Enthalpies of formation of primary, secondary, and tertiary amineborane adducts in tetrahydrofuran solution

The enthalpies of solution of primary, secondary, and tertiary amines in THF were determined from calorimetric experiments for five primary, five secondary, and three tertiary amines. The enthalpies of formation of amineborane adducts from borane and the corresponding amines in THF solution were also determined. The differences in adduct formation enthalpies from borane and the corresponding amines can be explained by taking into account steric effects and the chain length of the substituents on the amine. In general, as the alkyl chain length, branching, or the number of chains increases, the formation enthalpy of amineborane adducts is less exothermic. That is to say, the steric effect is more important in tertiary and secondary amines than in primary ones. The enthalpy of solution of linear primary amines in THF was more endothermic as the alkyl chain increased and a similar behavior was observed with linear secondary and tertiary ones. An analysis is made of the amine structural factors which affect the amineborane adduct formation.     

Enthalpy of cooperative hydrogen bonding in complexes of tertiary amines with aliphatic alcohols: Calorimetric study

The work is devoted to the investigation of thermodynamics of specific interaction of the tertiary aliphatic and aromatic amines with associated solvents as which aliphatic alcohols were taken. Solution enthalpies of aliphatic alcohols in amines (tri-n-propylamine, 2-methylpyridine, 3-methylpyridine, N-methylimidazole) as well as amines in alcohols were measured at infinite dilution. The enthalpies of specific interaction (H-bonding) in systems studied were determined based on experimental data. The enthalpies of specific interaction of amines in aliphatic alcohols significantly lower than the enthalpies of hydrogen bonding in complexes amine–alcohol of 1:1 composition determined in base media due to the reorganization of aliphatic alcohols as solvents. The determination of solvent reorganization contribution makes possible to define the hydrogen bonding enthalpies of amines with clusters of alcohols. Obtained enthalpies of hydrogen bonding in multi-particle complexes are sensitive to the influence of cooperative effect. It was shown, that hydrogen bond cooperativity factors in multi-particle complexes of alcohols with amines are approximately equal for all alcohols when pyridines and N-methylimidazole as solutes are used. At the same time, H-bonding cooperativity factors in complexes of trialkylamines with associative species of alcohols decrease with increasing of alkyl radical length in alcohol and amine molecules.This work shows that the thermodynamic functions of specific interaction of solutes with associated solvents cannot be described using the H-bond parameters for the complexes of 1:1 composition.     

Enthalpy of cooperative hydrogen bonding in the complexes of triethyl- and tri-<Emphasis Type="Italic">n</Emphasis>-butylamines with alcohols: Effect of the alkyl chain length

The measurements of enthalpies of triethylamine and tri-n-butylamine dissolution in aliphatic alcohols and, vice versa, of aliphatic alcohols in amines were carried out. Enthalpies of specific interactions in the studied systems were calculated. The enthalpy of specific interaction determined in the alcohol medium, are significantly less than those obtained at dissolving alcohols in amines. The mechanism of specific interaction of amines with alcohols is discussed. Enthalpies of cooperative hydrogen bonds of tertiary amines with alcohol clusters are calculated. The dependences between the enthalpies of hydrogen bond and the spatial structure of interacting molecules are revealed.     

Density functional study of hydrogen bond formation between methanol and organic molecules containing Cl, F, NH2, OH, and COOH functional groups

Various hydrogen-bonded complexes of methanol with different proton accepting and proton donating molecules containing Cl, F, NH(2), OH, OR, and COOH functional groups have been modeled using DFT with hybrid B3LYP and M05-2X functionals. The latter functional was found to provide more accurate estimates of the structural and thermodynamic parameters of the complexes of halides, amines, and alcohols. The characteristics of these complexes are influenced not only by the principle hydrogen bond of the methanol OH with the proton acceptor heteroatom, but also by additional hydrogen bonds of a C-H moiety with methanol oxygen as a proton acceptor. The contribution of the former hydrogen bond in the total binding enthalpy increases in the order chlorides < fluorides < alcohols < amines, while the contribution of the second type of hydrogen bond increases in the reverse order. A general correlation was found between the binding enthalpy of the complex and the electrostatic potential at the hydrogen center participating in the formation of the hydrogen bond. The calculated binding enthalpies of different complexes were used to clarify which functional groups can potentially form a hydrogen bond to the 2'-OH hydroxyl group in ribose, which is strong enough to block it from participation in the intramolecular catalytic activation of the peptide bond synthesis. Such blocking could result in inhibition of the protein biosynthesis in the living cell if the corresponding group is delivered as a part of a drug molecule in the vicinity of the active site in the ribosome. According to our results, such activity can be accomplished by secondary or tertiary amines, alkoxy groups, deprotonated carboxyl groups, and aliphatic fluorides, but not by the other modeled functional groups.     

Mechanistic Study of the Role of Primary Amines in Precursor Conversions to Semiconductor Nanocrystals at Low Temperature

Primary alkyl amines (RNH₂) have been empirically used to engineer various colloidal semiconductor nanocrystals (NCs). Here, we present a general mechanism in which the amine acts as a hydrogen/proton donor in the precursor conversion to nanocrystals at low temperature, which was assisted by the presence of a secondary phosphine. Our findings introduce the strategy of using a secondary phosphine together with a primary amine as new routes to prepare high‐quality NCs at low reaction temperatures but with high particle yields and reproducibility and thus, potentially, low production costs.     

Mass spectrometric investigation of noncovalent complexation between a tetratosylated resorcarene and alkyl ammonium ions

Noncovalent complexation between tetratosylated tetraethyl resorcarene (1) and primary, secondary, and tertiary alkyl ammonium ions (mMe, dMe, tMe, mEt, dEt, tEt, dBu, and dHex) was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Interactions of the noncovalent complexes were investigated by means of competition experiments, collision-induced dissociation (CID) experiments, ion-molecule reactions with tripropylamine and gas phase H/D-exchange reactions with deuteroammonia. Gas phase ion-molecule reactions gave especially valuable information about the structure and properties of the complexes. Resorcarene 1 formed relatively stable 1:1 complexes with all aliphatic alkyl ammonium ions. Steric properties of the alkyl ammonium ions and proton affinities of the conjugate amines noticeably affected the complexation properties, indicating the importance of hydrogen bonding in these complexes. According to the competition experiments, the thermodynamically most stable host-guest complexes were formed with alkyl ammonium ions that were most substituted and had the longest alkyl chains. In CID experiments, release of an intact free guest ion or dissociation of the host was observed to depend on the proton affinity of the amine and the strength of the hydrogen bond that was formed. In ion-molecule reactions with tripropylamine, a guest exchange reaction occurred with all alkyl ammonium ion complexes with reaction rates mostly dependent on the steric properties of the original guest ion. In H/D-exchange reactions the N-H hydrogen atoms of the guest ion were exchanged with deuterium, whereas the resorcinol hydrogen atoms remained unchanged.     

Chromium‐Catalyzed Alkylation of Amines by Alcohols

The alkylation of amines by alcohols is a broadly applicable, sustainable, and selective method for the synthesis of alkyl amines, which are important bulk and fine chemicals, pharmaceuticals, and agrochemicals. We show that Cr complexes can catalyze this C?N bond formation reaction. We synthesized and isolated 35 examples of alkylated amines, including 13 previously undisclosed products, and the use of amino alcohols as alkylating agents was demonstrated. The catalyst tolerates numerous functional groups, including hydrogenation‐sensitive examples. Compared to many other alcohol‐based amine alkylation methods, where a stoichiometric amount of base is required, our Cr‐based catalyst system gives yields higher than 90 % for various alkyl amines with a catalytic amount of base. Our study indicates that Cr complexes can catalyze borrowing hydrogen or hydrogen autotransfer reactions and could thus be an alternative to Fe, Co, and Mn, or noble metals in (de)hydrogenation catalysis.     

Complex formation between α-cyclodextrin and amines in water and DMF solvents

Complexation between -cyclodextrin (-CD) and aliphatic amines in water and DMF solvents was studied by calorimetry. Amines form complexes with -CD in both solvents but the nature of the complexes is quite different. In DMF the amines donate a hydrogen from the amine N–H group to the cyclodextrin forming a normal hydrogen bonded complex. In DMF solutions with large amine concentrations, complexes other than 11 are observed. In contrast, in aqueous environment the amines form inclusion complexes in which the amine alkyl group penetrates the -CD cavity and is stabilized by van der Waals interactions. The equilibrium constants for the complexes formed in water solvent increase with increasing alkyl chain length due to an entropy effect.     

Heats of protonation of amines,diazacrown ethers and cryptands in methanol

The heats of protonation of different amines, diazacrown ethers and cryptands in methanol have been measured using calorimetric titrations. The values of the reaction enthalpies decrease in going from primary over secondary to tertiary amines. The results for the protonation of diazacrown ethers and cryptands are not comparable with those obtained for the alkyl amines. Additional interactions between the proton and the oxygen donor atoms influence the values of the reaction enthalpy for the first protonation. The results for the second protonation reaction indicate that this proton is located outside the cavities of the macrocyclic and macrobicyclic ligands. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydrogen bonding interaction between acrylic esters and monohydric alcohols in non-polar solvents: An FTIR study

The association between acrylic esters (methyl methacrylate, ethyl methacrylate and butyl methacrylate) and some monohydric (primary, secondary and tertiary) alcohols in non-polar solvents, viz. n-heptane, CCl4 and benzene has been investigated by means of FTIR spectroscopy. The most likely association complex between alcohol and acrylic ester is 1:1 stoichiometric complex through the hydroxyl group of alcohol and the carbonyl group of acrylic ester. The formation constant of the 1:1 complexes has been calculated using Nash method. It appears that the primary alcohols have larger formation constant than the secondary and tertiary alcohols. The results show that the proton donating power of the alcohols decreases in the order primary>secondary>tertiary and the association constant increases with the increase in carbon chain of the alkyl group of acrylic esters and alcohols. Also the results show a significant dependence of the association constant upon the solvents used. The solvent effect on the formation of hydrogen bond equilibria is discussed in terms of specific interaction between the solute and solvent.     

Hydrogen bond formation between aliphatic alcohols and tertiary amines

Hydrogen bond formation between tertiary amines and long chain and branched chain alcohols has been studied in order to understand the influence of chain length and the steric effect on the complex formation between tertiary amines and alcohols. On the addition of the amine to the alcohol the intensity of the monomeric OH band decreases and the new band appears corresponding to the alcohol—amine complex. The equilibrium constants of the complex formation are correlated by a two parameter equation. The three correlation equations obtained for three tertiary amines are: log K = 3.41 + 10.01σ* + 0.02χ (for triethylamine-alcohol) log K = 0.97 + 2.54σ* + 0.21χ (for tributylamine-alcohol) log K = 1.01 + 1.81σ* + 0.26χ (for trioctylamine-alcohol), where σ* is Taft's polar constant and χ the molecular connectivity index of the R skeleton of the alcohol.     

Thermochemistry of molecular complexes. 5. Molecular complexes of I2 with ethylbenzenes andn-alkylbenzenes

The enthalpies of formation and equilibrium constants are reported for molecular complexes of I₂ with five ethylbenzene and ninen-alkylbenzene donor molecules in CCl₄. The wavelength of maximum absorbance for each complex is also reported. For ethylbenzene donor molecules, the formation enthalpy and equilibrium constant for the complexes depend strongly on the number of ethyl groups attached to the benzene ring, but only weakly on the position of the groups. For then-alkylbenzene donor molecules, both the formation enthalpy and equilibrium constant for complex formation are indenpendent of the length of the alkyl chain. These results are consistent with previous observations on weak complexes of I₂ with substituted benzene donors.     

Excess enthalpies of binary mixtures of some propylamines + some propanols at 298.15 K

The molar excess enthalpies of 1,2- and 1,3-propanediamine + 1- or 2-propanol and 1,2- and 1,3-propanediol + 1- or 2-propaneamine have been determined at 298.15 K using a twin-microcalorimeter for a series of runs over the whole range of mole fractions. All excess enthalpies were large exothermic, in particular, the systems of amines + propanediols were more than −5 kJ mol⁻¹ at the minimum. Primary or secondary alcohols and amines showed systematically different enthalpic behaviors. Equilibrium constant K1 expressed in terms of mole fractions and standard enthalpy of the formation of a 1:1 complex have been evaluated by ideal mixtures of momomeric molecules and their associated complexes.     

Chromium-Catalyzed Alkylation of Amines by Alcohols

The alkylation of amines by alcohols is a broadly applicable, sustainable, and selective method for the synthesis of alkyl amines, which are important bulk and fine chemicals, pharmaceuticals, and agrochemicals. We show that Cr complexes can catalyze this C−N bond formation reaction. We synthesized and isolated 35 examples of alkylated amines, including 13 previously undisclosed products, and the use of amino alcohols as alkylating agents was demonstrated. The catalyst tolerates numerous functional groups, including hydrogenation-sensitive examples. Compared to many other alcohol-based amine alkylation methods, where a stoichiometric amount of base is required, our Cr-based catalyst system gives yields higher than 90 % for various alkyl amines with a catalytic amount of base. Our study indicates that Cr complexes can catalyze borrowing hydrogen or hydrogen autotransfer reactions and could thus be an alternative to Fe, Co, and Mn, or noble metals in (de)hydrogenation catalysis.     

Modification of reversed-phase separations of small molecules using non-ionic surfactants and mixed ionic-non-ionic surfactants

The effects of non-ionic surfactants, Tween 20 and Tween 60, on reversed-phase separations of small molecules have been examined. Tween compounds were found to partition irreversibly into the ODS material used, markedly decreasing capacity factors for the compounds tested. Compounds which could hydrogen bond were less affected. Ion pairing using either anionic or cationic surfactants was possible in the presence of the non-ionic surfactants. While reversed-phase effects predominate under these conditions, secondary effects on retention order were observed and attributed to hydrogen bonding. Primary amines were retained longer than the corresponding secondary amine while catechols were retained longer than the corresponding methoxyphenols.     

Enthalpies of solution and dilution of butanol and pentanol in dodecyltrimethylammonium bromide micellar solutions

The enthalpies of solution and of dilution of 1-butanol and 1-pentanol were measured in micellar solutions of dodecyltrimethylammonium bromide by systematically changing the concentration of alcohols and surfactant. The enthalpies of solution at infinite dilution of alcohols at each surfactant concentration were evaluated from a linear plot. This quantity increases with surfactant concentration (up to 0.8m) with a curvature which depends on the alcohol alkyl chain length. The difficulties arising for a quantitative treatment of both the enthalpies of dilution and of solution at finite alcohol concentrations are discussed. The dependence on the surfactant concentration of the standard enthalpies of solution and the enthalpies of dilution for m0 are rationalized. From the resulting equations the distribution constant, standard enthalpy of transfer, standard enthalpy of solution, and the alcohol-alcohol interaction parameter in the micellar phase are evaluated. The enthalpies of transfer obtained using this technique agree well with those previously reported from enthalpies of mixing. The distribution constants also agree with those reported in the literature from several approaches: mixing enthalpies, partial molar volumes, and the dependence of the cmc on added alcohol.     

Equilibria Between Molecular and Ionic Complexes with an NH⋯N Hydrogen Bond. Fluorinated Aromatic Amine as a Proton Donor

Ultraviolet absorption spectra in the range 300-200 K were used to study the composition and structure of complexes formed in solutions by the fluorinated amine (4-CF3C6F4)2NH as a proton donor with dibutylamine. A program is developed for quantitative analysis of sets of the spectra of equilibrium multicomponent systems, that allow to find spectral and thermodynamic characteristics of the individual components. In the systems in study, 1:1 and 1:2 fluorinated diamine-dibutylamine complexes are formed. The first of them in a molecular complex with an NHN hydrogen bond, and the second is an ionic proton-transfer complex. The equilibrium constants between the complexes and the free molecules are found, the enthalpies and entropies of formation of both complexes are found, and the spectra of the complexes are measured.     

The reaction of isocyanide—mercuric chloride complexes with amines. Preparation of guanidines

Isocyanide—mercuric chloride complexes react readily with an excess of primary and secondary amines to give guanidines and metallic mercury in high yields through a redox decomposition reaction. In the presence of triethylamine, isocyanide—mercuric chloride complexes react with an equimolar amount of a primary amine to give a carbodiimide and metallic mercury. An intermediate organomercuric compound was isolated in the reaction of the isocyanide—mercuric chloride complex with pyrrolidone.     

Composition and plasticizing effect of poly(carboxylic acid) complexes with amino compounds

Poly(carboxylic acid)-dimethylalkylamine complexes were prepared and examined by various methods including infrared spectrometry and chemical titrations. FTIR measurements provided some of the most complete and detailed insights into the type and the stoichiometry of the acid-base complexes. A (1:1) stoichiometric complexation of the poly(carboxylic acid) with tertiary amines was involved in protic solvents. A threshold degree of complexation of 42% was obtained in such a macromolecular system. The equilibrium constant of the proton transfer reaction K was estimated to be independent on the alkyl chain length of the base reagent. Besides the formation of the acid-base complexes, a plasticizing effect of the amine derivatives was demonstrated by differential calorimetry. A T_g depression could be both attributed to the amine molecules linked to the polymer backbone via ionic bonds and to the free molecules dissolved within the free volume of the polymer.     

Molecular organization of reactants in the kinetics and catalysis of liquid phase reactions: IX. The catalytic assistance of an alcohol as a component of the medium in the aminolysis of esters

The kinetics of the reaction ofp-nitrophenyl acetate with n-butylamine is studied in various solvents containing n-butanol as a component of the medium. The alcohol is shown to assist the aminolysis by the participation in the proton transfer from the amine molecule to ester. The stoichiometric composition of the polymolecular complexes of amine with the alcohol participating in the reaction is found from the kinetic data at low concentrations of n-butanol and the data on its association in solutions. At high concentrations of the alcohol, the kinetic data are described within the framework of a model that assumes the participation in the reaction of hydroxy groups of the alcohol in the composition of alcohol clusters. The rate of the process is determined by the concentration and sizes of the clusters. The complex kinetics of the catalytic assistance of the alcohol as a component of the medium are quantitatively interpreted according to the concepts on the role of the structural organization of the liquid in the kinetics of molecular reactions in solutions.