Amines reaction with benzylic

Alkyl halides with (3-hydrogens generally undergo only elimination reactions under the conditions of the vinyl substitution (100 C in the presence of an amine or other base). Exceptions are known only in cases where intramolecular reactions are favorable. Even alkyl halides without (3-hydrogens appear not to participate in the intermolecular alkene substitution since no examples have been reported, with the exception of reactions with benzyl chloride and perfluoroalkyl iodides. 

The reaction of the 5,7-dione (17) with primary amines led to the formation of three different thiadiazole derivatives depending on the reaction conditions. The reaction with benzyl amine at 75-80° produced N-benzyl-4-ureido-1,2,5-thiadiazole-3-carboxamide (18a). Reaction of both 17 and 18a with benzylamine under reflux for 1 hour... 

The most convenient way of a quat synthesis consists in the exhaustive methylation using primary or secondary fatty amines and methyl chloride to yield RN (CH3)3Cr (I) and R2N" (CH3)2Cr (II), respectively [101, 102], In order to enhance the quat yield the reaction is carried out in an aqueous or alcoholic solution of sodium carbonate at 60-95 °C. Tertiary amine quatemisation with benzyl chloride gives benzylalkyldimethylammonium, or "benzalkonium", chloride (III) ... 

Treating methyl 4-methylaminobenzoate with AT-chlorosulfonyl isocyanate in the presence of AICI3 leads to the benzo-l-thia-2,4-diazine 1,1-dioxide adduct, which after N-alkylation and reaction with benzylic amines affords the... 

Pg. 4 - Para. 2. Is it true that the aromatic primary amines reaction with epoxy (the selective reaction in this instance) is catalyzed by acid Salicylic acid in conjunction with an alcoholic hydroxyl carrier (benzyl elcoholi nonyl phenol, furfuryl alcohol, etc.) may do it. But I doubt it if CTBN will. Perhaps I m wrong. But this needs explaining. 

Our methodology is also useful for the preparation of aza-crown analogs, which should have better eomplexing properties. Diol 22 was converted into di-ester 51 and further in so-called homologated diol 52. Activation of both hydro)g l groups (as iodides) and reaction with benzyl amine provided macrocyclie derivative 53 in good yield (Scheme 12). 

A wide variety of quaternaries can be prepared. Alkylation with benzyl chloride may produce quaternaries that are biologically active, namely, bactericides, germicides, or algaecides. Reaction of a tertiary amine with chloroacetic acid produces an amphoteric compound, a betaine. 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Dibenzjiamine, [103-49-17, CgH CH2NHCH2CgH (bp, 300°C at 101.3 kPa) is produced by reaction of benzyl amine with benzaldehyde and hydrogenation of the Schiffs base. It is used in mbber and tire compounding, as a corrosion inhibitor, and as an intermediate in the production of mbber compounds and pharmaceutical products. 

Amino Acids. Chloroformates play a most important role for the protection of the amino group of amino acids (qv) during peptide synthesis (32). The protective carbamate formed by the reaction of benzyl chloroformate and amino acid (33) can be cleaved by hydrogenolysis to free the amine after the carboxyl group has reacted further. The selectivity of the amino groups toward chloroformates results in amino-protected amino acids with the other reactive groups unprotected (34,35). Methods for the preparation of protected amino acids on an industrial scale have been developed (36,37). A wide variety of chloroformates have been used that give various carbamates that are stable or cleaved under different conditions. 

The benzylation of a wide variety of aHphatic, aromatic, and heterocycHc amines has been reported. Benzyl chloride is converted into mono-, di-, and tribenzyl amines by reaction with ammonia. Benzylaniline [103-32-2] results from the reaction of benzyl chloride with aniline. Reaction with tertiary amines yields quaternary ammonium salts with trialkylpbospbines, quaternary phosphonium salts and with sulfides, sulfonium salts are formed. 

The second-order rate constants for the reaction of a number of amines with benzyl chloride are tabulated below. Calculate A// and A5 from the data. Offer an explanation for the relative reactivity order for the amines. What trends do you observe in A// with reactivity ... 

Rate Constants for the Reaction of Tertiary Amines with Benzyl Chloride... 

A -methyl-5//,7//-dibenzo[d,.g][l,5]telluroazocine 65, its thiooxide 67a (X=S, R= Me) (95JA6388). The same type of reaction with benzylamine and sodium selenide gives A-benzyl-5//,7//-dibenzo[d,g][l,5]telluroazocine selenoxide 67b (X = Se, R = CH2Ph). Reaction of the tellurium dibromide 66 with sodium sulfide carried out in the absence of the primary amines affords the eight-member Te,S-containing heterocycle 5//,7//-dibenzo[d,g][l,5]telluroazocine (92CL151). 

Reaction of dibenzylamine with ethylene oxide affords the amino alcohol, 82. Treatment of that product with thionyl chloride gives the a-sympathetic blocking agent, dibenamine (83). (Condensation of phenol with propylene chlorohydrin (84) gives the alcohol, 85. Reaction with thionyl chloride affords the chloride (86). Use of the halide to alkylate ethanolamine affords the secondary amine (87). Alkylation of this last with benzyl chloride... 

Palladium-catalyzed aminations of aryl halides is now a well-documented process [86-88], Heo et al. showed that amino-substituted 2-pyridones 54 and 55 can be prepared in a two-step procedure via a microwave-assisted Buchwald-Hartwig amination reaction of 5- or 6-bromo-2-benzyloxypyri-dines 50 and 51 followed by a hydrogenolysis of the benzyl ether 52 and 53, as outlined in Fig. 9 [89]. The actual microwave-assisted Buchwald-Hartwig coupling was not performed directly at the 2-pyridone scaffold, but instead at the intermediate pyridine. Initially, the reaction was performed at 150 °C for 10 min with Pd2(dba)3 as the palladium source, which provided both the desired amino-pyridines (65% yield) as well as the debrominated pyridine. After improving the conditions, the best temperature and time to use proved... 

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