Methylamine, reaction

Similar calculations were also carried out for the SnFI methylamination reactions of 2-R-3-nitro- and 2-R-3,6-dinitro-l,8-naphthyridines (R = FI, Cl, OCFI3, OFI, NFI2, NFICFI3, NFIPh). Tire calculations show that in these reactions the regioselectivity is also controlled by the interaction of the FIOMO of methylamine and LUMO of the nitro-1,8-naphthyridines and not by the formal charges (97LAR2601,97MI3). 

Methanogenesis from methylamines (Reaction 6, Table 2) follows almost the same route as methanol to CH4 and CO2 [227], although each system probably requires specific components for substrate transport, and to form a common methylated product. For example, extracts of M. barkeri grown on trimethylamine (TMA) produce methane from TMA + H2, but extracts from methanol- or dimethylamine-grown cells do not [227],... 

The stability of the metal chelate ring formed with Ni(II), Co(II), or Fe(II) and the donor group —N=C—C—N== (123) is responsible for the formation of Schiff base chelates of a-diketones and methylamine (reaction XCIX) instead of the polymeric condensation products obtained... 

The heats of formation of the intermediate methylamino-cr-adducts of 2-R-3-nitro- and 2-R-3,6-dinitro-l,8-naphthyridines (R = H, OCH3, OH, NH2, NHCH3, NHCsHs, Cl) and transition states of the SnH methylamination reaction of these nitro-l,8-naphthyridines were calculated by the PM3 method. The agreement between the calculated and observed results was found to be satisfactory (97LAR2601,97MI4). 

Methylamine evolved (fishy odour, alkaline reaction). 

An ethereal solution of diazomethane is usually prepared immediately before it is required for reaction. Two intermediates may be used for this purpose, viz., nitrosomethylurea and p-tolylsulphonylmethylnitrosamide a number of methods are available for obtaining the former the latter is prepared from methylamine and p-toluenesulphonyl chloride. Nitrosomethylurea is not very stable at room temperatures and must be kept at 0° on the other hand p-tolylsulphonylmethylnitrosamide is a stable solid, which can be kept for long periods at room temperature in a dark bottle. 

In order to secure the maximum conversion of the methylamine into the sul-phonylmethylamide, the p-toluenesulphonyl chloride is introduced in several portions, and sodium hydroxide solution is added after each portion to liberate the methylamine from the hydrochloride formed in the reaction ... 

The versatility of this reaction is quite apparent. One can use ammonium acetate to make MDA or amphetamine, or methylamine in methanol for MDMA. But methylamine is optimal because it gives higher yield and less byproducts. Also, if ammonium acetate is used, one must use either ammonia (NH3) or a primary amine (any of one s choosing. Strike supposes) in place of the triethyla-mine in the reaction. 

So now we have a modified method where one has ammonia, methylamine or ethylamine freebase saturated in a small amount of DMF. The author next suggested that a power pulse protocol would not necessarily be needed, but that the power output from the microwave should be between 20-40% of full power. Also, the water in the clay would still be needed for the reaction. 

Now, contrary to popular opinions, this method need not be conducted in a sealed pipe bomb. Secondary amination by substitution is as much a reaction of opportunity as it is of brute force and heat. In fact, heating can tend to cause the reformation of safrole and isosafrole. So the simplest way to do this would be to use 500mL of ammonium hydroxide or alcoholic ammonia or, for those wishing to make MDMA or meth, 40% aqueous methylamine or alcoholic methylamine (to tell you the truth, methylamine is preferable in this method because it is more reactive that ammonia so yield will increase). This 500mL is placed in a flask and into it is poured a solution of 35g bromosafrole (30g phenylisopropyl-bromide) mixed with 50mL methanol. The flask is stoppered and stirred at room temperature for anywhere from 3 to 7 days. The chemist could also reflux the same mixture for 6-12 hours or she could throw the whole mix into a sealed pipe bomb (see How to Make section) and cook it for 5 hours in a 120-130°C oil bath. 

The way the chemist knows that she has methylamine and not ammonium chloride is that she compares the look of the two types of crystals. Ammonium chloride crystals that come from this reaction are white, tiny and fuzzy. The methylamine hydrochloride crystals are longer, more crystalline in nature and are a lot more sparkly. The chemist leaves the methylamine crystals in the Buchner funnel of the vacuum filtration apparatus and returns the filtrate to the distillation set up so it can be reduced one last time to afford a second crop. The combined methylamine hydrochloride filter cake is washed with a little chloroform, scraped into a beaker of hot ethanol and chilled. The methylamine hydrochloride that recrystallizes in the cold ethanol is vacuum filtered to afford clean, happy product (yield=50%). 

To make methylamine we start with Acetamide. The general, unbalanced reaction process is thus ... 

Preheat a water bath on the stove (or wherever) to about 80C and place the stainless steel mixing bowl in it. Once the temperature of the solution hits about 65C, take the bowl out and set aside while stirring all the while. This is where it rearranges, and the reaction is exothermic enough to sustain it s temperature nicely. If you find the temperature climbing past 80C, immerse the bowl into some cold waiter briefly. After about 15 minutes the temperature will start to fall, at which point you should transfer the whole mess to the distilling flask. Before you continue you need to choose whether you want to make the hydrochloride salt or the aqueous solution of Methylamine, though. 

At the end of this time, allow to cool then add enough 25% Sodium Hydroxide solution to to get the pH above 11. Heat on a water bath or with gentle electric heat to drive the Methylamine off as a gas into the same beaker of Hydrochloric acid used as a trap during the reaction. 

Figure 17 10 presents the mechanism for the reaction between benzaldehyde and methylamine given m the first example The first two steps lead to the carbmolamme the last three show the dehydration of the carbmolamme to the imine Step 4 the key... 

Chloroacetic acid can be esterified and aminated to provide useful chemical intermediates. Amphoteric agents suitable as shampoos have been synthesized by reaction of sodium chloroacetate with fatty amines (4,5). Reactions with amines (6) such as ammonia, methylamine, and trimethylamine yield glycine [66-40-6J, sarcosine [107-97-17, and carhoxymethyltrimethylammonium chloride, respectively. Reaction with aniline forms /V-phenylglycine [103-01 -5] a starting point for the synthesis of indigo (7). 

Uses. Butyrolactone is principally consumed by the manufacturers by reaction with methylamine or ammonia to produce A/-meth5d-2-pyrrohdinone [872-50-4] and 2-pyrrohdinone [616-45-5] C H NO, respectively. Considerable amounts are used as a solvent for agricultural chemicals and polymers, in dyeing and printing, and as an intermediate for various chemical syntheses. 

PoIya.mines are condensation polymers containing nitrogen they are made by a variety of synthetic routes. Most of the commercial polyamines are made by reaction of epichlorohydrin with amines such as methylamine [25988-97-0] or dimethylamine [39660-17-8] (18,19). Branching can be increased by a dding small amounts of diamines such as ethylenediamine [42751-79-1]. A typical stmcture of this type of polyamine is stmcture (9). 

A modification of the direct process has recentiy been reported usiag a ckculating reactor of the Buss Loop design (11). In addition to employing lower temperatures, this process is claimed to have lower steam and electricity utihty requirements than a more traditional reactor (12) for the direct carbonylation, although cooling water requirements are higher. The reaction can also be performed ia the presence of an amidine catalyst (13). Related processes have been reported that utilize a mixture of methylamines as the feed, but require transition-metal catalysts (14). 

A convenient method for the synthesis of these low boiling materials consists of the reaction of /V,/V-dimethy1iirea [96-31-1] with toluene diisocyanate to yield an aUphatic—aromatic urea (84). Alternatively, an appropriate aUphatic—aromatic urea can be prepared by the reaction of diphenylcarbamoyl chloride [83-01-2] with methylamine. Thermolysis of either of the mixed ureas produces methyl isocyanate ia high yield (3,85). 

---