Substitution Reaction Of Amines Research Articles

Nucleophilic substitution reactions of unbranched alkyl amines using triazine reagents

Since amines are present in many organic, biological, and drug molecules, a strategy of synthesizing desired compounds by nucleophilic substitution reactions of these amines is very attractive. By using triazine reagents, we have found that nucleophilic substitution reactions of unbranched alkyl amines via morpholine derivatives are feasible. This method can be performed under milder reaction conditions than those in previously reported methods.

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX3PF2 (X = F, Cl): A Computational Study

ABSTRACTDetailed computational studies have been carried out to explain the unexpected differing reactions that occur between dimethylamine and the difluorophosphines, CX3PF2 (X = F, Cl). The reaction affords the thermodynamically controlled product chloroform in the case of X = Cl, whereas when X = F the analogous reaction pathway leading to fluoroform is hindered by a substantial reaction barrier in the gas phase, where the reaction should take place due to the volatility of the reactant. While the gas‐phase reaction energy gap is somewhat reduced when X = Cl, due to the stability of the migrating CCl3− moiety, the still substantial barrier does not account for the chloroform formation. Polarizable continuum model (PCM) calculations indicate a reduction of the barrier, facilitating the liquid‐phase reaction. The alternative gas‐phase reaction path, resulting in the aminolysis of a P—F bond is reversible and is shifted toward the product by capturing HF as the dimethylamino salt of the [CF3PF4H]− anion.

Direct N-alkylation of amines with alcohols using AlCl3 as a Lewis acid

Abstract A substitution reaction of amines with alcohols for N-alkylated amines has been developed using inexpensive AlCl3 without any ligand or additive. Either aromatic or aliphatic amines and primary or secondary alcohols perform the AlCl3-mediated reaction smoothly to afford various N-alkylated amines in satisfactory yields.

Foundations of organic chemistry: unity and diversity of structures, pathways, and reactions

Foundations of organic chemistry: unity and diversity of structures, pathways, and reactions

Synthesis of 2-Chloro-4,6-Diamino-5-Cyanopyrimidine and its Amino-Substituted Derivatives

The important pyrimidine intermediate 2-chloro-4,6-diamino-5-cyanopyrimidine was prepared by the cyclization of sodium salt of 1-amino-1-cyanamino-2,2-dicyanoethylene which was obtained from sodium dicyanamide and malononitrile via the nucleophilic addition in good yield and purity. The 4,6-diamino-5-cyanopyrimidines substituted with different amino groups could be synthesized by nucleophilic substitution reaction of amines, and they have good bactericidal activities to some funguses.

A New Approach to Anodic Substitution Reaction of Amines Using Acoustic Emulsification

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A New Approach to Anodic Substitution Reaction of Amines with Allyltrimethylsilane using Parallel Laminar Flow

not Available.

Nucleophilic Substitution Reaction of Amines with 3-Bromo-4-nitropyridine (and 2-Nitropyridine): A New Nitro-group Migration

On the reaction 3-bromo-4-nitropyridine with amine, three in stead of two expected products are separated. 2D NMR spectral data indicate the major product was an unexpected nitro-group migration product. To explore the rearrangement mechanism, a systematic study with various solvents and bases was undertaken. Results obtained indicate that nitro-group migration occurs in polar aprotic solvents; while expected nucleophilic substitution took place under all tested conditions.

Large steric effect in the substitution reaction of amines with phosphoimidazolide-activated nucleosides.

Aliphatic amines react with phosphoimidazolide-activated derivatives of guanosine and cytidine (ImpN) by replacing the imidazole group. The kinetics of reaction of guanosine 5'-phospho-2-methylimidazolide (2-MeImpG) with glycine ethyl ester, glycinamide, 2-methoxyethylamine, n-butylamine, morpholine, dimethylamine (Me2NH), ethylmethylamine (EtNHMe), diethylamine (Et2NH), pyrrolidine, and piperidine were determined in water at 37 degrees C. With primary amines, a plot of the logarithm of the rate constant for attack by the amine on the protonated substrate, log kSH(A), versus the pKa of the amine exhibits a good linear correlation with a Bronsted slope, beta nuc = 0.48. Most of the secondary amines tested react with slightly higher reactivity than primary amines of similar pKa. Interestingly, some secondary amines show substantially lower reactivity than might be expected: EtNHMe reacts about eight times, and Et2NH at least 100 times, more slowly than Me2NH although all three amines are of similar basicity. For comparison, the kinetics of reaction of guanosine 5'-phosphoimidazolide (ImpG) and cytidine 5'-phosphoimidazolide (ImpC) were determined with Me2NH, EtNHMe, and Et2NH, and similar results were obtained. These results establish that the increased steric hindrance observed with the successive addition of ethyl groups are not due to any special steric requirements imposed by the guanosine or the methyl on the 2-methylimidazole leaving group of 2-MeImpG. It is concluded that addition of ethyl and, perhaps, groups larger than ethyl dramatically increases the kinetic barrier for addition of aliphatic secondary amines to the P-N bond of ImpN. This study supports the observation that the primary amino groups on the natural polyamines are at least 2 orders of magnitude more reactive than the secondary amino groups in the reaction with ImpN.

Mechanisms and stereochemistry of amine substitution reactions at the carbon-nitrogen double bond

The reaction of (Z)-O-methyl-nitrobenzohydroximoyl chloride [4-NO 2 C 6 H 4 C(CI)=NOCH 3 ] with morpholine, piperidine, pyrrolidine, and azetidine gives the corresponding (Z)-amidoximes (4-NO 2 C 6 H 4 C(NR 1 R 2 )=NOCH 3 ]. The rate equations for these reactions in benzene solution contain both first-order and second-order terms in amine

Aromatic substitution reactions of amines with ring-substituted 1-phenyl-2,2,2-trifluoroethyl carbocations

Aromatic substitution reactions of amines with ring-substituted 1-phenyl-2,2,2-trifluoroethyl carbocations

Evidence for the fluxionality and structure in solution of intermediates of the type W(CO) 4(L) (L = lewis base)

Evidence based on amine substitution reactions in W(CO) 4(tmpa) (tmpa = N, N, N′, N′-tetramethyl-l,3-diaminopropane) and cis-(C 5H 10NH)(PPh 3)W(CO) 4 with PPh 3 and 13CO indicates (a) that the square pyramidal [W(CO) 4PPh 3] intermediate arising from amine dissociation is fluxional, and (b) that the intermediate containing PPh 3 in the equatorial plane of the square pyramid is thermodynamically more stable than that containing PPh 3 in the axial position.

Evidence for hydrogen-bonded intermediates in amine substitution reactions involving Group 6B metal pentacarbonyl amine derivatives with phosphines

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEvidence for hydrogen-bonded intermediates in amine substitution reactions involving Group 6B metal pentacarbonyl amine derivatives with phosphinesJ. Ewen and D. J. DarensbourgCite this: J. Am. Chem. Soc. 1975, 97, 23, 6874–6876Publication Date (Print):November 1, 1975Publication History Published online1 May 2002Published inissue 1 November 1975https://doi.org/10.1021/ja00856a053RIGHTS & PERMISSIONSArticle Views48Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (360 KB) Get e-Alerts Get e-Alerts

Evidence of trigonal bipyramidal transition state in amine substitution reactions of R3 1P, PtX2, NHR2 2 complexes

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Equilibrium studies of phosphine and amine substitution reactions of tungsten carbonyl

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEquilibrium studies of phosphine and amine substitution reactions of tungsten carbonylRobert J. Angelici and Carol M. IngemansonCite this: Inorg. Chem. 1969, 8, 1, 83–86Publication Date (Print):January 1, 1969Publication History Published online1 May 2002Published inissue 1 January 1969https://doi.org/10.1021/ic50071a020RIGHTS & PERMISSIONSArticle Views191Altmetric-Citations34LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (511 KB) Get e-Alerts Get e-Alerts

Steric influences in amine substitution reactions of trans-dichloro(diethylamine)(tri-n-propylphosphino)platinum(II) in methanol

Steric influences in amine substitution reactions of trans-dichloro(diethylamine)(tri-n-propylphosphino)platinum(II) in methanol