid [3] at potentials less positive than required for the analogous hydrocarbons. The oxidation process is irreversible in both solvents and cyclic voltammetry peak potentials are around 2.7 V V5. see. Loss of an electron from the carbonyl oxygen lone pair is considered to be the first stage in the reaction. In acetonitrile, two competing processes then ensue. Short chain, a-branched ketones cleave the carbon-carbonyl bond to give the more stable carbocation, which is then quenched by reaction with... 

The above reactions proceed via free radical coupling. An alternative system for photochemically driven hydrocarbon functionalization evidently proceeds via the carbanion, which is obtained from reduction of the initially formed free radical3. The carbanion reacts with acetonitrile to give, after in situ hydrolysis, the methyl ketone, e.g., formation of (tricyclo[3.3.1.13-7]dec-1-yl)ethanone6. 

The hydrocarbons 52a-52e and 52g contain four G=C double bonds. In addition to the conjugated diene unit, two isolated bonds are present. The exocyclic one is parallel and the endocyclic one is perpendicular to the local plane of symmetry of the diene portion. When the hydrocarbons 52a-52e and 52g are recoordinated to chromium by the reaction with tris(acetonitrile)-tricarbonylchromium(0) (55) [Eq. (32)], the complexes 46 are not obtained... 

The formation of the dicyclopropylmercury alone or in combination with the adsorbed radical type intermediates accounts for the observation that the substrate disappears at a faster rate than the reduction product appears The dicyclopropylmercury can then accept an electron to produce the anion and a cyclopropylmercury radical which in combination with the mercury surface becomes an adsorbed radical (equation 7) which can be recycled through the pathway of equation 5 or equation 6. The anions formed in equation 3, equation 5, and equation 7 react at the surface with acetonitrile solvent (equation 8) to yield the hydrocarbon. When deuterated acetonitrile was used the hydrocarbon isolated contained 76% deuterium The anion can also react with the electrolyte, tetraethylammonium bromide, in an elimination reaction (equation 9) to produce hydrocarbon, ethylene and triethylamine, all of which have been identified in the reaction mixture ... 

The electro-oxidation of an aromatic hydrocarbon containing a benzylic hydrogen, using solutions of perchlorates, tetrafluoroborates, or hexafluorophosphates in acetonitrile as the electrolyte, results in the formation of an acetamido derivative. This is essentially the electrochemical analog of the Ritter reaction. Again direct oxidation of the aromatic molecule has been regarded as the initial step in the overall reaction, e.g., in the reaction with toluene (II) (Scheme 2). Increasing amounts of the nucleophile, water. 

The action of n-butyllithium in THF at low temperature leads to the anion. After reaction with an electrophilic compound, the hydrolysis can generally be carried out in polar solvents (acetone, alcohols, acetonitrile) in the presence of mercury(II) chloride or oxide and water. In other cases, NBS, - chloramine T, cerium(IV) ammonium nitrate, n-tributyltin hydride, trialkyloxonium tetrafluthallium nitrate or photochemistry can be used. Desulfurization by Raney nickel gives hydrocarbons. ... 

Another metallocene, namely, decamethylosmocene, (Mc5C5)20s (catalyst 1.2), turned out to be a good precatalyst in a very efficient oxidation of alkanes with hydrogen peroxide in acetonitrile at 20 — 60 °C [9]. The reaction proceeds with a substantial lag period that can be reduced by the addition of pyridine in a small concentration. Alkanes, RH, are oxidized primarily to the corresponding alkyl hydroperoxides, ROOH. TONs attain 51,000 in the case of cyclohexane (maximum turnover frequency was 6000 h ) and 3600 in the case of ethane. The oxidation of benzene and styrene afforded phenol and benzaldehyde, respectively. A kinetic study of cyclohexane oxidation catalyzed by 1.2 and selectivity parameters (measured in the oxidation of n-heptane, methylcyclohexane, isooctane, c -dimethylcyclohexane, and trans-dimethylcyclohexane) indicated that the oxidation of saturated, olefinic, and aromatic hydrocarbons proceeds with the participation of hydroxyl radicals. 

As mentioned in Section 9.3, nitroisoxazolone 10 serves as a precursor of carbamoylnitrile oxide 6, which undergoes the cycloaddition with unsamrated hydrocarbons in a mixed solvent system (acetonitrile/water, 3/1, v/v) to afford isoxa-zoles 16 and isoxazolines 18. During a survey of reaction conditions, a trace amount of oxadiazole 28a (Figure 9.1) is detected in a reaction mixture (reaction temperature, 80 °C). The formation of 28a provides cmcial evidence for the cycloaddition of nitrile oxide 6 with acetonitrile 29a, which proceeds under relatively mUd conditions without any activation. 

Amm oxida tion, a vapor-phase reaction of hydrocarbon with ammonia and oxygen (air) (eq. 2), can be used to produce hydrogen cyanide (HCN), acrylonitrile, acetonitrile (as a by-product of acrylonitrile manufacture), methacrylonitrile, hen onitrile, and toluinitnles from methane, propylene, butylene, toluene, and xylenes, respectively (4). 

Irradiation of ethyleneimine (341,342) with light of short wavelength ia the gas phase has been carried out direcdy and with sensitization (343—349). Photolysis products found were hydrogen, nitrogen, ethylene, ammonium, saturated hydrocarbons (methane, ethane, propane, / -butane), and the dimer of the ethyleneimino radical. The nature and the amount of the reaction products is highly dependent on the conditions used. For example, the photoproducts identified ia a fast flow photoreactor iacluded hydrocyanic acid and acetonitrile (345), ia addition to those found ia a steady state system. The reaction of hydrogen radicals with ethyleneimine results ia the formation of hydrocyanic acid ia addition to methane (350). Important processes ia the photolysis of ethyleneimine are nitrene extmsion and homolysis of the N—H bond, as suggested and simulated by ab initio SCF calculations (351). The occurrence of ethyleneimine as an iatermediate ia the photolytic formation of hydrocyanic acid from acetylene and ammonia ia the atmosphere of the planet Jupiter has been postulated (352), but is disputed (353). 

Tetracyanoethylene oxide [3189-43-3] (8), oxiranetetracarbonitnle, is the most notable member of the class of oxacyanocarbons (57). It is made by treating TCNE with hydrogen peroxide in acetonitrile. In reactions unprecedented for olefin oxides, it adds to olefins to form 2,2,5,5-tetracyanotetrahydrofuran [3041-31-4] in the case of ethylene, acetylenes, and aromatic hydrocarbons via cleavage of the ring C—C bond. The benzene adduct (9) is 3t ,7t -dihydro-l,l,3,3-phthalantetracarbonitrile [3041-36-9], C22HgN O. 

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