Secondary aliphatic amines reactions

These Br nsted-type plots often seem to be scatter diagrams until the points are collated into groups related by specific structural features. Thus, p-nitrophenyl acetate gives four separate, but parallel, lines for reactions with pyridines, anilines, imidazoles, and oxygen nucleophiles.Figure 7-4 shows such a plot for the reaction of trans-cmmm c anhydride with primary and secondary aliphatic amines to give substituted cinnamamides.All of the primary amines without substituents on the a carbon (R-CHi-NHi) fall on a line of slope 0.62 cyclopentylamine also lies on this line. If this line is characteristic of normal behavior, most of the deviations become qualitatively explicable. The line drawn through the secondary amines (slope 1.98) connects amines with the structure R-CHi-NH-CHi-R. The different steric requirements in the acylation reaction and in the model process... 

The reaction is generally thought to involve carbonium-ion intermediates but several puzzling features remain. Secondary aliphatic amines give nitrosamines without evolution of N2 ... 

The deoxygeneration of nitroarenes by trivalent phosphorus compounds in the presence of amines is a useful route to 3/f-azepin-2-amines (cf. compounds 32, Section 3.1.1.4.2.2.). Subsequently, it has been shown, by carrying out the reaction in strongly basic solution, that the process can be extended to the synthesis of 1H-. 3H- and 5//-2-benzazepines from nitronaph-thalenes 43 For example, 1-nitronaphthalenes 3 with dimethyl phosphite in the presence of sodium methoxide and a primary or secondary aliphatic amine, yield the dimethyl 5//-2-ben-zazepin-3-yl phosphonates 4 accompanied, in some cases, by the isomeric 3//-2-bcnzazepin-3-yl phosphonates 5. 

Primary and secondary aliphatic amines, morpholine and 2-methylaziridine and aniline and even the sterically hindered 2.2,6,6-tetramethylpiperidine readily react with 6-bromo-trithiadiazepine 7, in certain cases in the presence of /V./V-diisopropylethylamine, at room temperature by substitution of the bromine atom ammonia, for example, yields trithiadiazepin-6-amine 22 (R1 = R2 = H). There is compelling evidence that these reactions proceed by an elimination-addition mechanism via the heteroaryne, trithiadiazepyne 21.391... 

Schmolukowski in 1917, a diffusion-controlled bimolecular reaction in solution at 25 °C can reach a value for th second-order rate constant k as high as 7 x 109 m 1s-1. Nitrosations of secondary aliphatic amines also have rates which are relatively close to diffusion control (see Zollinger, 1995, Sec. 4.1). 

Ethyleneimine reacts with (p-tolylsulfonyl)acetylene to give only the (Z)-product 115 via trans addition (equation 91), while primary and secondary aliphatic amines afford ( )-products76. With nonterminal acetylenes such as l-(ethylsulfonyl)-l-propyne, the reactions of ethyleneimine, n-propylamine and f-butylamine give mixtures of ( )- and (Z)-adducts. The double conjugate addition of sodium sulfide, selenide and telluride to bis(l-propynyl)sulfone (116) produces heterocycles (117) as illustrated in equation 9277. 

The reaction of 2-bromo-5-nitrothiazole with weakly basic secondary aliphatic amines gave the expected 2-amino products. The isomeric 5-bromo-2-nitrothiazole with such amines gave mixtures of the expected 5-amino products along with 2-aminated 5-nitrothiazole rearrangement products. A mechanism was proposed which involves the slow thermal isomerisation of the 5-bromo-2-nitrothiazole to the much more reactive 2-bromo isomer which competes, in the case of relatively weak amine nucleophiles, with direct but slow displacement of the 5-bromo group to form the normal displacement product <96JHC1191>. 

Nitroxyl radicals (AmO ) are known to react rapidly with alkyl radicals and efficiently retard the radical polymerization of hydrocarbons [7]. At the same time, only aromatic nitroxyls are capable of reacting with alkylperoxyl radicals [10,39] and in this case the chain termination in the oxidation of saturated hydrocarbons occurs stoichiometrically. However, in the processes of oxidation of alcohols, alkenes, and primary and secondary aliphatic amines in which the chain reaction involves the HOT, >C(0H)02 , and >C(NHR)02 radicals, possessing the... 

Unsymmetrical secondary aliphatic amines have been prepared by reaction of alkyl halides with benzylidene amines and subsequent hydrolysis 814 by reaction of alkyl halides with alkyl amines 5 by reduction of amine-aldehyde adducts 8-8 and by dealkylation of tertiary amines with dibenzoyl peroxide. ... 

Pyridine (and quinoline) which in so many respects are aromatic and comparable to benzene, lose this character completely on hydrogenation to piperidine (and hydroquinoline), which are entirely of the same nature as secondary aliphatic amines. The completely hydrogenated heterocyclic bases undergo degradation reactions which have become important particularly in the investigation of the constitution of alkaloids. A. W. Hofmann s method of opening rings by means of exhaustive methylation may be illustrated with piperidine. By thermal decomposition of the quaternary ammonium base a C—N-link-age is broken and at the same time water is eliminated. 

Success was obtained with Ru3(CO)i2 as catalyst precursor [6], but the most efficient catalysts were found in the RuCl2(arene)(phosphine) series. These complexes are known to produce ruthenium vinylidene spedes upon reaction with terminal alkynes under stoichiometric conditions, and thus are able to generate potential catalysts active for anti-Markovnikov addition [7]. Similar results were obtained by using Ru(r]" -cyclooctadiene)(ri -cyclooctatriene)/PR3 as catalyst precursor [8]. (Z)-Dienylcarba-mates were also regio- and stereo-selectively prepared from conjugated enynes and secondary aliphatic amines (diethylamine, piperidine, morpholine, pyrrolidine) but, in this case, RuCl2(arene) (phosphine) complexes were not very efficient and the best catalyst precursor was Ru(methallyl)2(diphenylphosphinoethane) [9] (Scheme 10.1). 

In the aliphatic series, primary amines are deaminated by nitrous acid, secondary aliphatic amines are A-nitrosated, while tertiary aliphatic amines form salts in the acidic medium followed by secondary reactions such as dealkylation [1, 21a, b]. 

Hydroperoxides and peroxides oxidize primary and secondary aliphatic amines to imines. Thus f-butyl hydroperoxide oxidizes 4-methyl-2-pentyl-amine to 2-(4-methylpentylidene)-4-methyl-2-pentylamine in 66% yield [29]. Di-r-butyl peroxide reacts in a similar manner [29]. However, this reaction is... 

Formaldehyde reacts with primary and secondary aliphatic amines but not with tertiary amines. The reactions with methyl and dimethyl amines proceed as follows HCHO + HaN. CH, - H. CH(OH). HN. CHS, HCHO + HN(CHj)a - HCH(OH). N(CHS)S The reaction of formaldehyde with... 

Schotten-Baumann reaction, 582, 584, 780, 784 see also Benzoates Sebacic acid, 469, 938,939 Secondary aliphatic amines, 413 crystalline derivatives of, 422 reactions of, 421, 1072 table of and derivatives of, 424 Secondary alkaryl amines, 562, 570, 571 Secondary aromatic amines, 559, 562 crystalline derivatives of, 652 reactions and characterisation of, 649 1173 ... 

The thiophene ring is opened and sulfur extruded as hydrogen sulfide when 3,4-dinitrothiophene is reacted with piperidine. The product contains two nitroenamine units coupled to each other (Scheme 140). Other secondary amines react similarly (69CC549). Secondary aliphatic amines also react with 2-nitrothiophene to form the nitrodienamines (426) in 50-80% yield. It is believed that the reaction involves addition of the amine at position 5, followed by proton transfer and ring opening to give the thiol which, in the presence of air, oxidatively dimerizes to (426) (Scheme 141). In one case the thiol has been trapped as the silver salt and methylated (74JCS(P1)2357). 

In this section axe considered all reactions of aziridines which do not result in quatemization of the nitrogen atom or opening of the three -mem Wed ring (see sections II.4 and H.5 below). In general, aziridines exhibit the behavior characteristic of secondary aliphatic amines. However, frequently special precaution are needed to prevent aide-reactions due to opening of Hie ring. 

Amidines and sulfonamides have also been used as linkers for primary or secondary aliphatic amines (Entries 4, 5, and 7, Table 3.23). These derivatives are stable under basic and acidic reaction conditions and can only be cleaved by strong nucleophiles. Phenylalanine amides can be hydrolyzed by treatment with certain enzymes (Entry 8, Table 3.23), and can therefore be used for linking amines to supports compatible with enzyme-mediated reactions (CPG, some polyacrylamides, macroporous polystyrene, etc.). 

Support-bound triazenes, which can be prepared from resin-bound secondary aliphatic amines and aromatic diazonium salts [455], undergo cleavage upon treatment with acids, leading to regeneration of the aromatic diazonium salts. In cross-linked polystyrene, these decompose to yield nitrogen and, preferentially, radical-derived products. If the acidolysis of polystyrene-bound triazenes is conducted in the presence of hydrogen-atom donors (e.g. THF), unsubstituted arenes can be obtained (Entries 8 and 9, Table 3.47). In the presence of alkenes or alkynes and Pd(OAc)2, the initially formed diazonium salts undergo Heck reaction to yield vinylated or alkynylated arenes (Entry 10, Table 3.47). Similarly, unsubstituted arenes can be obtained by oxida-... 

Polystyrene-bound secondary aliphatic amines and /V-alkyl amino acids can be ally-lated by treatment with a diene and an aryl iodide or bromide in the presence of palla-dium(II) acetate (Entry 14, Table 10.3). As the diene, 1,3-, 1,4-, and 1,5-dienes can be used, and, besides aryl halides, heteroaryl bromides have also been successfully used [63], This remarkable reaction is likely to proceed via the formation of an aryl palladium complex, with subsequent insertion of an alkene into the C-Pd bond. The resulting organopalladium compound does not undergo ( -elimination (as in the Heck reaction), but isomerizes to an allyl palladium complex, which reacts with the amine to give the observed allyl amines. 

V-Substituted 3-aminobenzo[6]thiophenes are readily obtained by heating thioindoxyl with the appropriate primary or secondary aromatic amine,539 541,553,554 or primary aliphatic amine541 (Section VI, 1,2). 3-A7,jV-I)ialkylaminobemo[ ]thiophenes are best obtained by reaction of 3-bromobenzo[6]thiophene-1,1 -dioxide with a secondary aliphatic amine, followed by reduction of the product with lithium aluminum hydride (Section VI,P,2,/).541 3-Amino-2-nitrobenzo[6]-thiophene and its A-substituted derivatives are conveniently obtained... 

The reactions of - -t and 7 with secondary aliphatic amines are proposed to occur via formation of a nonfluorescent singlet ex-ciplex which yields a dialkylaminyl-l,2-diphenylethyl radical pair. The stereoselective formation of 69 indicates that radical pair combination is exclusively an in-cage process which competes effectively with rotation of the 1,2-diphenylcyclobutyl radical. The limiting quantum yields for the formation of 68 and 69 in nonpolar solvent are 0.14 and 0.16, respectively. Unlike the reaction of It with tertiary aliphatic amines, the quantum yield for the formation of 68 decreases with increasing solvent polarity (113). 

Most work on aminomercuration has employed secondary aliphatic amines, or primary or secondary anilines. Primary amines have been successfully employed using mercuric perchlorate or mercuric nitrate.197 No reactions utilizing ammonia have been reported. While excess amine or various ether solvents can be used, it is sometimes desireable to add water.198 199... 

Sulfite ion forms a complex of structure III (Refs 44 80), which is a source of yield loss during the purification of TNT if the pH exceeds 8. Cyanide ion also forms a compd of structure III (Ref 44) the kinetics of this reaction has been studied (Ref 76), TNT, as the anion I, can react with itself to form adducts of type II it can similarly react with 13 >5-trinitrobenzene (Ref 57). Primary and secondary aliphatic amines form a-complexes (Refs 46 58), but tertiary amines (in an aprotic solvent), and aromatic amines, form ir-complexes instead. Upon soln in liq ammonia, a complex of type III is initially formed, with no evidence of I (Ref 105). With time, a second NH2 group becomes attached to the ring carbon with the methyl group this compd has cis- and transisomers. Removal of the ammonia gave a red... 

The complexes of long-chain primary-secondary aliphatic amines with TNT have low water solubility and may be useful for the removal of TNT from aq solns (Ref 97). The rapid reaction with isopropylamine in acetone has been studied as a possible procedure for the neutralization of TNT in land mines (Ref 88). No products were isolated, but kinetic and thermal data were obtained... 

Chloro-7-nitrobenz-2,l,3-oxadiazole (NBD-C1) reacts with primary and secondary aliphatic amines to produce intensely fluorescent derivatives. Although anilines, phenols and thiols react with NBD-C1, they produce derivatives which do not fluoresce or which are only weakly fluorescent. This limits the types of compounds which can be analyzed with this reagent and thus makes the technique more selective. This selectivity is desirable in trace analysis because of a lower degree of interference from co-extractives. The general reaction scheme for formation of the fluorescent amine derivatives is shown in Fig.4.50. 

Yoshida et al. were the first to report the synthesis of carbamate esters by the direct reaction of aliphatic amines, C02 and alkyl halides [47]. The process involved the O-alkylation of intermediate alkylammonium carbamate salt, and required relatively, severe conditions (333-393 K 4MPa C02), long reaction times (1-2 days) and an excess of amine (2.5 equiv.) with respect to the alkylating agent. The method was shown to be effective only with secondary aliphatic amines which, however, were converted into organic carbamates in low to moderate yield and with modest selectivity because of significant side-formation of N-alkylation products. 

Monocarbamates of 1,2-diols can be obtained also by the direct reaction of epoxide with primary or secondary aliphatic amines in the presence of C02... 

The synthesis of hydroxycarbamates from secondary aliphatic amines, C02 and epoxides has been found to be catalyzed by (5,10,15,20-tetraphenylporphinato) aluminum(III) acetate, AI(TPP)(02CCH3) [80], Scheme 6.14 illustrates the mechanism proposed for the catalytic process, which can be carried out under not severe conditions (293-343 K 0.1-5 MPa C02 pressure). The key step here is the insertion of epoxide into the Al-O bond of the A1-carbamate A (Scheme 6.14), which preliminarily forms by the reaction of A1(TPP)(02CCH3) with the amine and C02. Protolytic cleavage of the Al-alkoxide bond in the insertion product, C, by dialkylcarbamic acid regenerates the catalytkally active carbamato-species A and... 

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