Methylamine yield

Tolylsulphonylmethylnitrosamide is obtained as follows. Interaction of p-toluenesulphonyl chloride and methylamine yields p toluenesulphonylmethyl amide ... 

Dehydiation with POCl, followed by N-alkylation with isobutylene, gives the cyano ester intermediate, which on treatment with methylamine yields (64), a compound having good herbicidal activity (eq. 15). 

The original commercial source of E was extraction from bovine adrenal glands (5). This was replaced by a synthetic route for E and NE (Eig. 1) similar to the original pubHshed route of synthesis (6). Eriedel-Crafts acylation of catechol [120-80-9] with chloroacetyl chloride yields chloroacetocatechol [99-40-1]. Displacement of the chlorine by methylamine yields the methylamine derivative, adrenalone [99-45-6] which on catalytic reduction yields (+)-epinephrine [329-65-7]. Substitution of ammonia for methylamine in the sequence yields the amino derivative noradrenalone [499-61-6] which on reduction yields (+)-norepinephrine [138-65-8]. The racemic compounds were resolved with (+)-tartaric acid to give the physiologically active (—)-enantiomers. The commercial synthesis of E and related compounds has been reviewed (27). The synthetic route for L-3,4-dihydroxyphenylalanine [59-92-7] (l-DOPA) has been described (28). 

Glycocoll.—By the action of primary and secondary amines, corresponding" aniino-acids aie foinied. Chloiacetic acid and methylamine yield sarcosine,... 

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). 

The conversion of sterically hindered carboxylic acids to A-methoxy-A-methyl amides can be efficiently carried out with methanesulfonyl chloride, 3 equivalents of triethy-lamine and A-methoxy-A-methylamine. Yields for this process range from 59% to... 

When the 6-chloropyrazino[2,3-f]-l,2,6-thiadiazine 37 was reacted with ammonia, the 6-amino derivative 39 was isolated, as shown in Scheme 2. The treatment of compound 38 with excess methylamine yielded the bis-methylamino compound 40, the result of chlorine displacement by nucleophilic attack at the fully conjugated ring accompanied by transamination <2003HCA139>. 

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... 

Reductive animation of a ketone with methylamine yields a secondary amine. Methamphetamine is /V-mcthyl-1 -phenyl-2-propanamine. 

Reaction of this epoxide with methylamine yielded the mixture of position isomers7S9 and 190. The isomers were separated by column chromatography on silica gel, and the structures correlated by studying their NMR spectra. 

If an amine is used, instead of ammonia, to react with anthraquinone-l-.sul-fonic acid, the corresponding derivative of I-aminoanthraquinone is formed. For example, methylamine yields methylaminoanthraquinone, which, like the non-methylated base, is an important starting material for valuable anthraquinone dyes. 

Reduction of N-(3-bromopropyl)isoquinolinium bromide (4) with lithium tri-/-butoxyaluminum hydride (1, 620-625 2, 251-252 3, 188) gives the 1 -dihydroiso-quinolinc (5), which on treatment with cthanolic methylamine yielded (6), the N-methyl analog of (3, n = 2). 

Conversion of aUoximes to nitriles.1 The dehydration of aldoximes to nitriles can be effected by reaction with methyl isocyanate in DMF in the presence of triethylamine to give an O-(methylcarbamoyl) aldoxime. The carbamate decomposes at 110-120° to give the nitrile and carbon dioxide and methylamine. Yields of nitriles are 65-99%. 

This variation on the activated aluminum method of reductive alkylation has the advantage of using methylamine hydrochloride directly in the reaction soup. Since methylamine is now very dangerous or impossible to obtain commercially, and also since the best method for making methylamine yields methylamine hydrochloride, the usefulness of this variation is obvious. 

Various 3-substituted aminoquinoxaline-2-thiones have been prepared from quinoxaline-2,3-dithione. For example, treatment of the dithione with methylamine yields 3-methylaminoquinoxaline-2-thione, and the corresponding reaction with hydrazine hydrate yields 3-hydrazino-quinoxaline-2-thione. The latter compound is also obtained by treatment of 2,3-dichloroquinoxaline with thiourea and then with hydrazine hydrate. When 2-chloroquinoxaline 1-oxide is heated with thiourea in methanol at room temperature, an unidentified solid m.p. 184-185° is obtained alkaline hydrolysis of methanol-soluble products gives quinoxaline-2-thione in 41% yield. A method of some general applicability is illustrated by the preparation of the thioxo compound 4 from o-anilinoaniline (3). °... 

Treatment of sodium cobaltinitrite with methylamine yields the complexes [Co(MeNH2)g (N02)jt]" (x = 4, n = 1 x = 3, n - 0). Methylamine is much more easily displaced than ammonia. ... 

Carbon-11 Products Formed in Methylamine. Yield as % of Total Gaseous Sample... 

Norflurazone production is based on the condensation of 3-trifluormethyl-phenylhydrazine and mucochloric acid followed by cyclization with acetic anhydride to give 4,5-dichloro-2-(3-trifluormethylphenyl)pyridazin-3-one (54). Nucleophilic substitution of 54 with methylamine yields norflurazon [34]. 

Other methods of preparing pyridonimines have been reported. l-Cyano-2-methylpenta-3-yne-l-ene (DC-179) reacts with alkylamines to yield Ar-alkyl-2-pyridonimines for example, methylamine yields 1,4,6-trimethyl-2-pyridonimine (DC-180, R = CHa). ... 

Then, as shown in Scheme 13.65, repeating the reaction sequence with N,N-dimethylurea (prepared by simply heating urea with A -methylamine) yielded the corresponding Al,Al-dimethyl-4,5-diamino-2,6-dioxypyrimidine and heating that bisamine, in 90% formic acid yielded the corresponding A -formyl derivative, which was cyclized to theophylline with sulfuric acid. 

By a similar procedure 4-methylbenzophenone was reacted with methylamine. Yield 68% b.p. 140°-142°C/2.4mm. 

Now let s draw the forward scheme. Bromocyclohexane is converted to a Grignard reagent, which subsequently reacts with carbon dioxide to produce the carboxylic acid (after acid work-up). Conversion to the acid chloride, followed by reaction with methylamine, yields an intermediate amide. This intermediate is then reduced to the corresponding amine. Finally, reaction with acetyl chloride (upon treatment with excess amine) produces the desired product. 

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