Phenyl methylamine

Vanillylamine [(4-hydroxy-3-methoxy-phenyl)methylamine] is the substrate of choice for the formation of vanillin with the help of amine oxidase. It can be obtained by cleavage of capsaicin (N-[(4-hydroxy-3-methoxy-phenyl)methyl]-8-methyl-6-nonenamide) isolated from pepper and capsicum [83]. As natural vanillin extracted from beans of Vanilla planifolia is rare and extremely expensive, this pathway for the production of natural vanillin is regarded to have a great potential. The vanillin obtained by the process can be labelled as natural if the cleavage of capsaicin is performed enzymatically. 

In the second method (Scheme 26) a 3-oxo ester is synthesized from an acid chloride and 2,2-dimethyl-l,3-dioxane-4,6-dione. Then, reductive amination of the 3-oxo ester with a-methyl(phenyl)methylamine provides a 3-amino- 3-alkyl propionic acid ester. This compound is then converted into the corresponding aldehyde, which is condensed with an eno-late to afford the final product. A representative synthetic procedure of this method is given in detail. 

The allylic amination with benzylamine or related amines such as (3,4-dimethoxy-phenyl)methylamine catalyzed by palladium coordinated with the dihydroxylated ferrocenylphosphine 8b takes place with high enantioselectivity (Scheme 2-30) [27]. Thus, reaction of l,3-diphenyl-2-propenyl ethyl carbonate 41 with benzylamine gives a quantitative yield of allylic amination product 42 with > 97% ee. High enantioselectivity is also obtained in the allylic amination of 2-propenyl esters 43 substituted... 

Although a variety of primary and secondary amines can be utilized as nitrogen nucleophiles, amina-tion of allylic substrates with ammonia has been reported to be unsuccessful, lltetefore, bis(p-methoxy-phenyl)methylamine, sodium p-toluenesulfonamide or sodium azide have been utilized instead of ammonia. In the presence of a palladium catalyst, imides, such as phthalimide, react with allylic esters with the exception of geranyl and linalyl acetates. O-Geranyl- and 0-linalyl-isourea derivatives, however, reacted with phthalimide giving the expected -allylic phthalimides in 65% and 71% yields, respectively, ... 

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)...

Migration to the developing electron sextet at nitrogen is not restricted to hydrogen. In (79) there is methyl migration with formation of methylamine and acetone in the acid-catalyzed decomposition of (80), phenyl migration leads to aniline and acetaldehyde. 

We should distinguish between the phrases nucleophilic attack and nucleophilic catalysis. Nucleophilic attack means the bond-forming approach by an electron pair of the nucleophile to an electron-deficient site on the substrate. In nucleophilic catalysis this results in an increase in the rate of reaction relative to the rate in the absence of the catalyst. However, nucleophilic attack may not result in catalysis. Thus, if methylamine is reacted with a phenyl acetate, the reaction observed is amide formation, not hydrolysis, because the product of the nucleophilic attack is more stable than is the ester to hydrolysis. 

On boiling the methiodide with 70% sulfuric acid an N-methyl-oxo derivative was obtained, and this in turn gave 3-amino-2-phenyl-quinoline, methylamine, and ammonia on fusion with soda lime. The bulk of the evidence therefore favors quaternization at N-2 (cf, 154), in which case the acid-hydrolysis product is 155. Quaternization at N-2 would be expected because of the steric influence of the 10-phenyl group and the influence of the 4-amino group (cf. 4-hydroxy-pyridazine ) in the pyridazine-type ring, although the partial double-bond character of that ring is probably different from that in pyridazine itself. 

Dichloro-s-triazine and its 6-alkyl analogs are as easily hydrolyzed by water as trichloro-s-triazine and, on suspension in aqueous ammonia (25°, 16 hr), the first is diaminated in good yield. 2,4-Bistrichloromethyl-6-methyl- and -6-phenyl-s-triazines (321) require a special procedure for mono-alkoxylation (0-20°, 16 hr, alcoholic triethylamine) disubstitution occurs at reflux temperature (8 hr). Aqueous triethylamine (100°, 3 hr) causes complete hydroxy-lation of 2,4,6-tris-trichloromethyl-s-triazine which can be mono-substituted with ammonia, methylamine, or phenoxide ion at 20°. 

In conclusion, all results obtained thus far on this reaetion show that it is espeeially the 4-position in the 3-nitro-l,8-naphthyridines whieh is strongly favored toward the attaek of the earbanion of ehloromethyl phenyl sulfone. When position 4 is oeeupied by a substituent no reaetion oeeurs. Tliis behavior is in aeeordanee with the behavior observed in reaetions with liquid ammonia and liquid methylamine. 

Ethyl 1 -substituted 7-hydroxy-5-oxo-1,2,3,5-tetrahydropyrido[ 1,2,3-<7e] quinoxaline-6-carboxylates were reacted with A- [3,5-bis(trifluoromethyl)-phenyl]methyl methylamine to yield carboxamides (01MIP12). 

Ninety-eight grams of 6-chloro-2-chloromethyl-4-phenylquinazoline 3-oxide hydrochloride were introduced into 600 cc of ice cold 25% methanolic methylamine. The mixture was initially cooled to about 30°C and then stirred at room temperature. After 15 hours the reaction product which precipitated was filtered off. The mother liquor was concentrated in vacuo to dryness. The residue was dissolved in methylene chloride, washed with water and dried with sodium sulfate. The methylene chloride solution was concentrated in vacuo and the crystalline residue was boiled with a small amount of acetone to dissolve the more soluble impurities. The mixture was then cooled at 5°C for 10 hours and filtered. The crystalline product, 7-chloro-2-methylamino-5-phenyl-3H-1,4-benzodiazepine 4-oxide, was recrystallized from ethanol forming light yellow plates, MP 236° to 236.5°C. 

A solution of N-(2-aminobenzvl)-1-phenyl-2-metKylaminoethanol-1 was prepared by the reaction of a-bromo-acetophenone and (2-nitrobenzyl)methylamine, followed by hydrogenation of the nitro group by means of nickei on diatomaceous earth at room temperature and reduction of the CO group by means of sodium borohydride. The intermediate thus produced was dissolved in 100 ml of methylene chloride and introduced dropwise into 125 ml of sulfuric acid at 10° to 15°C. After a short standing, the reaction mixture was poured onto ice and rendered alkaline by means of a sodium hydroxide solution. Dy extraction with ether, there was obtained 1,2,3,4-tetrahydro-2-methyl-4-phenyl-8-amino-iso-quinoline. The base is reacted with maleic acid to give the maleate melting point of the maleate 199° to 201°C (from ethanol). 

The first synthesis of a 3//-3-benzazepine, e.g. 65 (R1 = R2 = Me), was achieved by the condensation of phthalaldehyde with a bis[(alkoxycarbonyl)methyl]methylamine.24"25 With sodium methoxide as the base, A%V-bis[(methoxycarbonyl)methyl]pheiiylaniine condenses with the dialdehyde in a similar manner to give dimethyl 3-phenyl-3//-3-benzazepine-2,4-dicar-boxy late (65, Rl — Ph R2 — Me).99 However, replacement of methoxide by potassium tert-butoxide results in formation of 3-phenyl-3//-3-benzazepine-2,4-dicarboxylic acid (65, R1 = Ph R2 = H).25... 

Organo-silane werden durch Elektrolyse an der C-Metall-Bindung gespalten. So erhalt man z. B. aus Trimethyl-phenylathinyl-silan in Methylamin/Lithiumchlorid (s. a. S. 577) an Platin-Elektroden Phenyl-acetylen (38% d.Th.). Als Nebenprodukte fallen infolge Hydrierung Trimethyl-(2-phenyl-athyl)-silan (10% d.Th.) und A thy T benzol (30% d.Th.)... 

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. 

CASRN 2032-59-9 molecular formula C11H16N2O2 FW 208.26 Plant/Surface Water. Several transformation products reported by Day (1991) include 4-amino-/n-tolyl-7V-methylcarbamate (AA), 4-amino-3-methylphenol (AC), 4-formamido-/n-tolyl-TV-methylcarbamate (FA), 7V-(4-hydroxy-2-methylphenyl)-yV-methylformamide (FC), 4-methyl-formamido-/n-tolyl-7V-methylcarbamate (MFA), 4-methylamino-/n-tolyl-Wmethylcarbamate (MAA), 3-methyl-4-(methylamino)phenyl-Wmethylcarbamate (MAC), phenol, methylamine, and carbon dioxide. MAA was not detected in natural water but was detected in fish tissues following exposure to aminocarb-treated water in the laboratory. The metabolites FA, AC, and MAC were detected in Canadian forests treated with aminocarb but the metabolites AA, MAA, and FC were not detected (Day, 1991). 

---