以微孔β沸石为硅铝源合成强酸性介孔分子筛

以微孔β沸石为硅铝源,通过碱处理和以十六烷基三甲基溴化铵为模板剂,合成了具有较强酸性的六方结构介孔分子筛材料B-MCM-41,并采用XRD、N₂吸附脱附、FT-IR、²7Al MAS NMR、HRTEM和水热处理等手段对其进行了结构表征,采用NH₃-TPD对其进行了酸性表征。实验结果表明,B-MCM-41具有明显强于常规介孔分子筛的酸性,且在C⁺₁0混合芳烃加氢脱烷基化反应中表现出了良好的催化性能。这主要是由于碱溶液将β沸石降解为沸石结构单元,在表面活性剂作用下五元环次级结构单元被引入了介孔铝硅酸盐B-MCM-41的结构。     

The Synthesis and Mechanistic Considerations of a Series of Ammonium Monosubstituted H-Phosphonate Salts

A series of ammonium monosubstituted H-phosphonate salts were synthesized by combining H-phosphonate diesters with amines in the absence of solvent at 80 °C. Variation of the ester substituent and amine produced a range of ionic liquids with low melting points. The products and by-products were analyzed by spectroscopic and spectrometric techniques in order to get a better mechanistic picture of the dealkylation and formal dearylation observed. For dialkyl H-phosphonate diesters, (RO)₂P(O)H (R=alkyl), the reaction proceeds via direct dealkylation with the reactivity increasing in the order R=iPr<Et<Me corresponding to DFT calculated activation enthalpies of 22.6, 20.8, and 17.9 kcal mol⁻¹. For the diphenyl H-phosphonate diesters, (PhO)₂P(O)H, the dearylation was found to proceed via phenol-assisted formation of a 5-coordinate intermediate, (PhO)₃PH(OH), from which P(OPh)₃ and water were eliminated. The presence of an equivalent of water then facilitated the formation of P(OH)₂OPh and the amine, R'NH₂, subsequently abstracted a proton from it to yield [(PhO)PH(O)O]^-[R'NH₃]⁺.     

Chemistry of naphthazarin derivatives. 11. Trisubstituted hydroquinone derivatives in the preparative synthesis of naphthazarins

The Friedel—Crafts acylation of trimethylhydroquinone, 3,5-diethyl-2-hydroxyhydroquinone, and 3,5-diethyl-1,2,4-trimethoxybenzene with dichloromaleic or citraconic anhydride in an AlCl₃—NaCl melt is accompanied by o-C-dealkylation to afford functionally substituted naphthazarins.     

Dealkylation ofpara-nitrophenyldimethyl thiophosphate in micellar and liquid-crystalline media of then-decylammonium chloride-n-decylamine-water system

The kinetics of decomposition of p-nitrophenyldimethyl thiophosphate (1) were investigated spectrophotometrically in the n-decylammonium chloride-n-decylamine-water system (DAC-DA-H₂O), in which micellar or lamellar liquid-crystalline phases are formed as a function of the concentration of components. It was shown that1 is dealkylated in both phases. An increase in the surface charge density of associates decreases the rate of dealkylation. The activation energy in the lamellar phase is significantly higher than in the micellar phase.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1042–1048, May, 1992.     

Seletivitätsbestimmung von Katalysatoren zur Toluolentalkylierung durch Einsatz von Toluol-14C-7

Die bei der katalytischen Toulolentalkylierung mögliche Konkurrenzreaktion der Spaltung des aromatischen Kernes führt zu unerwünschten Verlusten an Aromaten und kann infolge ihrer starken exothermen Wärmetönung bei der technischen Realisierung des Verfahrens Schwierigkeiten bei der thermischen Beherrschung des Reaktors bewirken. Bereits in der Entwicklungsphase des Katalysators ist man somit auf ein Verfahren angewiesen, das es erlaubt, diese Ringspaltung sicher nachzuweisen und quantitativ zu bestimmen.

In der vorliegenden Arbeit wird eine Tracermethode unter Einsatz von Toluol-¹⁴C-7 beschrieben, die diese Forderung weitgehendst erfüllt.     

Acidic N-dealkylation in nitrotriazolium salts

New selective synthesis of 1-alkyl-5-nitro-1,2,3-triazoles and 1-alkyl-4-nitro-1,2,3-triazoles has been developed, involving acid N-dealkylation of the relative 4-nitro-1,2,3- and 3-nitro- 5-R-1,2,4-triazolium salts. The assortment of novel 1-alkyl- 4(5)-nitro-1,2,3-triazoles has been thus essentially expanded. Treatment of relative 3-nitro-1,2,4-triazolium salts with HCl or HBr proceeds mostly as S_N^ipso-substitution of the nitro group.     

The Hydrolysis of Phosphinates and Phosphonates: A Review

Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of P-esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of P-esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review.     

Investigation of the reactions of pyrocatechol derivatives with AlBr3 by NMR spectroscopy

Alkylpyrocatechols are dealkylated by AlBr₃ in CH₂Br₂. The formation of stable carbenium ions (tert-butyl, methylcyclopentyl, and l-adamantyl) was detected by¹H NMR spectroscopy. Pyrogallol and 2,3-dihydroxynaphthalene are coordinated with AlBr₃ in the tautomeric keto form, and 2-mercapto-4-methylphenol forms a complex in the hydroxy form. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1158–1160, June, 1997.     

2,6-二羟基甲苯的合成

2;6-二羟基甲苯的合成;二羟基甲苯;间苯二酚;二氯乙烷;烷基化;甲酰化;黄鸣龙反应     

Anilinic N‐Oxides Support Cytochrome P450‐Mediated N‐Dealkylation through Hydrogen‐Atom Transfer

The mechanism of N‐dealkylation mediated by cytochrome P450 (P450) has long been studied and argued as either a single electron transfer (SET) or a hydrogen atom transfer (HAT) from the amine to the oxidant of the P450, the reputed iron–oxene. In our study, tertiary anilinic N‐oxides were used as oxygen surrogates to directly generate a P450‐mediated oxidant that is capable of N‐dealkylating the dimethylaniline derived from oxygen donation. These surrogates were employed to probe the generated reactive oxygen species and the subsequent mechanism of N‐dealkylation to distinguish between the HAT and SET mechanisms. In addition to the expected N‐demethylation of the product aniline, 2,3,4,5,6‐pentafluoro‐N,N‐dimethylaniline N‐oxide (PFDMAO) was found to be capable of N‐dealkylating both N,N‐dimethylaniline (DMA) and N‐cyclopropyl‐N‐methylaniline (CPMA). Rate comparisons of the N‐demethylation of DMA supported by PFDMAO show a 27‐fold faster rate than when supported by N,N‐dimethylaniline N‐oxide (DMAO). Whereas intermolecular kinetic isotope effects were masked, intramolecular measurements showed values reflective of those seen previously in DMAO‐ and the native NADPH/O₂‐supported systems (2.33 and 2.8 for the N‐demethylation of PFDMA and DMA from the PFDMAO system, respectively). PFDMAO‐supported N‐dealkylation of CPMA led to the ring‐intact product N‐cyclopropylaniline (CPA), similar to that seen with the native system. The formation of CPA argues against a SET mechanism in favor of a P450‐like HAT mechanism. We suggest that the similarity of KIEs, in addition to the formation of the ring‐intact CPA, argues for a similar mechanism of Compound I (Cpd I) formation followed by HAT for N‐dealkylation by the native and N‐oxide‐supported systems and demonstrate the ability of the N‐oxide‐generated oxidant to act as an accurate mimic of the native P450 oxidant.