I Methylamine

Caution.—If the ethanol used to extract the methylamine hydrochloride is not absolute, i.e., if it contains traces of water, considerably less than the above suggested quantity will be required for the extraction, because the solubility of the hydrochloride will be markedly increased by the water present. The recrystallised material will now, however, contain traces of ammonium chloride. 

For the aqueous solution Place 16mL of cool distilled water into your bubbler setup. The "expected, not theoretical, yield of Methylamine from this amount of reactants is 7 grams. I have used a plastic aquarium aerator tube as the bubbler with excellent results. Sure beats using an inverted funnel. 

Fig. 3. Synthesis of fluoxetine (31). 3-ChIoro-I-phenyl-I-propanol reacts with sodium iodide to afford the corresponding iodo derivative, followed by reaction with methylamine, to form 3-(methyl amin o)-1-phenyl-1-propan 0I. To the alkoxide of this product, generated using sodium hydride, 4-fluorobenzotrifluoride is added to yield after work-up the free base of the racemic fluoxetine (31), thence transformed to the hydrochloride (51)...

Merck and Maeder have patented the manufacture of arecaidine by loss of water from l-methyl-4-hydroxypiperidine-3-carboxylic acid. A method of producing the latter has been describd by Mannich and Veit and has been developed by Ugriumov for the production of arecaidine and arecoline. With the same objective, Dankova, Sidorova and Preobrachenski use what is substantially McElvain s process,but start by converting ethylene oxide, via the chlorohydrin and the cyanohydrin, into -chloropropionic acid. The ethyl ester of this with methylamine in benzene at 140° furnishes methylbis(2-carbethoxyethyl) amine (I) which on refluxing with sodium or sodium Moamyloxide in xylene yields l-methyl-3-carbethoxy-4-piperidone (II). The latter is reduced by sodium amalgam in dilute hydrochloric acid at 0° to l-methyl-3-carbethoxy-4-hydroxypiperidine (III) which on dehydration, and hydrolysis, yields arecaidine (IV R = H), convertible by methylation into arecoline (IV R = CH3). 

The intermediate products (I) and (II) lose water, forming hydrohydrastinine and oxyhydrastinine respectively. Alkaline permanganate converts oxyhydrastinine into hydrastinic acid (III), C HgOgN, needles, m.p. 164° this in turn is oxidised by dilute nitric acid to hydrastic acid methylimide (IV), CJ0H7O4N, m.p. 227-8°, which, when warmed with potassium hydroxide solution, furnishes methylamine and hydrastic acid (V). 

I. The cleavage of a methylamine can be accomplished photochemically in the presence of an electron acceptor such as 9,10-dicyanoanthracene. ... 

A mixture of 114.5 g of 5-(3-chloropropylidene)dlbenzo[a i] cyclohepta[1,4] diene, 75 ml of benzene, and about 400 ml of methylamine is heated in an autoclave at 120°Cfor six hours. The excess methylamine is distilled from the reaction mixture under vacuum and the residue is stirred with 300 ml of water. Acidification of the mixture with hydrochloric acid causes the separation of the hydrochloride of 5-(3-methylaminopropylidene)dlbenzo[a,dlcyclo-hepta[ 1,4] diene. The product is collected by filtration and is purified by recrystallizatlon from a mixture of absolute ethanol and ethyl acetate. MP 210°C to 212 C. 

One problem with reductive amination as a method of amine synthesis is that by-products are sometimes obtained. For example, reductive amination of benzaldehyde with methylamine leads to a mixture of iV-methylbenzylamine and i -methyldibenzylarnine. How do you suppose the tertiary amine byproduct is formed Propose a mechanism. 

In THF/Lithiumchlorid/Ammoniak werden 17a- und 17/l-Hydroxy-3-mcthoxy-ostra-pentaen-(l,3,510,6,8) bei -40° an Platin in hoher Ausbeute zu 77a- bzw. 17(i-Hydroxy-3-methoxy-ostratetraen-(2,510,6,8) reduziert. Wirdstatt Ammoniak Methylamin verwen-det, so erhalt man bei -10° 7 7a- und 17(3-Hydroxy-3-methoxy-dstratrien-(2,5w,7)9 ... 

Methylamine Ethylamine n-Propylamine Mo-Propylamine n-Butylamine. iso-Butylamiiie ec. -B utylamiiie n-Amylamine. i o-Amylamino n-Hexylamine. n-Heptylamine... 

The first bipolar axis (DMSO/ethanol) accounts for the contrast between compounds with NO2 substitutions and those without. Compounds with a NO2 substituent systematically obtain higher scores on this bipolar axis than others. The second bipolar axis (methylenedichloride/ethanol) seems to produce an order of the substituents according to their electronic properties. To emphasize this point we have reproduced the log double-centered biplot again in Fig. 31.10. The dashed line near the middle separates the class of NO2 substituted chalcones from the other compounds. Further, we have joined substituents by line segments according to the sequence CF3, F, H, methyl, ethyl, I -propyl, t-butyl, methoxy, phenyl and di-methylamine. The electronic properties of these substituents vary progressively from electron acceptors to electron donors [ 11 ] in accordance with their scores on the second bipolar axis. 

A versatile synthesis of monoamine platinum(II) complexes of the type ptCl3(amine)], where the nature of the amine ligand can be varied readily, involves treatment of the iodo-bridged dimer [PtI(/r-I)L]2 (L = NH3, methylamine, ethylamine, isopropylamine, cyclobutylamine, and... 

Several silver(I) complexes of the macrocyclic Schiff base derived from the [2+2] condensation of terephthalaldehyde and 3-azapentane-1,5-diamine or A,A -bis(3-aminopropyl)methylamine have been described.509,510 The reaction of 2,ll-diaza-difluoro-m-[3,3]-cyclophane with 2,6-bis (bromomethyl)pyridine lead to the 3 + 3 addition product, which gives a complex with two silver... 

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