Triethyl Benzyl Ammonium Research Articles

Phase transfer catalysis: Kinetics and mechanism of hydroxide ion initiated dichlorocarbene addition to styrene catalysed by triethylbenzylammonium chloride

The kinetics of dichlorocarbene addition to styrene was studied under phase-transfer catalytic conditions using aqueous sodium hydroxide as the base and triethylbenzyl ammonium chloride as the phase-transfer catalyst. The reaction was carried out at 40°C under pseudo first-order condition by keeping aqueous sodium hydroxide and chloroform in excess. The fiogress of the reaction was monitored by gas chromatography. The effects of various experimental conditions on the rate of the reaction were studied and based on the results obtained a suitable mechanism has been proposed.

Neue oder verbesserte Synthesen für Germa- und Germa-sila-alkane und ihre chlorierten Vorstufen / New or Improved Syntheses for Germa- and Germa-sila-alkanes and their Chlorinated Precursors

Reaction of germanium powder and Cl3SiCH2Cl at 350 °C yields the l-germa-3-silapropane Cl3SiCH2GeCl3, and (Cl3SiCH2)2GeCl2, in a “Direct Synthesis”. Cl3GeCH2CH2GeCl3 is obtained from HGeCl3 and C2H2 as a “Hydrogermylation” product. Addition of CH2=CHSiCl3 to HGeCl3 yields the 1-germa-4-silabutane Cl3SiCH,CH2GeCl3, and Cl3GeCH2C(GeCl3)=CH2 is obtained similarly from ClCH2C=CH and HGeCl3-NEt3. These Chlorogermanes or -germanes/silanes are converted into the corresponding germanes (silanes) by treatment with LiAlH4 in tetralin as a solvent in the presence of triethyl(benzyl)ammonium chloride. The products are isolated in high yields and identified by standard analytical techniques, including 73Ge NMR spectroscopy. Owing to their high volatility they are potential feed-stock gases for CVD experiments to generate a-GeC:H or a-Ge,Si,C:H materials.

1,1-Dichlorocyclopropane derivatives of α and β ionones. Structure determination of 3R,3′S-bis[3-methyl-5-(1′,3′,3′-trimethylcyclohex-1′-en-2′-yl)-2(1H)-furanone

1,1-Dihalocyclopropane derivatives and furanones were synthesized from ±α- and β-ionones using CHCl3, NaOH, and triethylbenzyl ammonium chloride (TEBAC). 2D NMR and single-crystal X-ray analyses of the products are reported. Keywords: addition of 1,1-dihalocarbenes to ionones, phase transfer addition of 1,1-dihalo systems, formation of cyclopropanes.

Synthesis of desyl esters by the application of phase transfer catalysis and a study of the fluorescent properties of 2-substituted i,5-diphenyloxazoles derived from desyl esters

Desyl alcohol was converted to desyi chloride by the application of phasetransfer catalysis using triethyl benzyl ammonium chloride (TEBA) in aqueous sodium hydroxide and chloroform at 0–5° C. The desyl chloride thus obtained was condensed with the potassium salts of various carboxylic acids under phase-transfer catalysis using PEG-400 to give the desyl esters in excellent yields. These were cyclized to 2-substituted4,5-diphenyloxazoles. 2-(4-Nitrophenyl)-4,5-diphenyloxazole was reduced to the 2-(4-aminophenyl) derivative, which upon acetylation yielded 2-(4-acetamidophenyl)-4,5-diphenyloxazole. The fluorescent properties of the 2-substituted 4,5-diphenyloxazoles were studied.

UV, IR, 71Ga and 17O NMR Spectroscopic studies of the 12-Molybdogallate Heteropolyanion

Abstract UV, IR, 7Ga and 17O NMR spectra clearly demonstrate the Keggin structure for the new heteropolyanion—12-molybdogallate (12-MGA). The UV spectrum of the 12-MGA solution has charge-transfer bands at 49,000, 40,000 and 32,500 cm−1, which have been attributed to oxygen-to-molybdenum(VI) transitions. The IR spectra of the synthesized samples of 12-MGA contain the expected triplet of bands, which could be assigned to molybdenum-oxygen stretching vibrations. The data obtained from the 71Ga and 17O NMR spectroscopy confirmed the tetrahedral oxygen environment of the gallium atoms and the Keggin structure of 12-MGA. The 71Ga NMR chemical shifts of crystalline (TEBA)5GaMo12O40 (TEBA—triethylbenzyl ammonium) as well as of aqueous solutions of 12-MGA are situated in the range characteristic of a tetrahedral oxygen environment of gallium (223 ppm relative to Ga(H2O)63+). In these solutions GaMo6O24H63− polyanions can co-exist (52 ppm). The 17O NMR spectrum of Na5GaMo12O40 has three resonances with chemical shifts of 923, 575 and 568 ppm (relative to H2O) and an intensity ratio 1:1:1, which is similar to the spectra of other Keggin heteropolyanions. The changes of the nature and length of the MoO bonds in the 12-molybdogallate relative to the parent 12- molybdophosphate are discussed.

The chemistry of polycyclic arene imines. V. Reactions of phenanthrene 9,10‐imine with nucleophiles under phase transfer conditions

AbstractReactions of phenanthrene 9,10‐imine (1) with alkyl halides, sodium azide and ammonium thiocyanate in two liquid phase systems were investigated. In the presence of aqueous sodium hydroxide and alkyl halides triethylbenzylammonium (TEBA) salts promote N‐alkylation of 1 with preservation of the aziridine ring. Tetrabutylammonium (TBA) salts catalyze nucleophilic substitutions in which the three membered ring is cleaved. Aqueous sodium azide reacts with 1 to give trans‐10‐azido‐9,10‐dihydro‐9‐phenanthrenamine (2). Ammonium and potassium thiocyanate cause expansion of the aziridine ring; while the unsubstituted imine 1 yields the 2‐thiazolamine derivative 4, N‐butylphenanthrene 9,10‐imine (8) froms trans‐3a,11b‐dihydro‐3‐butylphenanthro[9,10‐d]thiazol‐2‐imine (9) with an exocyclic CN bond. The structure of 9 was established by X‐ray crystal analysis.

Molecular movement and magnetic relaxation of 13C-nuclei of organic ions in the ion exchange resin phase

Fourier spectroscopy in the regime of the total hetero nuclear decoupling of 13C—{ 1H} has been used to measure the spin-spin and spin-lattice relaxation times of the 13C nuclei of the triethylbenzyl ammonium ion in completely saturated Dowex-50 and KRS resins with a content of crosslinker 2, 4, 8 and 12% at 33°C. Analysis of the findings coupled with the results of measurement of the Overhausser nuclear coefficient indicates the strongly hindered character of the movement of the ion rising with increase in the degree of crosslinking of the resin, slowing of the molecular movement of the counter-ion is not accompanied by appreciable changes in the position of the resonance signals of the 13C nuclei. In all the resins studied major deviations of the ratio of the relaxation times T 1/ T 2 from unity were observed. The lower boundary of the correlation times of the total rotation of the ion is 0·1 nsec.

Cu2+ in pseudotetrahedral symmetry: Magnetic anisotropy, susceptibility, and EPR of bis(trimethyl- and triethyl benzyl ammonium) tetrachlorocuprate (II) from 300 to 77 K

The paramagnetic anisotropies and EPR at X-band in single crystals and the mean susceptibilities of the compounds M2I[(CuCl4)] (where MI = trimethylbenzylammonium (A) or triethylbenzylammonium (B)) belonging to the space group P21/n with four formula units in the unit cell and of ionic symmetry D2d are measured in the temperature range 300 to 77 K. The magnetic anisotropy measurements show the presence of two magnetically inequivalent ions in the unit cell contrary to deductions from X-ray. The peak-to-peak line width in EPR spectrum in the ac plane changes appreciably at 77 K with respect to room temperature. The experimental results are fitted to the theoretical expressions. Im Temperaturbereich von 300 bis 70 K werden paramagnetische Anisotropien und X-Band-EPR in Einkristallen sowie die mittleren Suszeptibilitaten der Verbindungen M2I[(CuCl4)] (wobei MI = Trimethylbenzylammonium (A) oder Triathylbenzylammonium (B) darstellt) untersucht, die zur Raumgruppe P21/n gehoren mit vier Formeleinheiten in der Einheitszelle und der ionischen Symmetrie D2d. Die Messungen der magnetischen Anisotropie ergeben zwei magnetisch inaquivalente Ionen in der Einheitszelle im Gegensatz zu den Rontgenstrahlenergebnissen. Die Linienbreite des EPR-Spektrums in der ac-Ebene andert sich bei 77 K betrachtlich gegenuber Zimmertemperatur. Die experimentellen Ergebnisse werden an theoretische Ausdrucke angepast.

Mechanism of catalytic action in the synthesis of polycarbonates by interfacial condensation

IN OBTAINING polycarbonates formed by interracial condensation, it has been suggested that tertiary amines and salts of quaternary ammonium bases, the use of which makes it possible to obtain high molecular weight polycarbonates [1], should be used as catalysts. In reference [2], the suggestion was expressed that tertiary amines form salts of N,N-carbonyldiamine [(NRaCONRa)~+Clz -] with phosgene, and that these salts transfer from the aqueous into the organic phase and react with aliphatic-aromatic oxy-compounds with the formation of neutral esters, esters of chlorocarbonic acid and free amine. However, such a mechanism cannot explain the difference in effect of the various amines and salts of quaternary ammonium bases on the yield and molecular weight of the polycarbonates formed. Moreover, this cannot explain the effect of the concentration of the tertiary amine on the yield and molecular weight of the polymers. I f the action of the catalyst leads only to a retardation in the hydrolysis of phosgene, then it is not clear why the optimum amount of phosgene required during the synthesis is considerably greater than the theoretical amount, nor is it clear what the role is of the catalyst when it is added after the introduction of phosgene into the reaction system. We have tested t h e following compounds as catalysts during the synthesis of polycarbonates: triethylamine (I), triethylbenzyl ammonium chloride (II), dlmethylphenylbenzyl ammonium chloride (III), tetraethyl ammonium chloride (IV), tetraethyl ammonium bromide (V), tetrabutyl ammonium iodide (VI), triethylmethyl ammonium bromide (VII), and hexamethylene tetramine (VIII). The results obtained in the synthesis of the polycarbonate from 2,2-di-(4-oxy3-methylphenyl)propane with the use of these catalysts are shown in Table 1. From Table 1 it can be seen that the best results were obtained with the use of catalysts I and II , and somewhat poorer results by the use of catalyst I I I . With the aim of clarifying the behaviour of the catalysts in the reaction system, we qualitatively determined the solubility of the catalysts in the solvent and we followed the changes which took place in the catalyst solution on adding

0.1M ジメチル-ベンジル-フェニルアンモニウム塩化物-塩酸系における諸元素の行動

ジメチル-ベンジル-フェニルアンモニウム塩化物の0.1Mクロロホルム溶液と塩酸の系における,ナトリウムよりネプツニウムに至る約60種の元素の行動を輸入またはJRR-1で照射して作った放射性核種を用いて調べた。水溶液の塩酸の濃度は0.5, 1, 2, 4, 6, 8, 10および12Nの8点をとり,これに対する有機相との間の分配比を求めた。分配比の測定に用いた放射性核種の原子価は明瞭でないものもあるが,最も普通の化学形を選んだ。酸の濃度に対する分配比は各元素により異なるが,周期律表の族についてはかなりの規則性がみられた。 Fe (III)では特に鉄の量の変化による分配比の変化を調べた。これらの結果より数種の元素の相互分離に適した酸の濃度が求められた。この系で求められた結果を塩酸-陰イオン交換樹脂系や,チオシアン酸-トリエチル-ベンジルアンモニウム塩化物系と比較しかなりの類似点を見出したが,一般にこの系では分配比が小さいことがわかった。