Butylamine, reaction with

In one of the early crucial experiments towards unravelling the reaction pathways observed, Shaw has elegantly demonstrated that in the case of ethyl and tert-butylamine reactions with N3P3CI6 the incoming nucleophile determines the type of product formed [18,53] (Eqs. 14-17)... 

Substituted Amides. Monosubstituted and disubstituted amides can be synthesized with or without solvents from fatty acids and aLkylamines. Fatty acids, their esters, and acid halides can be converted to substituted amides by reaction with primary or secondary aLkylamines, arylamines, polyamines, or hydroxyaLkylamines (30). Di- -butylamine reacts with oleic acid (2 1 mole ratio) at 200—230°C and 1380 kPa (200 psi) to produce di-A/-butyloleamide. Entrained water with excess -butylamine is separated for recycling later (31). 

Other secondary amines such as pyrrolidine, di- -butylamine, tetrahydro-quinoline, n-benzylamine, and piperidine were also found to be capable of effecting this reduction. Interestingly, morpholine does not reduce enamines as readily (47) and its acid-catalyzed reaction with norbornanone was reported (45) to give only the corresponding enamine (93), although trace amounts of the reduction product were detected when cyclohexanone was treated with morpholine under these conditions (47a). The yield of morpholine reduction product was increased by using higher temperatures. 

The adaptation of the Bischler-Napieralski reaction to solid-phase synthesis has been described independently by two different groups. Meutermans reported the transformation of Merrifield resin-bound phenylalanine derivatives 32 to dihydroisoquinolines 33 in the presence of POCI3. The products 34 were liberated from the support using mixtures of HF/p-cresol. In contrast, Kunzer conducted solid-phase Bischler-Napieralski reactions on a 2-hydroxyethyl polystyrene support using the aromatic ring of the substrate 35 as a point of attachment to the resin. The cyclized products 36 were cleaved from the support by reaction with i-butylamine or n-pentylamine to afford 37. 

In non-polar solvents, the reaction with piperidine is best represented by a two-term kinetic form indicating a mixed 2nd- and 3rd-order reaction. Also, base catalysis by tri-ri-butylamine was observed. This kinetic pattern is strongly reminiscent of the results obtained with nitro-activated benzenes.Another interesting result is that stepwise replacement of chlorine atoms by amino groups results in marked... 

Amines can be N-alkylated by reaction with alcohols, in a sealed tube with irradiation by microwaves, with the alcohol and RuCl2(PPh3)2, or by treatment with the amine, SnCl2 and Pd(PPh3)4. Chlorodiethylaluminum (Et2AlCl), with a Cu(ll) catalysts can N-ethylate aniline derivatives. tcrt-Butylamines can be prepared from isobutylene, HBr and the amine by heating a sealed tube. ... 

The last reaction perhaps involves an intermediate such as 33a which expells a proton and dimethyl sulfide. Formation of the Schiff s base with t-butylamine, reduction with sodium borohydride and hydrogenolysis of the benzyl ether produces sulfonterol (28). Despite the fact that the methylene hydrogen of sulfonterol must be much less acidic than of the corresponding urea proton on carbuterol or the sulfonamide proton on soterenol, good bioactivity is retained. 

Condensation of that intermediate with epichlorohydrin in the presence of a catalytic amount of piperidine affords the chlorohydrin 213, admixed with some epoxide. Reaction with tertiary butylamine completes construction of the propanolamine side chain. Displacement of the remaining halogen atom of 214 with morpholine under more strenuous conditions affords timolol (215). ... 

Lithium r-butyl(trialkylsilyl)amides, LiN(SiR,)C(CH,)v The t-butyl(trialkylsilyl)amines are prepared by deprotonation of r-butylamine and reaction with a trialkylsilyl chloride yields are 50-70%. They are converted to the corresponding lithium amides by BuLi in THF. 

The last few years have seen numerous applications of spin trapping to biological systems, and in these the trapping of hydroxyl radicals has assumed some importance. This work has been confined almost exclusively to nitrone scavengers 4 the fact that the hydroxyl adduct [6] of DMPO is much more persistent than that [7] of the commonly used nitrone, benzylidene-t-butylamine-N-oxide ( phenyl t-butyl nitrone ,3 or PBN) [3], may be due to a fragmentation reaction, with subsequent oxidation of the cr-hydroxybenzyl radical, as shown. 

The same displacement occurs in the hydrolysis of picrylimidazole238 (103). 103 reacts with n-butylamine in water239 to yield picric acid (from the reaction with water) and N-n-butyl-2,4,6-trinitroaniline. The dependence of k0bs values (s 1 moP1 dm3) on pH values indicates the presence (and importance) of equilibrium 27 on the reaction pathway of the... 

These studies have been recently extended to the reaction of n-butylamine (di-BA) and piperidine (PIP) with other aromatic substrates, such as l-chloro-2,4-dinitrobenzene (CDNB) and 4-chloro-3-nitrotrifluoromethylbenzene (CNTFB) in hexane, benzene, mesitylene and binary mixtures of hexane with the aromatic solvents, and the results are consistent with Scheme 4 which includes the proposal of a preferential solvation with the donor solvent, D115. As expected, a decrease in rate was observed in the reactions with butylamine with increasing amounts of the donor solvent, which was attributed to the formation of the EDA complex with the solvent. The result is expressed by equation 18 which, in the limiting case where Ks [Pg.1247]

The SjvAr reactions with amines in chloroform show a peculiar behaviour and the rates cannot usually be correlated with reactions in other solvents. It has been observed in the reaction of 2,4-dinitrochlorobenzene with piperidine480 and in the reaction of 1,2-DNB with butylamine115 that chloroform exerts a special solvent effect due to its known hydrogen-bond donor ability. Thus, an association between the solvent and the nucleophile can be postulated as a side-reaction to the S Ar115. Associations of chloroform with amines are known122 and the assumption of a partial association between piperidine or butylamine and chloroform as the cause of the downward curvature in the plots of k vs [amine] seems plausible. 

Phenyl 2,6-dinitro-4-trifluoromethylphenyl sulphide. Chamberlain and Crampton130 studied also the reaction of phenyl 2,6-dinitro-4-trifluoromethylphenyl sulphide with amines in DMSO. They observed a single rate process with butylamine giving the expected substituted product again, the observed rate constant increased with [butylamine]. In the reaction with pyrrolidine a rapid reaction giving the 3-pyrrolidino adduct was observed, which could be suppressed by addition of pyrrolidinium perchlorate. Under these conditions the expected 1-substituted product was formed. 

The classical two-step base-catalysed S Ar reaction with amines, B, follows the third-order kinetic law given by equation 2. As noted in Section II, this equation predicts a straight line in the plot of a vs [B] or a downward curvature. But several SjvAr reactions with amines in aprotic solvents studied in the last decade exhibit an upward curvature, as is shown in Figure 10 for the reactions of 2,4-dinitroanisole with w-butylamine and the SvAr reaction of 2,6-dinitroanisole with n-butylamine in benzene143. In these systems, if a/[B] is plotted vs [B], straight lines are obtained and a downward curvature may be observed in some cases (as shown in Figure 11 for the reaction of 2,4-dinitroanisole with butylamine in benzene at 60 °C), which demonstrates that a new kinetic law is obeyed... 

Catalysis by DABCO in the reactions of FDNB with piperidine, r-butylamine, aniline, p-anisidine and m-anisidine (usually interpreted as base catalysis as in Section B) was also assumed to occur by the formation of a complex between DABCO and the substrate14913. The high (negative) p-value of —4.88 was deemed inappropriate for the usually accepted mechanism of the base-catalysed step (reaction 1). For the reactions with p-chloroaniline, m- and p-anisidines and toluidines in benzene in the presence of DABCO a p-value of —2.86 was found for the observed catalysis by DABCO (fc3DABC0). The results were taken to imply that the transition state of the step catalysed by DABCO and that of the step catalysed by the nucleophile have similar requirements, and in both the nucleophilic (or basicity) power of the nucleophile is involved. This conclusion is in disagreement with the usual interpretation of the base-catalysed step. 

It was shown that the derived expression for k is equation 28. (Section III.D). If k-i = (/t2 +/t3 [ 151 ). at high [B] equation 28 may be transformed into equation 30, which is responsible for the plateau observed in some cases [e.g. the reactions of 2,4-dinitroanisole with cyclohexylamine in benzene (Figure 11) and in cyclohexane (not shown)]143,144 and it was also observed in the reactions with n-butylamine in benzene at 60 °C (the reactions at 80 °C show a slight curvature, tending to a farther asymptotic behaviour). In all the S Ar systems studied by other authors, in which fourth-order kinetics were found, the observation of a similar plateau in the plots of La/[B] vs [B] was not reported. 

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