Mechanism of Aniline Methylation on Zeolite Catalysts Investigated by In Situ 13C NMR Spectroscopy

The alkylation reaction of aniline with methanol on zeolites HY and CsOH/CsNaY was studied by in situ ¹³C NMR spectroscopy under flow and batch conditions. Attention was focused on the identification of intermediates and on the determination of the formation mechanisms of N-methylaniline, N,N-dimethylaniline, and toluidines. To refine the main steps of the reaction, the transformations of the following individual compounds and intermediates, which were detected in the course of alkylation, were studied: dimethyl ether, surface methoxy groups, methylanilinium ions, formaldehyde, and N-methyleneaniline. It was found that N-methylaniline and N,N-dimethylaniline were formed as a result of aniline methylation by methanol dehydration products (methoxy groups or dimethyl ether) on acidic zeolites or as a result of alkylation by formaldehyde or methoxy groups on basic zeolites. Toluidines were formed by the isomerization ofN-methylanilinium ions, which were produced only on acidic zeolites, rather than by the direct alkylation of aniline.     

C-alkylation of m-cresol with n- and iso-propanol over iron catalyst

The gas-phase alkylation of m-cresol (3-methylphenol) with n-and iso-propanol was investigated. The reactions were carried out in a continuous process at atmospheric pressure over an iron catalyst that contains Cr, Si and K oxides. It is possible to obtain n and iso-propyl derivatives of m-cresol with satisfactory selectivity.     

Separation of iron(III) and gold(III) by paper chromatography using mixed solvents containing diisopropyl ether

The separation of iron(III) and gold(III) by partition paper chromatography has been investigated employing a mixture of diisopropyl ether (IPE) and n-alcohol saturated with hydrochloric acid (initial acid concentration 5.0 M) as solvent. Methyl, ethyl, n-propyl, n-butyl, and n-pentyl alcohols were used as components of the solvent. The content of n-alcohol in the initial organic phase was varied. It was found that the R_f values for both of the metals increased with an increase in the carbon-to-oxygen ratio in the alcohol (except in the case or iron(III) and n-pentyl alcohol), and with an increase in the alcohol content in the initial organic phase (except in the case of iron(III) and n-propyl alcohol). The best separation results were obtained by using the systems: hydrochloric acid (5.0 M)-IPE-n-propyl alcohol (50:35:15) gDR_f = 0.56, hydrochloric acid (5.0 M)-IPE-ethyl alcohol (50:15:35) ΔR_f = 0.51, and hydrochloric acid (5.0 M)-IPE-n-pentyl alcohol (50:35:15) ΔR_f = 0.37.     

Aqueous solution ofN-methylmorpholineN-oxide as a stationary liquid phase in steam chromatography

The retention of more than 70 voltatile organic compounds of different classes was studied by steam chromatography using aqueous solutions ofN-methylmorpholineN-oxide as the stationary liquid phase (SLP). The effects of temperature and composition of the mobile phase on the retention factors (k) for polar and nonpolar sorbates were elucidated. An unusual order of elution of aliphatic alcohols was noted, namely,tert-butyl alcohol <sec-butyl alcohol < isopentyl alcohol <isobutyl alcohol<isopropyl alcohol <n-pentyl alcohol <n-butyl alcohol <n-propyl alcohol <ethanol <methanol. The retention of cyclohexanol was longer than those of benzyl alcohol andn-hexyl alcohol. Nitrogen-containing compounds were selectively separated on the water-organic SLP studied. For example, the retention of aniline was much longer than those of its derivatives,N,N-dimethylaniline andN,N-diethylaniline, having higher boiling points. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1077–1084, June, 2000.     

Effect of pretreatment temperature on the acidity and aniline alkylation activity over HZSM-5

HZSM-5 zeolites with SiO₂/Al₂O₃ ratios of 30–280 are pretreated at 773 K and 1173 K. The effect of pretreatment temperature on acidity measured by ammonia desorption and aniline alkylation activity over these zeolites in the entire SiO₂/Al₂O₃ ratio range studied is discussed.IICT Communication No.: 3399     

Selective N-Monoalkylation of aniline derivatives by use of alkali cation exchanged X- and Y-type zeolites

Alkali cation exchanged X- and Y-type zeolites are employed to promote the reactions of aniline derivatives with alkylating agents in organic solvent. The N-alkylation is accelerated by the cooperative function of the acid and base sites on the potassium cation exchanged X- and Y-type zeolites to give the N-monoalkylated product in very high selectivity. Especially the use of the zeolite is found to be effective for N-alkylation of deactivated aromatic amines like nitroaniline. The highly selective N-monoalkylation is attributed to the reaction occurring inside the homogeneous narrow cavities of zeolites.     

Selective alkylation of xylenes by alcohols on zeolite catalysts

The peculiarities of catalytic performance of crystalline aluminosilicates of different types and compositions (X, Y including dealuminated Y, mordenite, pentasil ZSM-5), as well as of amorphous aluminosilicate catalyst in conversion of xylene + alcohol mixtures were studied. New data were obtained for alkylation ofo-xylene withtert-butyl alcohol, concerning controlling the selectivity and stability of the zeolite catalysts in reactions proceeding with the participation of water, including the water evolved during the reaction, in particular by controlling the acidic properties and hydrophobycity of the zeolites. A catalyst ensuring production of 1,2-dimethyl-4-tert-butylbenzene (DMTBB) with a 94% yield and selectivity of alcohol conversion to the target product of 94–97% was developed. The catalyst can be used as the basis for a high-performance and environmentally safe method for the synthesis of DMTBB. The catalysts developed can be also used for selective alkylation ofo-xylene by C₃-C₅ alcohols and for alkylation ofm-xylene bytert-butyl alcohol.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No, 12, pp, 2912–2917, December, 1996.     

Polymerization of aromatic nuclei. XXVI. Poly(p-phenylene): Friedel–crafts alkylation,molecular weight,and propagation mechanism

Poly(p-phenylene) was alkylated with n-propyl bromide, n-propyl chloride, and isopropyl bromide in the presence of aluminum chloride. Apparently, the reactions involve dialkylation with n-propyl halides and alternating mono- and dialkylation with isopropyl bromide. Alkylation with ethyl or n-butyl bromide was unsuccessful. The dialkylated polymer was sufficiently soluble to allow molecular weight determination. Mechanistic aspects of alkylation and propagation are treated.     

Indirect determination of thiamazole with the <Emphasis Type="Italic">n</Emphasis>-propyl alcohol-ammonium sulfate-H<Subscript>2</Subscript>O system by the extraction-flotation of CuSCN

In this paper, a new method for the determination of thiamazole by the extraction-flotation of CuSCN with n-propyl alcohol-ammonium sulfate-H₂O system was described. The experiment indicated that in the presence of SCN⁻, Cu(II) was reduced to Cu(I) by thiamazole because of the formation of CuSCN. In the course of phase separation of n-propyl alcohol from water, the precipitated CuSCN remained at the interface of n-propyl alcohol and water. A good linear relationship was obtained between the flotation yield of CuSCN and the amount of thiamazole. The detection limit of thiamazole was found to be 0.12 μg/mL and the linear range was 0.15–4.0 μg/mL with a correlation coefficient 0.9995. As a preliminary application, this method has been successfully applied to the determination of thiamazole in pharmaceutical formulations, human plasma and urine samples. The recoveries were in the range 98–103%, and the relative standard deviation values were not higher than 3.08%. The text was submitted by the authors in English.     

Anilines as C‐Nucleophiles in Ir‐Catalyzed Intramolecular Asymmetric Allylic Substitution Reactions

Anilines generally act as N‐nucleophiles in transition‐metal‐catalyzed allylic substitution reactions. In this paper, a highly enantioselective intramolecular Friedel–Crafts‐type allylic alkylation of aniline derivatives was realized by using an iridium catalyst derived from [Ir(cod)Cl]₂ and (R _a)‐BHPphos. Various tetrahydroisoquinilin‐5‐amines were obtained in moderate to good yields, excellent enantioselectivity and regioselectivity under mild reaction conditions. BHPphos=N ‐benzhydryl‐N ‐phenyldinaphthophosphoramidite.     

Endocyclische SN-Reaktionen am gesättigten Kohlenstoff? Vorläufige Mitteilung

Fig. 1 illustrates a definition of the terms endocyclic and exocyclic SN-reactions, referring to intramolecular nucleophilic substitution processes that occur by an SN₂-analogous mechanism. Crossing experiments show that the methyl transfer I → II (see scheme 1) does not follow the formally appealing mechanism of the endocyclic SN-process III; the reaction proceeds intermolecularly under all conditions investigated. Kinetic measurements indicate that the methyl transfer XI → XII (see scheme 3) occurs in a similar fashion. This behaviour is believed to follow from the preference of tetrahedral carbon for backside attack by the nucleophile in SN₂-reactions. The general experience, according to which intramolecular reaction paths over cyclic transition states with ring sizes of 5 or 6 are preferred to their intermolecular counterparts, is not to be extrapolated to SN₂-reactions at tetrahedral carbon.     

S,N‐Chelated organotin(IV) compounds containing 6‐phenylpyridazine‐3‐thiolate ligand—structural,antibacterial and antifungal study

A series of tri‐ and diorganotin(IV) compounds containing potentially chelating S,N‐ligand(s) (L^SN, where L^SN is 6‐phenylpyridazine‐3‐thiolate) were prepared and structurally characterized by multinuclear NMR spectroscopy. X‐ray diffraction techniques were used for determination of the structure of compounds containing one [(L^SN)Ph₂SnCl], two [(n‐Bu)₂Sn(L^SN)₂] and the combination of two L^SN and one L^CN [(L^CN)(n‐Bu)Sn(L^SN)₂] (where L^CN is {2‐[(CH₃)₂NCH₂]C₆H₄}‐) ligands. The coordination number of the tin atom varies from five to seven and is dependent on the number of chelating ligands present. The formation of the five‐membered azastanna heterocycle is favored over the formation of four‐membered azastannathia heterocycle in compounds containing both types of ligands. The di‐n‐butyl‐substituted compounds are the most efficient ones in inhibition of growth of yeasts, molds and G⁺ bacteria strains. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthese de fluoro-2 thiocyanates

2-Fluorinated thiocyanate compounds have been prepared by action of KSCN on an homologous series of 2-fluorotosylates in ethanol at about 100°C. The isomerization giving isothiocyanic derivatives does not take place under these conditions. The analysis of the NMR spectra on three members of the series has shown that the mechanism is of the SN₂ type.     

Synthesis of derivatives of prenylacetic acids by reactions of alkyl malonate, cyanoacetate, and acetoacetate with alkylating reagents in ionic liquids

A method for the synthesis of carboxylic acid derivatives containing one or two —CH₂CH _n (Me)CH _n+1CH₂— fragments (n = 0, 1) was developed. The method is based on the alkylation of (di)alkyl malonates, cyanoacetates, and acetoacetates with acyclic prenyl halides in ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate. For the ambident ethyl acetoacetate anion, the reactions with prenyl halides devoid of a double bond in the allylic position relative to the halogen atom carried out in the ionic liquids give mixtures of C- and O-alkylation products, while in the case of allylic prenyl halides, only C-alkylation products are formed. The reactions of ethyl 2-geranylmalonate and 2-geranylacetoacetate with bromocyclohexane and 1-chloro-3-dimethylaminopropane in ionic liquids provided derivatives of pharmacologically active geranylacetic acids. The product yields are higher than those in molecular organic solvents. The ionic liquids were recovered and reused in the alkylation.     

A hierarchically zeolite Y for the N-heterocyclic compounds synthesis

High activity and selectivity of the hierarchical H-Ymmm zeolite in the synthesis of practically important pyridines (by interaction of C₂–C₄ alcohols with formaldehyde and ammonia, cyclocondensation of acetaldehyde and propanal with ammonia), dialkyl quinolines (by reaction of aniline with aldehydes) and alkyl dihydroquinolines (by reaction of aniline with ketones- acetone, acetophenone) were revealed in the research.The advantages of the micro-meso-macroporous H-Ymmm zeolite over the microporous H-Y zeolite in the synthesis of pyridines and quinolines were demonstrated. In the products formed by the reaction of ethanol with formaldehyde and ammonia, picolines (up to 63%) and lutidine are predominant in H-Ymmm, Pb-H-Ymmm and Fe-H-Ymmm zeolites. The interaction of n-propanol (n-butanol) with formaldehyde and ammonia in the presence of H-Ymmm zeolite with high selectivity produced 3,5-lutidine (up to 90%) or 3,5-diethylpyridine (85%). H-Ymmm zeolite makes it possible to prepare 2-methyl-5-ethylpyridine with 87% selectivity (reaction of acetaldehyde with ammonia) and 2-ethyl-3,5-dimethylpyridine with 58% selectivity (reaction of propanal with ammonia).The synthesis of dialkylquinolines and dialkyltetrahydroquinolines with a total selectivity of 65–73% by the interaction of aniline with C₃–C₅ aldehydes has been carried out. The dihydroquinoline derivatives with the selectivity of up to 70% have been synthesized by the reaction of aniline with ketones (acetone, acetophenone).     

SUBSTITUENT EFFECTS OF PHOSPHORUS-CONTAINING GROUPS. THE ELECTRONIC EFFECTS IN ANILIDES AND PHENYL ESTERS

Abstract

¹³C NMR shielding parameters have been determined for the N-phosphorylated aniline and O-phosphorylated phenol derivatives, Ph–Y–P(O)Z₂ (Y=NH, O), and for their complexes with titanium tetrachloride. Inductive and resonance substituent constants were calculated using the dsp approach for the neutral and charged substituents. The results are compared with those for the corresponding neutral and charged acetyl derivatives. Shielding effects and substituent constants are discussed in terms of the interactions of the lone pair at Y with the aromatic ring and with the acyl center. It is concluded that no significant p _π-d _π back-donation from Y to the phosphorus atom operates in the systems studied.     

Preparation of 1,2- and 1,4-dihydro derivatives of 6,7-dimethyl-2,3-diphenylquinoxaline via its dianion formed by reductive metallation

Treatment of 6,7-dimethyl-2,3-diphenylquinoxaline with sodium in tetrahydrofuran formed a monomeric dianion. The chemical behavior of this dianion was investigated by a variety of reagents. As the result, alkylation reactions gave 1,2-dihydro derivatives, while acylation reactions occured at 1,4-positions. Annulation of the pyrazine ring system was accomplished by treating the dianion with oligomethylene dichlorides, Cl(CH₂) _n Cl, n = 2–4.     

Photochromic behavior of copolymers of indolinospirobenzopyrane methacrylic derivatives

Three photochromic 3,3-dimethyl-6′-nitroindolinospirobenzopyran methacrylic derivatives have been synthesized, namely, 1-methyl 8′-methacryloxymethyl (A), 1-(β-methacrylamidoethyl) (B), and 1-(β-methacryloxyethyl) (C). They have been copolymerized with methyl, isobutyl, and n-propyl methacrylates. The photochromic behavior of these copolymers in the solid state has been compared to that of the homologous isobutyric compounds dissolved in corresponding polymeric matrices. The kinetics of decoloration were resolved in three simultaneous first-order reactions with rate constants k₁, k₂, and k₃. The influence of the polarity of the polymeric matrix and of the photochrome incorporation has been examined. The rates of decoloration of the copolymers with isobutyl and n-propyl methacrylate are very sensitive to the glass transition temperature T_g; the activation energy of decoloration increases markedly above T_g, from 19.8 to 36.5 kcal; below T_g the entropy of activation is strongly negative (around -20 e.u.), above T_g strongly positive. These effects are interpreted on the basis of an increasing chain segment mobility above T_g.