Methylamine, reaction with

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. 

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). 

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)...

The alkylthio group is replaceable by nucleophiles. The positions 7 and 4 react under mild conditions in that order the 2-alkylthio functions require more drastic treatment. Conversion of l-methyl-4-methylthiopteridin-2-one (157) into the 4-methylamino derivative (158) can be achieved by stirring with methylamine at room temperature (equation 48). The reactivity of an alkylthio group can often be further enhanced by oxidation to the corresponding sulfoxide and sulfone. Thus, reaction of l,3-dimethyl-7-methylthiolumazine (160) with m-chloroperbenzoic acid yields 7-methylsulfinyl- (161) and 7-methylsulfonyl-l,3-dimethyllumazine (162 equation 49) (82UP21601). 4-Amino-2-methylthio-7-... 

Laurylmethylamine has been prepared by the reaction of lauryl alcohol with methylamine under pressure in the presence of catalysts at high temperature, by heating lauryl chloride with methylamine in alcoholic or aqueous medium under pressure, and by the reaction of lauryl halides with aqueous methylamine. Cetylmethylamine has been prepared by the catalytic debenzyla-tion of benzylcetylmethylamine. ... 

Dibenzo[d,g][l,5]telluroazocines 65 are the only representatives of Te, N-containing eight-membered heterocycles known thus far. Treatment of bis(2-bromomethylphenyl)tellurium dibromide 66 with methylamine followed by reduction of the reaction mixture with sodium sulfide gives, instead of the expected... 

Reaction of 2,4-xylidine with methylamine and ethyl orthoformate leads to the amidine 119 condensation of that product with a second mole each of orthoformate and 2,4-xylidine gives the scabicide amitraz (120) [29]. 

A solution of 4-chlorobenzaldehyde is reacted with (3-mercaptopropionic acid and with methylamine. The mixture is refluxed in benzene and water is removed from an overhead separator. The reaction mixture was cooled, washed with dilute ammonium hydroxide and water, and the benzene was removed by distillation in vacuo. The oily residue was taken up in ether from which it crystallized. The precipitate was recrystallized twice from ether to yield 2-(4-chlorophenvl)-3-methyl-4-metathiazanone. 

Alkaloids vary widely in structure, from the simple to the enormously complex. The odor of rotting fish, for example, is caused largely by methylamine, CH3NH2, a simple relative of ammonia in which one of the NH3 hydrogens has been replaced by an organic CH3 group. In fact, the use of lemon juice to mask fish odors is simply an acid-base reaction of the citric acid in lemons with methylamine base in the fish. 

Show the products you would obtain by acid-catalyzed reaction of 3-pentanone with methylamine, CH3NH2, and with dimethylamine, (CT NH. 

In another case, for the reaction of a strong acid such as HN03 with methylamine, CH H, the net ionic equation is... 

Acetamido-l//-l,5-benzodiazepine-3-carbonitrilc forms the pyrimidine derivative 10 by reaction with methylamine.290... 

In addition, several addition reactions have been reported for the iron complex [Fe(CNCH3)j] with hydrazine and with methylamine (99) the products (XVI) and (XVII), respectively, are described. A crystal structure study on the latter compound was carried out. 

By contrast, alkylamination of naphthazarin (7) in the presence of sodium dithionite followed by oxidation gives l,4-bis(alkylamino)-5,8-naphthoquinone (31).18,19 However, Kikuchi and co-workers20 obtained isomeric l,5-bis(alkylamino)-4,8-naphthoquinone (32) from the reaction of leuco naphthazarin (33) with alkylamine They also isolated 5-alkylamino-leuco-naphthazarin (34) as an intermediate, which is further aminated at the 1-position to give 32. Bloom and Dudek21 have studied the structure of leuco aminonaphthoquinones and their tautomeric equilibria in solution. They concluded that the reaction of leuco naphthazarin (33) or the leuco compound (35) derived from l,5-diamino-4,8-naphthoquinone (36) with methylamine gives mixtures of l,4-bis(methylamino)-31 (R = Me) and 1,5-bis(methylamino)naphthoquinones 32 (R = Me) after oxidation of leuco aminonaphthoquinones (Scheme 10). Some of the structures of leuco aminonaphthoquinones are shown in Scheme ll.20... 

In a similar sequence, reaction of ketoester 52 with 2-thienylmagnesium bromide gives a modest yield of the benzilic ester 53. Transesterification of this with aminoalcohol 51, prepared analogously to 45 by starting with methylamine, gives, after quaternization with methyl bromide, heteronium bromide... 

Parker, Raphael, and Wilkinson have investigated a synthetic approach to tropinone (124), which they call the acetylenic route (78). Reaction of hexa-1,5-diyne-l,6-dicarboxylate (145) with methylamine yields the pyrrolidine derivative (146), which by catalytic hydrogenation affords the diester 147 (79,50). 

Another beautiful example of an early domino process is the formation of daphnilactone A (0-19), as described by Heathcock and coworkers [17]. In this process the precursor 0-17 containing two hydroxymethyl groups is oxidized to give the corresponding dialdehyde, which is condensed with methylamine leading to a 2-azabutadiene. There follow a cycloaddition and an ene reaction to give the hexacycle 0-18, which is transformed into daphnilactone A (0-19) (Scheme 0.6). 

Figure 4. shows the route from the high boiling residue of the direct synthesis to silicon carbo-nitride fibers. Methylchlorodisilanes and trichlorosilanes as additives are mixed in a specific ratio and react with methylamine and a small amount of ammonia to form an aminodisilane/oligosilazane. The subsequent polycondensation reaction of this mixture by heating to 250 °C yields a soluble and melt spinnable polysilazane. In comparision with the polysilane the properties of the polysilazane depend on the ratios of the disilanes/silanes and methylamine/ammonia and also on the reaction conditions. 

The replacement of the N-NO2 group by an R-NH2 has been found to occur more smoothly with the 1-nitroinosines (51) than with the 3-nitrouridines (44). Reaction of 51 with methylamine gave ring opening al-... 

The starting diol was transformed into the dibromide by elemental bromine with triphenyl phosphine adduct which undergoes the Arbuzov-Michaelis reaction under somewhat drastic conditions at 150 °C (step a). Catalytic removal of the benzyl group was performed by a Pd/C catalyst (step b) and the alcohol formed was allowed to react with dichloropurine in the presence of triphenylphosphine and diethylazodicarboxylate (Mit-sunobu reaction) (step c). Finally the desired product was obtained by reaction with methylamine (step d) and the removal of ethyl groups at the phosphorus centre was performed by transilylation using trimethyliodosilane (step e). 

Tetryl (8) can be synthesized in two steps from 2,4-dinitrochlorobenzene (231). Thus, reaction of the latter with methylamine under aqueous conditions yields 2,4-dinitro-lV-methylaniline (228), which readily undergoes nitration to tetryl (8) on treatment with mixed... 

Dimethylolnitramine (252) readily participates in Mannich condensation reactions treatment of a aqueous solution of (252) with methylamine, ethylenediamine and Knudsen s base (254) (generated from fresh solutions of ammonia and formaldehyde) yields (253), (255) and (239) (DPT) respectively. The cyclic ether (258) is formed from the careful dehydration of dimethylolnitramine (252) under vacuum. ... 

Further transformation of the ester group in 126 was easily achieved. Thus, 126 with methylamine and 2-dimethylaminoethylamine gave the lactams 127 a and 127b. Reaction of the free acid derived from 126 with thionyl chloride yielded the lactone 127 c (Scheme 42) [7m, 60 a]. 

Diazo-5-phenyl-1,2,4-triazole reacted with methylamine to give the corresponding triazene (83JHC1629). Triazeno polymer 240 was formed by a self-coupling reaction of the diazotriazole obtained from guanazole... 

The bioreduction of carbonyl compounds with reductases has been exploited for many years, especially in the case of ketones, with baker s yeast Saccharomyces cerevisiae) being the most popular biocatalyst [45]. For instance, yeast treatment of 3-chloropropiophenone affords the expected (lS)-3-chloro-l-phenylpropan-l-ol, which was treated with trifluorocresol in tertrahydrofuran in the presence of tri-phenylphosphine and diethyl azodicarboxylate at room temperature to give (3R)-l-chloro-3-phenyl-3-[4-(trifluoromethyl)phenoxy]propane and the later reaction with methylamine leads to (R)-fluoxetine that is an important serotonin uptake inhibitor (Scheme 10.19) [46]. 

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