- A 'meta effect' in the fragmentation reactions of ionised alkyl phenols and alkyl anisoles
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The competition between benzylic cleavage (simple bond fission [SBF]) and retro-ene rearrangement (RER) from ionised ortho, meta and para RC 6H4OH and RC6H4OCH3 (R = n-C3H7, n-C4H9, n-C5H11, n-C7H15, n-C9H19, n-C 15H31) is examined. It is observed that the SBF/RER ratio is significantly influenced by the position of the substituent on the aromatic ring. As a rule, phenols and anisoles substituted by an alkyl group in meta position lead to more abundant methylene-2,4-cyclohexadiene cations (RER fragmentation) than their ortho and para homologues. This 'meta effect' is explained on the basis of energetic and kinetic of the two reaction channels. Quantum chemistry computations have been used to provide estimate of the thermochemistry associated with these two fragmentation routes. G3B3 calculation shows that a hydroxy or a methoxy group in the meta position destabilises the SBF and stabilises the RER product ions. Modelling of the SBF/RER intensities ratio has been performed assuming two single reaction rates for both fragmentation processes and computing them within the statistical RRKM formalism in the case of ortho, meta and para butyl phenols. It is clearly demonstrated that, combining thermochemistry and kinetics, the inequality (SBF/RER) metaorthopara holds for the butyl phenols series. It is expected that the 'meta effect' described in this study enables unequivocal identification of meta isomers from ortho and para isomers not only of alkyl phenols and alkyl anisoles but also in other alkyl benzene series. Copyright
- Bouchoux, Guy,Sablier, Michel,Miyakoshi, Tetsuo,Honda, Takashi
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p. 539 - 546
(2012/09/22)
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- The separation and synthesis of lipidic 1,2- and 1,3-diols from natural phenolic lipids for the complexation and recovery of boron
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A study has been made of the semi-synthesis of 1,3-diols (anacardic alcohols) from natural phenolic lipid resources from Anacardium occidentale and Anacardium giganteum which have given C15 and C11 derivatives, respectively. An isomeric 1,3-diol (isoanacardic alcohol) has been obtained from cardanol separated from technical cashew nut-shell liquid. Homologous1,3-diols have been synthesised from a range of synthetic 2-alkyl-, 3-alkyl- and 4-alkylphenols and from 6-alkylsalicylic acids. The natural 1,2-diol, urushiol, from Rhus vernicifera has been purified. All these lipidic compounds have been studied for their complexation and the potential recovery of boron as boric acid.
- Tyman, John H.P.,Mehet, Satinderjit K.
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p. 177 - 199
(2007/10/03)
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- Alkylphenol synthesis using heteropoly acid catalysts
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Disclosed is a one step method for synthesis of alkylphenols which comprises reacting phenol with the corresponding olefin under adiabatic conditions in the presence of a catalyst comprising a heteropoly acid represented by the structure: where x=P or Si, M=Mo or wv and n is an integer which is 4 or 5, alone, or deposited on an inert support, at a temperature of from 60° C. to 250° C. and a pressure of from near atmospheric to about 500 psi.
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- Mannich reaction products derived from alkenyl succinic acid anhydride, a polyamine and sulphur linked alkylphenols and their use as lubricants
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Disclosed is a mannich reaction product which is obtainable by reacting an alkenyl succinic acid or an alkenyl succinic anhydride, a polyamine, an aldehyde and a sulfurized alkylphenol represented by the general formula (I). wherein R2 indicates an alkyl group having 4 to 25 carbon atoms, m indicates an integer of 1 to 8, x indicates 1 or 2, and z indicates an integer of 1 to 9. Useful as a detergent-dispersant which has excellent stability at high temperatures and has an oxidation stability, a detergent-dispersant containing the same, a process of producing it, and fuel oil and lubricating oil compositions comprising it.
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- Preparation of nonionic surfactants by oxyalkylation with a phenolic activated magnesium catalyst
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Nonionic surfactants containing a narrow molecular weight distribution is obtained by the use of a magnesium-containing catalyst which comprises reacting a reactive hydrogen compound selected from the group consisting of monohydric alcohols having from about 6 to 30 carbon atoms with an alkylene oxide having from 2-4 carbon atoms at a temperature at which the reaction proceeds in the presence of at least a catalytic amount of a phenolic activated magnesium catalyst containing phosphorus.
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- Epoxy pyrrolidone based non-ionic surfactants
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The invention relates to compounds having the formula: STR1 wherein X is STR2 B is C8-24 alkyl--; STR3 Y and Z are each H or C1-12 alkyl; m is an integer having a value of 1 to 100; n is an integer having a value of 2 to 50; p is an integer having a value of 0 or 1; s is an integer having a value of 1 or 2; R' is H or CH3 and A is H or STR4 wherein R" is hydrogen or methyl and r is an integer having a value of from 1 to 100. The invention also relates to the process for the preparation of said compounds, as well as the process of using them as a surfactant or complexing agent and compositions therefor.
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- Process for treating 2-ethylhexyl p-methoxycinnamate in the presence of a phenol
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A process for treating 2-ethylhexyl p-methoxycinnamic acid ester is described. The process comprises heating, preferably distilling, the ester in the presence of a phenol to insure that the ester is considered Ames negative.
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- Catalysts for alkoxylation reactions
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Catalysts producing a sharply peaked alkoxylation distribution during the alkoxylation of organic materials comprise mixtures of BF3 and metal alkyls or metal alkoxides, SiF4 and metal alkyls or metal alkoxides, or mixtures of these catalysts.
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- Methods of alkoxylation
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Catalysts comprising mixtures of HF and metal alkoxides and mixed metal alkoxides produce a sharply peaked alkoxylation distribution during the alkoxylation of organic materials.
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- Catalysts for alkoxylation reactions
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Catalysts and a method of using said catalysts for the alkoxylation of a variety of materials is disclosed. Catalysts so described produce alkoxylates having a very sharp alkoxylate distribution. The catalysts are supported and unsupported dialkoxy and dialkyl metal fluorides and halides and alkyl metal difluorides and dihalides.
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- Dispersion of aromatic isocyanatosulfonic acid uretdiones in organic polyisocyanates and a process for their preparation
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The instant invention is directed to non-sedimenting dispersions of finely divided solid aromatic isocyanatosulfonic acid uretdiones in non-sulfonic polyisocyanates and a process for their preparation.
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- Oximes
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O-Hydroxyphenyl benzyl ketoximes, preferably containing as substituents one or more alkyl or alkoxy groups containing a total of from 3 to 25 carbon atoms, are used to extract metals from aqueous solutions of their salts as complex compounds soluble in water-immiscible organic solvents. The ketoximes are prepared from the corresponding ketones by reaction with hydroxylamine.
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