Amines benzylic

It is prepared by the direct chlorination of toluene in the presence of PClj. It is purified by fractionation from the unchanged toluene and the higher chlorinated products. It is used for benzylating amines and for preparing benzyl alcohol. 

D) Bmzylamides. Many acids when heated directly with benzyl-amine in the presence of ammonium chloride as a catalyst give the... 

Give the structure of the expected product formed when benzyl amine reacts with each of the following reagents... 

Novolaks. Novolak resins are typically cured with 5—15% hexa as the cross-linking agent. The reaction mechanism and reactive intermediates have been studied by classical chemical techniques (3,4) and the results showed that as much as 75% of nitrogen is chemically bound. More recent studies of resin cure (42—45) have made use of tga, dta, gc, k, and nmr (15). They confirm that the cure begins with the formation of benzoxazine (12), progresses through a benzyl amine intermediate, and finally forms (hydroxy)diphenyknethanes (DPM). 

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. 

MAO is known to occur in at least two forms, MAO A and MAO B, based on substrate selectivity, inhibition by various dmgs, and cloning experiments. Clorgyline [17780-72-2] is a specific inhibitor of MAO A, which displays a substrate specificity for NE and serotonin. Deprenyl [2323-36-6] is a selective inhibitor of MAO B, and displays a substrate preference for P-phenylethylamine and benzyl amine. Dopamine and tyramine are substrates for both enzymes. 

ANILINES, BENZYL AMINES, AND ANALOGUES An orally active local anesthetic agent that can be used as an (intiarrhythmic agent is meobenti ne (57). Its patented synthesis starts with -hydroxyphenyl nitrile and proceeds by dimethyl sulfate etherification and Raney nickel reduction to Alkylation of -methyl-dimethylthiourea with completes l.he synthesis of meobenti ne (57). ... 

A 100 gallon lined jacketed kettle provided with cooling is charged with 100 lb of benzyl-amine and 150 liters of water. The mixture is cooled to 5°C and with stirring 119 lb of /3-chloropropionyl chloride and a solution of 45 lb of sodium hydroxide pellets in 40 liters of water are added simultaneously at such a rate that the temperature does not exceed 10°C. During this period the pH of the mixture should be on the alkaline side but below pH 9.5. When the addition is complete the pH should be about 8. The mixture is stirred overnight in the cold, and the solid product is filtered. The filter cake is reslurred with about BO gallons of water, filtered, and air-dried. Yield, 12B pounds. 

Athyl-benzyl-amin — Athyl-(2-phenyl-dthyl)-amin —> Athyl-(2,2-diphenyl-dthyl)-amin — Athyl-(2,2-dimelhyl-propyl)-amin-Hydrochlorid... 

Alcohols can be selectively bound to the same host type if they are combined with an amine and vice versa, considering that a cation and an anion will be formed through a proton transfer. The so-formed alkoxide anion will bind to the boron atom, while the ammonium ion will be complexed by the crown ether (147, Fig. 39). Competition experiments involving benzyl-amine have shown enhanced selectivity for the complexation of alcohols with... 

Since amines react more readily than alcohols in noncatalyzed reactions with anhydrides, the reaction is more difficult and initially required stoichiometric catalyst loadings [107], but could be performed in a catalytic sense with an O-acylated azlactone as acylating agent, which does not react with a benzylic amine at —50°C, but is capable of acylating the catalyst [108, 109]. Depending on the buUdness of the substrate, selectivities ranged from S = 11 to 27 (s = [ enantiomer l]/[ enantiomer 2])-... 

Recently, Backvall et al. reported that a p-methoxy derivative of dirutheitium complex 1 racemizes benzyl amines at 90-100°C in toluene and the DKRs using it were achieved successfully (Scheme 5). More than ten benzylic amines were transformed to the corresponding amides with good yields and high ee. ... 

The strategy for the asymmetric reductive acylation of ketones was extended to ketoximes (Scheme 9). The asymmetric reactions of ketoximes were performed with CALB and Pd/C in the presence of hydrogen, diisopropylethylamine, and ethyl acetate in toluene at 60° C for 5 days (Table 20) In comparison to the direct DKR of amines, the yields of chiral amides increased significantly. Diisopropylethylamine was responsible for the increase in yields. However, the major factor would be the slow generation of amines, which maintains the amine concentration low enough to suppress side reactions including the reductive aminafion. Disappointingly, this process is limited to benzylic amines. Additionally, low turnover frequencies also need to be overcome. 

Note The following solvent systems were tried but gave no separation dioxane/water (7 3, v/v) n-butanol saturated with water amyl alcohol/ace-tone/water/benzyl amine (40 35 20 5, v/v) 2,6-lutidine/water/ethnol/diethylamine (55 25 20 1, v/v). 

Imines, on the contrary, proved particularly reactive under these conditions (Fig. 4.34). For example, Jones and Selenski report that the introduction of one equivalent of methyl magnesium bromide to benzaldehyde 5 stirring at —78 °C in the presence of one and half equivalents of the imine that is derived from the condensation of benzyl amine and benzaldehyde proceeds immediately to the aminal 65 in 94% yield.27 Only the trans isomer is observed from this low-temperature cycloaddition. While the relative stereochemistry appears to be result of an exo transition state, we suspect that initial cis adduct from and endo addition may epimerize under these conditions. 

Reaction selectivity of the parent ortho-QM has also been explored with a variety of amino acid and related species.30 In these examples, the rates of alkylation and adduct yields were quantified over a range of temperatures and pH values. The initial QM3 was generated by exposing a quaternary benzyl amine (QMP3) to heat or ultraviolet radiation (Scheme 9.10). Reversible generation of QM3 was implied by subsequent exchange of nucleophiles at the benzylic position under alternative photochemical or thermal activation.30 Report of this work also included the first suggestion that the reversible nature of QM alkylation could be used for controlled delivery of a potent electrophile. 

Direct oxidation of diphenylmethanes is of little practical value as color formers. In liquid sulfur dioxide, leuco diphenylmethane 12 (Scheme 2) undergoes hydride abstraction by triphenylcarbenium perchlorate at the benzylic amine position to form immonium ion7 13, whereas in acetonitrile... 

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