Methy lamine

Aliphatic analogues of aniline and nitrobenzene were discovered somewhat later. Methy-lamine and ethylamine were first prepared by Wurtz in 184914, and thereafter many aliphatic amines were made and their properties studied13, particularly by Hofmann15. 

A Ag/Pd-cathode hydrogenates 2-butyne-1,4-diol and acetylene dicarboxylic acid exclusively to the cis-olefin [323]. Similar results were obtained at a Cu net covered with spongy silver [324]. With dimethyl butynedioate the cis/trans ratio of the product dimethyl butenedioate on a Pd black cathode decreased with increasing pH both in electrolytic and catalytic hydrogenation [325]. On the other side at a Hg cathode a trans addition to alkynes occurs [326]. In methy-lamine/liCl, dialkylacetylenes are reduced to trans-olefins. Nonconjugated aromatic internal acetylenes are selectively reduced to aromatic trans-olefins [327]. 

Reduction in liquid NH3 and NaCl at Pt electrodes gives a 90% yield of a mixture consisting of 85% (A) (Fig. 60) and 14% (C) [329]. The hydrogenations in methy-lamine or ammonia are cathodic Birch reductions in which the final protonation of the intermediate anion leads to the thermodynamically more favorable trans product. 

The pATa values for the amines ammonia, methy-lamine, dimethylamine, and trimethylamine are 9.2, 10.6, 10.7, and 9.8 respectively. The electron-donating effect of the methyl substituents increases the basic strength of methylamine over ammonia by about 1.4 pATa units, i.e. by a factor of over 25 (10 " = 25.1). However, the introduction of a second methyl substituent has a relatively small effect, and the introduction of a third methyl group, as in trimethylamine, actually reduces the basic strength to nearer that of methylamine. 

In a more recent study, Westman and Lundin described the solid-phase synthesis of aminopropenones and aminopropenoates, respectively30 as intermediates for heterocyclic synthesis. Two different three-step methods for the preparation of heterocycles have been developed. The first method involved formation of a polymer-bound ester from a IV-protected glycine derivative and Merrifield resin (Scheme 7.10a), while the second method employed an interesting approach utilising simple aqueous methy-lamine solution for functionalisation of the solid support (Scheme 7.10b). In this latter approach, a variety of hetero cycles were readily synthesised from the generated polymer-bound benzylamine using a two-step protocol (see Section 5.3.3). 

This synthetic procedure, using the hydrochloride salt of the amine and sodium cyanoborohydride in methanol, seems to be quite general for ketone compounds related to 3,4-methylenedioxyphenylacetone. Not only were most of the MD-group of compounds discussed here made in this manner, but the use of phenylacetone (phenyl-2-propanone, P-2-P) itself appears to be equally effective. The reaction of butylamine hydrochloride in methanol, with phenyl-2-propanone and sodium cyanoborohydride at pH of 6, after distillation at 70-75 °C at 0.3 mm/ Hg, producedN-butylamphetamine hydrochloride (23.4 g from 16.3 g P-2-P). And, in the same manner with ethylamine hydrochloride there was produced N-ethyl-amphetamine (22.4 g from 22.1 g P-2-P) and with methy lamine hydrochloride there was produced N-methylamphetamine hydrochloride (24.6 g from 26.8 g P-2-P). The reaction with simple ammonia (as ammonium acetate) gives consistently poor yields in these reactions. 

N-methylcarbamate and N.N -dimethylcarbamates have been determined in soil samples by hydrolyses with sodium bicarbonate and the resulting amines reacted with 4-chloro-7-nitrobenzo-2,l,3-oxadiazole in isobutylmethylketone solution to produce fluorescent derivatives [307]. These derivatives were separated by thin-layer chromatography on silica gel G or alumina with tetrahydro-furan-chloroform (1 49) as solvent. The fluorescence is then measured in situ (excitation at 436 nm, emission at 528 and 537 nm for the derivatives of methy-lamine and dimethylamine, respectively). The method was applied to natural water and to soil samples containing parts per 109 levels of carbamate. The disadvantage of the method is its inability to differentiate between carbamates of any one class. 

Methyl isocyanate can be made from phosgene (COCl2) and methy-lamine (CH3NH2), which would circumvent use of the isocyanate. Methyl isocyanate is a very dangerous chemical and was responsible for the deaths of over 2500 people in the worst industrial accident ever, that of the carbamate insecticide plant in Bhopal, India on December 3, 1984. 

Sarcosine is a naturally occurring amino acid but is made industrially by reacting methy-lamine with monochloroacetic acid (MCA), a common reagent also used in the manufacture of betaines. 

Raw materials. N-methyl taurine is the reaction product of sodium isethionate and methy-lamine (see Figure 4.28). Taurine can be made by using ammonia instead of methylamine, but has little use in surfactants. 

The carboxyl group occupies a prominent place in protein structure and function and is commonly taken to be ionized as a carboxylate, particularly when paired in a salt bridge with a Whereas this may be the case in a protein environment, it is not obvious that a —COOH group will donate its proton to a base to form an ion pair in the gas phase. For example, SCF calculations with a polarized 6-31G basis set indicate that neither methy-lamine nor an arginine model is able to extract a proton from acetic acid so as to form an ion pair. On the other hand, there is some indication that correlation might stabilize the ion pair for formic acid -f methylamine. ... 

Another method for the synthesis of tetryl is the treatment of methy-lamine with 2,4-or 2,4-dinitrochlorobenzene to give dinitrophenyl-methylamine. Later, this is treated with nitric acid to tetryl (Eq. 12.3) [4, 8]. 

The cathode potential necessary for the production of solvated electrons is rather negative the standard potential of the hydrated electron has been calculated to be —2.68 V versus NHE. Also, in other solvents compatible with its formation, very negative potentials must be used for example, in liquid ammonia the generation of ens is achieved at —2.47 V versus Ag/AgN03 (0.1 M) [306], but the dissolution standard potential measured in HMPA was found to be —3.44 V versus Ag/AgC104 (0.1 M) [307]. Similarly, in methy-lamine f — 50°C), a potential of —2.90 V versus Ag/AgN03 was reported [308]. 

Tris(dimethylaminomethyl)phenol, 3694 Tris(hy droxy methy l)methy lamine. 1731 Urea, 0475... 

I have found that the lower alkylamines may be separated one from the other by taking advantage of their differences in basicity. In my preferred process, the amines, preferably the alkylamines or methy-lamines, desirably in the form of their hydrohalide, or hydrochloride salts, are treated with an alkaline material in sufficient quantity and of sufficient strength to displace one or more of the amines fi om its salt. 

Methamphetamine or l-phenyl-2-(methy-lamine)propane is another widely abused drug. It is also known as speed . At higher doses, this strong CNS stimulant produces delusions and bizarre visual and auditory hallucinations. Chronic use at high doses can produce schizophrenia-like conditions. The toxic and psychological effects are similar to those of other amphetamine drugs. Its pharmaceutical uses have been discontinued. 

To a solution of 0.5 g oxadiazole in 90 mL methanol was added 10 mL ethanolic methy-lamine (in a large excess). The solution was apportioned into two quartz tubes and then irradiated for 1.5 h. After removal of the solvent, the residue was chromatographed to give 10% of starting material and 60% of l-methyl-3-phenyl-l,2,4-triazolin-5-one, m.p. 218-219°C. Similarly, irradiation of 0.5 g oxadizaole in the presence of 20 mL methanolic ammonia for 1.5 h, followed by the workup of the residue with minimum of methanol and filtration, afforded 0.25 g 3-phenyl-l,2,4-triazolin-5-one, m.p. 325-330°C. Chromatography of the mother liquor gave additional 0.05 g 3-phenyl-l,2,4-triazolin-5-one and 0.05 g starting material (10%) the total yield for this reaction was 60%. 

Exactly 0.04 mol / -fluorobenzaldehyde and 1.5 mL 40% aqueous solution of methy-lamine were dissolved in 20 mL methanol, and the mixture was cooled to 0°C. Over a course of 1 h, 0.02 mol dimethyl oxoglutarate was added dropwise to the mixture under stirring at 0°C. The solution was allowed to stand overnight at 5°C. The resulting precipitate was filtered and washed by ether to give 3.84 g dimethyl 2,6-di-(4-fluorophenyl)-Ai-methyl-4-piperidone-3,5-dicarboxylate, in a yield of 46%, m.p. 128-130°C. When no precipitate formed, the solvent was removed in vacuo at 40-50°C, and the remaining residue was dissolved in ethanol or treated with Et20 to obtain the crystal. 

The odor of fish is due primarily to amines, especially methy-lamine (CH3NH2). Fish is often served with a wedge of lemon, which contains citric acid. The amine and the acid react forming a product with no odor, thereby making the less-than-fresh fish more appetizing. Using data from Appendix D, calculate the equilibrium constant for the reaction of citric acid with methylamine, if only the first proton of the citric acid (Kgi) is important in the neutralization reaction. 

Iron, steel, stainless steel, Monel, and some plastics have proven satisfactory in methy-lamine service. Copper, copper alloys (including brass and bronze), zinc (together with zinc alloys and galvanized surfaces), and aluminum are corroded by the methylamines and should not be used in direct contact with them. Mercury and the methylamines can explode on contact, and instruments containing mercury must never be used with the methylamines. Among gasket and packing materials satisfactory for use with them are compressed asbestos, polyethylene, Teflon, and carbon steel or stainless steel wound asbestos. 

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