Synthesis and characterization of 4-dimethylamino-N-triphenylmethylpyridinium chloride,a postulated intermediate in the tritylation of alcohols

4-Dimethylamino-$\text{N}$-triphenylmethylpyridinium chloride ($\text{1}$) reacts with primary but not secondary alcohols to produce trityl ethers in good yield; in addition, amines may be selectively $\text{N}$- tritylated witth $\text{1}$ in the presence of alcohols.     

Selective reduction of the N-O bond in n-oxides and in nitrones by sodium hydrogen telluride

Sodium hydrogen telluride reduces $\text{tert}$.-amine $\text{N}$-oxides to the corresponding amines in very high yield, but does not reduce sulphoxides. This reagent also reduces nitrones to $\text{sec}$.-amines at pH6 and to imines at alkaline pH (10–11).     

Decomposition of arilazides and p-tosylazide by thf/n-botyllithium. A new source of diazomethmne

Variously substituted arylazides, as well as $\text{p}$-tosylazide, when allowed to react at room temperature with THF previously treated with $\text{n}$-butyllithium, undergo a rapid decomposition affording the corresponding amines and fomamides, together with diazomethane. This diazo transfer (with deformylation) reaction is thought to involve the enolate of the acetaldehyde generated by the known cycloreversion of THF in the presence on $\text{n}$     

WCl6/LiAlH4 Promoted transformation of imines into secondary and tertiary amines

The reaction of WCl₆/LiAlH₄ with imines, R′NCHR, gave tertiary amines, R′N(CH₂R)₂, and secondary amines, R′NHCHRCH₂R. Isotope labeling experiments revealed that the reaction involved two types of azatungstenacyclobutanes, $\text{WNR′CHRC}$HR and $\text{WCHRNR′C}$HR, produced from the reaction of an alkylidene tungsten intermediate with the imine CN double bond. Formation of these metallacyclobutanes is highly dependent on the solvent used.     

Solvolytic behavior of p-dimethylamino-α-bromostyrene in water solutions

Nmr and UV studies show that $\text{p}$-dimethylamino-$\text{α}$-bromostyrene, I, undergoes S_Nl reaction in H₂O and HClO₄ (^kS_Nl = 6 × 10^?1sec.^?1 at 25°). The vinyl cation has an extraordinary selectivity for capture by aromatic amines relative to H₂O, including I itself to give the dimer II.     

Reductive cleavage of axially disymmetric tertiary amines and quaternary ammonium salts by lithium aluminium hydride. Synthesis of new 1,1′-binaphthyl substituted amines

Axially disymmetric tertiary amines or quaternary ammonium salts $\text{A}$ are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines $\text{B}$, substituted by a binaphthyl unit, with high yields and absence of racemization.     

Nitroethylene nitroethylation of amines

The nitroethylation of amiens is demonstrated to be a general reaction for bases in the pK_a range of 2 – 8 and that it proceeds through a key intra-molecular quenching step. The reaction, illustrated with aromatic amines, aliphatic amines and heterocyclic bases, offers $\text{inter}$$\text{alia}$ attractive routes to diverse heterocyclic systems.     

Comparative reactions between aziridines and F2, COF2, CF3OF

In CFCl₃, aziridines $\text{I}$ react with F₂(6 %/N₂,  20°C), COF₂ (20 %/N₂,  40°C) and CF₃OF [1] (20 %/N₂,  40°C).Substitution products are obtained : l-(aziridine)carbonyl fluorides $\text{II}$ and l-Fluoroaziridines $\text{III}$

In (Et)₂O, aziridines $\text{I}$ react with COF₂ (20 %/N₂, 10°C) and we have the carbonyl fluorides $\text{IV}$.

Products IV can be thermally decomposed into β fluoro isocyanates.In CFCl₃, N substituted aziridines $\text{V}$ react with F₂(6%/N₂, 20°C) and with CF₃OF [2] (20%/N₂, 40°C). No reaction is observed with COF₂in our conditions (5% to 25%/N₂, 80°C to + 40°C).Addition products are obtained : N Fluoro amines β fluorinated $\text{VI}$, N Fluoro and NN difluoro amines β trifluoro methoxylated $\text{VII}$ and $\text{VIII}$.

with R = SO₂Ø, COØNO₂, Cl.     

Perfluoroalkyl derivatives of nitrogen. Part LI [1]. Reaction of the N-halogenobistrifluoromethylamines (CF3)2NX (X=Cl,Br) with norbornadiene

Reaction of the amines (CF₃)₂NX (X=Cl,Br) with norbornadiene either in solvent (CH₂Cl₂) at ?78 °C in the dark or in the vapour phase at 20 °C in daylight gives a mixture of 3-halogeno-5-($\text{NN}$-bistrifluoromethylamino)nortricyclene ($\text{exo}$, $\text{endo}$-and $\text{exo}$, $\text{exo}$-isomers) and $\text{exo}$-5-($\text{NN}$-bistrifluoromethylamino)- $\text{anti}$-7-halogenonorbornene in quantitative yield formed $\text{via}$ halonium ion addition to the diene. The reaction of the amine (CF₃)₂NBr in solvent Me₂O or Et₂O at ?78 °C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene ($\text{exo}$, $\text{endo}$- and $\text{exo}$, $\text{exo}$-isomers) and the amine (CF₃)₂NR (R=Me, Et) in high yield.     

Synthèse et thermolyse de dérivés disilyles des acides hydroxamiques : Sur une nouvelle voie d'accès aux esters isocyaniques et aux amines

Thermolysis of disilylated hydroxamic acids $\text{7}$, readily prepared from hydroxamic acids $\text{5}$ and hexamethyl disilazane, leads to the corresponding isocyanates $\text{4}$ ; an application to the synthesis of amines is reported.     

Stability of fluorenylemthoxycarbonylamino groups in peptide synthesis. Cleavage by hydrogenolysis and by dipolar aprotic solvents

$\text{N}$-Fluorenylmethoxycarbonyl derivatives of amines are unexpectedly cleaved by catalytic hydrogenation with t$\text{1}\text{2}$ 3–33 h. under various conditions. They are also cleaved on standing in the solvents dimethylformamide, dimethylacetamine, and $\text{N}$-methylpyrrolidone, but much more slowly.     

Stereochemistry of nucleophilic attack by amine on a cationic π-allylnickel complex

Reaction of the π-allylnickel complex $\text{3}$ with morpholine gave a 1:1 mixture of the amines $\text{4}$ and $\text{5}$ indicating that the amine has attacked the π-allyl moiety from the side trans to nickel.     

Katalytische reaktionen von aminen mit olefinen

Tetramethylethylenediamine (TMED) reacts with ethylene (propene) under the influence of catalytic amounts of alkyllithium to give dimethylvinylamine and dimethylethylamine (dimethylisopropylamine). In competitive reactions alkyl-lithium and the amides formed by this with primary or secondary amines in presence of tetramethylethylenediamine enhance the addition of primary or secondary amines to ethylene more strongly than in the absence of the diamine. The pressures are $\text{1}\text{5}$ to $\text{1}\text{10}$ of those needed when sodium catalysts are used and the temperatures required are 50–100° lower. Dimethylamine but not diethylamine, which however reacts with cycloolefins containing strained double bonds, adds to propene.     

Stereospecific formation of amidines by 1,1-addition of amines to isocyanides

Addition of secondary amines to isonitriles in the presence of AgCl at low temperature gives isolable but thermodynamically unstable Z-amidines; only the more stable $\text{6E}$ undergoes ring expansion to the imidazoline $\text{7}$.     

New facile synthesis of N-sulfinylamine derivatives using N,N′-sulfinylbisimidazole and N-(chlorosulfinyl)imidazole

Treatment of amine derivatives such as amines, sulfonamides, and amides with N,N′-sulfinylbisimidazole $\text{1}$ and N-(chlorosulfinyl)imidazole $\text{2}$$\text{in situ}$ respectively gives the corresponding N-sulfinylamine derivatives ($\text{3}$); the latter reaction using N-(chlorosulfinyl)imidazole $\text{2}$ yields $\text{3}$ in almost quantitative yields at 20°C under mild conditions.     

Monitored aminolysis of 3-acylthiazolidine-2-thione : A new convenient synthesis of amide

3-Acylthiazolidine-2-thiones ($\text{1}$) were easily prepared and they were treated with several amines in dichloromethane to give amides $\text{4}$ in very high yields within a short time. Aminoalcohols and aminophenols were selectively converted into acylaminoalcohols and acylaminophenols, respectively, by this reaction. One can monitor the reaction by disappearance of the yellow color of the starting material $\text{1}$. Some amide alkaloids ($\text{1}$$\text{5}$–$\text{1}$$\text{8}$) have effectively been synthesized.     

Rapid reductive-carboxylation of secondary amines. One pot synthesis of tertiary N-methylated amines

Various tertiary N-methylated amines were synthesized by using a new reductive-carboxylation approach. Secondary amines, on carboxylation with carbon dioxide under moderate reaction conditions, afforded their corresponding carbamate esters, which, on $\text{in situ}$ lithium aluminum hydride reduction, gave desired tertiary N-methylated amines in high yield.     

A chiral reagent inducing asymmetry in electrophilic amination reactions

The chiral amination reagent (?)-$\text{1}$ was prepared from (?)-ephedrine, configurationally determined by X-ray structure analysis and reacted with carbon nucleophiles to yield the optically active amines $\text{4a-d}$ with up to 44% ee.     

Highly selective transport of biogenetic amines and drugs by using functionalized “acyclic crown ether”

Acyclic crown ether $\text{1}$, containing quinoline terminal groups, showed effective transport selectivity for some kinds of biogenetic amines and drugs of biological significances over alkali metal cations, which was not attained by using a typical cyclic crown ether $\text{3}$.     

Ouverture par HF-pyridine des aziridines bicycliques. II. Derives α,β-ethyleniques diversement substitues

The ring opening of three isomeric α,β-ethylenic aziridines by HF-pyridine has been studied. The reaction proceeds, depending on temperature, solvent or structure, either to expected 2-fluoro amines and 4-fluoro allylic amines or to elimination products. A type of Wagner-Meerwein rearrangement was observed and benzene as solvent gave a type of Friedel-Crafts reaction. The steric constraints may explain the differences in the yields of $\text{cis}$ and $\text{trans}$ addition products. Also, the rigid structures allow the detection of vicinal couplings and the study of configuration and conformation.