A Study of the Electrochemical Behavior of Copper in Acid Medium in Presence of Some Organic Amine Compounds

The rate of corrosion of copper metal in presence of methyl amine, dimethyl amine, diethyl amine, triethyl amine, diethanol amine, and triethanol amine determined by measuring the anodic limiting current. The factors used are type of organic amine compounds and its concentration, concentration of H₃Po₄, viscosity of solution, density, diffusion coefficient, and rate of rotation. It has been found that, the rate of corrosion decrease in presence of these compounds. The inhibition percentage ranged from 9.72% to 80.14% depending on the type of inhibitor and its concentration. It is suggested that the decrease in the rate of corrosion is attributed to the increase in interfacial viscosity of the solution and decrease the diffusion coefficient of the copper ion. It has been found that we can apply the Langmuir, Flory-Huggins, and kinetic adsorption isotherms. It has been found that the rate of inhibition is increases in order: methyl amine, dimethyl amine, diethyl amine, triethyl amine, diethanol amine, and triethanol amine. The rate of corrosion depends on the H₃Po₄ concentration as well as on the electrode height. The limiting current in undivided cells is higher than in divided cells due to the uprising H₂ bubbles, which enhances the rate of corrosion. Also, the rate of corrosion was found to increase by increasing the speed of rotating electrode. The dimensionless groups were calculated, and the relation between them was given and the equation given as following: Sh = 0.5046 Re^0.7201(Sc)^0.33 for methyl amine; Sh = 0.5381 Re^0.7157(Sc)^0.33 for dimethyl amine; Sh = 0.4887 Re^0.7356(Sc)^0.33 for diethyl amine; Sh = 0.5167 Re^0.7207(Sc)^0.33 for triethyl amine; Sh = 0.5373 Re^0.7238(Sc)^0.33 for diethanol amine; and Sh = 0.4958 Re^0.7280(Sc)^0.33 for triethanol amine.     

Effect of para-substituents and solvent polarity on the formation of triphenylboroxine.amine adducts

Density functional theory (B3LYP//6-311+G) calculations including Poisson-Boltzmann implicit solvent and NMR were used to study the formation of a series of para-substituted triphenylboroxine.amine adducts with respect to their phenylboronic acid monomers and free amine in solution. Our calculations suggest that the intermediate prior to forming trimer.amine is a dimer.amine adduct. Formation of dimer.amine can proceed via two pathways. Electron-donating substituents favor dimerization of two monomers before addition of the amine, and electron-withdrawing substituents favor formation of a monomer.amine adduct before addition of the second monomer. We also find that pi-electron acceptors destabilize formation of the dimer and trimer with respect to its monomers. Electron-withdrawing substituents favor adduct formation. Adduct formation is enthalpically stabilized by increasing the polarity of the solvent but differential solubility of the monomer compared to trimer.amine also has an effect on the equilibrium constant.     

Selective N-Monomethylation of Primary Amines via N-Trialkylsilyl-Lithioamines

Transformation of a primary amine to a secondary amine can be achieved by reaction with an alkyl halide in the presence of an excess of the primary amine to suppress multiple alkylation, but, in general, direct alkylation is not the preferred method when the product alkylated amine is more nucleophilic than the startirg amine. More efficient procedures involve a relative vitiation of the nucleophilicity of the monoalkylated product with respect to that of the unalkylated substrate. Such an effect may be realised by the incorporation of monovalent activating groups (Z), which increase the acidity of the amido-proton and allow alkylation of a stabilised amidoanion, often generated in situ, this species being more reactive than a simple amine. Since in the conversion of a primary to a secondary amine only one amido-proton remains after incorporation of the activating group, further N-alkylation is obviated (Scheme 1.)     

Stereochemistry of imine reduction by a hydroxycyclopentadienyl ruthenium hydride

The stereochemistry of hydrogen transfer from [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COD)]Ru(CO)(2)D to N-aryl imines to give amine complexes was shown to be mostly trans stereospecific. Stereospecific hydrogen transfer is proposed to generate an amine and a coordinatively unsaturated ruthenium intermediate in close proximity. Coordination of the amine is proposed to occur faster than lone pair inversion of the amine. In contrast, hydrogen transfer to N-alkyl imines is stereorandom. It is proposed that stereochemistry is lost in part due to the reversibility of the hydrogen transfer being faster than amine coordination.     

Solution NMR and X‐Ray Structural Studies on Phthalocyaninatoiron Complexes

The addition of primary amines as solubilizing reagents for phthalocyaninatoiron complexes is shown to afford six‐coordinate bis(amine)phthalocyaninato complexes, i.e., [Fe(amine)₂(pc)] 2 (amine = decan‐1‐amine) and 3 (amine = benzylamine), with the two new N‐donors occupying the trans‐axial positions. The new complexes were characterized by extensive NMR measurements in THF solution. For complex 3 with the benzylamine ligand, the solid‐state structure was determined by X‐ray diffraction methods. Complex 2 is sufficiently labile in THF solution to exchange one amine ligand against CO (gas) affording an equilibrium mixture containing [Fe(amine)(CO)(pc)] 4 .     

Kinetics and mechanism of base catalysed ethyl cyanoformate addition to aldehydes

The mechanism by which tertiary amines catalyse the formation of cyanohydrin carbonates from aldehydes and alkyl cyanoformates is investigated by means of a kinetic study. The reaction rate shows a second order dependence on amine concentration unless the amine is sterically hindered, when the rate has a first order dependence on amine concentration. The catalytic activity of the amine correlated with its pK_aH. On the basis of these results, a mechanism is proposed in which the amine acts as a base to activate a water molecule, which reacts with the ethyl cyanoformate generating cyanide in situ.     

Behavior of Allylamines in the System KOH-DMSO

Isomerization of triallylamine in the system KOH-DMSO at 90-100°C leads to formation of tris-(1-propenyl)amine in quantitative yield. Under similar conditions, diallyl(ethyl)amine is converted into ethyl-bis(1-propenyl)amine, 1-ethyl-3-methylcyclohexane. Diallylamine in KOH-DMSO gives rise to a complexmixture of products consisting of bis(1-propenyl)amine, methylbis(1-propenyl)amine, 1-ethyl-3-methylcyclo-hexane, and 2-ethyl-3,5-dimethylpiperidine. Ways of formation of these products are discussed.     

Polymerization photoinitiated by carbonyl compounds. X. Methyl methacrylate polymerization photoinitiated by fluorenone in the presence of triethylamine

The photoinitiation efficiency of the fluorenone/triethylamine (TEA) system in the polymerization of methylmethacrylate (MMA) has been evaluated as a function of the monomer concentration, the amine concentration, and the polarity of the reaction medium. The polymerization proceeds readily in low polarity media (benzene/monomer), but it is negligible in more polar solvents (acetonitrile/monomer). The polymerization rate increases with the amine concentration up to 0.01 M TEA. Further increase in amine concentration produces a decrease in the polymerization rate. A similar behavior was observed for the fluorenone photoreduction yield and the yield of fluorenone derived radicals. All these processes are considered to involve the excited triplet, while quenching of the excited singlet by the amine decreases the rate of these processes. However, the decrease in photoinitiation efficiency observed at high amine concentration is larger than that expected from the singlet quenching extent, as estimated from the effect of the amine on the fluorescence yield under the same experimental conditions. This discrepancy indicates that other process(es) must contribute to the protection afforded by high amine concentrations. Quenching of the charge transfer intermediate by the amine is postulated as a competitive process that could explain the above mentioned effects. © 1994 John Wiley & Sons, Inc.     

A Simple Method of Protecting a Secondary Amine with Tert Butyloxycarbonyl (Boc) in the Presence of a Primary Amine

A simple method for chemically differentiating primary and secondary amines is described in which the primary amine is condensed with benzaldehyde to form an imine leaving the secondary amine available to be protected with BOC. The imine is then hydrolyzed to provide the free primary amine.     

Catalyst-free chemoselective N-tert-butyloxycarbonylation of amines in water

[Structure: see text] Catalyst-free N-tert-butyloxycarbonylation of amines in water is reported. The N-t-Boc derivatives were formed chemoselectively without any isocyanate, urea, N,N-di-t-Boc, and O/S-t-Boc as side products. Chiral amines, esters of alpha-amino acids, and beta-amino alcohol afforded optically pure N-t-Boc derivatives. Amino alcohol and 2-aminophenol afforded the N-t-Boc derivative without oxazolidinone formation. Selectivity was observed during competition of aromatic amine vs aliphatic amine, amine vs amino acid ester, amine vs amino alcohol, and primary amine vs secondary amine.     

利用萤光光谱测定高分子端基叔胺值

<正> 近年来,利用萤光或磷光方法研究高分子的物理性质和化学性质,已愈益引起人们的兴趣,并取得了一定的结果。本工作利用了ππ跃迁克分子消光系数大(ε>10~4)的特性,用萤光光谱来测定PMMA的端基叔胺值,此法具有快速、简便、用量少、灵敏等优点。     

Mechanism for the reduction of the mixed-valent MnIIIMnIV[2-OHsalpn]2+ complex by tertiary amines

The mixed-valent dimanganese(III/IV) complex MnIIIMnIV(2-OHsalpn)2+, 1, is cleanly reduced in acetonitrile by aliphatic tertiary amines to give the dimanganese(III) product MnIII2(2-OHsalpn)2, 2. Thorough characterization of the organic reaction products shows that tributylamine is converted to dibutylformamide and propionaldehyde. Kinetic studies and radical trapping experiments suggest that this occurs via initial single-electron transfer from the amine to 1 coupled with C-H alpha proton transfer from the oxidized amine. EPR spectroscopy and base inhibition studies indicate that coordination of the amine to 1 is a critical step prior to the electron transfer step. Rate data and its dependence on the amine indicate that the ability of the amine to reduce 1 is correlated to its basicity rather than to its reduction potential. Weakly basic amines were unable to reduce 1 irrespective of their reduction potential. This was inferred to indicate that proton transfer from the amine radical cation is also important in the reduction of 1 by tertiary amines. Comparison of the activation energy with reaction thermodynamics indicates that proton transfer and electron transfer must be concerted to explain the rapidity of the reaction. The fate of the amine radical is dependent on the presence of oxygen, and labeling studies show that oxygen in the organic products arises from dioxygen, although incorporation from trace water was also observed. These data indicate that inhibition of the hydrolytic quenching of the amine radical in an aprotic solvent results in a different fate for the amine radical when compared to amine oxidation reactions in aqueous solution. The proposed mechanism gives new insight into the ability of amines with high reduction potential to reduce metal ions of lower potential. In particular, these data are consistent with the ability of small amines and certain amine-containing buffers to inhibit manganese-dependent oxygen evolution in photosynthesis, which arises in some cases as a result of manganese reduction and its concomitant loss from the PS II reaction center.     

Thermodynamics and kinetics of methylboroxine.amine adduct formation: a computational study

Density functional theory (B3LYP//6-311+G*) calculations including Poisson-Boltzmann implicit solvent were applied to study the formation of the trimethylboroxine.amine adduct with respect to methylboronic acid monomers and free amine in solution. Potential intermediates and transition states between intermediates were calculated to assess the thermodynamic and kinetic factors controlling this transformation. Our calculations suggest that the rate-determining steps are condensation reactions to form dimers and trimers, and closure of the boroxine ring. Fast amine exchange is expected throughout the transformation, and the most-stable intermediate is a dimer.amine adduct. Using our calculated barriers for the methyl system as a template, we assess the conversion of phenylboronic acid to the triphenylboroxine.amine adduct and find that the pathway is most likely similar, except that the transformation is thermodynamically and kinetically more favored for the phenyl system in the presence of pyridine.     

从介孔分子筛原粉研制高效吸附二氧化碳的有机胺-介孔复合材料

固态有机胺二氧化碳吸附剂具有高选择性、低腐蚀性、易再生等特点,有着减少二氧化碳排放的潜在应用前景.但是,如何在大量引入氨基的同时,保持氨基在载体上具有高分散度是制备固态胺吸附剂的难题.本文综述了近年来固体胺二氧化碳吸附剂的研究进展,重点介绍开拓利用介孔分子筛原粉的分级结构,将有机胺涂布到介孔分子筛孔道中的丝状胶束以及胶束和硅壁之间的间隙中,可以显著地提高二氧化碳的吸附量.     

Mass spectrometry of 4-amino-4′-nitroazobenzene compounds

The mass spectra of 32 substituted 4-amino-4′-nitroazobenzene compounds have been recorded and the most intense peaks have been used to characterize these spectra. It was found that the spectra of 4-amino-4′-nitroazobenzene compounds are characterized by peaks due to: (1) molecular ions, (2) fragment ions formed by cleavage of one of the carbon-nitrogen bonds adjacent to the azo linkage with the positive charge remaining with the amine fragment, (3) ions formed by cleavage alpha to the amine nitrogen with the charge remaining with the amine substituent, (4) ions formed by cleavage beta to the amine nitrogen with the loss of the amine substituent fragment, (5) secondary ions formed by cleavage beta to the amine nitrogen with the loss of the amine substituent fragment from the primary amine fragment (2), and (6) ions formed by loss of NO from the molecular ion. This work shows that 4-amino-4′-nitroazobenzene compounds exhibit fragmentation which is dependent in a consistent manner on the types of substituents. This work provides a basis for a systematic approach to the identification of 4-amino-4′-nitroazobenzene compounds.     

Influence of the amine structure on the polymerization of methyl methacrylate photoinitiated by aromatic ketone/amine

The polymerization of methyl methacrylate photoinitiated by 2‐chlorothioxanthone in the presence of amines of different structures has been investigated. The photoinitiation efficiency of these systems is highly dependent on the structure of the amine. The polymerization rate increases with the amine concentration, reaching a constant value in an amine concentration range of 10–30 mM. At these amine concentrations, aliphatic hydroxyalkyl amines are more efficient photoinitiators than the corresponding alkyl‐substituted compounds. Dimethylanilines with electron‐acceptor substituents in the 4‐position give higher polymerization rates than electron‐donor‐substituted anilines. The photophysics of these photoinitiation systems has been studied in the polymerization medium. These data show that the singlet and triplet excited states of thioxanthones are efficiently deactivated by the amine. Rate constants are well correlated to the oxidation potential of the amine. These studies have allowed us to simulate the dependence of the photoinitiation efficiency with the amine concentration and indicate that the active radicals are produced from the interaction of the ketone triplet with the amine. Also, photochemical studies have allowed us to establish that the dependence of the polymerization rate on structural features of amines is mainly due to differences in the fraction of produced active radicals that add to the monomer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2888–2893, 2002     

Preparation, crystal structure, and solid-state optical property of a disulfonic acid/amine fluorescent complex composed of 4,4′-biphenyldisulfonic acid and 2-naphthylethylamine

Solid-state disulfonic acid/amine fluorescent host complexes including methanol (MeOH) as guests were successfully prepared using 4,4′-biphenyldisulfonic acid and 2-naphthylethylamine as component molecules. Although the crystal structure of the obtained host complex is similar to that of the corresponding dicarboxylic acid/amine host complex, the solid-state photo-luminescence quantum yield of the disulfonic acid/amine fluorescent host complex is increased relative to those of the corresponding dicarboxylic acid/amine host complex.     

The role of amine in the mechanism of pentathiepin (polysulfur) antitumor agents

A computational and experimental study is presented, which provides the first evidence that amine has an opportunity to engage in bonding with pentathiepin to promote its decomposition. The study provides mechanistic insight into the process that gives rise to pentathiepin biological activity. Primary or secondary amine will allow for an intramolecular addition to the pentathiepin ring at the nearest sulfur (S1). In contrast, tertiary amine adds reversibly to S1, because nitrogen cannot lose its positive charge by deprotonation. This precludes the amine promotion step. An energetically low-lying process is characterized, corresponding to S3-loss triggered by nucleophilic activation with a primary or secondary amine. Pentathiepin desulfurization via S3-unit transfer is supported by a trapping study with norbornene. That the amine may confer an enhanced reactivity in the natural products varacin, 1, and lissoclinotoxin A, 2, adds to the understanding of the pathway for pentathiepin activation and may provide new design concepts that have potential applications for this class of biocides.     

三聚磷酸二氢铝与有机胺的插层反应特征

采用IR、XRD、SEM、EDS、DT-TG和滴定实验等技术手段研究主体三聚磷酸二氢铝(ATP)与客体甲胺、乙胺、正丙胺和正丁胺等有机胺的插层反应特性。 实验结果表明,ATP与甲胺、乙胺、正丙胺、正丁胺发生了化学反应,有机胺中的N与ATP层间-OH上的H形成配位键。 这些有机胺通过插层反应改变了ATP的酸性、层间距和热分解温度,但没有改变颗粒的层状形貌。 层间距从0.795 nm增大至1.71 nm,层间距d与有机胺的碳原子数Cn呈线性关系：d=0.229Cn+0.811,R2=0.9986。 有机胺分子链越长则越具有剥离倾向。     

On the loss of ammonia from phenylalkyl amines

The molecular ion-minus-ammonia [M – NHJ] fragmentation of (3-phenylpropyl) primary amines is a major contributor to the total ion current. This fragmentation occurs to a lesser extent in the lower and higher homologs, (2-phenethy1)- and (4-phenylbuty1)amine. The loss of methylamine and dimethylamine from N-methyl-(3-phenylpropyl)amine and N,N-dimethyl-(3-phenylpropy1)amine respectively is essentially absent. Deuterium labeling has shown that C-3 is the primary source of hydrogen abstracted in the [M ? NHJ] fragmentation of (3-pheny1propyl)amine.