Alkylation of nitrogen compounds

Alkylation of nitrogen compounds by sulfuric esters. The use of sulfuric esters as alkylating agents for ammonia derivatives is limited substantially to dimethyl and diethyl sulfate. Under not too drastic conditions only one alkyl group is transferred from the ester to the amine component transfer of the second group usually occurs only at 160-200°. 

Alkylation of nitrogen compounds by phosphoric esters. There are few records of the alkylation of nitrogen compounds by phosphoric esters. Billman et al.841 give the following general directions for alkylation of aromatic amines the phosphoric ester is wholly dealkylated under these conditions. 

Reaction No. 5 (Table 11) is part of a synthetically useful method for the alkylation of aromatic compounds. At first the aromatic carboxylic acid is reductively alkylated by way of a Birch reduction in the presence of alkyl halides, this is then followed by an eliminative decarboxylation. In reaction No. 9 decarboxylation occurs probably by oxidation at the nitrogen to the radical cation that undergoes decarboxylation (see... 

Nitrous acid or alkyl nitrites react with a number of nitrogen compounds to yield tetrazoles. For example, hydrazidines (87), which can be prepared in situ from the corresponding iminoesters, react with nitrous acid or its derivatives to give 1-substituted tetrazoles (88).150-152 This reaction (Eq. 17), is one of the most extensively used methods for the synthesis of... 

Atomic charges have been calculated by semi-empirical method (AMI) for nitrogen atoms of two triazolo[4,3-A -[l,2,4,5]tetrazines in order to assess the site of alkylation of these compounds <2000ARK259>. The results are summarized in Table 1. 

Sha et al. (45) reported an intramolecular cycloaddition of an alkyl azide with an enone in an approach to a cephalotaxine analogue (Scheme 9.45). Treatment of the bromide 205 with NaN3 in refluxing methanol enabled the isolation of compounds 213 and 214 in 24 and 63% yields, respectively. The azide intermediate 206 underwent 1,3-dipolar cycloaddition to produce the unstable triazoline 207. On thermolysis of 207 coupled with rearrangement and extrusion of nitrogen, compounds 213 and 214 were formed. The lactam 214 was subsequently converted to the tert-butoxycarbonyl (t-Boc)-protected sprrocyclic amine 215. The exocyclic double bond in compound 215 was cleaved by ozonolysis to give the spirocyclic ketone 216, which was used for the synthesis of the cephalotaxine analogue 217. 

These results are interesting because amino heterocycles show a quite different behavior under neutral and alkaline conditions, e.g., aminothiazole derivatives are alkylated at the ring nitrogen in weakly acidic and neutral media and at the exo nitrogen in highly alkaline medium.200 Therefore, the use of PTC to promote exo nitrogen alkylation of azaaromatic compounds may be of interest. 

In spite of all of the work, the kinetics and mechanism of alkyl-substituted dibenzothiophene, where the sulfur atom may be sterically hindered, are not well understood and these compounds are in general very refractory to hydrodesulfurization. Other factors that influence the desulfurization process such as catalyst inhibition or deactivation by hydrogen sulfide, the effect of nitrogen compounds, and the effect of various solvents need to be studied in order to obtain a comprehensive model that is independent of the type of model compound or feedstock used. 

ALKYLATIONS OF CARBONYL COMPOUNDS VIA THEIR NITROGEN DERIVATIVES... 

J.l Regiochemistry and Stereochemistry of Alkylations of Nitrogen Derivatives of Carbonyl Compounds... 

It was also reported that pyridines and pyrroles were e two major types of nitrogen compounds in shale oil (7). Also, Brown and co-workers (5) identified alkyl-pyridines, cycloalkanopyridines, alkylanilines, quinolines, tetrahydroquinolines, and tetrahydroisoquinolines in hydrocracked shale oil naphtha (8). 

The presence of alkylated heterocyclic nitrogen compounds in processed shale oil can cause sedimentation. This especially becomes problematic in... 

In C-alkylation of other compounds containing nitrogen atoms. Chi s group [35] has done a lot of work. They have described a novel approach for pyrrole C-alkylation in which [BMIM][SbFg] and CH CN as a mixture was onployed for the synthesis of 2-(3-phenylpropyl)pyrrole from pyrrole and 7-bromo-3-phenylpropane with the results that 81% yield was achieved at 115 C for 44 h with 5% yield of dialkylated compound. It is obvious that the ionic Uqnid demonstrated an important driving force in the regioselective alkylation of pyrrole. Moreover, it is worthy to be noted that in this reaction, no Lewis add/base catalysts were needed. 

Wender, I., and P. Pino, eds., Organic Syntheses via Metal Carbonyls, Wiley, Vol. 1, 1968 (cyclic polymerization of acetylenes organic synthesis via alkyl and acyl Co carbonyls reactions of nitrogen compounds). 

Dehydration of nitrogen compounds is a well-known route to nitriles. Alkyl, aralkyl, aryl, and heteroaryl amides are readily converted into the corresponding nitriles using trichloromethyl chloroformate as the dehydrating agent (Scheme 130) the work-up is... 

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