Methyl- amine hydrochloride

C) 10 g of 6-chloromethyl-morphanthridine are passed into 150 ml of a solution of methyl-amine in benzene (10%). After storage of the solution for 20 hours at 0° to 5°C the methyl-amine hydrochloride formed is sucked off and the filtrate evaporated to dryness. There remains as residue 11 g of crude 6-methylaminomethyl-morphanthridine. 

C02 —116% yellow platelets, mp 274.5-5.0° with decompn prepd by the action of methyl amine hydrochloride On 4-fluoro-2, 3,4 -trinitroazobenzene in eth, yield 95.8%... 

N-Methyl-N-methoxycarbamoyl chloride made by phos-genation of methoxy methyl amine hydrochloride is a very useful intermediate for the synthesis of N-methoxy ureas herbicides. However, we found the method to be unsatisfactory for the production on a large scale, because of rather low yields and also of technical difficulties. To overcome these problems, we developed a new procedure based on the reaction of phosgene with methoxy methyl amine sulfate as depicted in scheme 124. Sulfuric acid formed is easily removed by decantation (Ref. 177). 

Schopf and Lehmann (29) have also obtained a yield of 70-85% by modifying Robinson s synthesis. A dilute buffered solution of succindialdehyde, methyl-amine hydrochloride and acetone dicar-boxylate were mixed at 25 and at pH 5.0. 

Experiment Treat some solid methyl amine hydrochloride in a small test-tube with a concentrated solution of caustic potash, or caustic soda, and warm gently. A gas, smelling like ammonia, is evolved, which burns with a pale flame. 

Which solution would be more acidic a 0.10 M solution of aniline hydrochloride, C5H5NH3CI (K = 4.2 X 10 ° for aniline, CgHjNH2), or a 0.10 M solution of methyl-amine hydrochloride, CH3NH3CI = 5.0 X 10 for methylamine, CH3NH2) Justify your choice. 

The monomer tri-isocyanto-trimethyl-borazine (TITMB) was synthesized from trichloro-trimethyl-borazine (TCTMB) according to the method reported in the literature [12]. The Intermediate TCTMB was synthesized via a modification of the procedure of Brown and Laubengayer [13]. Methyl-amine hydrochloride and excess of BCI3 were refluxed in chlorobenzene for 6h and then maintained for 16h at 80°C. The reaction mixture was filtered warm, vacuum dried and subsequently sublimed under reduced pressure. A slight increase in yield (12%) of pure TCTMB was achieved. 

Meihylamine hydrochloride method. Place 100 g. of 24 per cent, methyl-amine solution (6) in a tared 500 ml. flask and add concentrated hydrochloric acid (about 78 ml.) until the solution is acid to methyl red. Add water to bring the total weight to 250 g., then introduce lSO g. of urea, and boil the solution gently under reflux for two and three-quarter hours, and then vigorously for 15 minutes. Cool the solution to room temperature, dissolve 55 g. of 95 per cent, sodium nitrite in it, and cool to 0°. Prepare a mixture of 300 g. of crushed ice and 50 g. of concentrated sulphuric acid in a 1500 ml. beaker surrounded by a bath of ice and salt, and add the cold methylurea - nitrite solution slowly and with mechanical stirring and at such a rate (about 1 hour) that the temperature does not rise above 0°. It is recommended that the stem of the funnel containii the methylurea - nitrite solution dip below the surface of the acid solution. The nitrosomethylurea rises to the surface as a crystalline foamy precipitate. Filter at once at the pump, and drain well. Stir the crystals into a paste with about 50 ml. of cold water, suck as dry as possible, and dry in a vacuum desiccator to constant weight. The yield is 55 g. (5). 

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)...

AcCl, MeOH, 95-100% yield. This is a convenient method for generating anhydrous HCl in methanol. These conditions are also used to prepare methyl esters from carboxylic acids and for the formation of amine hydrochlorides. ... 

The benzene was distilled from the extract and the residue of d-N-methyl-N-benzyl-)3-phenyl-isopropylamine was distilled at reduced pressure. The thus obtained free base, distilling at 127°C at a pressure of 0.2 mm of mercury and having an np of 1.5515, was dissolved in ethyl acetate and a molar equivalent of ethanolic hydrogen chloride was added thereto. Anhydrous ether was added to the mixture and d-N-methyl-N-benzyl-)3-phenylisopropyl-amine hydrochloride precipitated from the reaction mixture as an oil which was crystallized from ethyl acetate to give crystals melting at 129° to 130°C. 

The reaction of diethyl acetyl- and propionylmalonates with hydroxyl-amine hydrochloride or its N-methyl derivative in ethanol afforded the appropriate ethyl 3-alkyl-2,5-dihydro-5-oxo-4-isoxazolecarboxylate (88-TL6339). 

As indicated in Table 3, reducing the excess methanol to only a 3 fold molar excess (rendering a nearly solvent free process) far exceeded expectations and allowed significant reductions in the catalyst levels. Under these conditions, catalyst turnover numbers exceeding 10,000 mol MPA/mol Pd were achieved with a turnover frequency of >3400 mol MPA/mol Pd/h. The reaction mixtures obtained from this process formed two liquid phases and the product spontaneously separated from the amine and amine hydrochloride. As a consequence of eliminating large methanol excesses, the methyl pivaloylacetate concentration in the product was raised to 26 wt. % without additional reaction time being required. This represents an additional ca. 2.5 fold improvement in reactor productivity. No attempt was made to reduce the methanol further. 

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. 

Hydroxylamine hydrochloride (8) Hydroxyl amine, hydrochloride (9) (5470-11-1) 4-Acetyl pyridine oxime Ketone, methyl 4-pyridyl oxime (8) Ethanone, l-(4-pyridinyl)- oxime (9) (1194-99-6)... 

Nielsen (81CS(18)135) prepared thieno[2,3-4]pyrimidin-4(3//)-ones in 43-90% yield by heating 2-acylaminothiophene-3-carboxylates (330) with phosphorus pentoxide, N,N -dimethylcyclohexylamine and an amine hydrochloride at 180 °C. By raising the temperature to 240 °C, thieno[2,3-4]pyrimidin-4-amines (331) were obtained in 27-34% yield (Scheme 92). Phenyl N,N -dimethylphosphorodiamidate [(MeNH)2P(0)OPh], a well-known reagent for the synthesis of 3-methyl-4-oxo-3,4-dihydroquinazolines (77S180), reacts with thiophene derivatives of type (330) to give 3-methylthieno[2,3-4]pyrimidin-4(3/f)-ones (78ACS(B)303). 

Methyl l-methyl-4-nitropyrrole-2-carboxylate (4 450 g, 2.44 mol) was dissolved in EtOAc (8L). A slurry of 10% Pd/C (40 g) in EtOAc (800 mL) was then added and the mixture was stirred under a slight positive pressure of H2 (ca. 1.1 atm) for 48 h. Pd/C was removed by filtration through Celite and washed with EtOAc (1 x 50 mL) and the volume of the mixture was reduced to ca. 500 mL cold Et20 (7L) was added and HC1 gas gently bubbled through the mixture. The precipitated amine hydrochloride was then collected by filtration to give a white powder yield 380 g (82%). 

Dioxo-l-imidazolidinyl)imino]methyl]formyl chloride Hydrogen chloride Amine hydrochloride Phosphorus oxychloride... 

To a stirred mixture of the above amine hydrochloride (55.0 g, 0.22 mole) and [[(2,4-dioxo-l-imidazolidinyl)imino]methyl]formyl chloride (42.0 g, 0.22 mole) was added a solution of 440 ml of dimethylformamide and 44 ml of pyridine. The mixture was stirred for 20 h and poured into 2 L of water. The solid was collected by filtration and washed with ethanol and ether to give 36.0 g (28%) of N-[2-(4-bromophenyl)-2-oxoethyl]-[[(2,4-dioxo-l-imidazolidinyl)-imino]methyl]formamide, melting point 267°-269°C (recrystallization from 2200 ml acetic acid). 

Methyl-(l-naphthylmethyl)amine hydrochloride Sodium carbonate Dimethylformamide Cinnamyl chloride... 

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