- Preparation method of antioxidant 330
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The invention relates to the technical field of chemical material processing, in particular to a synthetic method for preparing a hindered phenol antioxidant 330. The method comprises the following steps: reducing 3, 5-di-tert-butyl-4-hydroxybenzoic acid serving as an initial raw material into 3, 5-di-tert-butyl-4-hydroxybenzyl alcohol, and condensing the 3, 5-di-tert-butyl-4-hydroxybenzyl alcoholwith mesitylene under the action of an acid catalyst to generate the antioxidant 330. In the condensation reaction process, the phase transfer catalyst polyethylene glycol is utilized to improve thecatalytic effect of the concentrated sulfuric acid and reduce the consumption of the concentrated sulfuric acid, thereby having higher industrial value. The reaction yield is high, the optimal yield can reach 95%, the purity of the obtained reduction product is high, and in the industrial process, aftertreatment is simple. Therefore, the antioxidant 330 is synthesized by taking 3, 5-di-tert-butyl-4-hydroxybenzoic acid as an initial raw material and reducing 3, 5-di-tert-butyl-4-hydroxybenzoic acid into alcohol, and the method is a process route with relatively high industrial value.
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Paragraph 0027; 0029; 0031; 0033
(2021/01/29)
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- Synthetic method of antioxidant
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The invention discloses a synthesis method of an antioxidant, which comprises the following steps: reacting cyanuric chloride with an intermediate 8 and an intermediate 11 in sequence through temperature control to prepare an intermediate 12, hydrolyzing the intermediate 12, grafting a product on nano silicon dioxide to prepare the antioxidant; wherein the antioxidant is grafted with the nano silicon dioxide, so that the antioxidant can be fully dispersed when being mixed with a polymer, does not migrate along with the increase of service time, contains hindered phenol and phosphite structures, can provide hydrogen atoms to prevent the formation of chain free radicals, and reacts with the chain free radicals to achieve the purpose of inhibiting oxidation. Meanwhile, unstable hydrogen peroxide can be decomposed into stable compounds, so that formation of new free radicals is prevented, and the purpose of terminating a chain reaction is achieved.
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Paragraph 0014; 0032; 0035; 0039; 0042; 0046; 0049; ...
(2021/06/23)
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- Unusual transformation of 4-hydroxy/methoxybenzylic alcohols via C[sbnd]C ipso-substitution reaction using proton-exchanged montmorillonite as media
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We present here proton-exchanged montmorillonite-mediated an unusual transformation of 4-hydroxy and 4-methoxybenzylic alcohols to form symmetrical benzylic ethers and diarylmethanes under mild conditions. Nuclear magnetic resonance spectroscopy and density functional theory calculations support a plausible mechanism, which includes a distinctive aromatic C[sbnd]C ipso-substitution reaction with a hydroxymethyl group as the C-based leaving group.
- Chen, Dongyin,Chen, Xuan,Dong, Zezhong,Jiang, Nan,Li, Fei,Yun, Yangfang,Zhou, Yu
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supporting information
(2020/11/12)
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- Comparative evaluation of the antioxidant activity of some ortho-substituted mono- and dialkylphenols with the para-positioned hydroxymethyl group
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The para-hydroxymethyl derivatives of 2,6-di-tert-butylphenol, 2,6-diisobornylphenol, 2-isobornyl-6-tert-butylphenol, 2-isobornyl-6-methylphenol, and 2-isobornylphenol were synthesized. A comparative evaluation of the antioxidant properties of the synthesized compounds was carried out in in vitro models. The activity of derivatives is predetermined by the number and bulkiness of the substituents at the ortho positions relative to the phenolic OH group and is consistent with the relationships previously identified by us for other phenolic antioxidants.
- Buravlev, E. V.,Fedorova, I. V.,Kutchin, A. V.,Shevchenko, O. G.
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p. 1573 - 1578
(2020/09/21)
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- Synthetic method of 4-hydroxymethyl-2, 6-di-tert-butylphenol
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The invention provides a synthetic method of 4-hydroxymethyl-2, 6-di-tert-butylphenol. The synthetic method includes the steps of adopting the 2, 6-di-tert-butylphenol and paraformaldehyde or formaldehyde aqueous solution as starting material, adding solvent and catalysts, performing one-step reaction in a hydrothermal synthesis reactor and under a certain reaction temperature for a certain reaction time and then generating a target product. The synthetic method of 4-hydroxymethyl-2, 6-di-tert-butylphenol has the advantages of simple steps, convenient operation, green reaction process, and higher synthesis efficiency than an existing synthesis method.
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Paragraph 0007; 0008; 0009
(2018/10/26)
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- Structure, thermal stability, antioxidant activity and DFT studies of trisphenols and related phenols
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Two kinds of trisphenols have been successfully synthesized and their structures were confirmed by IR spectra, 1HNMR, 13CNMR, mass spectra and X-ray diffraction. They exhibited better thermal stability than both monophenol and bisphenols due to their higher molecular weight. Moreover, their antioxidant activities have been investigated in lubricant oil using PDSC and RBOT. The results showed that the o-trisphenol 3b exhibited the best antioxidant activity while the p-trisphenol 3a was the worst. In addition, their relationship between structures and properties has been further explored by a series of DFT calculations including the BDE values, the IP values and the Gibbs free energy barriers for the reaction between phenols and methylperoxyl radicals.
- Yu, Shasha,Wang, Yishan,Ma, Yujie,Wang, Limin,Zhu, Jia,Liu, Shenggao
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p. 159 - 170
(2017/10/05)
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- Preparation method of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol
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The invention discloses a preparation method of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and belongs to the technical field of organic synthesis. In the technical scheme, a reaction is carried out to 2,6-di-tert-butyl-phenol and a Vilsmeier reagent in a non-protonic solvent at 60-80 DEG C to generate 3,5-di-tert-butyl-4-hydroxybenzaldehyde; and then the 3,5-di-tert-butyl-4-hydroxybenzaldehyde is reacted with a strong-protonic reducing agent to generate the target product, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol. The method is free of special catalyst and is free of gas in the reactions, is high in reaction yield, and is free of complex product post-treatment step, so that the method has wide application prospect.
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Paragraph 0015
(2017/08/30)
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- Hydrogenation of aldehydes and ketones to corresponding alcohols with methylamine borane in neat water
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GRAPHICAL ABSTRACT Chemoselective hydrogenation of various aldehydes and ketones with methylamine borane (MeAB) in neat water was investigated. MeAB is suitable for green organic reactions, for MeAB is a nontoxic, environmentally benign, and easily handled reagent. Aldehydes were selectively and rapidly hydrogenated in excellent yields (86-97%) for 30 min, but hydrogenation of aromatic ketones needed over 20 h at room temperature because of their poor water solubility and steric hindrance. Thus we investigated polyethylene glycol (PEG400) and acidic cation-exchange D072 resin as catalysts to accelerate the hydrogenation reaction of aromatic ketones and achieved excellent yields within several hours. PEG 400 and D072 resin are both suitable for green organic reactions. The D072 resin was reused up to four times without any significance loss in activity.
- Duan, Yifan,Bai, Ruijiao,Tian, Jun,Chen, Ligong,Yan, Xilong
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p. 2555 - 2564
(2014/08/05)
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- Hydrolysis of the quinone methide of butylated hydroxytoluene in aqueous solutions
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Butylated hydroxytoluene or BHT is an antioxidant commonly used in pharmaceutical formulations. BHT upon oxidation forms a quinone methide (QM). QM is a highly reactive electrophilic species that can undergo nucleophilic addition. Here, the kinetic reactivity of QM with water at various apparent pH values in a 50% (v/v) water-acetonitrile solution at constant ionic strength of I =?0.5 (NaCl)4, was studied. The hydrolysis of QM in the presence of added acid, base, sodium chloride, and phosphate buffer resulted in the formation of only one product--the corresponding 3,5-di-tert-butyl-4-hydroxybenzyl alcohol (BA). The rate of BA formation was catalyzed by the addition of acid and base, but not chloride and phosphate species. Nucleophilic excipients, used in the pharmaceutical formulation, or nucleophilic groups on active pharmaceutical ingredient molecule may form adducts with QM, the immediate oxidative product of BHT degradation, thus having implications for drug product impurity profiles. Because of these considerations, BHT should be used with caution in formulations containing drugs or excipients capable of acting as nucleophiles.
- Willcockson, Maren Gulsrud,Toteva, Maria M.,Stella, Valentino J.
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p. 3579 - 3585
(2013/09/24)
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- GREEN AND ATOM-ECONOMICAL PROCESSES FOR PRODUCING PHENOLIC ANTIOXIDANTS
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Processes for producing 1,3,5-trimethyI-2,4,6-tris(3,5-dialkyl-4- hydroxybenzyl)benzene are provided, in particular such processes that utilize 2,6-di-tert- butylphenol, paraformaldehyde, a secondary amine, mesitylene, and acetic acid.
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Page/Page column 8-9
(2011/02/24)
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- Antiviral use of a 2,6-di-t-butylphenol compound substituted in 4 position against herpes viruses and papillomaviruses
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A therapeutical use is provided for cornpounds selected from the group which consists of (a) phenols of formula (I): STR1 wherein R is a C1-12 alkyl group, a C2-12 alkenyl group, a C2-12 alkynyl group, a C1-12 alkoxy group, a formyl group, a C2-12 alkanoyl group, a C1-12 hydroxyalkyl group, a primary, secondary or tertiary amide group, an OCH3 group, CH2 OH or a COOH group or an A--COOH group where A is a C1-11 aliphatic hydrocarbon residue; and (b) the corresponding salts and esters thereof when R is COOH or A--COOH; for obtaining an antiviral drug for use in the human or veterinary therapeutical treatment of viral diseases.
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- Alkylation of 2'-deoxynucleosides and DNA by quinone methides derived from 2,6-Di-tert-butyl-4-methylphenol
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4-Alkylphenols, such as the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT), exhibit toxicities that appear to be mediated by their oxidative metabolism to electrophilic quinone methides. Reactions of these Michael acceptors with simple nucleophiles and proteins have been reported, but little information is available on quinone methide binding to the competing nucleophilic sites in DNA. In the present investigation, 2'-deoxynucleoside adducts generated in vitro with two BHT-derived quinone methides, 2,6-di- tert-butyl-4-methylenecyclohexa-2,5-dienone and 6-tert-butyl-2-(2'-hydroxy- 1',1'-dimethylethyl)-4-methylenecyclohexa-2,5-dienone (BHTOH-QM) were isolated and identified. Both quinone methides produced adducts at the 1- and N2-positions of deoxyguanosine (dG) and the N6-position of deoxyadenosine (dA). In addition, a labile adduct formed at the 7-position of dG, which degraded to the corresponding 7-alkylguanine derivative. Additional work was conducted with BHTOH-QM, the more reactive of the two quinone methides. This species also formed stable adducts at the N4-position of deoxycytosine (dC) and the 3-position of thymidine and formed a labile adduct at the 3-position of dC that underwent hydrolytic cleavage to regenerate dC. In mixtures of deoxynucleosides treated with [14C]BHTOH-QM, alkylation occurred primarily at the N2- and 7-positions of dG and the N6-position of dA and occurred secondarily at the 1-position of dG. Treatment of calf thymus DNA with this quinone methide yielded N6-dA and N2-dG adducts with the former predominating. The unstable 7-dG adduct was detected by analysis of the 7- alkylguanine product from depurination. These results demonstrate that quinone methides are most likely to damage DNA through alkylation of the exocyclic amino groups of purine residues and possibly also by attack at the 7-position of dG followed by depurination.
- Lewis, Mark A.,Yoerg, Darla Graff,Bolton, Judy L.,Thompson, John A.
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p. 1368 - 1374
(2007/10/03)
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- Identification of Degradation Products of Terbutol in Environmental Water from Golf Courses
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Degradation products of terbutol (2,6-di-tert-butyl-4-methylphenyl N-methylcarbamate) in drainage and ground water from golf courses, on which terbutol had been applied as a herbicide, were identified by capillary GC/MS and reversed-phase HPLC. terbutol and 4-carboxy-, N-demethyl-, and 4-carboxy-N-demethylterbutol were detected in all water samples at concentrations of parts per billion levels.In addition, 4-(hydroxymethyl)- and 4-formylterbutol, 2,6-di-tert-butyl-4-methylphenol (BHT), and 4-(hydroxymethyl)-, 4-formyl-, and 4-carboxy-BHT were observed in some water samples at concentrations of parts per thousand levels.These results demonstrated that terbutol applied on golf courses was mainly degraded by N-demethylation, oxidation of the 4-methyl group, and hydrolysis of the carbamate ester linkage. Keywords:Terbutol; 2,6-di-tert-butyl-4-methylphenyl N-methylcarbamate; identification; degradation
- Suzuki, Toshinari,Yaguchi, Kumiko,Ohnishi, Kazuo,Suga, Tetsuya
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p. 1712 - 1717
(2007/10/02)
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- Oxidation Using Quaternary Ammonium Polyhalides. IX. Oxidation of Hindered Phenols with Benzyltrimethylammonium Tribromide
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Reactions of hindered phenols, such as 2,6-di-t-butyl-4-methylphenol, 3,5-di-t-butyl-4-hydroxybenzyl alcohol, and 2,6-di-t-butylphenol, with benzyltrimethylammonium tribromide were carried out in dichloromethane in the presence of water, t-butyl alcohol, or aqueous sodium hydroxide at room temperature.Sequential reaction processes were provided by the obtained products.
- Kajigaeshi, Shoji,Morikawa, Yukihiro,Fujisaki, Shizuo,Kakinami, Takaaki,Nishihira, Keigo
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p. 1060 - 1062
(2007/10/02)
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- SUBSTITUTED DIALKYLAMINOMETHYLPHENOLS IN AN EXCHANGE REACTION WITH CARBOXYLIC ACID ANHYDRIDES
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Carboxylic acid benzyl esters are formed in the reaction of carboxylic acid anhydrides with N,N-dialkyl-4(2)-hydroxy-substituted benzylamines. 4-Hydroxy-3,5-di-tert-butylbenzyl acetate exchanges an acetyl fragment for an alkoxyl fragment and benzylates phenol derivatives in the presence of an acid.
- Nikiforov, G. A.,Bannikov, G. F.,Mal'donado, I. K. A. Romero,Malysheva, R. D.,Ershov, V. V.
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p. 2530 - 2535
(2007/10/02)
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- Reaction product of a rosin acid and an antidegradant
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There is disclosed a reaction product of a rosin acid and a polyfunctional compound having at least one functional group capable of reacting with a carboxylic acid functionality and another functional group having antidegradant properties. The reaction products of this invention can be used as antidegradants in polymeric compositions and lubricating oil compositions.
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- Electroorganic Reactions. 31. Quinonemethide Radical-Anions and Dianoins: Their Cathodic Generation and Reactivity
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The cathodic reactions of a number of relatively stable quinonemethides have been examined in detail by cyclic voltammetry, controlled potential coulometry, and rigorous product analysis following preparative-scale electrolyses.The results of cyclic voltammetric experiments differ in some respects from those of earlier polarographic work.The lifetimes of the electrogenerated radical-anions and dianions, in the absence of added electrophile, are governed by steric hindrance.Hindered intermediates are relatively long-lived yet hydrogenate in the presence of proton donor and alkylate in the presence of methyl iodide.Less hindered analogue efficiently and rapidly dimerize, at carbon, with concomitant protonation or O-methylation depending on added electrophile.The ambident cathodically generated nucleophiles alkylate at both carbon and oxygen, and the competition is crucially dependent on the cation (Bu4N+ or Li+).Fuchsone 3 gives reduction products which vary with initial concentration and on the presence, or otherwise, of oxygen.Efficient reaction between oxygen and triarylmethyl radicals generated, e.g., from 3 has been demonstrated.
- Goulart, Marilia O. F.,Utley, James H. P.
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p. 2520 - 2525
(2007/10/02)
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- Reactions of 4-Hidroxycyclohexa-2,5-dienones under Acidic Conditions
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The 4-hydroxy-4-phenyl-2,6-di-t-butylcyclohexa-2,5-dienone (2) undergoes reaction in acidic conditions to give, inter alia, derivatives of an arene-1,2-diol.In poorly nucleophilic media, the 1,1'-biphenyl-4-ol (16) and the 5-phenyl-o-benzoquinone (37) are the main products.Isolation of the 4-(2-methylpropyl)cyclohexadienone derivatives (41) and (42) provides the first examples of intermolecular trapping of a four-carbon unit.The products are consistent with the intervention of the phenoxenium ion (44); the formation of the 2-methyl-1,3-benzodioxole (43) testifies to the intermediacy of such a powerful oxidant.Whereas the 4- phenyl-2-t-butyl-p-quinol (5) gave a complex mixture from which only the 1,1'-biphenyl-4-ol derivative (24) was isolated, the 2,6-di-isopropyl- and 2,6-dimethyl-analogues (4) and (6) afforded mainly the arene-1,3-diol derivatives (48) and (47), respectively.The 4-methyl-2,6-di-t-butyl-p-quinol (7) gave products arising from nucleophilic attack on an intermediate p-quinone methide; dimers were the major products in the absence of a good nucleophile.
- Davis, Brian R.,Gash, Diana M.,Woodgate, Paul D.,Woodgate, Sheila D.
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p. 1499 - 1508
(2007/10/02)
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