9-Aminomethyl

1-Methylgramine (356) generally reacts analogously to gramine, but with potassium cyanide it yields a mixture of the 2-cyano-3-methyl (357) (by S N reaction) and the 3-cyanomethyl derivatives. 

Indole-2,3-quinodimethanes, generated from 2-methylgramine, undergo intermolecular cycloaddition reactions with dienophiles similar to that of (325) (82T2745). 

Carboxylic acids show most of the standard reactions of benzoic acid. Amides, esters, hydrazides, azides and nitriles can be prepared by standard methods. Thiophenes form stable acid chlorides, furans unstable ones, and A-unsubstituted pyrroles do not form them. 

The acid dissociation constants of some representative carboxylic acids are given in Table 4. 

Pyrrole-3-carboxylic acid (358) is appreciably weaker than benzoic acid and this is attributed to the stabilization of the undissociated acid by electron release from nitrogen. The 2-carboxylic acids of furan, thiophene, selenophene and tellurophene are all stronger acids than benzoic acid 

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The desired pyridylamine was obtained in 69 % overall yield by monomethylation of 2-(aminomethyl)pyridine following a literature procedure (Scheme 4.14). First amine 4.48 was converted into formamide 4.49, through reaction with the in situ prepared mixed anhydride of acetic acid and formic acid. Reduction of 4.49 with borane dimethyl sulfide complex produced diamine 4.50. This compound could be used successfully in the Mannich reaction with 4.39, affording crude 4.51 in 92 % yield (Scheme 4.15). Analogous to 4.44, 4.51 also coordinates to copper(II) in water, as indicated by a shift of the UV-absorption maximum from 296 nm to 308 nm. 

Pyridyl)hydrazine (Aldrich), 4-acetylpyridine (Acros), N,N,N -trimethylethylenediamine (Aldrich), methylrhenium trioxide (Aldrich), InQj (Aldrich), Cu(N0j)2-3H20 (Merck), Ni(N03)2-6Il20 (Merck), Yb(OTf)3(Fluka), Sc(OTf)3 (Fluka), 2-(aminomethyl)pyridine (Acros), benzylideneacetone (Aldrich), and chalcone (Aldrich) were of the highest purity available. Borane dimethyl sulfide (2M solution in THE) was obtained from Aldrich. Methyl vinyl ketone was distilled prior to use. Cyclopentadiene was prepared from its dimer immediately before use. (R)-l-acetyl-5-isopropoxy-3-pyrrolin-2-one (4.15) has been kindly provided by Prof H. Hiemstra (University of Amsterdam). 

Chiral N,N-disubstituted 2-(aminomethyl)pyrrolidines as catalysts for asymmetric acylation of alcohols 99YGK598. 

Aminomethyl-1-methyl-5-chloro-3(o-fluorophenyl)indole HCI Chromic anhydride Ammonia Hydrogen chloride... 

A solution of 60 g of chromic anhydride in 40 ml of water was added dropwise to a suspension of 60 g of 2-aminomethyl-1 -methyl-5-chloro-3-(o-fluorophenyl)-indole hydrochloride in 600 ml of acetic acid. The mixture was stirred at room temperature overnight. To the reaction mixture was added 1.1 liters of ether and 1 liter of water and then 800 ml of 28% ammonium hydroxide, in small portions. The ethereal layer separated, washed with water, dried, and concentrated under reduced pressure. The residue (51.8 g) was dissolved in 100 ml of ethanol, and 100 ml of 20% ethanollc hydrogen chloride was added to the solution and the mixture was cooled. The precipitate was collected by filtration to yield 46.5 g of 1 -methyl-7-chloro-5-(o-fluorophenyl)-1,3-dihydro-2H-1,4-benzodiazepine-2-one hydrochloride, melt-... 

Acetic anhydride (7 ml) was added to a solution of 6.16 g of crude 2-aminomethyl-7-chloro-... 

The resulting precipitate is collected by filtration, washed with water followed by ethanol, and dried to give 56.3 g of crude 2-aminomethyl-1 -methyl-5-nitro-3-phenyllndole hydrochloride, melting point 263°C to 267°C. 

Dibenz[c 1c ]azepine (32 a) is obtained by acid-mediated cyclization of 2 -(aminomethyl)bi-phenyl-2-carbaldehyde (31 a), which is generated in situ by reduction of the oxime acetal 30a.85 The acetyl 30 a and benzoyl 30c oximes behave similarly and give the dimethyl and diphenyl derivative 32 b and 32 c, respectively. 

Diboran kann besonders dann zur Reduktion von Nitrilen mit Erfolg eingesetzt werden, wenn Lithiumalanat und auch Lithiumalanat/Aluminiumchlorid nicht die gewunschten Resultate zeigen. Aus tert.-Butyl-malonsaure-dinitril erhalt man z.B. nur durch Reduktion mit Diboran l-Amino-3,3-dimethyl-2-aminomethyl-butan (36—48% d. Th.)2. 

Aminomethyl-pyridin hzw. Pyridin-2-carbonsaure-[pyridyl-(2)-metbylimid]-amid ... 

Hydroxy-phenyl) -dthylamin 5 2-Aminomethyl-1, l-diphenyl-butanol ... 

Zur Reduktion von Pyridin-2-carbonsaure-imid-athylester zum 2-Aminomethyl-pyri-din s. S. 114. 

C24H25NO 127927-43-9) see Saquinavir tris(trimethylsilyloxy)ethylene (CiiH2g03Si3 69097-20-7) see Saquinavir (-)-(S)-l-trityl-2-(aminomethyl)pyrrolidine (C24H26N2 98598-84-6) see Remoxipride 5 -0-trityl-2,3 -anhydro thymidine (C29H24N2O4 25442-42-6) see Zidovudine trityl chloride... 

Many other examples have been prepared (2) from the corresponding aminomethyl heterocycles using the very versatile reaction between HHTs and diaryl phosphites, as demonstrated specifically above for the 5-phenyl-l,3,4-oxadiazole system. Conversion of the 2-aminomethyl-l,3,4-oxadiazole 68 to the required HHT intermediate 69 was accomplished... 

GABAc receptors are defined by their insensitivity to bicuculline and their activation by conformationally restricted analogues of GABA such as CACA and (+)-CAMP (15, 2i -2-(aminomethyl)cyclopropanecarboxylic acid). They are blocked by picrotoxin but can be selectively antagonised by TPMPA (l,2,5,6-tetrahydropyridin4-ylphosphinic acid). Unlike GABAa receptors, they are not affected by benzodiazepines, barbiturates or anaesthetics (Barnard et al. 1998 Bormann 2000 Chebib and Johnston 2000). 

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