Phenyltrimethylammonium

There is increasing evidence that the ionisation of the organic indicators of the same type, and previously thought to behave similarly, depends to some degree on their specific structures, thereby diminishing the generality of the derived scales of acidity. In the present case, the assumption that nitric acid behaves like organic indicators must be open to doubt. However, the and /fp scales are so different, and the correspondence of the acidity-dependence of nitration with so much better than with Hg, that the effectiveness of the nitronium ion is firmly established. The relationship between rates of nitration and was subsequently shown to hold up to about 82 % sulphuric acid for nitrobenzene, />-chloronitrobenzene, phenyltrimethylammonium ion, and p-tolyltrimethylammonium ion, and for various other compounds. ... 

Wheland intermediate (see below) as its model for the transition state. In this form it is illustrated by the case mentioned above, that of nitration of the phenyltrimethylammonium ion. For this case the transition state for -nitration is represented by (v) and that for p-substitution by (vi). It is argued that electrostatic repulsions in the former are smaller than in the latter, so that m-nitration is favoured, though it is associated rvith deactivation. Similar descriptions can be given for the gross effects of other substituents upon orientation. 

A systematic nomenclature for nAChRs has yet to evolve. An N nomenclature describes receptors present ia muscle as N. These are activated by phenyltrimethylammonium (PTMA) (15) and blocked by t5 -tubocurariae (16) and a-bungarotoxiu (a-BgT) (17). N2 receptors are present ia ganglia and are activated by l,l-dimethyl-4-phenylpipera2inium (DMPP) (18) and blocked by trimethaphan (19) and bis-quatemary agents, with hexamethonium (20) being the most potent. 

Bromination of 5j5-3-ketones yields the equatorial 4 -bromo compounds (22) as the thermodynamic or kinetic products,although the presence of a considerable amount of 2-bromo isomer has been reported in bromination with phenyltrimethylammonium bromide-perbromide. This is in keeping with other evidence that enolization of 5j5-3-ketones is not specifically directed to C-4. Cleaner results would probably be obtained via thermodynamic enol acelylation. ... 

The ionization eonstant should be a function of the intrinsic heterolytic ability (e.g., intrinsic acidity if the solute is an acid HX) and the ionizing power of the solvents, whereas the dissoeiation constant should be primarily determined by the dissociating power of the solvent. Therefore, Ad is expeeted to be under the eontrol of e, the dieleetrie eonstant. As a consequenee, ion pairs are not deteetable in high-e solvents like water, which is why the terms ionization constant and dissociation constant are often used interchangeably. In low-e solvents, however, dissociation constants are very small and ion pairs (and higher aggregates) become important species. For example, in ethylene chloride (e = 10.23), the dissociation constants of substituted phenyltrimethylammonium perchlorate salts are of the order 10 . Overall dissociation constants, expressed as pArx = — log Arx, for some substanees in aeetie acid (e = 6.19) are perchloric acid, 4.87 sulfuric acid, 7.24 sodium acetate, 6.68 sodium perchlorate, 5.48. Aeid-base equilibria in aeetie acid have been earefully studied beeause of the analytical importance of this solvent in titrimetry. 

The metal catalyst is not absolutely required for the aziridination reaction, and other positive nitrogen sources may also be used. After some years of optimization of the reactions of alkenes with positive nitrogen sources in the presence of bromine equivalents, Sharpless et al. reported the utility of chloramine-T in alkene aziridinations [24]. Electron-rich or electron-neutral alkenes react with the anhydrous chloramines and phenyltrimethylammonium tribromide in acetonitrile at ambient temperature, with allylic alcohols being particularly good substrates for the reaction (Schemes 4.18 and 4.19). 

Two methods that are particularly convenient for large-scale synthesis of aziridines are discussed below. Both utilize readily available chloramine salts, such as chloramine-T, as sources of nitrogen. The first method involves direct olefin azir-idination catalyzed by phenyltrimethylammonium tribromide (PhNMe3+Br3 PTAB) [42]. In the second method, 1,2-hydroxysulfonamides, conveniently obtained by osmium-catalyzed aminohydroxylation of olefins, are converted into aziridines by one-pot cyclodehydration. 

The log rate versus acid strength curve for the latter compound is of the exact form expected for reactions of the free base, whilst that of the former compound is intermediate between this form and that obtained for the nitration of aniline and phenyltrimethylammonium ion, i.e. compounds which react as positive species. That these compounds react mainly or entirely via the free base is also indicated by the comparison of the rate coefficients in Table 8 with those in Table 5, from which it can be seen that the nitro substituent here only deactivates weakly, whilst the chloro substitutent appears to activate. In addition, both compounds show a solvent isotope effect (Table 9), the rate coefficients being lower for the deuterium-containing media, as expected since the free base concentration will be lower in these. 

In this work, Brand and Horning158 showed that the rate of sulphonation of phenyltrimethylammonium ion was linearly related to the calculated concentration of protonated sulphur trioxide HSO3, indicating it to be the electrophile. Added sulphate anions reduced the rate for 4-nitrotoluene in direct proportion to their concentration, and this followed from the equilibrium... 

Polk et al. reported27 that PET fibers could be hydrolyzed with 5% aqueous sodium hydroxide at 80°C in the presence of trioctylmethylammonium bromide in 60 min to obtain terephthalic acid in 93% yield. The results of catalytic depolymerization of PET without agitation are listed in Table 10.1. The results of catalytic depolymerization of PET with agitation are listed in Table 10.2. As expected, agitation shortened the time required for 100% conversion. Results (Table 10.1) for the quaternary salts with a halide counterion were promising. Phenyltrimethylammonium chloride (PTMAC) was chosen to ascertain whether steric effects would hinder catalytic activity. Bulky alkyl groups of the quaternary ammonium compounds were expected to hinder close approach of the catalyst to the somewhat hidden carbonyl groups of the fiber structure. The results indicate that steric hindrance is not a problem for PET hydrolysis under this set of conditions since the depolymerization results were substantially lower for PTMAC than for die more sterically hindered quaternary salts. 

In a 300-mL round-bottom flask, a 5% sodium hydroxide solution (250 mL) was heated to 80° C in a constant-temperature bath. The catalysts were added in the following amounts in separate experiments trioctylmethy-lammonium chloride (TOMAC) (0.04 g, 0.0001 mol) trioctylmethylammo-nium bromide (TOMAB) (0.045 g, 0.0001 mol) hexadecyltrimethylammo-nium bromide (HTMAB) (0.045 g, 0.0001 mol) tetraethylammonium hydroxide (TEAOH) (0.015 g, 0.0001 mol) and phenyltrimethylammonium chloride (PTMAC) (0.02 g, 0.0001 mol). PET fibers (1.98 g, 0.01 mol) were added to the mixture and allowed to react for 30, 60, 90, 150, and 240 min. Upon filtration, any remaining fibers were washed several times with water, dried in an oven at 130-150°C, and weighed. The results are shown in Table 10.1. 

Phenyl-ethynyl-terminated resins, 267 Phenyltrimethylammonium chloride (PTMAC), 549 Phillips-type catalysts, 431 PhNCO-2-ethyl hexanol reaction, 229 Phosgenation, 222... 

Phenyltrimethylammonium Ion, N+(CH3)S-CaHe.—In this ion, as in toluene, we ignore the electrons involved in bonds from nitrogen to the attached groups, and consider only the inductive effect. The positive charge on the nitrogen atom increases its electron affinity to a value still greater than that for neutral nitrogen, so that we... 

By introducing reasonable values (about 2 for nitrogen, 4 for oxygen) for the electron affinity parameter relative to carbon, 8, and for the induced electron affinity for adjacent atoms (32/8i = Vio), we have shown that the calculated permanent charge distributions for pyridine, toluene, phenyltrimethylammonium ion, nitrobenzene, benzoic acid, benzaldehyde, acetophenone, benzo-nitrile, furan, thiophene, pyrrole, aniline, and phenol can be satisfactorily correlated qualitatively with the observed positions and rates of substitution. For naphthalene and the halogen benzenes this calculation does not lead to results... 

As these solid agents, some quaternary ammonium tribromides such as pyridinium hydrobromide perbromide (ref. 1), phenyltrimethylammonium tribromide (ref. 2), tetramethylammonium tribromide (ref. 3), and tetrabutyl-ammonium tribromide (ref. 4) have already been reported as mild and selective brominating agents (Fig. 1). 

If in the quaternary ion a /3-hydrogen is not available, as in tetramethyl-, benzyltrimethyl- or phenyltrimethylammonium hydroxide, reaction 4.101 cannot occur, but reaction 4.102 still can this means that the quaternary ammonium ions without a /1-hydrogen are appreciably more stable, so that the type of base concerned is mainly the commercially available one (in alcoholic solution) (CH3)4NOH appears especially attractive, although the (CH3)4N salts are less soluble in non-aqueous media than, for instance, (C4H9)4N salts. 

Phenyltrimethylammonium sulfo-methylate, 53, 111 Phenyltrimethylammonium tribromide, selective bromina-tion with, 53, 112, 114 4-Phenylurazole, from 4-phenyl-1-carbethoxysemicarbazide and potassium hydroxide,... 

Tosylhydrazones react with phenyltrimethylammonium tribromide under phase-transfer catalysed basic conditions to yield, initially, a-bromo- and derivatives which, under the basic conditions, eliminate one equivalent of HBr to yield unstable 2-tosylazopropenes [27]. 

The bromination-dehydrobromination route is in many cases preferable [Scheme 2 80JCS(P1)2081], using bromine, N-bromosuceinimide (NBS), or phenyltrimethylammonium tribromide (PTAB). The resulting mono-bromo, geminal, or vicinal dibromo and tribromo derivatives (e.g., 5a,b) are often preferentially dehydrobrominated by Jones method [73JCS(P1)968] using lithium salts in dimethylformamide (DMF). Bases such as triethyla-mine, sodium methoxide, and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were also used. 

Dextromethorphan Dextromethorphan, (9a, 13a, 14a)-3-methoxy-17-methylmorphinane (23.2.1), is synthesized from ( )-3-hydroxy-iV-methylmorphinane by methylating the phenol hydroxyl group using phenyltrimethylammonium chloride and sodium methoxide in methanol. The resulting racemic product ( )-3-methoxy-Af-methyhnorphinane is separated into isomers using D-tartaric acid, which produces dextromethor-phan [1,2]. 

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