Methylamine alcohol amination

Acetylated lanolin alcohol Hetlan AC Jeelan MOD Protalan MOD 61788-55-4 Bioflavonoids 61788-59-8 CE-618 Emery 2253 Emer 2254 Exceparl MC Methyl cocoate 61788-60-1 Methyl cottonseed Norfox MCS 61788-61-2 Base MT Emery 2203 Estol 1501 Estrasan 3 Exceparl MT Kemester 143 Methyl tallowate Norfox MTL 61788-62-3 Armeen M2C Dicoco methylamine Jet Amine M2C Kemamine T-6501 Noram M2C 61788-63-4 Amine M2HBG Amine M2HBG-S Armeen M2HT... 

They are very soluble in water, alcohols, ethers, and most polar solvents. At low temperatures, aqueous methylamines form crystalline hydrates CH3NH2-3H20, (CH3)2NH 7H2O, and (CH3)3N IOH2O. In the presence of ammonia, methylamines react explosively with mercury so instruments containing mercury should not be used on methylamines. The amines also are flammable in air. Their flammability ranges as well as some of their important physical properties are listed in Tables 28.16 and 28.17. 

So, how does this whole thing work It s as simple as it sounds. An alcoholic solution of nitromethane and MDP2P is dripped into a mass of amalgamated aluminum immersed in alcohol first reducing the nitromethane to methylamine, allowing the Schiff base of the amine and ketone to form which is then further reduced to the desired MDMA. 

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. 

Ammonia has always been the starting material for the synthesis of aliphatic amines. Thus, processes have been developed for the condensation of NH3 with alkyl halides (Hoffman reaction) or with alcohols in the presence of various catalysts. The latter reachon, first discovered by Sabatier in 1909 [8, 9] is nowadays the main method of industrial production of light amines (e.g. methylamines 600 000 t/yr) [5]. 

Similarly, ionized alcohols and ethers containing a chain of at least three contiguous carbon atoms attached at one end to the oxygen atom frequently expel water or the alcohol derived from the smaller alkyl group76-80. However, the corresponding ionized amines rarely eliminate ammonia or small alkylamines in great abundance. This contrast reflects energetic factors. Water and small alcohols are extremely stable molecules (AHf = —240 and —190 kJ mol-1, respectively, for water and methanol), but ammonia and methylamine are not particularly stable (AHf = —20 and —25 kJmol-1, respectively)82,83. Moreover,... 

Many amines, like other organic compounds, are known by their common names. Their lUPAC names follow that of naming of alcohols, but the ending amine is used. A common practice is to list the names of the groups attached to the nitrogen followed by the ending amine. Thus, CHj-NH would be methylamine. The simplest aromatic is called aniline ... 

The hrst step in the preparation of the antidepressant maprotiline (33-5) takes advantage of the acidity of anthrone protons for incorporation of the side chain. Thus treatment of (30-1) with ethyl acrylate and a relatively mild base leads to the Michael adduct saponihcation of the ester group gives the corresponding acid (33-1). The ketone group is then reduced by means of zinc and ammonium hydroxide. Dehydration of the hrst-formed alcohol under acidic conditions leads to the formation of fully aromatic anthracene (33-2). Diels-Alder addition of ethylene under high pressure leads to the addition across the 9,10 positions and the formation of the central 2,2,2-bicyclooctyl moiety (33-3). The hnal steps involve the construction of the typical antidepressant side chain. The acid in (33-3) is thus converted to an acid chloride and that function reacted with methylamine to form the amide (33-4). Reduction to a secondary amine completes the synthesis of (33-5) [33]. 

EXTENSIONS AND COMMENTARY N-Methyltryptamine (monomethyltryptamine, NMT) is an alkaloid that has been found in the bark, shoots and leaves of several species of Virola, Acacia and Mimosa. However, the major snuffs associated with these plant have been shown to also contain 5-MeO-DMT and are discussed there. NMT has been synthesized in a number of ways. One can react 3-(2-bromoethyl)indole with methylamine. NMT can be isolated as the benzoyl derivative from the methylation of tryptamine with methyl iodide followed by reaction with benzoyl chloride, with the hydrolysis of this amide with alcoholic KOH. It can also be synthesized from indole with oxalyl chloride, with the resulting glyoxyl chloride reacting with methylamine in ether to give indol-3-yl N-methylglyoxalylamide (mp 223-224 °C from IPA) which is obtained in a 68% yield, which is reduced to NMT to give the amine hydrochloride (mp 175-177 °C from ) in a 75% yield. The most simple and direct synthesis is the formamide reduction given above. 

Of the numerous reactions the most thoroughly studied is dehydrochlorination [12] (Scheme 2.3). Common dehydrochlorinating agents include alcoholic alkali [4], liquid ammonia [13], methylamine [13], LiCl in dimethylformamide (DMF) [14], MOH or M2CO3 (M = K or Na) in DMF [15] and tertiary and heterocyclic amines [16]. Moreover, some diaryltrichloroethanes, such as dichlordiphenyl-trichloroethane (DDT), may undergo thermal dehydrochlorination near 170-200 °C. 

The triethylamine salt of 2,2-dimethyl-3-(3,4-methylenedioxyphenyl)-propionic acid (5.4 g amine, 11.4 g acid) was dissolved in 10 mL 11,0 and diluted with sufficient acetone to maintain a clear solution at ice-bath temperature. A solution of 6.4 g ethyl chloroformate in 40 mL acetone was added to the 0 °C solution over the course of 30 min, followed by the addition of a solution of 4.1 g sodium azide in 30 mL H20. Stirring was continued for 45 min while the reaction returned to room temperature. The aqueous phase was extracted with 100 mL toluene which was washed once with H20 and then dried with anhy drou s Mg S04. Thi s org ani c sol uti on of the azide was heated on a steam bath until nitrogen evolution had ceased, which required about 30 min. The solvent was removed under vacuum and the residue was dissolved in 30 mL benzyl alcohol. This solution was heated on the steam bath overnight. Removal of the excess benzyl alcohol under vacuum left a residue 13.5 g of l-(N-(benzyloxycarbonyl)amino)-1,1 -dimethyl-2-(3,4-methylenedioxyphenyl)ethane as an amber oil. The dimethyl group showed, in the NMR, a sharp singlet at 1.30 ppm in CDCH,. Anal. (C19H2lN04) C,H. This carbamate was reduced to the primary amine (below) or to the methylamine (see under MDMP). 

The latter, on reaction with methylamine yielded via the P-epoxide 373, the trans-a aminoalcohol 374, which was N-acylated to the amide 375. Acid-catalysed dehydration of the tertiary alcohol 375, led to the olefin 375, from which the key radical precursor, the chlorothioether377 was secured in quantitative yield by reaction with N-chlorosuccinimide. In keeping with the earlier results recorded for structurally related compounds, 377 on heating in the presence of ruthenium dichloride and triphenylphosphine also underwent a 5-exo radical addition to generate the cyclohexyl radical 378 which recaptured the chlorine atom to furnish the a-chloro-c/5-hydroindolone 379. Oxidation of thioether 379 gave the corresponding sulfoxide 380, which on successive treatment with trifluoroacetic anhydride and aqueous bicarbonate led to the chloro-a-ketoamide 381. The olefin 382 resulting from base induced dehydrochlorination of 381, was reduced to the hydroxy-amine 383, which was obtained as the sole diastereoisomer... 

For synthesis of N-substituted aziridinyl ketones, primary amines such as methylamine [11, 12, 13], cyclohexylamine [8, 11, 14, 15, 16, 17] and benzyla-mines [17, 18, 19, 20] are introduced in the reaction instead of ammonia. These reactions can be carried out in different solvents, such as alcohols, benzene, toluene, dimethylformamide, etc. On the basis of this chemistry, aziridinyl ketones containing either one or more three-membered cycles can be synthesized (e.g., compounds 7 and 10 Scheme 1.3). 

Me2S04 is used under basic conditions as source of a methyl nucleophile. It can thus transform alcohols into methyl ethers or transform amines into the methylamine. Usually a phase transfer catalyst such as tetrabutylammonium iodide is added to the aqueous basic solution.4 Other reagents to create methyl ethers include iodomethane or trimethoxonium tetrafluoroborate (Meerwein s reagent).5... 

The parallelism in reactions with HMPT and mixtures of phosphorus pentoxide and amines can best be realized by looking at the mechanism of HMPT reactions [1 5 ]. In the reaction of p-methoxy-benzylalcohol with HMPT which produce the corresponding N,N-dimethylbenzyl amine--p-methoxybenzyl phosphate was identified in the XP NMR spectrum of the reaction mixture. Since pyrophosphate was also observed during the reaction of the benzyl alcohol with HMPT, the intermediate formation of the metaphosphate anion can be assumed. Addition of the benzyl alcohol to that anion then produce the benzyl phosphate. Phosphate ions are known to be good leaving groups so that a benzylamine can easily be produced from the phosphate by reaction with di-methylamine released from the dimethylammonium ion. The phosphoric acid produced during the reaction is believed to react with HMPT, so that more dihydro-gen-bis(dimethylammonium) pyrophosphate is formed. 

Birch reduction11 is the partial reduction of aromatic rings by solvated electrons produced when alkali metals dissolve (and react) in liquid amines. Typical conditions are sodium in liquid ammonia or lithium in methylamine. These electrons add to benzene rings to produce, probably, a dianion 57 that is immediately protonated by a weak acid (usually a tertiary alcohol) present in solution. The anions in the supposed intermediate 57 keep as far from each other as they can so the final product is the non-conjugated diene 58. It is important to use the blue solution of solvated electrons before it reacts to give hydrogen and NaNH2. 

The reaction of primary amines with aldehydes and ketones do not give the products expected from nucleophilic addition alone. This is because of the further reaction taking place once nucleophilic addition occurs, e.g. consider the reaction of acetaldehyde (ethanal) with a primary amine methylamine (Following fig.). The product contains the methylamine skeleton, but there is no alcohol group and there is a double bond between the carbon and the nitrogen. This product is known as imine or a Scbiffbase. 

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