Tetramethylammonium compounds

Nambu, N., R. Takahashi, K. Suzuki, and Y. Sasaki. 2013. Electrolytic properties of tetramethylammonium compound in highly concentrated solutions and its application to electric double-layer capacitors. Electrochemistry 81 811-813. 

Ammonium Compounds. Salts and hydroxides containing quadricovalent nitrogen are named as a substituted ammonium salt or hydroxide. The names of the substituting radicals precede the word ammonium, and then the name of the anion is added as a separate word. For example, (CH3)4N+I is tetramethylammonium iodide. 

Physical Properties. Most quaternary compounds are soHd materials that have indefinite melting poiats and decompose on heating. Physical properties are determined by the chemical stmcture of the quaternary ammonium compound as well as any additives such as solvents. The simplest quaternary ammonium compound, tetramethylammonium chloride [75-57-0] is very soluble ia water (163) and iasoluble ia nonpolar solvents. As the molecular weight of the quaternary compound iacreases, solubiUty ia polar solvents decreases and solubiUty ia nonpolar solvents iacreases (164—166). For example, trimethyloctadecylammonium chloride [112-03-8] is soluble ia water up to whereas dimethyldioctadecylammonium chloride [107-64-2] has... 

Double asymmetric induction operates when the azomethine compound is derived from a chiral a-amino aldehyde and a chiral amine, e.g., the sulfin-imine 144 [70]. In this case, the R configuration at the sulfur of the chiral auxihary, N-tert-butanesulfinamide, matched with the S configuration of the starting a-amino aldehyde, allowing complete stereocontrol to be achieved in the preparation of the diamine derivatives 145 by the addition of trifluo-romethyl anion, which was formed from trifluoromethyltrimethylsilane in the presence of tetramethylammonium fluoride (Scheme 23). The substituents at both nitrogen atoms were easily removed by routine procedures see, for example, the preparation of the free diamine 146. On the other hand, a lower diastereoselectivity (dr 80 20) was observed in one reaction carried out on the imine derived from (it)-aldehyde and (it)-sulfinamide. 

A. Joll, T. Huynh and A. Heitz, Off line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids decarboxylation of some ortho and/ or para substituted aromatic carboxylic acids, J. Anal. Appl. Pyrol., 70, 151 167 (2003). 

Workers at Spectra Group, Ltd. (5) have recently investigated use of borate compounds (tetramethylammonium triphenylbutyl borate (1), and butyryl choline triphenyl butylborate (5) in conjunction with DIBF, OPPI and DIDMA. 

In addition to substitution N-bromosuccinimide also forms addition compounds although in small amounts. Such addition reactions are catalysed by tetra-alkyl ammonium salts. Thus while with cyclohexene allylic substitution occurs, in presence of tetramethylammonium bromide, 1 2 dibromocyclohexane is obtained as the main product. 

Many of the salts which have been prepared are explosive and sensitive to heat or impact. These include chlorites of copper (violent on impact), hydrazine (monochlorite, inflames when dry), nickel (explodes at 100°C but not on impact), silver (at 105° or on impact), sodium, tetramethylammonium, mercury, thallium and lead (which shows detonator properties). Several other chlorites not isolated and unstable in solution include mono-, di- and tri-methylammonium chlorites. The metal salts are powerful oxidants [1], Chlorites are much less stable than the corresponding chlorates, and most will explode under shock or on heating to around 100°C [2], Individually indexed compounds are ... 

Solid lithium aluminium hydride can be solublized in non-polar organic solvents with benzyltriethylammonium chloride. Initially, the catalytic effect of the lithium cation in the reduction of carbonyl compounds was emphasized [l-3], but this has since been refuted. A more recent evaluation of the use of quaternary ammonium aluminium hydrides shows that the purity of the lithium aluminium hydride and the dryness of the solvent are critical, but it has also been noted that trace amounts of water in the solid liquid system are beneficial to the reaction [4]. The quaternary ammonium aluminium hydrides have greater hydrolytic stability than the lithium salt the tetramethylammonium aluminium hydride is hydrolysed slowly in dilute aqueous acid and more lipophilic ammonium salts are more stable [4, 5]. 

The regiospecificity of the exclusive O-acylation [8] and O-phosphorylation [9] of P-dicarbonyl compounds (Chapter 3) also illustrates the effect of phase-transfer catalysts on the stereochemical course of reactions. Similarly, directed reduction of P-hydroxy ketones using tetramethylammonium trisacetoxyborohydride leads to the preferential formation of the anti dihydroxy system in high yield with a stereoselectivity >95% [10] (Section 11.4). 

The Heidelberg group (Diehl et al., 2001) chose (carboxymethyl) trime-thylammonium hydroxide, commonly known as betaine (Figure 4.33) as a substitute for DMSO. Why these researchers selected betaine and did not consider other additives was not discussed. However, we do know from other works (see cited references) that this compound is effective in reducing stability differences between A T and G C base pairing during hybridization, much like the action of tetramethylammonium chloride or formamide (Rees et al., 1993). Thus, betaine also provides a simple means to denature DNA and maintain such probes in a single-stranded state. 

The above speculation [21] may be extended to include the related quaternary ammonium compounds such as xylocholine (XXXIX). It is probable that the volumes of the guanidinium ion and the trimethylammonium group are similar. The ionic radius of the guanidinium ion (IX) is about 3A the ionic radius of the tetramethylammonium ion has been estimated [300] to be 3-4A, although rather smaller values have also been proposed [301-303]. Crystallographic analyses of muscarine iodide [304], choline chloride [305] and acetylcholine bromide [306] have revealed that the carbon to nitrogen distance is about l-SA, and that a hydrogen bond (C-H-0 distance 2-87-3 07A) exists in the crystals of these compounds. 

Materials. Epoxy novolac, DEN-431, obtained from Dow Chemical Co. was selected as the epoxy component. A 3,3 -diazidodiphenyl sulfone synthesized in our laboratory (5) was used as the azide compound. Poly(/7-vinyl phenol) obtained from Maruzen Oil Co. was used as the phenolic resin matrix. The coating solvent was cyclohexanone. The developer used in this study was 0.1 N tetramethylammonium hydroxide aqueous solution. 

Bis(tetramethylammonium) hexa-/z-carbonyl-hexacarbonylhexanickelate(2—) is obtained as shiny red crystals. The compound is air sensitive both in solution and in the solid state. 

Tetramethylammonium fluoride is a highly effective reagent for the preparation of selectively fluorinated aromatic compounds. 2-Nitrobenzaldehyde (5) is converted to 2-fluorobenzalde-hyde (6) in 60% yield.190... 

According to le Roux [53] tetramethylammonium nitrate has no explosive properties it did not detonate even when initiated by a strong charge of PETN. Attempts to provoke explosive decomposition by impact failed. Le Roux suggested that the compound might be used as an ingredient of explosive mixtures, for instance blended with cyclonite or incorporated in a fusible mixture with ammonium nitrate (see Vol. III). 

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