2-Aminomethyl-4-methyl

Bei der Palladium(ll)-chlorid bzw. Palladiumkomplex-katalysierten Reaktion von Allen mit Ammoniak oder primaren Aminen erfolgt sowohl C,C-Verkniipfung von zwei Molekii-len Allen als auch Ammoniak- bzw. Amin-Addition. Das hierbei entstehende primare bzw. sekundare Amin kann seinerseits eine weitere Addition eingehen, so daB man ein Gcmisch von N-unsubstituiertem (im Fall von Ammoniak) bzw. N-Alkyl-substituiertem (im Fall von Alkylamin) 2-Aminomethyl-3-methyl-l,3-butadien und dem entsprcchenden Bis-[3-me-thyl-2-methylen-3-butenyl -amin erhalt, dessen Zusammensetzung von den Reaktionsbe-... 

Amino-2,3-dimethyl Hydrochloride p-Toluenesulfonyl 2-Aminomethyl-3-methyl Picrate... 

Pyrrolidines have been prepared by 1,3-dipolar cycloaddition of N-(benzyli-dene)trimethylsilylamine/TMSOf 20 and methyl acrylate, N-methylmaleimide, or dimethyl maleate [35]. More recently, methyl trans-3-cyanociruiamate 1479 was reacted with N-benzyl-N-(trimethylsilylmethyl)aminomethyl methyl ether 1480 and trifluoroacetic acid in CH2CI2 at 0°C and 24°C to afford, via 1481, the pyrrolidine derivative 1482 in high yield and MeOSiMe3 13a [35a] (Scheme 9.20). Several... 

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). 

Ethyl and butyl esters of poly(vinyl methyl ether)/maleic anhydride (PVM/MA) copolymer were introduced in the early 1960s for use in hair sprays. These polymers also have free carboxy acid groups that can be neutralized. Recommended neutralization is 10%, but products can be found in the range of 5—30%, and recommended neutralizers include ammonium hydroxide, aminomethyl propanol, and triisopropano1 amine. These were the most widely used polymers in hair sprays before their use decreased dramatically in the early 1990s. 

For a viable commercial process, the selection of materials and the choice of synthetic route is governed primarily by cost, not by overall yield. The selection of starting material is dictated usually by the desked C-3 substituent. For cephalosporins containing 3-acetoxymethyl or 3-(substituted)methyl such as 3-thiomethyl and 3-aminomethyl derived moieties, the most dkect synthetic route is from cephalosporin C, whereas pencillin V or G is the preferred starting material for the synthesis of the C-3 methyl cephalosporins. The three chemical transformations (2), (5), and 6) can potentially be carried out in a variety of ways, the precise sequence being determined by a balance of competing factors such as cost and optimization of yield (87). 

In many cases, substituents linked to a pyrrole, furan or thiophene ring show similar reactivity to those linked to a benzenoid nucleus. This generalization is not true for amino or hydroxyl groups. Hydroxy compounds exist largely, or entirely, in an alternative nonaromatic tautomeric form. Derivatives of this type show little resemblance in their reactions to anilines or phenols. Thienyl- and especially pyrryl- and furyl-methyl halides show enhanced reactivity compared with benzyl halides because the halogen is made more labile by electron release of the type shown below. Hydroxymethyl and aminomethyl groups on heteroaromatic nuclei are activated to nucleophilic attack by a similar effect. 

Imidazo[4,5-6]pyridine, 1,2-dimethyl-methylation, 5, 618 Imidazo[4,5-6]pyridine, 2,3-diphenyl-synthesis, 5, 636 Imidazo[4,5-6]pyridine, 6-halo-alkylation, 5, 616 aminomethylation, 5, 616 Imidazo[4,5-6]pyridine, 2-(4-hydroxy-6-methylpyrimidin-2-ylamino)-synthesis, 5, 637... 

Jap-KIingermarm reactions, 4, 301 oxidation, 4, 299 reactions, 4, 299 synthesis, 4, 362 tautomerism, 4, 38, 200 Indole, 5-amino-synthesis, 4, 341 Indole, C-amino-oxidation, 4, 299 tautomerism, 4, 298 Indole, 3-(2-aminobutyl)-as antidepressant, 4, 371 Indole, (2-aminoethyl)-synthesis, 4, 278 Indole, 3-(2-aminoethyl)-synthesis, 4, 337 Indole, aminomethyl-reactions, 4, 71 Indole, 4-aminomethyl-synthesis, 4, 150 Indole, (aminovinyl)-synthesis, 4, 286 Indole, 1-aroyl-oxidation, 4, 57 oxidative dimerization catalysis by Pd(II) salts, 4, 252 Indole, 1-aroyloxy-rearrangement, 4, 244 Indole, 2-aryl-nitration, 4, 211 nitrosation, 4, 210 synthesis, 4, 324 Indole, 3-(arylazo)-rearrangement, 4, 301 Indole, 3-(arylthio)-synthesis, 4, 368 Indole, 3-azophenyl-nitration, 4, 49 Indole, 1-benzenesulfonyl-by lithiation, 4, 238 Indole, 1-benzoyl photosensitized reactions with methyl acrylate, 4, 268 Indole, 3-benzoyl-l,2-dimethyl-reactions... 

Reaction of 2-amino-4/f-pyrido[l,2-n]pyrimidin-4-ones 143 with HNMei -HCl and paraformaldehyde in Dowtherm A afforded a mixture of 3-(A,A-dimethylamino)methyl derivatives 144 and bis-compounds 145 (93FES1225). Mannich reaction of 9-hydroxy-2-methyl-4//-pyri-dor],2-nlpyrimidin-4-one (146) yielded 8-aminomethyl derivatives 147 (94KFZ(10)23). 

A side chain 7-[3-(mesyloxymethyl)phenoxy]rnethyl group of a perhy-dropyrido[l,2-u]pyrazine was converted to 7-[3-(aminomethyl)phenoxy]-methyl groups by the treatment with different amines (99MIP9). 

Amino group of 7-aminomethyl-2-substituted perhydropyrido[l,2-u]pyr-azines were reacted with 2-bromopyridine and 2-chloropyrimidines to give 7-(hetarylamino)methyl derivatives in the presence of Na2C03 in DMF at 100-120°C for 18h in 13-51% yields (00MIP15). An aminomethyl group of... 

The derivative from an isomeric fused system has been described as a sedative-hypnotic compound. The synthesis starts by condensation of the aminopicoline 32 with the haloketone 33. The resulting pyrrolo[l,2-a]pyridine 34 then undergoes a Mannich reaction with formaldehyde and dimethylamine to give the aminomethylated derivative 35. After quatemization of the di-methylamino group in 35 with methyl iodide, the ammonium group is displaced by cyanide to... 

A solution of 192 g of 1 -phenethyl-4-hydroxy-4-aminomethyl piperidine in BOO cc of diethyi-carbonate is heated for 1 /i hours to refiux at about B0°C in the presence of sodium methylate (prepared for immediate use from 2 g of sodium). After this time, the ethyl alcohol formed during the reaction is slowly distilled while the maximum temperature is reached. The excess ethyl carbonate is distilled under reduced pressure. A crystallized residue Is then obtained, which is stirred with 400 cc of water and 400 cc of ether. The solution is filtered and 125 g (77.6%) of practically pure product melting at 232°C to 233°C, are obtained. 

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-... 

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. 

Benzyl alcohol, a-vinyl- [Benzene-methanol, a-ethenyl-), 106 Bcnzylamine-polystyrene [Benzene, di-ethenyl-, polymer with ethenyl-benzene, aminomethylated), 95 Benzyl bromide [Benzene, (bromo-methyl)-, 78... 

Iron, cyclopentadienyl[(dimethyl-aminomethyl)cyclopenta-dienyl]-, methiodide j, 40,31 (Iron, cyclopentadienyl[(hydroxy-methyl)cyclopentadienyl]- [,... 

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