Aminomethylation acetonitrile

Tolmetin Tohnetin, l-methyl-5-n-tolylpyrrol-2-acetic acid (3.2.61) is synthesized from 1-methylindole, which is aminomethylated using formaldehyde and dimethylamine, forming 2-dimethylaminomethyl-l-methylindol (3.2.57). The product is methylated by methyl iodide, giving the corresponding quaternary salt (3.2.58). Reaction of the product with sodium cyanide gives l-methylpyrrole-2-acetonitrile (3.2.59), which is acylated at the free... 

Most polymers belonging to this class are water-soluble only in their protonated form. As a consequence, most potentiometric titrations of these polymers have been performed with OH starting from their hydrochlorides, either in water or in mixed solvents, such as water/dioxane, water/sulfolane, water/acetonitrile 64). Many poly[thio-l-(N,N-dialkyl-aminomethyl)ethylene]s are optically active, and in these cases ORD and CD techniques may be used to study their protonation behaviour, in addition to potentiometric techniques. 

N-Heterocyclic substrates are the most used for Mannich reactions, usually in acetic acid as a solvent, but methyleneinunonium salts in acetonitrile are also frequently employed as reagents. Such conditions appear adequate to overcome the chemoselectivity problem posed by the formation of the undesired N-aminomethylated product. Apart from rare exceptions, the rules genoally followed are as follows ... 

In the case of tribenzyl and trimethyl amine, a-substitution products could be obtained using diethyl malonate or diethylphosphonate as nucleophiles, if 2,4,6-collidine was used as base in an acetonitrile electrolyte [20]. In this way, dialkyl aminomethyl phosphonates and malonates could be obtained in good yield. 

Several kinetic studies have been reported on nickel(II) complexes including acetonitrile exchange (134, 136) with complexes formed by nickel(II) and 2,2, 2"-triaminotriethylamine, (130) 2,2, 2"-tri(V V-dimethylamino)-triethylamine, (130) 2,2-di(hydroxymethyl)-1 -propanol, (135) 2,2-di(aminomethyl)-l-propylamine, (135) 2,2-di(aminomethyl)-1-propanol (135) and 2,2, 2"-trihydroxytriethylamine. (135)... 

Six-membered heterocycles have been prepared from cyclopropanes by a diverse selection of methods. Thermolysis of an acetonitrile solution of the hydrobromide of the aminomethyl cyclopropyl ketone 32 in a sealed tube caused cleavage of the cyclopropane ring, which was followed by cyclization to afford the piperidone derivative 33. The non-narcotic analgesic pentazocine was obtained from 33 in several steps. ... 

In 1982, Ohga and Mariano first reported the photoallylation of iminium salts. The photoreaction of iminium salts with allyl-trimethylsilane in acetonitrile affords allylated compounds via the addition of an allyl radical to an a-aminomethyl radical. Allyl radicals are produced via the cleavage of C-Si bonds of allylsilane radical cations and the a-aminomethyl radicals are generated by one-electron reduction of iminium salts as shown in Scheme 4. 

The Mannich reaction for the aminomethylation of CH-acidic compounds has provided numerous tertiary phosphine-containing macrocycles <84ZC365>. For example, the reaction of bis(hydroxy-methyl)phenylphosphine with aniline or (i )-(-H)- or (5)-(—)-A, 7V -bis(l-phenyl-1-ethyl)-ethylenediamine in boiling acetonitrile or ethanol gives the l,5-diaza-3,7-diphosphacyclooctane (166) (77% yield) <80TL1409> or the optically active l,5-diaza-3-phosphacycloheptanes (167 R = (R)- or (S)-PhCHMe) (92% yield) <80TL3467>, respectively. Nickel carbonyl and molybdenum carbonyl complexes of (166) were reported. 

CHP were heated in acetonitrile at 100°C in a sealed NMR tube, the formation of 12b was clearly indicated by the appearance of a sharp singlet at 55 ppm. Proof of the formation of 12b was provided by the addition of an authentic sample to the reaction mixture after partial thermolysis, leading to an increase in intensity for all appropriate NMR signals. We suggest that is formed by addition of CHP to the formaldehyde N-methylanilinium ion, generated from a-aminomethyl radical 1 one-electron oxidation. 

All reactions run in acetonitrile using an excess of triethylamine as base under 80 psig carbon dioxide pressure at -lO C (triaminononane = 4-aminomethyl-l,8-octanediamine, HMD = 1,6-diamindiexane). 

Arakawa and coworkers [45] developed the on-line photoreaction cell depicted in Figure 5.3 and performed a series of studies on the detection of reaction intermediates in photosubstitution and photooxidation of Ru(II) complexes. The photosubstitution of Ru(bpy)2B [bpy = 2,2 -bipyridine B = 3,3 -dimethyl-2,2 -bipyridine (dmbpy) or 2-(aminomethyl)pyridine (ampy)] was studied in acetonitrile and pyridine. Irradiation of Ru(bpy)2B and related complexes yields a charge-transfer excited species with an oxidized Ru center and an electron localization on the bpy moiety. The excited-state complex underwent ligand substitution via a stepwise mechanism that includes ant] bidentate ligand (Scheme 5.6). Photoproducts such as Ru(bpy)2S2 (S = solvent molecule) and intermediates with a monodentate (mono-hapfo-coordination) B ligand, Ru(bpy)2BS, and Ru(bpy)2BSX+ (X=C10/, PF ) were detected. Other studies also identified photo-oxidized products of several mixed-valence Ru(II) complexes upon irradiation (7i> 420 nm) [31b, 46]. 

Anhydrous HCl introduced at -30° into a soln. of 1,3,5-tri-n-propylhexahydro-triazine in anhydrous acetonitrile, then a soln. of phenol in acetonitrile added, and allowed to stand 24 hrs. at room temp. p-(n-propylaminomethyl)phenol. Y 56%. - p-Substitution is favored by this method in contrast to conventional aminomethylating agents, whidi favor o-substitution. F. e. s. D. D. Reynolds and B.C. Cossar, J. Heterocyclic Chem.5,605(1971) 3,4-dihydro-2H-l,3-benzoxazmes cf. ibid. 8, 611. 

Fig. 12. CD changes of optically active poly [thio-l-(iV-iV-diethyl aminomethyl) ethylene] (chlorhydrate form XXI) in 50-50 KCl 0.05M-acetonitrile mixture as a function of the degr of protonation 1 ...

Fig. 13. Changes of pH -a- r gp/C- - [w] JJo and [0], 3, of optically active poly[thio-l-(yV-7V-diethyl-aminomethyl) ethylene ] (hydrochloride form (XXI) in a (1 1, v/v) 0.05 M KCl -acetonitrile solvent system, as a function of the degree of protonation 0 (in dioxane for =0) (from...

A suspension of powdered 91 %-paraformaldehyde in glacial acetic acid and coned. H2SO4 heated at 50 until dissolved, cooled to ca. 35 , acetonitrile added dropwise at 35-45 , stirring continued until the spontaneous reaction is completed, jn-xylene added, heated slowly to 65-75 whereupon a self-sustaining reaction occurs with formation of a homogeneous mixture, finally heated 5 hrs. at 85-90 crude N,N -diacetyl-4,6-dimethyl-l,3-di(aminomethyl)benzene. Y 75%. F. e. s. G.L. Parris and R. M. Ghristenson, J. Org. Ghem. 25, 1888 (1960). 

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