cas 128-39-2, 2,6-Di-tert-butylphenol | Articles data

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Oxidation of 2,6-Di-tert-butylphenol by Molecular Oxygen. 2. Catalysis by Cobaltous Polyamine Chelates through Their (μ-Peroxo)- and (μ-Peroxo)(μ-hydroxo)dicobalt(III) Complexes
The oxidation of 2,6-di-tert-butylphenol by molecular oxygen is catalyzed by the cobaltous chelates of tetraethylenepentamine (TETREN), dipicolyldiethylenetriamine (PYDIEN), and 1,4,10,13-tetraaza-7-thiatridecane (TATTD), through their (μ-peroxo)dicobalt(III) complexes and by those of dipicolylethylenediamine (PYEN), tris(aminoethyl)amine (TREN), and triethylenetetramine (TRIEN) through their (μ-hydroxo)(μ-peroxo)dicobalt(III) complexes.Reaction products are identified as the oxidative coupling product 3,3'5,5'-tetra-tert-butyldiphenoquinone and the partial oxygen insertion product, 2,6-di-tert-butylbenzoquinone.The rates of reaction of the substrate as well as the formation of products are shown to be first order with respect to the concentrations of both the cobalt-dioxygen complex and the substrate.The reaction with (4+) does not occur in the absence of free molecular oxygen in solution and occurs at a reduced rate under air relative to oxygen.
Bedell, Stephen A.,Martell, Arthur E.
p. 7909 - 7913
(1985)
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Formation and properties of a catalyst based on sodium and potassium hydroxides in the reaction of 2,6-di-tert-butylphenol with methyl acrylate
The nature of the cation (K+ or Na+) in hydroxides affects the temperature plot of the equilibrium constant of the reaction of KOH and NaOH with 2,6-di-tert-butylphenol (ArOH) and the conversion of KOH and (or) NaOH to potassium or sodium 2,6-di-tert-butyl phenoxides, which are catalysts for the alkylation of ArOH by methyl acrylate. The kinetic method for determination of the composition of the catalyst formed from NaOH and ArOH was proposed. The nature of the cation in phenoxides ArOK or ArONa is a factor determining the kinetics of the reaction of ArOH with methyl acrylate. Two different kinetic schemes were proposed to describe the transformation of ArOH in the presence of ArONa or ArOK.
Volod'kin,Zaikov
p. 2189 - 2195
(2002)
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Ethylene/hindered phenol substituted norbornene copolymers: Synthesis and NMR structural determination
A new family of ethylene-based copolymers with controlled amounts of a norbornene comonomer (NArOH) bearing a stabilizing antioxidant functionality (2,6-di-tert-butyl phenol) was prepared. Due to unavoidable exo/endo equilibrium operative in NArOH comonomer, a complete and detailed NMR assignment of the structure of the prepared ethylene/N ArOH copolymers was carried out for the determination of the exo/endo ratio inside the polymer. These novel functionalized comonomers can be considered suitable starting material for preparing ethylene-based copolymers, with tunable comonomer content, as non-releasing macromolecular antioxidant additives for specific application in safe food and/or drug packaging 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 Copolymers of ethylene with an antioxidant phenolic functionalized norbornene comonomer have been prepared and their structure fully determined by NMR. These novel materials can be used as non-releasing macromolecular antioxidant additives for specific application in safe food and/or drug packaging. Copyright
Viglianisi, Caterina,Menichetti, Stefano,Assanelli, Giulio,Sacchi, Maria Carmela,Tritto, Incoronata,Losio, Simona
p. 4647 - 4655
(2012)
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Tertiary butylation of phenol on Cu1-xCoxFe 2O4: Catalysis and structure-activity correlation
A systematic study of catalytic tertiary butylation of phenol was carried out with isobutene as a function of temperature, feed composition, time on stream, space velocity, and catalyst composition on Cu1-xCo xFe2O4 (x=0 to 1) system. Tertiary butylation of phenol gives three products, namely, 2-tert-butyl phenol, 4-tert-butyl phenol, and 2,4-di-tert-butyl phenol. The phenol conversion and selectivity of these products depend on the reaction parameters. A good correlation was found between the activity, in terms of phenol conversion and various product selectivities for this reaction, and the acid-base properties of the catalysts. High activity is achieved with x=0.5 composition, illustrating the importance of a 1:1 combination of Cu and Co and the necessity for optimum concentrations of acid-base centers for this reaction. A reaction mechanism involving the interaction of phenoxide from phenol and the tert-butyl cation from isobutene on Cu1-xCoxFe2O4 is proposed. X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopic analysis of fresh and spent catalysts revealed a partial reduction of metal ions due to reaction. Valence band studies clearly revealed an increase in the overlap of metal ion 3d bands from fresh to spent catalysts as reflected from a large decrease in the energy gap between them. The better catalytic results observed with x=0.5 are attributed to an optimum distribution of Cu species with heteroatom neighbors, maximum overlap between the Cu and Co 3d bands, and intermediate acid-base character.
Mathew, Thomas,Rao, Bollapragada S.,Gopinath, Chinnakonda S.
p. 107 - 116
(2004)
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Highly efficient alkylation of phenol with tert-butyl alcohol using environmentally benign Bronsted acidic ionic liquids
A series of SO3-H functionalized environmentally benign Bronsted acidic ionic liquids were prepared using triethylamine, 1-methyl imidazole, pyridine, diethanolamine, 1,4-butane sultone and methane sulfonic acid as the starting materials. These synthesized ionic liquid catalysts were characterized using spectroscopic tools like 1H NMR, 13C NMR. The catalytic activity of the synthesized ionic liquids was investigated in tert-butylation of phenol with tert-butyl alcohol. The effect of kinetic parameters like reaction time, reaction temperature, reactant mole ratio, reactant to catalyst mole ratio, on the conversion of phenol and selectivity to 2-tert-butyl-phenol and 2,4-di-tert-butyl-phenol were investigated. Phenol conversion upto 94.2% was achieved at temperature as low as 80 °C and low alcohol to phenol molar ratio of 2:1, ionic liquid to phenol ratio of 1:1 and reaction time of 2 h. The catalyst was found to retain its activity even after 8 recycles and was completely recoverable. The plausible reaction mechanism was formulated based on product distribution. The kinetic data was found to agree well with classical phenomenological models and the kinetic parameters were estimated. The experimental results were further validated by Density Functional Theory (DFT) optimizations of the ionic liquid structures performed at the B3LYP/6-311G??level using Gaussian 09 package.
Patra, Tanmoy,Ahamad, Salahuddin,Upadhyayula, Sreedevi
p. 228 - 236
(2015)
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Synthesis and structural characterization of a 4-coordinate molybdenum(VI) dioxo diaryloxide, MoO2(O-2,6-t-Bu2C6H3)2·Ho-2,6-t-Bu2C6H3
The facile solution synthesis and spectroscopic and structural characterization of 4-coordinate MoO2(OAr)2. ArOH (1) where Ar = 2,6-di-tert-butylphenyl are described. MoO2(O-2,6-t-Bu2C6H3)2·HO-2,6-t-Bu2C6H3 (1) was synthesized by addition of LiOAr to MoO2Cl2 in CH3CN. Yields are reduced by concurrent oxidation of the phenolic anion to form 3,3',5,5'-tetra-tert-butyl-4,4'-diphenoquinone (4). Relatively strong Mo=O double bonds and p-electron donation from the aryloxide oxygens appear to compensate for the unsaturation of the pseudotetrahedral metal center.
Hanna, Tracy A.,Incarvito, Christopher D.,Rheingold, Arnold L.
p. 630 - 631
(2000)
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Guaiacol demethoxylation catalyzed by Re2O7 in ethanol
Re2O7 is used to convert guaiacol in alcohols at 280–320 °C. In ethanol, guaiacol is deoxygenated and alkylated, and the major products are phenol and alkylphenols (including ethylphenol, diethylphenol, diisopropylphenol, di-tert-butylphenol and 2,6-di-tert-butyl-4-ethylphenol), accounting for 97 mol% of all products after 6 hour reaction at 320 °C. Both catechol and phenol are the intermediates of guaiacol demethoxylation. Among the substituents, ethyl is directly provided by ethanol while isopropyl and tert-butyl are formed by the addition of methyl to ethyl step by step. In addition, Re2O7 has negligible activity for the saturation of benzene ring so it does not cause considerable over-consumption of reductant. The actual catalyst for guaiacol demethoxylation is likely a ReIV?VI species.
Yan, Fei,Sang, Yushuai,Bai, Yunfei,Wu, Kai,Cui, Kai,Wen, Zhe,Mai, Fuhang,Ma, Zewei,Yu, Linhao,Chen, Hong,Li, Yongdan
p. 231 - 237
(2019/08/12)

Alkylation of Phenols with tert-Butanol Catalyzed by H-Form of Y Zeolites with a Hierarchical Porous Structure
tert-Butyl-substituted phenols have been synthesized via the reaction of phenol, o-, m-, and p-cresols with tert-butanol under the action of CBr4-promoted Y-zeolites in the H-form with a hierarchical porous structure.
Bayguzina,Makhiyanova,Khazipova,Khusnutdinov
p. 1554 - 1559
(2019/10/14)

Ambident Reactivity of Phenolate Anions Revisited: A Quantitative Approach to Phenolate Reactivities
Prompted by the observation that the regioselectivities of phenolate reactions (C versus O attack) are opposite to the predictions by the principle of hard and soft acids and bases, we performed a comprehensive experimental and computational investigation of phenolate reactivities. Rate and equilibrium constants for the reactions of various phenolate ions with benzhydrylium ions (Aryl2CH+) and structurally related quinone methides have been determined photometrically in polar aprotic solvents. Quantum chemical calculations at the SMD(MeCN)/M06-2X/6-31+G(d,p) level confirmed that O attack is generally favored under kinetically controlled conditions, whereas C attack is favored under thermodynamically controlled conditions. Exceptions are diffusion-limited reactions with strong electrophiles, which give mixtures of products arising from O and C attack, as well as reactions with metal alkoxides in nonpolar solvents, where oxygen attack is blocked by strong ion pairing. The Lewis basicity (LB) and nucleophilicity (N, sN) parameters of phenolates determined in this work can be used to predict whether their reactions with electrophiles are kinetically or thermodynamically controlled and whether the rates are activation- or diffusion-limited. Comparison of the measured rate constants for the reactions of phenolates with carbocations with the Gibbs energies for single-electron transfer manifests that these reactions proceed via polar mechanisms.
Mayer, Robert J.,Breugst, Martin,Hampel, Nathalie,Ofial, Armin R.,Mayr, Herbert
p. 8837 - 8858
(2019/07/08)

Highly selective conversion of guaiacol to: Tert -butylphenols in supercritical ethanol over a H2WO4 catalyst
The conversion of guaiacol is examined at 300 °C in supercritical ethanol over a H2WO4 catalyst. Guaiacol is consumed completely, meanwhile, 16.7% aromatic ethers and 80.0% alkylphenols are obtained. Interestingly, tert-butylphenols are produced mainly with a high selectivity of 71.8%, and the overall selectivity of 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-4-ethylphenol is as high as 63.7%. The experimental results indicate that catechol and 2-ethoxyphenol are the intermediates. Meanwhile, the WO3 sites play an important role in the conversion of guaiacol and the Br?nsted acid sites on H2WO4 enhance the conversion and favour a high selectivity of the tert-butylphenols. The recycling tests show that the carbon deposition on the catalyst surface, the dehydration and partial reduction of the catalyst itself are responsible for the decay of the H2WO4 catalyst. Finally, the possible reaction pathways proposed involve the transetherification process and the alkylation process during guaiacol conversion.
Mai, Fuhang,Cui, Kai,Wen, Zhe,Wu, Kai,Yan, Fei,Chen, Mengmeng,Chen, Hong,Li, Yongdan
p. 2764 - 2771
(2019/02/01)

Method for preparing hydrocarbyl phenol by catalytic conversion of phenolic compound in presence of molybdenum-based catalyst
The invention discloses a method for preparing hydrocarbyl phenol by catalytic conversion of a phenolic compound in the presence of a molybdenum-based catalyst. The method comprises mixing a phenoliccompound, a molybdenum-based catalyst and a reaction solvent, adding the mixture into a sealed reactor, feeding gas into the reactor, heating the mixture to 150-350 DEG C, carrying out stirring for areaction for 0.5-2h, then filtering to remove a solid catalyst and carrying out rotary evaporateion to obtain a liquid product. The phenolic compound has a wide source, a cost is low, product alkyl phenol selectivity is high, an added value is high, alcohol or an alcohol-water mixture is used as a reaction solvent, environmental friendliness is realized, pollution is avoided, any inorganic acids and alkalis are avoided in the reaction process, the common environmental pollution problems in the biomass processing technology are solved, the reaction conditions are mild, the process can be carried out at a low temperature, high-efficiency conversion of the reactants can be realized without consuming hydrogen gas and the method is suitable for large-scale industrial trial production.
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Paragraph 0040-0041; 0070; 0073; 0079; 0084; 0089; 0100-0107

(2018/04/02)

Phenol o-position alkylation method
The invention provides a phenol o-position alkylation method which comprises the following step: in the presence of a catalyst, a phenol substance and an alkylating agent react, wherein the catalyst is an aryl zinc salt generated from a reaction of zinc and a phenol compound; the alkylating agent is olefin; the phenol substance comprises polyphenol such as catechol and hydroquinone, and further comprises one to two alkyl groups, or halide based phenols; the alkyl group is straight-chain or branched paraffin with 1-10 carbons. By adopting the phenol o-position alkylation method, the preparation efficiency is greatly improved, and the conversion rate can be further increased. The invention further provides a method for preparing 2,6-di-tert-butyl-4-methylphenol, and a reaction kettle for preparation.
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Paragraph 0049; 0050; 0051; 0052; 0053-0056

(2017/08/27)

Preparation method of propofol and structural analogues of propofol
The invention relates to a preparation method of propofol and structural analogues of propofol. The preparation method comprises the steps as follows: preparing an intermediate from p-hydroxybenzoic acid and alkyl alcohol as raw materials under the action of a solid acid catalyst, and then preparing a target product by a decarboxylase reaction. The preparation method has the characteristics of being green in synthesis, realizing biotransformation, causing little pollution, producing few by-products and the like, and is suitable for industrial production; the purity of the prepared products such as propofol is 99.6% or higher, which meets various medicinal standards.
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(2017/08/28)

3-tertiary butyl-4-hydroxyphenylpropionic acid preparation method
The invention relates to a 3-tertiary butyl-4-hydroxyphenylpropionic acid preparation method. The 3-tertiary butyl-4-hydroxyphenylpropionic acid preparation method solves the problems of poor reaction selectivity, low yield and serious environmental pollution in the existing preparation process of 3-tertiary butyl-4-hydroxyphenylpropionic acid. The 3-tertiary butyl-4-hydroxyphenylpropionic acid preparation method comprises the following steps: step one, carrying out dealkylation reaction; step two, carrying out selective hydrolyzation, extracting to obtain a water phase and an organic phase, and recycling a solvent from the organic phase to obtain an organic phase concentrate; step three, separating and purifying to obtain crude 3-tertiary butyl-4-hydroxyphenylpropionic acid; recrystallizing the 3-tertiary butyl-4-hydroxyphenylpropionic acid to obtain the pure 3-tertiary butyl-4-hydroxyphenylpropionic acid, and recycling the solvent from a recrystallized mother solution to obtain mother solution recovered materials for later use; and step four, using the organic phase concentrate obtained in the step two as dealkylation reaction raw materials, recycling and reacting. The products prepared by the method are white crystals and have the purity of up to above 98.5%; the total yield of the products reaches above 90%; and the preparation method is used for preparing the 3-tertiary butyl-4-hydroxyphenylpropionic acid.
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Paragraph 0064-0067

(2017/09/01)

Hydrolysis of isobutylaluminum aryloxides studied by 1H NMR and quantum chemical methods
The results of 1H NMR and quantum chemical studies of hydrolysis of isobutylaluminum aryloxides are presented. According to the data of 1H NMR spectroscopy, the hydrolysis of monomeric diisobutylaluminum aryloxides (2,6-Bu2 t—C6H3O)AlBu2 i and (2,6-Bu2 t,4-Me—C6H2O)AlBu2 i occurs selectively at the Al—OAr bond to form the corresponding sterically bulky phenol and polyisobutylaluminoxane. At the molar ratios Al: H2O = 2, the formed sterically bulky phenol reacts slowly with diisobutylaluminum monoaryloxide to form isobutylaluminum diaryloxide. Dimeric aryloxide [(2-But—C6H4O)AlBu2 i]2 is not hydrolyzed under similar conditions. The quantum chemical calculations confirmed the experimental results: the hydrolysis at the Al—OAr bond has a lower energy barrier than that at the Al—C bond because of the formation of HH2O…OO?Ar hydrogen bonds.
Faingol’d,Zharkov,Bravaya,Chernyak
p. 1958 - 1965
(2017/04/03)

Selective oxidative homo-and cross-coupling of phenols with aerobic catalysts
Simple catalysts that use atom-economical oxygen as the terminal oxidant to accomplish selective ortho-ortho, ortho-para, or para-para homo-couplings of phenols are described. In addition, chromium salen catalysts have been discovered as uniquely effective in the cross-coupling of different phenols with high chemo-and regioselectivity.
Lee, Young Eun,Cao, Trung,Torruellas, Carilyn,Kozlowski, Marisa C.
supporting information
p. 6782 - 6785
(2014/06/09)

Synthesis of phenolic antioxidants with isobornyl and tert-butyl fragments
Hybrid antioxidants, phenols with a terpene and tert-butyl substituents, were synthesized by the alkylation of 2-tert-butyl-4-methylphenol with camphene and 2-isobornylphenol with tert-butyl chloride in the presence of acidic heterogeneous catalysts, montmorillonite KSF and FIBAN K-1. Antioxidant activity of the synthesized terpenophenols was evaluated using spectrophotometry.
Fedorova,Chukicheva,Shumova,Kutchin
p. 1103 - 1110
(2013/08/23)

PROCESS FOR PRODUCING A T-BUTYL PHENOL FROM A C4 RAFFINATE STREAM
This invention relates to processes for producing various t-butyl phenols, such as 2,6-di-tert-butyl phenol and ortho-tert-butyl phenol, by selectively reacting phenol or a substituted phenol with an isobutylene-containing C4 raffinate stream. The 2,6-di-tert-butyl phenol and ortho-tert-butyl phenol can be transalkylated to form other tert-butyl phenols, such as para-tert-butyl phenol, 2,4-di-tert-butyl phenol.
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Page/Page column 9

(2011/06/25)

Easier preparation of 2,6-Di-tert-butylphenyl derivatives 1
Despite steric shielding by the 2,6-di-tert-butylphenyl group (super-2,6-xylyl=xyl*), inexpensive sodium phenolate (xyl*-ONa) reacts with dimethyl sulfate to produce only xyl*-OCH3 (94%) with complete suppression of the alternative 4-methylation. Reductive cleavage of xyl*-OCH3 by elemental lithium with the help of an electron carrier generates xyl*-Li, which in turn yields xyl*-CO2H (63%). The corresponding 4-methyl-derivatives of these compounds were obtained analogously. The acid chloride xyl*-COCl (77% yield) acylates HalMgCH 2R to give only xyl*-COCH3 (86%) or xyl*-COEt (97%). These two ketones react with n-butyllithium (no carbonyl addition) and Cl-PO(OEt)2 to furnish only the enol phosphates xyl*-C(=CH 2)OPO(OEt)2 (84%) or xyl*-C(=CHCH 3)OPO(OEt)2 (up to 70%), respectively. Only 1,2-elimination occurs when the latter two products are treated with tert-butyllithium, affording xyl*-CCH (68%) or xyl*-CCMe (88%), respectively. Georg Thieme Verlag Stuttgart - New York.
Knorr, Rudolf,Rossmann, Eva Christine,Knittl, Monika
experimental part
p. 2124 - 2128
(2010/09/04)

Scope and limitations of lithium-ethylenediamine-THF-mediated cleavage at the α-position of aromatics: Deprotection of aryl methyl ethers and benzyl ethers under mild conditions
The scope and limitation of lithium-ethylenediamine-THF-mediated reductive bond cleavage at the α-position of aromatics were examined. Very mild conditions such as lithium metal (5 equiv) and ethylenediamine (7 equiv) in oxygen-free THF were quite effective for the demethylation of aromatic ethers even at as low as -10°C. Allyl benzyl ethers were also deprotected under these conditions with very little change of the allylic alcohol moiety. Through this study, 2,6-dimethylbenzyl (m-xylylmethyl, MXM) group was developed as an alternative of benzyl group, which is readily cleavable under the above mentioned reductive conditions.
Shindo, Takeyuki,Fukuyama, Yasuaki,Sugai, Takeshi
p. 692 - 700
(2007/10/03)

Thioether substituted hydroxybenzophenones and stabilized compositions
2-Hydroxybenzophenone derivatives substituted in the 4′-position by a thioether moiety exhibit enhanced absorption in the UV at longer wavelength. Compositions comprising organic material subject to actinic degradation are beneficially stabilized with such derivatives.
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(2008/06/13)

Process for functionalising a phenolic compound carrying an electron-donating group
The invention concerns a method for functionalizing a phenolic compound bearing an electron-donor group, in said group para position, inter alia a method for the amidoalkylation of a phenolic compound bearing an electron-donor group, and more particularly, a phenolic compound bearing an electron-donor group preferably, in the hydroxyl group ortho position. The method for functionalizing in para position with respect to an electron-donor group carried by a phenolic compound is characterised in that the phenolic compound bearing an electron-donor group is subjected to the following steps: a first step which consists of protecting the hydroxyl group in the form of a sulphonic ester function; a second step which consists in reacting the protected phenolic compound with an electrophilic reagent; optionally, a third step deprotecting the hydroxyl group.
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(2008/06/13)

Process for producing 3,3',5,5'-tetra-t butylbiphenol
A batch or continuous process produces highly pure 3,3',5,5'-tetra-t-butylbiphenol suitable as a starting material for the synthesis of 4,4'-biphenol. The process for producing 3,3',5,5'-tetra-t-butylbiphenol comprises conducting an oxidation coupling of purified 2,6-di-t-butylphenol(i) or crude 2,6-di-t-butylbiphenol(ii), said crude 2,6-di-t-butylphenol being obtained by reacting isobutylene with phenol in the presence of an aluminum catalyst, and removing the aluminum catalyst. The 2,6-di-t-butylphenol is oxidatively coupled in an alkali metal catalyst mixture comprising (1) an alkali metal catalyst and alkylphenols, or (2) alkali metal catalyst, alkylphenols and phenol to produce 3,3',5,5'-tetra-t-butylbiphenol. The oxidative coupling is conducted together with 10-30% by weight of phenol and/or t-butylphenol per 100% by weight of 2,6-di-t-butylphenol in the presence of an alkali metal catalyst.
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(2008/06/13)

Color-stabilized basic monomers, process for producing the same and method for handling the same
Color-stabilized basic monomers are provided. Said basic monomers are obtained by adding, to a basic monomer ?e.g. an N,N-dialkylaminoalkyl (meth)acrylate or an N,N-dialkylaminoalkyl (meth)acrylamide!, at least one member selected from the group consisting of amido group-containing compounds, phosphorous acid esters, phosphoric acid esters and phosphines and at least one phenol compound represented by the general formula: STR1 wherein R5, R6, R8 and R9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R7 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The color-stabilized basic monomers are more resistant to coloration when they are handled under such conditions that the oxygen concentration in the gas phase contacting therewith is 0.01 to 10% by volume.
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(2008/06/13)

A novel protecting group for hindered phenols
Boc2O and DMAP were used to protect hindered phenols as their Boc derivatives under mild conditions. Deprotection conditions were developed to suppress loss of a tert-butyl group from the aromatic ring, or alkylation of an additional tert-butyl group at an unsubstituted ortho or para position.
Hansen, Marvin M.,Riggs, Jennifer R.
p. 2705 - 2706
(2007/10/03)

Lubricant composition
A composition comprising a) a lubricant or a hydraulic fluid and b) at least one compound of the general formula I STR1 in which x=1 or 2 and, if x=1, R is as defined for R1 or R3 --O-- or, if x=2, R is as defined for R8, and R1 and R3 are, for example, alkyl, cycloalkyl, alkenyl, phenyl, naphthyl, aralkyl or alkaryl, or alkyl, cycloalkyl, alkenyl, phenyl, naphthyl, aralkyl or alkaryl, which are monosubstituted or polysubstituted by groups from the series comprising halogen, cyano, nitro, e.g. --OCH3 or e.g. --COOCH3, or alkyl, cycloalkyl, alkenyl, aralkyl or alkaryl which are interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR2 or alkyl, cycloalkyl, alkenyl, aralkyl or alkaryl which are monosubstituted or polysubstituted by groups from the series comprising halogen, cyano, nitro, e.g. --OCH3 or e.g. --COOCH3 and interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR3 and R2 is NR4 R5, --OR6 or --SR7, and R4 and R5 are identical or different and are, for example, --H, alkyl, phenyl, naphthyl, aralkyl or alkaryl, or R4 and R5, together with the N atom linking them, form, for example, a piperidine or morpholine radical, and R6 and R7 can be alkyl which may be interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR4 or are, for example, phenyl, naphthyl, alkaryl or aralkyl, and R8 can be alkylene which may be interrupted by at least one --O-- group or alkylidene which may be interrupted by at least one --O-- group. Some of the compounds of the formula I are novel. The compositions show an improved stability towards oxidative degradation, confer protection under extreme pressures and reduce frictional wear.
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(2008/06/13)

Effect of Solvation on the Bond Dissociation Energies of Phenolic Antioxidants
The effect of solvent on the bond dissociation energies (BDEs) of the oxygen-hydrogen bond in substituted phenolic antioxidants has been investigated by means of an EPR technique.On changing the solvent from benzene to tert-butanol the BDE's were found to increase by ca. 2.2 kcal/mol for phenols without ortho substituents, by ca. 1 kcal/mol for 2,6-dimethyl substituted phenols while in 2,6-di-tert-butyl phenols they seem to be substantially unaffected.This behaviour has been interpreted by admitting that the BDE increase observed in tert-butanol is essentially due to the solvation of the hydroxylic hydrogen which stabilises the phenol, leaving the energy of the phenoxyl radical unaltered.Thus, solvation effects are expected to be large with unhindered phenols and relatively unimportant in phenols containing bulky substituents in the proximity of the OH group.
Pedrielli, Pamela,Pedulli, Gian Franco
p. 509 - 512
(2007/10/03)

Amorphous modification of 1,1',1"-nitrilo(tri-2-propyl-tris-[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl] phosphite)
The new amorphous modification of 1,1',1"-nitrilo{tri-2-propyl-tris-[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)]phosphite } is obtained by cooling rapidly said compound from the melt to ambient temperature. This amorphous form is an effective process stabilizer for polyolefins, particularly polypropylene.
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(2008/06/13)

Reaction pathways for ambident aryloxide O- and C-nucleophiles in SNAr displacement versus Meisenheimer complex formation with picryl halides. Stereoelectronic effects on regioselectivity
To probe regioselectivity in Meisenheimer complexation, the reaction of two picryl halides (PiX where X = F, Cl) with a series of aryloxide nucleophiles (phenoxide, 2,4,6-trimethylphenoxide and 2,6-di-t-butylphenoxide) were monitored by 1H NMR spectroscopy in dimethyl sulphoxide at ambient temperature and in acetonitrile-dimethoxyethane(MeCN-DME) at low temperature (-40°C). The reactions of both picryl halides with the ambident (oxygen versus carbon) nucleophile, phenoxide ion (PhO-), and 2,4,6-trimethylphenoxide (mesitoxide, MesO-) leads to clean SNAr displacement of X via the oxygen site of the nucleophile to form the respective aryl picryl ethers, i.e. phenyl picryl ether (3a) and mesityl picryl ether (3b). Meisenheimer complex formation at C-1 or C-3 was not detected in these systems. With 2,6-di-t-butylphenoxide (2,6-DTBPhO-), where oxygen attachment of the aryloxide is precluded by the bulky ortho t-butyl groups, para-carbon attachment was found to occur at C-1 to give picryl 2,6-di-t-butylphenol (3d) in competition with C-attack at C-3 to give the respective carbon-bonded Meisenheimer complexes [X = Cl (4) and X = F (5)]. For both picryl halides, the ratio of 3d, the product of C-1 attack, to the product of C-3 attack, 4 or 5, was roughly 7:1. These findings are considered with regard to the nucleofugality of the halide, X, steric hindrance (F-strain) to attack by the aryloxides at the various positions and stereoelectronic stabilization of C-1 adducts afforded by n → σ* donation.
Manderville, Richard A.,Dust, Julian M.,Buncel, Erwin
p. 515 - 528
(2007/10/03)

A mechanistic approach to the reaction of 2,6-di-tert-butylphenol with an iodinating agent in methanol: Electrophilically assisted solvolysis of intermediary 4-iodocyclohexa-2,5-dienones
Reactions of the title phenol (1) and of 4-iodophenol 2 with an iodinating agent, I2 and H2O2, are conducted in MeOH for varying times with varying amounts of I2, and the results are compared. The reaction of 1 gives 2, 4,4′-biphenol 3, 4,4′- diphenoquinone 4, 4-methoxyphenol 5, and p-benzoquinone 6, exclusively. The yields of the phenolic products (2, 3, and 5) vary with reaction time, but they disappear or almost disappear eventually, to make 4 and 6 the almost exclusive products. The reaction of 2 always gives 4 and 6 alone. In both of the reactions of 1 and of 2, employment of a higher initial I2 concentration not only completes the formation of 4 and 6 faster but also makes the final proportion of 6 higher. However, the ultimate yield of 6 from the reaction of 1 is significantly higher than that from the reaction of 2, irrespective of the initial I2 concentration. These results are interpreted as follows. 4-Iodocyclohexa-2,5-dienone 12, the primary product of electrophilic iodination of 1, undergoes solvolysis (methanolysis), which is electrophilically assisted by I2. The solvolysis of 12 can be so fast as to overwhelm its prototropic rearrangement to give 2. 4-Methoxycyclohexa-2,5-dienone 13, which is the primary product of the methanolysis of 12 and is suggested to be detectable by 1H NMR spectroscopy, is converted into 6 via 5. Benzoquinone 6 can also arise from 4,4-diiodocyclohexa-2,5-dienone 7, the product of iodination of 2, by an analogous mechanism. The selectivity of the formation of 6 from 7 is low because the competing reaction, homolytic scission of the C-I bond in 7, predominates. The mechanism of the formation of 3 and 4 is also discussed.
Omura, Kanji
p. 2006 - 2012
(2007/10/03)

Perfluoroalkyl substituted hydroxyphenylalkanoic ester antioxidants and stabilized compositions
Perfluoroalkyl substituted neopentyl alcohols can be reacted with substituted hydroxphenylalkanoic esters to form perfluoroalkyl containing hydroxyphenylalkanoic ester antioxidants. The perfluoroalkyl substituted hindered hydroxyphenyl alkanoates are stablizers which confer superior processing stability to polymers processed at elevated temperatures such as polypropylene, as well as protecting said polymers from thermal and oxidative degradation.
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(2008/06/13)

3,9-carbohydrate substituted 2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane phosphite stabilizers
Carbohydrate substituted phosphites of Formula I STR1 where A is a carbohydrate residue are effective stabilizers for polymers processed at elevated temperatures and subject to thermal or oxidative degradation.
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(2008/06/13)

Beta crystalline modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite]
The beta crystalline modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] is obtained by crystallizing said compound from the melt at elevated temperatures. The beta crystalline form is an effective process stabilizer for polyolefins, particularly polypropylene.
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(2008/06/13)

Carbohydrate substituted dibenzo(d,f)(1,3,2)dioxaphosphepin stabilizers
Carbohydrate substituted dibenzo[d,f][1,3,2]dioxaphosphepin compounds of formula I STR1 where A is a carbohydrate residue are effective stabilizers for polymers processed at elevated temperatures and subject to thermal or oxidative degradation.
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(2008/06/13)

Substituted 1,4-diamino-2-butene stabilizers
N,N,N',N'-Tetrasubstituted 1,4-diamino-2-butenes where the substituents are alkyl, cycloalkyl, aralkyl, aryl or mixtures thereof provide effective antioxidant protection to lubricants and/or synthetic polymers.
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(2008/06/13)

A New Synthetic Approach to Pyridinium N-Phenoxide Betaine Dyes
The reaction of 3,5-di-tert-butyl-4-oxo-2,5-cyclohexadienylidene (3d) with pyridine affords 2,6-di-tert-butyl-4-(2,4,6-tri-tert-butylpyridinio)phenolate (1d) - which is not accessible by the classical route via pyrylium salts - in reasonable yield.Carbene 3d is generated by thermal decomposition of the corresponding quinone diazide 2d in cyclohexane.Betaine 1d shows the expected large solvatochromism. - Key Words: Betaine dye / Solvatochromism / Ylide / Carbene reaction
Sander, Wolfram,Hintze, Frank
p. 267 - 270
(2007/10/02)

Phenolic derivatives of 2,5-dimercapto-1,3,4-thiadiazoles
Disclosed are novel compounds prepared by reacting 2,5-dimercapto-1,3,4-thiadiazole, aliphatic or aromatic aldehyde and alkylated phenol in the molar ratio of 1:1:1 to 2:2:1. The 2,5-dimercapto-1,3,4-thiadiazole may be substituted in the 2-position by terpene, polymeric and succinate residues. The compounds are effective antiwear agents and antioxidants when incorporated into lubricating compositions.
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(2008/06/13)

2-(2-hydroxy-3-perfluoroalkyl thiomethyl-5-alkylphenyl)2H-benzotriazoles and stabilized compositions thereof
2-(2-Hydroxy-3-perfluoroalkylthiomethyl-5-alkylphenyl)-2H-benzotriazoles are prepared by reacting the Mannich base hydrohalide or quaternary salt of a 2-(2-hydroxy-5-alkylphenyl)-2H-benzotriazole with a perfluoroalkyl mercaptan. The products exhibit outstanding efficacy in protecting organic substrates from light induced deterioration as well as good resistance to loss by volatilization or exudation during the processing of stabilized compositions at elevated temperatures.
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(2008/06/13)

Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-triazine derivatives
1-Hydrocarbyloxy-2,2,6,6-tetramethylpiperidine derivatives of s-triazines having functional groups such as hydroxy, amino, carboxy, epoxy, isocyanate or the like present are capable of chemically bonding with polymer substrates having anhydride, epoxide, alkoxymethylmelamine or isocyanate moieties present. This chemical bonding prevents migration or loss of the stabilizer during subsequent processing or end-use application of the stabilized polymer.
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(2008/06/13)

Substituted 1-hydroxy-2,6-diaryl-4-piperidone ketals and polymer compositions stabilized therewith
1-Hydroxy-2,6-diaryl-4-piperidone ketal derivatives, such as the compound of formula I STR1 wherein Ar1 and Ar2 are each phenyl, R1 to R6 are all hydrogen, X1 and X2 are each --O-- and T is a direct bond, are novel compounds and are effective process stabilizers, such as polypropylene, for polymers processed at elevated tempertures providing both good melt flow stabilization and good resistance against discoloration during said processing.
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(2008/06/13)

N-Allyl/benzyl substituted phenylenediamine stabilizers
Compositions are described which comprise (a) a lubricant, subject to oxidative or thermal degradation, and (b) at least one compound of formula I wherein, R5, R6, R7 and R8 are independently hydrogen, alkenyl of 3 to 18 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, -CN, -NO6, halogen, -ORψ, -NR?R?, -SR?, -COOR and -CONR54R55 where Rψ, R?, R?, R?, R , R54 and R55 are independently hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, aryl of 6 to 10 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or aralkyl of 7 to 15 carbon atoms. Some of the compounds of formula one are novel.
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(2008/06/13)

Substituted 1-aminonaphthalenes and stabilized compositions
Substituted 1-aminonaphthalenes of formula I STR1 wherein n is 1-3, Ar is arylene, R1 and R2 are independently hydrogen, alkyl or phenyl, R3 is hydrogen, alkyl or substituted alkyl, and R4 and R5 have independently the same definitions as R3 or are independently aryl, substituted aryl or cycloalkyl, are effective stabilizers for lubricating oil or polymer compositions. The instant compounds are particularly effective in lubricating oil compositions when used with a diarylamine antioxidant.
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(2008/06/13)

Substituted 2,3-dihydroperimidine stabilizers
N-Allyl and N-methylene-thio substituted 2,3-dihydroperimidine compounds are very effective antioxidant stabilizers for organic material subject to oxidative or thermal degradation, particularly for lubricant compositions.
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(2008/06/13)

New triazole compounds
New triazole compounds, useful as metal deactivators and/or antioxidants in organic material, having the formula I: wherein X is the triazole residue of formula II: or the benzotriazole residue of formula III or IIIA: in which R is hydrogen or methyl.
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(2008/06/13)

Triazole compounds useful as metal deactivators
Composition comprising a functional fluid or fuel susceptible to degradation by a metal; and b) a metal deactivator having the formula I: in which X is a group having the formula II or III: in which R is hydrogen or C1-C4 alkyl. The compounds of formula I are new.
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(2008/06/13)

2-Propanol derivatives as corrosion inhibitors
New composition comprises a functional fluid in contact with ferrous metal and a corrosion inhibiting amount of at least one compound of formula (I) STR1 or a derivative thereof in which R1, R2 and R3 are, independently, hydrogen, a C1 -C15 straight or branched chain alkyl residue, a C5 -C12 cycloalkyl residue, a C6 -C15 aryl residue or C7 -C12 alkaryl residue, and R4 and R5 are, independently, hydrogen, 2-hydroxyethyl or 2-hydroxypropyl with the provisos that (a) R4 and R5 are not simultaneously hydrogen, (b) when R4 and R5 are each --CH2 --CH2 --OH, R1 and R2 are not simultaneously hydrogen and R3 is not a pentyl residue and (c) that polyalkylene and phenol or polycarboxylic ester co-additives are absent; as well as salts thereof. Some of the compounds of formula I are new.
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(2008/06/13)

Corrosion inhibiting composition
A composition, in contact with a corrodable metal surface, which composition comprises: (a) an aqueous-based or oil-based system; and (b) as inhibitor for protecting the metal surface against corrosion, at least one compound having the formula I: STR1 as well as salts or partial esters thereof wherein: n is 0 or an integer ranging from 1 to 20, R is a straight or branched chain C4 -C30 alkyl group, optionally interrupted by one, two or three oxygen atoms or substituted by one, two or three hydroxy groups, a C5 -C12 cycloalkyl group, a C6 -C10 aryl group optionally substituted by one, two or three C1 -C12 alkyl groups, or a C7 -C13 aralkyl group which is optionally substituted by a hydroxyl group; R1 is H or a straight- or branched chain C1 -C4 alkyl group; R2 is H, a straight or branched chain C1 -C4 alkyl group or CO2 H; R3 is H, a straight or branched chain C1 -C4 alkyl group, --CH2 CO2 H or --CH2 CH2 CO2 H; R4 is H, a straight or branched chain C1 -C4 alkyl group or CO2 H; R5 is H, a straight or branched chain C1 -C4 alkyl group, CH2 CO2 H or CH2 CH2 CO2 H; provided that at least one group R4 must be CO2 H, with the provisio, that compositions comprising an oil-based system and a compound having the formula STR2 wherein R, R1 and R2 are hydrogen or alkyl radicals, having a total from 10 to 38 C-atoms, are excluded.
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(2008/06/13)

N-substituted tetrahydroquinolines for use as antioxidants in lubricants
Compounds useful as additives for lubricants, hydraulic oils and metal-working fluids include those of formula IV STR1 where R1 and R2 are independently alkyl or substituted aryl, R3 and R13 are independently hydrogen or methyl, R6 is alkyl, alkenyl, aralkyl or substituted benzyl, and R15 and R16 are independently hydrogen, alkyl, aryl or aralkyl.
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(2008/06/13)

Mercaptotriazine derivatives as lubricant additives
Compounds of the formula STR1 and of the formula STR2 in which X and X' are, for example, --S--CHR1, --NR2 R3, --S--R3, --NR2 R3 or --OR3, R1 is, for example, --H, alkyl, cycloalkyl or phenyl, R2 and R3 are, for example, --H, alkyl, cycloalkyl or phenyl, or R2 and R3 together form a 3- to 7-membered heterocyclic ring, and R is alkylene, and compositions containing at least one compound of the formulae I and/or II and at least one lubricant, one hydraulic fluid or one metal working fluid, the compounds of the formula I and/or II being used as extreme pressure and wear-reducing additives.
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(2008/06/13)

Lubricant compositions
The present invention provides a lubricant composition comprising a lubricating oil and, as multifunctional additive, at least one compound having the formula I: or amine salts thereof; wherein R1 and R2, independently, are hydrogen or methyl; n and m, independently, are 0 or 1; and X is SR3 or NR4R3 wherein R3 is C12-C20 linear or branched alkyl R4 and R5 are independently, C8-C20 linear or branched aikyl provided that those compounds of formula I are excluded in which m and n are each 0, X is S-C8-C20 linear or branched alkyl and R1 and R2 are as defined.
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(2008/06/13)

Corrosion inhibition
The present invention provides a composition in contact with a corrodable metal surface, comprising a functional fluid and, as corrosion inhibitor, a compound having the formula I: as well as salts or esters thereof, wherein, R1 is C4-C20 linear or branched alkyl, phenyl or C7-C20 alkylphenyl;, R2 is C1-C12 linear or branched alkyl, phenyl or C7-C20 alkylphenyl, or arylalkyl containing 7-20 carbon atoms;, X is CH2, O or S;, Y is O or S; and, Z is -(CH2)n- in which n is 1, 2, 3, 4 or 5, or Z is -CH2-CH(CH3)-. Some of the compounds of formula I are new.
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(2008/06/13)