Hydrocarbons, hydrocarbon oximes

Acids Esters polyhydroxy compounds oximes. and some aryl-alkyl hydrocarbons. hydrocarbons. ketones. Nitriles. 

In organic acid media, NaCNBHj is converted to acyloxycyanoborohydrides whose reactivity is comparable to that of NaBH4 in CF3COOH, especially concerning the reduction of imines to amines, tosylhydrazones to saturated hydrocarbons, oximes to hydroxylamines, or reductive amination. Depending on the substrate, NaBH4 or NaCNBHj is recommended (Sections 3.3.1, 3.3.4) [GNl]. 

Nitrosyl chloride reacts with aliphatic hydrocarbons at room temperature under the influence of light to give a complex mixture of substitution products. When the reaction is run on cyclohexane at —25°, however, the pure oxime hydrochloride crystallizes from the reaction mixture with virtually no side products. 

Oxime carbamates have high polarity and solubility in water and are relatively chemically and thermally unstable. They are relatively stable in weakly acidic to neutral media (pH 4-6) but unstable in strongly acidic and basic media. Rapid hydrolysis occurs in strongly basic aqueous solutions (pH > 9) to form the parent oxime/alcohol and methylamine, which is enhanced at elevated temperature. Additionally, oxime carbamates are, generally, stable in most organic solvents and readily soluble in acetone, methanol, acetonitrile, and ethyl acetate, with the exception of aliphatic hydrocarbons. Furthermore, most oxime carbamates contain an active -alkyl (methyl) moiety that can be easily oxidized to form the corresponding sulfoxide or sulfone metabolites. 

It is believed that SCR by hydrocarbons is an important way for elimination of nitrogen oxide emissions from diesel and lean-burn engines. Gerlach etal. [115] studied by infrared in batch condition the mechanism of the reaction between nitrogen dioxide and propene over acidic mordenites. The aim of their work was to elucidate the relevance of adsorbed N-containing species for the F>cNOx reaction to propose a mechanism. Infrared experiments showed that nitrosonium ions (NO+) are formed upon reaction between NO, NOz and the Brpnsted acid sites of H—MOR and that this species is highly reactive towards propene, forming propenal oxime at 120°C. At temperatures above 170°C, the propenal oxime is dehydrated to acrylonitrile. A mechanism is proposed to explain the acrylonitrile formation. The nitrile can further be hydrolysed to yield... 

On treatment with a base such as NaOMe or even LLAIH4, mono-cycloadducts of mesitonitrile oxide and polycyclic aromatic hydrocarbons have been cleaved to yield the corresponding oximes, which are oxidized to ketones by the Dess— Martin method. The same ketones have been obtained by reductive ring opening of the mono-cycloadducts with Raney Ni (438). 

HPO [Hydroxylamine phosphate oxime] A process for making caprolactam, an intermediate in the manufacture of polyamides. It differs from related processes, such as HSO, in producing less of the ammonium sulfate by-product. Developed by DSM Research, The Netherlands, operated by DSM Polymers and Hydrocarbons, and offered for license by Stamicarbon. 

Figure 16. Total ion current plot for the GC/MS analysis of selected aldehyde o-methyl oximes in the presence of fipyfold excess hydrocarbons. (Methoxime doublet peaks are from chromatographic resolution of syn and anti conformers.)...

The enthalpy of fomation of two such species has been measured, namely the cyclopropane and cycloheptane derivatives. The difference between the values for these two species, both as solids, is 238.1 kJmol . Is this difference plausible Consider the difference between the enthalpies of formation of the parent cycloalkanes as solids, 194 kJ mol . The ca 44 kJ mol discrepancy between these two differences seems rather large. However, there are idiosyncracies associated with the enthalpies of formation of compounds with three-membered rings and almost nothing is known at all about the thermochemistry of compounds with seven-membered rings. Rather, we merely note that a seemingly well-defined synthesis of cycloheptyl methyl ketone was shown later to result in a mixture of methyl methylcyclohexyl ketones, and superelectrophilic carbonylation of cycloheptane resulted in the same products as methylcyclohexane, namely esters of 1-methylcyclohexanecarboxylic acid. The difference between the enthalpies of formation of the unsubstituted alicyclic hydrocarbons cycloheptane and methylcyclohexane as solids is 33 kJmol . This alternative structural assignment hereby corrects for most of the above 44 kJ mol discrepancy in the enthalpies of formation of the two oximes. More thermochemical measurements are needed, of oximes and cycloheptanes alike. 

Thermolysis of tetrazole oximes (478) in a suitable hydrocarbon solvent, or pyrolysis without it, produces 3,5-disubstituted 1,2,4-oxadiazoles (480) (Scheme 75) (81BSB193 87BSB675 91MIP137367). in the case of 5-unsubstituted tetrazoles (478 R = H), the reaction goes by two concomitant pathways, which imply elimination of hydrazoic acid or nitrogen. 

Slightly alkaline solutions containing ketones or other acidic hydrocarbons often react with nitroprusside to give a red coloration, which rapidly fades. The resulting solution contains [(CN)5Fe(H20)] and the oxime of the organic compound [126]. 

To be consistent, the same conclusion should be drawn for the dimethyl-oxime complexes. The difficulty here is to answer the question as to why other flat, uncharged, molecules do not stack in a similar fashion. It is believed that in fact they would do so were it not for factors such as mutual repulsion of u-electrons, as in condensed hydrocarbons (214). An examination of the bond lengths shown in Fig. 10 indicates that in the dimethyl-glyoxime complexes the ir-bonding is not nearly so extensive as commonly imagined. Similarly, it is known that aromatic donor-acceptor complexes, e.g, quinhydrone, stack in a fashion very similar to the dimethylglyoximc complexes (166a), and also show abnormal dichroism (182). 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Many compounds have been tested as ignition quality improvers—additives which shorten the ignition delay to a desirable duration. An extensive review in 1944 (6, 43) listed 303 references, 92 dealing with alkyl nitrates and nitrites 61 with aldehydes, ketones, esters, and ethers 49 with peroxides 42 with aromatic nitro compounds 29, with metal derivatives 28 with oxidation and oxidation products 22 with polysulfides 16 with aromatic hydrocarbons nine with nitration and four with oximes and nitroso compounds. In 1950, tests at the U. S. Naval Engineering Experiment Station (48) showed that a concentration of 1.5% of certain peroxides, alkyl nitrates, nitroaikanes, and nitrocarbamates increased cetane number 20 or more units. 

In the solid state, the metal atoms in bis(salicylaIdoximato)copper(II) show two additional contacts with the oxime oxygens of adjacent molecules, resulting in a distorted octahedral structure. However, the axial Cu—O distance (2.66 A) is much longer than the metal—ligand distances in the square-planar array (Cu—O, 1.92 A and Cu—N, 1.94 A).154 Studies by ESR of copper(II) extracts of the commercial reagent SME 529 (14 R = Me, R = C9H)9) have shown that the copper complex exists as a square-planar species in hydrocarbon solutions, but that five-coordinate adducts are formed in the presence of ammonia or pyridine.155... 

Bis(salicylaldoximato)nickel(II) is diamagnetic in the solid state, but becomes partially paramagnetic in solution in chloroform157 and aqueous dioxane.151 This is likely to be due to molecular association or solvation,158 rather than to the adoption of a distorted tetrahedral structure in solution.151 The nickel(II) complex readily forms pseudo-octahedral bis-adducts in the presence of large amounts of amines,159 160 although analogous complexes of commercial orffto-hydroxy-oximes have been reported to retain the square-planar structure in hydrocarbon solution in the presence of moderate amounts of ammonia or aliphatic amines.161... 

Cis- and /ra s-isomers sometimes differ in their half-wave potentials, so that the individual isomers can be distinguished and in some instances their mixtures analysed. Differences in the values for cis- and trans-isomers have been reported for azocompounds (115, 116) (but cf. (117 bis 119)), oximes (120), unsaturated carbonyl compounds (121—123), unsaturated hydrocarbons (124), etc. In some cases, the heights of the waves of isomers at a given pH, or the pK values differ, so that mixtures of isomers can be analysed. This is possible for mixtures of fumaric and maleic acids (125—128), citraconic and mesaconic acids (125), etc. 

Acetochlor amide Acifluorfen-sodium phenyl ether Aclonifen phenyl ether Acrinathrin pyrethroid Alachlor amide Alanycarb oxime amide Aldicarb oxime amide Aldoxycarb oxime amide Aldrin halogenated hydrocarbon Allethrin pyrethroid Allidochlor amide Alloxydim oxime... 

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