Methylated ammonium compounds

Toluhydroquinone and methyl / fX butyUiydroquinone provide improved resin color retention 2,5-di-/-butyIhydroquinone also moderates the cure rate of the resin. Quaternary ammonium compounds, such as benzyl trimethyl ammonium hydroxide, are effective stabilizers in combination with hydroquinones and also produce beneficial improvements in color when promoted with cobalt octoate. Copper naphthenate is an active stabilizer at levels of 10 ppm at higher levels (150 ppm) it infiuences the cure rate. Tertiary butylcatechol (TBC) is a popular stabilizer used by fabricators to adjust room temperature gelation characteristics. 

QuaterniZation. Quaternary ammonium compounds are formed by alkylation of alkyl, alkyl dimethyl, dialkyl, and dialkylmethyl fatty amines with methyl chloride, dimethyl sulfate, or benzyl chloride (1,3,7,12,29). 

The most successful of these products contain high ratios of VP to DMAEMA and are partially quatemized with diethyl sulfate (Polyquaternium 11) (142—144). They afford very hard, clear, lustrous, nonflaking films on the hair that are easily removed by shampooing. More recendy, copolymers with methyl vinyl imidazoliiim chloride (Polyquaternium 16) (145) or MAPTAC (methacrylamidopropyltrimethyl ammonium chloride) (Polyquaternium 28) have been introduced. Replacement of the ester group in DMAEMA with an amide analog as in Polyquaternium 28 results in a resin resistant to alkaline hydrolysis and hence greater utility in alkaline permanent-wave and bleach formulations (see Quaternary ammonium compounds). 

Methylene chloride is easily reduced to methyl chloride and methane by alkaU metal ammonium compounds in Hquid ammonia. When the vapor is contacted with reduced nickel at 200°C in the presence of excess hydrogen, hydrogen chloride and elementary carbon are produced. Heating with alcohoHc ammonia at 100—125°C results in hexamethylenetetramine, (CH2) N4, a heterocycHc compound with aqueous ammonia at 200°C, hydrogen chloride, formic acid, and methylamine are produced. 

An alternative route from l-aminoanthraquinone (17) has been proposed. Methylation is preferably carried out usiag dimethyl sulfate or methyl iodide ia an organic solvent ia the presence of alkah metal hydroxide and a catalytic amount of quaternary ammonium compound (98). 

The determination of alkyltrimethyl ammonium compounds with the general formula RN (CH3)3X surfactant were performed using CF-FAB and ESI. The compounds examined were dodecyl-, tetradecyl-, and hexadecyl-trimethyl ammonium compounds dissolved in water. The product ion spectra of dodecyltrimethyl ammonium compound and its methyl-deuterated homologue were presented. The product ion at m/z 60 [(CH3)3NH]+of the non-deuterated compound at m/z 228 was the only ion that shifted after deuteration to m/z 69 [38],... 

The use pattern for methyl chloride in the United States in 1992 and 1995 was (%) methyl chlorosilanes used as intermediates for silicones, 80 methyl cellulose manufacture, 6 quaternary ammonium compounds, 5 agricultural chemicals, 5 butyl rubber production, 2 and miscellaneous, 2 (Anon., 1992, 1995). 

According to the 1981-83 National Occupational Exposure Survey (NOES, 1997), approximately 10 000 workers in the United States were potentially exposed to methyl chloride (see General Remarks). Occupational exposures to methyl chloride may occur in its production and in the production of silicones, methyl cellulose, quaternary ammonium compounds and other chemical agents. Data on workplace exposures to methyl chloride have been presented in a previous monograph (lARC, 1986). 

Preservatives such as sodium benzoate, sorbic acid, and methyl and propyl parabens have been used in liquid and semisolid dosage forms. There have been reports that the parabens have been inactivated when used in the presence of various surfactants. This loss of activity was thought to be due to the formation of complexes between the preservative and the surfactant. The interaction between polysorbate (Tween) 80 and the parabens has been demonstrated by a dialysis technique (Ravin and Radebaugh, 1990). It has also been shown that molecular complexes form when the parabens are mixed with polyethylene glycol (PEG) and methylcellulose. The degree of binding was less than that observed with Tween 80. Sorbic acid also interacts with Tweens but does not interact with PEGs. The quaternary ammonium compounds are also bound by Tween 80, which reduces their preservative activity. 

The chloride is used to manufacture silicones, tetramethyl lead and triptane (2,2,3 trimethylbutane). Lesser uses include the manufacture of butyl rubber, higher halogenated methanes, methyl cellulose, quaternary ammonium compounds, methyl mercaptan, methionine, fungicides and pesticides (primarily the Me-arsenate herbicides). Recently the chlorinated fluorocarbons have replaced CH3CI as high volume refrigerants and propellants (ref. 32) Tables 12 and 13 list the chemical and physical properties and potential numbers of workers exposed to the monohalomethanes. 

Here, the catalyst was ammonium compound 27, and 1 served as F-source. Under optimized conditions, methyl indanone carboxylate 26 was fluorinated with up to 68% ee. 

Fig. 6.9. Electrochromatogram of two antidepressant drugs (amitriptyline 1, nortriptyline 2) and a related quaternary ammonium compound (methyl amitriptyline 3) obtained by isocratic elution in 30.6 cm long channel. Conditions mobile phase, 5 mmol/L sodium phosphate, pH 2.5, containing 70% acetonitrile (v/v) flow rate of the mobile phase through the inlet reservoir, 50 pL/min applied voltage, 12 kV (400 V/cm) electrokinetic injection, 1 kV, 5 s UV detection at 239 nm sample concentration, 0.10-0.15 mg/mL. (Reprinted with permission from [33]. Copyright 2000 American Chemical Society).

Figure 6.2. (Upper panel) The four major classes of organic osmolytes (I) sugars and polyhydric alcohols (polyols) (II) amino acids and amino acid derivatives (III) methylated ammonium and sulfonium compounds and (IV) urea. (Figure modified after Somero and Yancey, 1997.) (Lower panel) Structures of charged osmolytes accumulated in extremely halophilic archaea (after Martin et al., 1999). Note that these osmolytes commonly represent a type of organic osmolyte that is found in many bacteria or eukaryotes to which a charged group has been attached. Typically, the charged group is anionic, for example, a phosphate or a carboxylate group.

Quaternary ammonium compounds are important as osmoprotectants in times of water deficiency and cold stress, as well as being constituents of membrane phospholipids, p-Alanine and phosphoethanolamine are each methylated three times on their nitrogens to produce the products P-alanine betaine and phosphocholine, respectively (Fig. ll.l).24"27 An example of O-methylation and N-methylation occurring on the same molecule can be found in the indole alkaloid vindoline from Catharanthus roseus (Fig. 11.1) 28,29... 

Some organic compounds contain ionic bonds. For example, the structure of methyl-ammonium chloride (CH3NH3C1) cannot be drawn using just covalent bonds. That would require nitrogen to have five bonds, implying ten electrons in its valence shell. The correct structure shows the chloride ion ionically bonded to the rest of the structure. 

Methyl chloride is the only chlorinated methane with good growth. The principal use for methyl chloride is in the manufacture of chlorosilanes (89%) for the silicone industry. Other smaller uses are for methyl cellulose ether, quaternary ammonium compounds, herbicides, and butyl rubber. 

Sandia National Laboratories decontaminating foam (licensed to Modec Inc., Denver, Colorado) is a solution (MDF-100) composed of two parts part a a solution of 6.6% V,VAUV"dV -penta-methyl,-V -tallow alkyl 1,3-prop-anamine diammonium 2.6% tallow pentamethyl propane quaternary ammonium compounds benzyl-C12-18 alkyl dimethyl 1% isopropyl alcohol, and part b a solution of 8% hydrogen peroxide. Mixing the two parts results in a foamlike product which lasts for up to 30 min (Figure 71.2). 

The asymmetrical tertiary amines are used exclusively as starting materials for the manufacture of quaternary ammonium compounds, cationic and amphoteric surfactants, and amine oxides. Quaternary ammonium compounds used as bactericides and algicides are produced by the reaction of tertiary amines with benzyl chloride, methyl chloride, or dimethyl sulfate. Of these, the benzyl ammonium chloride salt is the most widely used. 

The compound formed from the amine is a substituted ammonium salt, viz., methyl ammonium iodide. It is known more generally, however, as methyl amine hydriodide, and is usually written, CHs—NH2—HI. When this salt is treated with a stronger base, e.g., sodium hydroxide, the amine is again formed just as ammonia, NH3, is set free from its salts by the same reagent. 

These salts are known as tetra-methyl ammonium salts or quaternary compounds. 

The tertiary amine group in this last compound being more strongly basic than the primary amine group in amino acetic acid would more readily form an inner ammonium salt. There is also a tetra-methyl ammonium iodide compound formed analogous to the tetra-methyl ammonium salts of the alkyl amines. 

Betaine is the tetra-methyl ammonium inner salt compound already referred to (p. 386). It is really a tri-methyl derivative of glycine. 

---