Tertiary Alkylamines Research Articles

Amine oxidation. Part 13. Electrochemical oxidation of some substituted tertiary alkylamines

The anodic oxidation of some polyamines and amino-alcohols has been studied by linear sweep voltammetry at a glassy-carbon electrode in basic aqueous methanol. Although most of the substrates show one oxidation wave, a few show two. It is concluded that the second, less anodic wave comes from the oxidation of substrate diffusing to the anode, whereas substrate adsorbed to the anode gives rise to the more anodic wave. In general the introduction of an electron-withdrawing heteroatom substituent into a tertiary amine destabilises the aminium radical forming in the potential-determining step and raises the oxidation peak potential, the magnitude of this effect being related to the separation between the substituent and the oxidation centre. In some of the substrates through-bond or through-space interactions occur. These effects, which stabilise the forming aminium radical and lower the Ep value, are superimposed on the inductive or field effects.

Nucleophilic character of alkyl radicals. XIV. Homolytic δ‐aminoalkylation of protonated quinoxaline

AbstractA new general reaction of wide synthetic interest, involving homolytic δ‐aminoalkylation of quinoxaline in acidic medium, is described. Primary and secondary alkylamines, through the corresponding N‐chloroamines, and tertiary alkylamines, through the corresponding N‐oxides, are used. The mechanism of the reaction, involving intramolecular hydrogen abstraction by amino radical cations, and the unusual selectivity are discussed in terms of nucleophilic character of the alkyl radicals and of polar effects in the aromatic substitution.

Organic sulfur mechanisms. 19. Sulfene–tertiary amine zwitterions and base size effects in sulfene condensations

The effect of changing the size of the tertiary alkylamine has been investigated in two systems: (a) the reaction of phenylmethanesulfonyl chloride with a tertiary amine, and (b) the formation of the β-sultone from the reaction of chloral, ethanesulfonyl chloride, and a tertiary amine. In the first reaction the yield of stilbene (3) or stilbene episulfone (4) increases and that of the thiobenzoyl chloride S-oxides (5) decreases as the size of the base decreases, as expected for a mechanism involving a tertiary amine – sulfene zwitterion in the formation of the stilbene products. In the second reaction the yield of the β-sultone is much enhanced by the use of a small amine; the latter observation precludes a simple sulfene–chloral cycloaddition mechanism and points to a zwitterionic intermediate derived from the amine and either the sulfene or chloral.

Nematicidal activity of secondary and tertiary alkyl amides and amines

Several C11 to C15 amides and amines that disrupt growth in certain insects showed high nematicidal activity in direct contact tests. Two amides and 9 amines killed Panagrellus at 5-10 ppm. Of these, 1 amide and 3 amines killed Meloidogyne larvae at 20 ppm.

Amine oxidation. Part XI. Oxidation of some substituted tertiary alkylamines and some NN-dimethylphenethylamines with potassium hexacyanoferrate(III)

Download options Please wait... Article information DOI https://doi.org/10.1039/P29760001172 Article type Paper Download Citation J. Chem. Soc., Perkin Trans. 2, 1976, 1172-1176 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Amine oxidation. Part XI. Oxidation of some substituted tertiary alkylamines and some NN-dimethylphenethylamines with potassium hexacyanoferrate(III) J. R. L. Smith and L. A. V. Mead, J. Chem. Soc., Perkin Trans. 2, 1976, 1172 DOI: 10.1039/P29760001172 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author John R. Lindsay Smith Leonard A. V. Mead

The Thermal Decomposition of Alkoxycarbonyl Thiocyanates and Isothiocyanates

Alkoxycarbonyl thiocyanates and isothiocyanates have been decomposed thermally under reduced pressure at temperatures of 240–375°. Primary systems yield primarily alkyl thiocyanates, whereas secondary and tertiary systems yield alkyl isothiocyanates. The viability of using this reaction in a conversion of primary alcohols to primary alkyl thiols and secondary and tertiary alcohols to tertiary alkyl amines is discussed.

ChemInform Abstract: THE REACTION OF PROPIOLIC ACID ESTERS WITH TERTIARY AMINES, FORMATION OF BETAINES

AbstractUmsetzung des Propiolsäureesters (Ia) mit den Aminen (IIa)‐(IIc) bzw. des Propiolsäureesters (Ib) mit den Aminen (IIa) bzw. (IIc) in stark wäßrigem Medium führt zur Bildung entsprechender Betaine (III); als hauptsächliche Nebenprodukte werden ferner entsprechende trans‐Acrylate (IV) gebildet.

The Reaction of Propiolic Acid Esters with Tertiary Amines. Formation of Betaines

Reaction of propiolate esters, H—C≡C—CO2R, with tertiary alkylamines R′3N in highly aqueous media yields betaines of the type trans R′3N+ •CH=CH•CO2−. The spectral and chemical properties of these derivatives are discussed as well as the mechanism of their formation. The major by-product of reaction is the corresponding trans-3-alkoxyacrylate RO—CH=CH—CO2R.

Formation of terminal secondary and tertiary alkylamines by single-step synthesis from carbon monoxide, steam and monomethylamine and dimethylamine, respectively

In a single-step synthesis, terminal N-monomethyl-N-alkylamines and N, N-dimethyl-N-alkylamines were obtained from carbon monoxide, steam and monomethylamine or dimethylamine, respectively. The reaction mechanism is similar to that suggested by Kolbel and Trapper/1, 2/for the synthesis of primary amines.

Organometallic compound with Lewis base—IV : Dimerization of methyl crotonate by aluminum alkyl-tertiary amine complex

Aluminum alkyl-tertiary amine complex was found to induce the catalytic dimerization of methyl crotonate (MCr) to dimethyl 2-methylpent-4-ene-1,3-dicarboxylate ( 1) and dimethyl 2-methylpent- cis-3-ene-1,3-dicarboxylate ( 2). The of the γ-hydrogen of the MCr molecule. Dimer 2 is formed through the isomerization of dimer 1. The complex of AlR 3 with a bidentate ligand, sparteine, produces dimer 1, selectively. The complex of AlR 3 with monodentate ligand NEt 3, on the other hand, induces the isomerization of dimer 1 to the cis-form of dimer 2. The coordination number of aluminum alkyl-tertiary amine complex seems to control the dimerization mechanism of MCr.

Amine oxidation. Part VII. The effect of structure on the reactivity of alkyl tertiary amines towards alkaline potassium hexacyanoferrate(III)

Kinetic studies on the oxidation of N-methyl- and N-deuteriomethyl-di-n-butylamine confirm that the rate-determining step is an electron-transfer from the nitrogen to the potassium hexacyanoferrate(III); the relative rate of reaction kH/kD is 1·04. The influence of deuteriation on the product distribution (isotope effect 3·6) indicates that the second step is a product-determining proton loss.Further information about the electron-abstraction and the nature of the first transition state has been obtained from the rates of oxidation of a selection of cyclic tertiary amines. The results are in accord with the transition state occurring late on the reaction co-ordinate. Thus, in the transition state electron-transfer from the amine to the hexacyanoferrate(III) is almost complete and the configuration of the nitrogen resembles that of the intermediate aminium radical cation rather than that of the substrate.The order of increasing ease of oxidation of bridgehead bicyclic amines, triethylenediamine monomethiodide, quinuclidine, and triethylenediamine is discussed in the light of these conclusions.

Preparation of tertiary amine derivatives from commercially available alcohols and their properties as surfactants

AbstractHigher tertiary amines were prepared by transalkylation of triethylamine with commercially available alcohols such as Tergitol 15‐S‐3 and tridecyl alcohol. This reaction carried out at 250–300 C and 20 kg/cm2 initial hydrogen pressure, using Cu−Cr−Mn−O catalyst, gave about 80% yield of higher alkyl tertiary amines. Tertiary amine hydrochlorides, quaternary ammonium bromides and amine oxides were prepared from these tertiary amines. Specific surface tension, wetting power, foaming power and foam stability were measured. The characteristic properties with respect to tertiary amine derivatives containing ether linkages were observed. These products have excellent wetting power, reduced surface tension, low foaming power and unstable foam.

The Detection of the N-Methyl Group by Infrared Spectroscopy

N-Methyl compounds exhibit a weak to medium absorption band in the 2820–2760 cm−1 region, which is characteristic for the N-methyl group. This diagnostic test is shown to be applicable to potassium bromide spectra and to the wide variety of molecules having an N-methyl substituent examined. Aldehydes, amino acid hydrochlorides, secondary and tertiary alkylamines, methoxy compounds, and nitrogen heterocyclic molecules exhibit absorption which may overlap this region and the detection of an N-methyl substituent for these classes of compound may be less definite. This diagnostic band is absent in potassium bromide spectra of the amine salts in which the nitrogen lone pair of electrons is involved in bond formation.

Adducts of copper(II) β-diketone chelates with tertiary alkylamines and alkylamine hydrochlorides

Adduct formation of Cu(chelate) 2 (chelate = anion of thenoyltrifluoroacetone, TTA, and trifluoroacetylacetone, TFA) with alkylamines and alkylamine hydrochlorides, S (S = tri- n-butylamine, TBA, tri- n-hexylamine, THA, tri- n-octylamine, TOA, tri- n-laurylamine, TLA, tri- n-hexylamine hydrochloride, THA·HCl, tri- n-octylamine hydrochloride, TOA·HCl and tri- n-laurylamine hydrochloride, TLA·HCl) have been studied spectrophotometrically. Visible and i.r. spectra suggest that alkylamines and alkylamine hydrochlorides form different adducts through bonding of different atoms. In the alkylamines the nitrogen atom is bonded to copper(II) while in the alkylamine hydrochlorides the chlorine atom is bonded to copper(II). Equilibrium constants for the adduct-formation reactions are calculated from the spectral change upon addition of the adduct-forming ligands. It is found that alkylamines and alkylamine hydrochlorides do not interact with Cu(chelate) 2 to the same extent. Furthermore, the complexes species, TOA·HTTA and TOA·HCl·HTTA, do not interact with Cu(chelate) 2.

Elements de fluorimetrie organique fonctionnelle-II

α-Amino acids are converted into fluorescent derivatives of dihydrolutidine. Primary and secondary alkylamines are determined by converting them into sulphonamides by means of 1-dimethylamino-naphthalene-5-sulphonyl chloride. A fluorescent adduct is given by the reaction of tertiary alkylamines with α,γ-anhydroaconitic acid in acetic anhydride, and a fluorescence is obtained by condensing indoles with formaldehyde in the presence of an oxidizing agent. Furfural, obtained by the dehydration of pentoses, is determined by converting it into a 1,8-dioxodecahydroacridine derivative. 2,6-Di-t-butyl- p-cresol allows the fluorimetry of Δ 4 and Δ 1,4-3,11-diketosteroids. The fluorescence of Pyronine G decreases under the action of Δ 5(10)-3-keto-19-norsteroids.

Study of Soluble Tungstate Species by Solvent Extraction

Abstract Tungsten is extracted from acidic tungstate solutions by the long-chain tertiary alkyl amine, tri-n-caprylamine, in benzene. Distribution data derived from solvent extraction are interpreted in terms of the predominating tungsten species present in the aqueous phase. The results show that the nature of the tungstate species extracted by tri-n-caprylamine changes markedly with the pH of the system. Further, the order of extraction is consistent with the order in which tungstate species should form as a function of the ratio of acid equivalents to moles of tungstate ions in solution.

Chloroform as hydrogen donor to some organophosphorus compounds and long-chain tertiary alkylamines

Chloroform as hydrogen donor to some organophosphorus compounds and long-chain tertiary alkylamines

The determination of small amounts of long-chain tertiary alkylamines and quarternary ammonium salts

Bromocresol green has been investigated as an alternative to ammonium erdmannate for the absorptiometric determination of small amounts of long-chain alkylamines and quaternary ammonium salts in aqueous solution in a solvent extraction procedure. The molecular absorption coefficient of the reagent at 615 nm is about 3 times that of the erdmannate ion at 353 nm; visual methods of comparison are simplified by the blue colour of the bromocresol green anion The sensitivity of both the bromocresol green and the erdmannate method may be increased by stripping the coloured reagents into a small volume of aqueous solution. Both methods are free of interference from iron, but the present procedure has the disadvantage of a blank which depends both on the pH and on the concentration of excess reagent.

Extraction mechanism of HCl, HBr and Hl by primary, secondary and tertiary long chain aliphatic amines

The extraction of HCl, HBr and Hl by primary, secondary and tertiary alkyl amines in benzene has been studied. The affinity constant of the acid-amine reaction has been determined by potentiometric titration for each amine with all the three acids. The affinity constant values decrease by increasing the amine size and decreasing the anion radius. Both these two opposite effects have been discussed in terms of electrostatic interaction in the organic phase and of ion-water interactions in the aqueous phase.

A new metabolite of chlorpromazine in human urine

CHLORPROMAZINE is metabolized by mental patients in a complex manner producing a large variety of compounds. Some of the known reactions are oxidation of the ring sulfur atom or of the alkyl nitrogen, demethylation of the tertiary alkyl amine, and hydroxylation of the phenothiazine ring. In this paper we report the isolation and identification of a new chlorpromazine metabolite, 2-chloro-10-(β-propionic acid) phenothiazine, found in urine of mental patients receiving chlorpromazine.