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Addition of nickel/aluminum alloy to alkaline solutions of compounds containing N-N or N-O bonds appears to offer a general and convenient means for reducing such compounds to the corresponding amines.The method has been successfully applied to the reduction of nitrosamines, hydrazines, hydroxylamines, hydroxylamine ethers, triazenes, nitramines, N-oxides, tetrazenes, and nitroso, azo, and azoxy compounds.

N,N'-Oxalyl and N,N'-malonyl derivatives of indigo and 6,6'-di-t-butylindigo were reduced with high quantum efficiencies to their semi-reduced radicals by visible light irradiation in the presence of tertiary amines.These semi-reduced radicals were reversibly autoxidized and thus oxidative dealkylation of tertiary amines was catalyzed photochemically by these indigos.

The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).

In the present study, ruthenium-catalyzed amination of alcohols by urea as a convenient ammonia carrier in the presence of free diphosphine ligands has been described. A number of ruthenium-phosphine complexes have been studied among which, [(Cp)RuCl(dppe)] was found as an efficient catalyst for alcohol amination reaction. The crystal structures of two new half-sandwich ruthenium complexes, [(Cp)RuCl(dppe)] and [(C6H6)RuCl2(PHEt2)], were determined by X-ray crystallographic analysis. Also the effect of using different supporting phosphines, ratio of raw materials and reaction temperature on conversion and selectivity was investigated. Under optimum reaction conditions high conversion (98percent) and chemo-selectivity toward secondary amines were obtained.

The synthesis of asymmetric secondary amines (ASA) is commonly achieved by N-alkylation of primary amines with alcohols. Here, we investigated the ASA synthesis via the direct amination of alcohols with nitriles, which avoids the synthesis, separation and purification of the primary amines in a first step. Specifically, the ASA synthesis via N-alkylation of butyronitrile (BN) with primary (n-propanol, iso-butanol and n-octanol) and secondary (2‐propanol, 2‐butanol and 2‐octanol) alcohols was studied on SiO2-supported Co, Ni and Ru catalysts. Competitive BN hydrogenation‐condensation reactions formed dibutylamine (the symmetric secondary amine) and tertiary amines as main secondary products. On Co/SiO2, the ASA selectivities for BN/primary alcohol reactions were between 49 and 58% at complete BN conversion, forming dibutylamine and tertiary amines as byproducts. For BN/secondary alcohol reactions, Co/SiO2 formed selectively (ASA + dibutylamine) mixtures containing 78–85% of ASA, thereby showing that the alcohol amination with nitriles is an attractive alternative route for the synthesis of valuable asymmetric secondary amines.

A new ruthenium catalytic system for the syntheses of secondary and tertiary amines via reductive N-alkylation of nitriles and N-alkylation of primary amines is proposed. Isomeric complexes 8 catalyze transfer hydrogenation and N-alkylation of nitriles in ethanol to give secondary amines. Unsymmetrical secondary amines can be produced by N-alkylation of primary amines with alcohols via the borrowing hydrogen methodology. Aliphatic amines were obtained with excellent yields, while only moderate conversions were observed for anilines. Based on kinetic and mechanistic studies, it is suggested that the rate determining step is the hydrogenation of intermediate imine to amine. Finally, ammonium formate was applied as the amination reagent for alcohols in the presence of ruthenium catalyst 8. Secondary amines were obtained from primary alcohols within 24 hours at 100 °C, and tertiary amines can be produced after prolonged heating. Secondary alcohols can only be converted to secondary amines with moderate yield. Based on mechanistic studies, the process is suggested to proceed through an ammonium alkoxy carbonate intermediate, where carbonate acts as an efficient leaving group.

The liquid-phase hydrogenation of butyronitrile to saturated amines was studied on silica-supported Ni catalysts prepared by either incipient-wetness impregnation (Ni/SiO2-I) or ammonia (Ni/SiO2-A) methods. A Ni/SiO2-Al2O3-I sample was also used. Ni/SiO2-I was a non-acidic catalyst containing large Ni0 particles of low interaction with the support, while Ni/SiO2-A was an acidic catalyst due to the presence of Ni2+ species in Ni phyllosilicates of low reducibility. Ni/SiO2-I formed essentially butylamine (80%), and dibutylamine as the only byproduct. In contrast, Ni/SiO2-A yielded a mixture of dibutylamine (49%) and tributylamine (45%), being the formation of butylamine almost completely suppressed. The selective formation of secondary and tertiary amines on Ni/SiO2-A was explained by considering that butylamine is not release to the liquid phase during the reaction because it is strongly adsorbed on surface acid sites contiguous to Ni0 atoms, thereby favoring the butylimine/butylamine condensation to higher amines between adsorbed species.

The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.

Nickel nanoparticles on the BAU-A active carbon or NaX zeolite catalyze hydrogenation of imines and enamines in a flow reactor in a gas phase or in a gas–liquid–solid catalyst system. The process occurs at atmospheric pressure of hydrogen and gives secondary or tertiary amines in a high yield.

The catalytic system generated in situ from the tetranuclear Ru-H complex with a catechol ligand (1/L1) was found to be effective for the direct deaminative coupling of two primary amines to form secondary amines. The catalyst 1/L1 was highly chemoselective for promoting the coupling of two different primary amines to afford unsymmetric secondary amines. The analogous coupling of aniline with primary amines formed aryl-substituted secondary amines. The treatment of aniline-d7 with 4-methoxybenzylamine led to the coupling product with significant deuterium incorporation on CH2 (18% D). The most pronounced carbon isotope effect was observed on the α-carbon of the product isolated from the coupling reaction of 4-methoxybenzylamine (C(1) = 1.015(2)). A Hammett plot was constructed from measuring the rates of the coupling reaction of 4-methoxyaniline with a series of para-substituted benzylamines 4-X-C6H4CH2NH2 (X = OMe, Me, H, F, CF3) (ρ = -0.79 ± 0.1). A plausible mechanistic scheme has been proposed for the coupling reaction on the basis of these results. The catalytic coupling method provides an operationally simple and chemoselective synthesis of secondary amine products without using any reactive reagents or forming wasteful byproducts.

Conversion of the starting nitriles and selectivity of the products formation during continuous hydrogenation of various nitriles catalyzed by Ni0/Ceokar-2 have been studied as functions of temperature. Performing the process at temperature 120–260°С has led to the formation of a mixture of products containing di- and trialkylamines as well as the corresponding imines and enamines.

A ruthenium-hydride complex, [Ru(H)(Cl)(CO)(PCy3)2], was found to be active in the highly selective redistribution of primary and secondary amines bearing an α-hydrogen atom. This new deaminative coupling of amines enables the highly selective synthesis of secondary amines from primary amines and of tertiary amines from secondary amines with the evolution of ammonia. A preliminary mechanistic view of this novel reaction based on catalytic experiments using NMR methods confirms the synthetic observations.

Abstract: The catalytic (Pd/Al2O3 and Pd/C; mean Pd size 2.5–3.0?nm from (S)TEM analysis) synthesis of di-butylamine (DBA) and tri-butylamine (TBA) from mono-butylamine (MBA) and DBA, respectively, in continuous gas phase operation is demonstrated. Exclusive production of DBA (from MBA) has been established over both catalysts where 453 ≤ T ≤ 523?K (?Ea = 79?kJ?mol?1). Greater activity for Pd/C is associated with higher levels of surface acidity (from NH3 chemisorption/TPD) and spillover hydrogen (from H2 TPD). Reaction of DBA over both catalysts when configured in series delivered full selectivity to TBA. Our results establish a novel clean alternative route for the continuous production of higher (secondary and tertiary) amines. Graphical Abstract: [Figure not available: see fulltext.]

Hydrogenation of aliphatic nitriles in the presence of nickel supported by NaX zeolite was studied. The data obtained were used to develop a continuous method for obtaining dialkylamines with the yield of the target product of up to 98%.

Reductive amination of carbonitriles catalyzed by nickel nanoparticles applied onto a solid support in a plug flow reactor in the gas phase or the gas–liquid–solid catalyst system occurs at atmospheric pressure of hydrogen affording the nonsymmetrical secondary or tertiary amines. The effect of the support type on the target product yield and conversion of the substrate has been studied.

Abstract: A new one-pot method has been introduced in this work for the synthesis of symmetrical primary, secondary, and tertiary alkyl amines from alkyl halides and 5-methyl-1,3,4-thiadiazole-2-amine as a nitrogen-transfer reagent. In this method, all three types of amines have been successfully prepared after changing the ratio of substrates and base control. In addition to the introduction of a new nitrogen-transfer reagent, other important features of this work include normal atmospheric conditions and excellent yields under mild reaction conditions.

The present invention relates to a preparation method of a carbonyl compound and a method for removing nitrogen-end protective group of an amide-based compound. The carbonyl compound is prepared by having a photocatalytic reaction of an amine-based group using water and an oxidizing agent. Therefore, the preparation method can prepare a carbonyl compound by usefully cutting carbon-nitrogen bonds at mild conditions, and such cutting reaction of carbon-nitrogen bonds can be usefully used for removing a protective group combined to an amide-based compound including amide or sulfonyl amide having carbon-nitrogen bonds.COPYRIGHT KIPO 2016

Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.

Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in isopropanol proceeds under atmospheric pressure of hydrogen within 6-15 h to yield mainly secondary amines. Hydrogenation of α-aminonitriles results in reductive decyanation. β-Aminonitriles undergo hydrogenolysis at the nitrogen-carbon bond.

De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Let′s iron it out! The title reaction enables the oxidative synthesis of amides directly from tertiary, noncyclic alkyl amines under synthetically useful, mild conditions through a biologically inspired approach employing oxidative iron catalysis. Mechanistic studies suggest that hemiaminals are likely intermediates in this reaction and that the catalytic system can be employed for other Cα-H oxidations of amines.

Amines were used as hydrogen donor for the borrowing hydrogen methodology with a heterogeneous catalyst. Supported copper catalysts catalyzed the self-condensation reaction of primary amines to secondary amines/imines with high efficiency. The recyclable, non-leaching catalyst is synthesized by a sol-gel method, which allows entrapping copper nanoparticles in an alumina matrix. The synthesized copper catalysts were found to be active in the self-coupling of primary amines to produce secondary amines. The hydrogen donor for the transfer hydrogenation appears to be the primary amine, and no additional hydrogen or hydrogen transfer reagent is required. To the best of our knowledge, this is the first report of a copper based catalyst for this type of reaction using the borrowing hydrogen scheme.

The invention relates to a method for producing a N-substituted amine compound by catalyzed alkylation. The method uses amine and alcohol or two kinds of amines as the reaction materials, employs composite metal oxides catalyst at a reaction temperature of 80-180° C. to catalyze the reaction for 6-36 hours, so as to produce the N-substituted amine compound. The reaction condition of the method of the invention is relatively moderate, using a catalyst made of cheap non-noble metals, which is non-caustic and easy to be separated and reused. The reaction does not need any medium and has relatively high conversion rate and selectivity.

The effect of solvent on Ni(10.5percent)/SiO2 activity and selectivity for the liquid-phase hydrogenation of butyronitrile to butylamines was studied at 373 K and 13 bar using ethanol, benzene, toluene and cyclohexane as solvents. In ethanol, a protic solvent, the Ni catalyst yielded n-butylamine (84percent) and dibutylamine (16percent). When non-polar solvents, such as cyclohexane, toluene or benzene, were used, the solvent-catalyst interaction strength determined the selectivity to n-butylamine: the stronger the solvent-catalyst interaction the higher the n-buylamine production. The yield to n-butylamine in non-polar solvents varied between 39percent (cyclohexane) and 63percent (benzene).

The complex [Ru(Triphos)(TMM)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane, TMM = trimethylene methane) provides an efficient catalytic system for the hydrogenation of a broad range of challenging functionalities encompassing carboxylic esters, amides, carboxylic acids, carbonates, and urea derivatives. The key control factor for this unique substrate scope results from selective activation to generate either the neutral species [Ru(Triphos)-(Solvent)H2] or the cationic intermediate [Ru(Triphos)-(Solvent)(H)(H2)]+ in the presence of an acid additive. Multinuclear NMR spectroscopic studies demonstrated together with DFT investigations that the neutral species generally provides lower energy pathways for the multistep reduction cascades comprising hydrogen transfer to C=O groups and C-O bond cleavage. Carboxylic esters, lactones, anhydrides, secondary amides, and carboxylic acids were hydrogenated in good to excellent yields under these conditions. The formation of the catalytically inactive complexes [Ru(Triphos)(CO)H2] and [Ru(Triphos)(μ-H)]2 was identified as major deactivation pathways. The former complex results from substrate-dependent decarbonylation and constitutes a major limitation for the substrate scope under the neutral conditions. The deactivation via the carbonyl complex can be suppressed by addition of catalytic amounts of acids comprising non-coordinating anions such as HNTf2 (bis(trifluoromethane)sulfonimide). Although the corresponding cationic cycle shows higher overall barriers of activation, it provides a powerful hydrogenation pathway at elevated temperatures, enabling the selective reduction of primary amides, carbonates, and ureas in high yields. Thus, the complex [Ru(Triphos)(TMM)] provides a unique platform for the rational selection of reaction conditions for the selective hydrogenation of challenging functional groups and opens novel synthetic pathways for the utilization of renewable carbon sources.

A synthesis of N-ethyl-n-butylamine with simple separation method in a fixed-bed reactor using CuO-NiO-PtO/γ-Al2O3 as the catalyst was proposed and investigated. The present catalytic system gave high activity and good selectivity, and the reaction conditions such as temperature and liquid hourly space velocity were optimized. Since no water was generated, the protocol proved to be easy to separate, and N-ethyl-n-butylamine was collected at 110 °C by distillation. The yield and the purity were 60.7 and 99.5 %, respectively.

Just add water! The title reaction is catalyzed by an acridine-based pincer complex (1, see scheme). This one-step transformation uses water as the only reagent in the absence of additional bases, oxidants, or reductants. Cyclization of 1,4-diaminobutane and 1,6-diaminohexane catalyzed by 1 leads to the formation of pyrrolidine and azepane, respectively. Copyright

Aerobic oxidative N-dealkylation of a variety of aliphatic tertiary amines and anilines catalyzed by rhodium(iii) tetra (p-sulfonatophenyl) porphyrin ((TSPP)RhIII) is achieved in aqueous solution using dioxygen as the sole oxidant.

Aliphatic and aromatic secondary amines were synthesised selectively by one pot reductive amination of nitriles with primary amines using Pt/C (3% by weight) catalyst in a continuous flow multichannel microreactor. Molecular hydrogen was used as a clean reducing agent at moderate reaction conditions. The Royal Society of Chemistry 2013.

The invention provides a multistage process for continuously preparing organic polyisocyanates, preferably diisocyanates, more preferably aliphatic or cycloaliphatic diisocyanates, by reaction of the corresponding organic polyamines with carbonic acid derivatives and alcohols into monomeric polyurethanes of low molecular mass, and the dissociation of said polyurethanes. The invention further provides an associated preparation process in which at certain reaction stages the polyisocyanates prepared and unutilizable residues are removed and reusable by-products and intermediates are recycled to preliminary stages.

Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from prepared from [Ru(acac) 3], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κ1O) 2(H2O)-(triphos)], [Ru(OAc-κ2O,O') (CH3SO3-κ1O)(triphos)], [Ru(CH 3SO3-κ1O)2-(H 2O)(triphos)] and [Ru2(μ-CH3SO 3)3-(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc-κ1O)(OAc- κ2O,O')(triphos)],[Ru(CH3SO3- κ1O)(CH3SO3-κ2O,O')- (triphos)], H[Ru(CH3SO3-κ1O) 3-(triphos)], [RuH(CH3SO3-κ1O) (CO)-(triphos)] and [RuH(CH3SO3-k2O,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.

The selective liquid-phase hydrogenation of butyronitrile to n-butylamine was studied in a batch reactor on Co(9.8%)/SiO2, Ni(10.5%)/SiO 2, Cu(9.2%)/SiO2, Pt(0.27%)/SiO2, Pd(0.33%)/SiO2, and Ru(1.8%)/SiO2 catalysts. At 373 K and 13 bar (H2), the initial butyronitrile conversion rate (rBN0, mmol/h g) followed the order Ni > Co > Pt > Ru > Cu > Pd. Cu/SiO 2 and Pd/SiO2 did not form n-butylamine and rapidly deactivated during the progress of the reaction. Pt/SiO2 produced mainly dibutylamine and only minor amounts of n-butylamine and tributylamine. In contrast, Ru/SiO2 formed preponderantly n-butylamine but also produced significant amounts of dibutylamine and butylidene-butylamine, an intermediate in the formation pathway of the secondary amine. The highest yield to n-butylamine was obtained on Ni/SiO2 (84%). Co/SiO2 was initially highly selective to n-butylamine but with the progress of the reaction the butylamine concentration in the reaction mixture diminished because it partially reacted with the solvent (ethanol) to form N-ethylbutylamine. In an attempt to reduce the formation of byproducts, Ni/SiO2 and Co/SiO2 catalysts were tested at lower temperatures and higher H 2 pressures. Butyronitrile was selectively converted to n-butylamine on Co/SiO2 at 343 K and 25 bar, yielding 97% of n-butylamine, similarly to the highest yields reported on Raney Co catalysts.

Versatile syntheses of secondary and tertiary amines by highly efficient direct N-alkylation of primary and secondary amines with alcohols or by deaminative self-coupling of primary amines have been successfully realized by means of a heterogeneous bimetallic Pt-Sn/γ-Al2O3 catalyst (0.5 wt % Pt, Pt/Sn molar ratio=1:3) through a borrowing-hydrogen strategy. In the presence of oxygen, imines were also efficiently prepared from the tandem reactions of amines with alcohols or between two primary amines. The proposed mechanism reveals that an alcohol or amine substrate is initially dehydrogenated to an aldehyde/ketone or NH-imine with concomitant formation of a [PtSn] hydride. Condensation of the aldehyde/ketone species or deamination of the NH-imine intermediate with another molecule of amine forms an N-substituted imine which is then reduced to a new amine product by the in-situ generated [PtSn] hydride under a nitrogen atmosphere or remains unchanged as the final product under an oxygen atmosphere. The Pt-Sn/γ-Al2O 3 catalyst can be easily recycled without Pt metal leaching and has exhibited very high catalytic activity toward a wide range of amine and alcohol substrates, which suggests potential for application in the direct production of secondary and tertiary amines and N-substituted imines.

Under the action of a twofold excess of KOH and heating in aqueous solution, and also under the conditions of the Stevens rearrangement (with KOH powder and a small amount of methanol) dialkyl-(4-hydroxy-2-butynyl)(3- phenylallyl)ammonium bromides form dialkyl[4-(1-phenylallyl)-2,5-dihydro-2- furyl]amines. Rearrangement-cleavage reaction also occurs under the same conditions.

The present invention generally relates to a process for preparing a 1,2-ethylenediamine; 1,2-propylenediamine; or a mixture thereof by way of a catalyzed reductive amination reaction employing hydrogen, a reductive amination catalyst, (C3-C40)polyhydric alcohol having at least three hydroxy groups on consecutive carbon atoms thereof, and primary amine, the catalyzed reductive amination reaction employing reaction conditions that are effective for reductively aminating at least two of the hydroxy groups of the (C3-C40)polyhydric alcohol and reductively eliminating at least one other of the hydroxy groups of the (C3-C40)polyhydric alcohol in such a way so as to give a 1,2-ethylenediamine; 1,2-propylenediamine; or a mixture thereof.

This study aims to characterize interindividual variability and individual CYP enzymes involved in the in vitro metabolism of the carbamate insecticide carbosulfan. Microsomes from ten human livers (HLM) were used to characterize the interindividual variability in carbosulfan activation. Altogether eight phase I metabolites were analyzed by LC-MS. The primary metabolic pathways were detoxification by the initial oxidation of sulfur to carbosulfan sulfinamide ('sulfur oxidation pathway') and activation via cleavage of the nitrogen sulfur bond (N-S) to give carbofuran and dibutylamine ('carbofuran pathway'). Differences between maximum and minimum carbosulfan activation values with HLM indicated nearly 5.9-, 7.0, and 6.6-fold variability in the km, Vmax and CLint values, respectively. CYP3A5 and CYP2B6 had the greatest efficiency to form carbosulfan sulfinamide, while CYP3A4 and CYP3A5 were the most efficient in the generation of the carbofuran metabolic pathway. Based on average abundances of CYP enzymes in human liver, CYP3A4 contributed to 98% of carbosulfan activation, while CYP3A4 and CYP2B6 contributed 57 and 37% to detoxification, respectively. Significant correlations between carbosulfan activation and CYP marker activities were seen with CYP3A4 (omeprazole sulfoxidation), CYP2C19 (omeprazole 5-hydroxylation) and CYP3A4 (midazolam 1′-hydroxylation), displaying r2=0.96, 0.87 and 0.82, respectively. Activation and detoxification pathways were inhibited by ketoconazole, a specific CYP3A4 inhibitor, by 90-97% and 47-94%, respectively. Carbosulfan inhibited relatively potently CYP3A4 and moderately CYP1A1/2 and CYP2C19 in pooled HLM. These results suggest that the carbosulfan activation pathway is more important than the detoxification pathway, and that carbosulfan activation is predominantly catalyzed in humans by CYP3A4.

The stability constants of hydrogen bonded ion pair or proton transfer complex formation of N,N'-dimethyl thiovioluric acid [DMTVA], N,N'- di-o-tolyl thiovioluric acid [DOTTVA], N,N'-di-m-tolyl thiovioluric acid [DMTTVA] and N,N'-di-p-tolyl thiovioluric acid [DPTTVA] with methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, n-butyl amine, dibutyl amine and tributyl amine have been determined spectroscopically in 95% (v/v) ethanol. The composition of the complexes is determined in solution potentiometrically and spectrophotometrically and substantiated by the element analysis and IR spectra of the isolated complexes. The stabilities of the thiovioluric acid-amine complexes have been correlated with the base strength of amines. The correlation between the mode of enolization in the acids and the structure of the proton transfer complex is discussed. The variation in proton transfer constants of acids has been explained on the basis of the changes in the distribution of electron density in the ring.

Rh/Mo catalysts formed in situ from Rh6(CO)16 and Mo(CO)6 are effective for the liquid phase hydrogenation of CyCONH2 to CyCH2NH2 in up to 87% selectivity, without the requirement for ammonia to inhibit secondary amine formation. Use of in situ HP-FTIR spectroscopy has shown that decomposition of metal carbonyl precursors occurs during an extended induction period, with the generation of recyclable, heterogeneous, bimetallic catalysts. Variations in Mo:Rh content have revealed significant synergistic effects on catalysis, with optimum performance at values of ca. 0.6, and substantially reduced selectivities at ≥1. Good amide conversions are noted within the reaction condition regimes 50-100 bar H2 and 130-160 °C. Ex situ characterization of the catalysts, using XRD, XPS and EDX-STEM, has provided evidence for intimately mixed (ca. 2-4 nm) particles that contain metallic Rh and reduced Mo oxides, together with MoO3. Silica-supported Rh/Mo analogues, although active, perform poorly at 150 °C and deactivate during recycle.

A facile and convenient way to prepare cyclic amines in water was achieved by the catalyst system composed of Ru/C and Al powder. The α,ω-diaminoalkanes, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diamino-heptane were converted to corresponding cyclic amines in good yields. The use of D2O provided a novel route to obtain deuterated cyclic amines in good yields.

(Chemical Equation Presented) To have an evaluation of the basic strength of aliphatic amines in ionic liquid solution, the stability constants relevant to the formation of amine/p-nitrophenol ion pairs were determined in different ionic liquids at 298 K.

Secondary and tertiary amines can be easily obtained from primary and secondary amines, respectively, in completely aqueous media, in the presence of a bicatalytic system formed of cheap commercial aluminum (Al) powder and 5% rhodium (Rh) or ruthenium (Ru) deposed on charcoal.

A process for the hydrogenation of carboxylic acids and/or derivatives, particularly amides, is described. The process includes reacting an acid or derivative such as an amide with a source of hydrogen in the presence of a catalyst system. The catalyst system obtainable by combining: (a) a source of ruthenium, and (b) a phosphine compound of general Formula I: (Formula I). The hydrogenation reaction is carried out in the presence of a low concentration of water or at low pressure or in the presence of a source of ammonia or the hydrogenation reaction is carried out in the absence of water or a combination of these factors is utilised. The invention also relates to the use of ammonia in the production of primary amines by hydrogenation of carboxylic acids and/or derivatives thereof or a process for the production of primary amines generally.

The present invention provides a salt represented by the formula (I): wherein P1, P2 and P3 each independently represent a C1-C30 alkyl group which may be substituted with at least one selected from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-C12 alkoxy group, or a C3-C30 cyclic hydrocarbon group which may be substituted with at least one selected from a hydroxyl group and a C1-C12 alkoxy group, provided that all of P1, P2 and P3 are not simultaneously phenyl groups which may be substituted, Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, and R represents a group represented by the formula: wherein A1 represents —OH or —Y1—OH, n represents an integer of 1 to 9, and Y1 represents a divalent C1-C6 saturated aliphatic hydrocarbon group; a group represented by the formula: wherein ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which one —CH2— group is substituted with —CO—, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; a group represented by the formula: wherein ring X2 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom of one —CH2— group is substituted with a hydroxyl group, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group; a group represented by the formula: wherein ring X3 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which one —CH2— group is substituted with —COO—, and at least one hydrogen atom in the monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and m represents an integer of 0 to 12; or a group represented by the formula: wherein ring X4 represents a C6-C30 polycyclic hydrocarbon group having tricycle or more, and at least one hydrogen atom in the polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group or a cyano group, and l represents an integer of 1 to 12. The present invention further provides a chemically amplified resist composition comprising the salt represented by the above-mentioned formula (I).

The para-toluenesulfonyl (Tos) protecting group is removed efficiently and quickly under neutral conditions from the corresponding protected primary and secondary amines using mischmetal in moderate to excellent yields.

(Chemical Equation Presented) N-Cl is no competition: Aryl halides were tolerated in an efficient ligandless CuCl-catalyzed electrophilic amination reaction of arylboronic acids with N-chloroamides (see scheme; Ac=acetoxy). This coupling proceeded smoothly at ambient temperature, and products were obtained with good to excellent yields.

The co-hydrogenation of acetonitrile and butyronitrile over Raney-Co was investigated in order to obtain insight into the mechanism underlying the formation of secondary amines. Acetonitrile was reduced much faster to the corresponding primary amine due to stronger adsorption on the catalyst surface. In parallel, dialkylimines were formed and subsequently converted to secondary amines. It is suggested that the dialkylimines are formed by reaction of partially hydrogenated intermediate species on the cobalt surface with amines. In this respect, n-butylamine was found to react much faster than ethylamine. The stronger inductive effect of the butyl chain is thought to facilitate nucleophilic attack of the amine at the α-C-atom of the surface species. By comparing the C2 and C4 balance for dialkylimines and dialkylamines, it was found that direct hydrogenation of the dialkylimine cannot be the only way of dialkylamine formation. Instead, it is suggested that alkyl group transfer occurs by reaction of a monoalkylamine with a dialkylimine and cross-transfer between two dialkylimines.

We demonstrate that secondary dialkylammonium salts can thread through the cavity of benzo-21-crown-7 to form [2]pseudorotaxanes with binding constants (527-1062 M-1 in acetone) higher than the corresponding values (135-261 M-1 in acetone) of the analogous complexes with their traditionally used host, dibenzo-24-crown-8. Based on this new benzo-21-crown-7/secondary dialkylammonium salt recognition motif, a [2]rotaxane was successfully prepared. The formation of these threaded structures was confirmed by proton NMR spectroscopy, electrospray ionization mass spectrometry, and X-ray single crystal analysis.

Amides can be hydrogenated to amines using a catalyst prepared in situ from [Ru(acac)3] and 1,1,1-tris(diphenylphosphinomethyl)ethane; water is required to stabilize the catalyst and primary amines can only be formed (selectivity up to 85%) if ammonia is also present. The Royal Society of Chemistry.

Nitriles are converted to primary amines with high selectivity using a newly developed alumina-supported rhodium catalyst. The high selectivity is obtained without any additives, which are often used to prevent the formation of higher amines. The catalyst is active under mild conditions In various solvents, which makes it specifically suitable for use in pharmaceutical applications or for other substrates that can react with additives like strong acids or bases.

Upon microwave irradiation in water, Pt/C converts primary amines into secondary amines in good yield via retro-reductive and reductive amination.

Retro-reductive animations, direct transformations of amines to ketones, were catalyzed by Pd/C in water under microwave irradiation. The Royal Society of Chemistry 2005.

A simple and convenient method for laboratory-scale reduction using Raney nickel is described. The reaction was achieved by the inclusion of sulfuric acid to a mixture of a substrate and Raney nickel. Using this method, several aryl bromides, benzyl alcohols, benzyl ethers, and benzylamines were cleaved at the carbon-bromine bond or at the benzylic position to afford corresponding hydrogenated products in good yields without the use of compressed hydrogen gas and without requiring any special apparatus.

The invention relates to novel cyclic and open-chain hydroxylamine esters and polymerizable compositions comprising these hydroxylamine esters and an ethylenically unsaturated monomer or oligomer. The invention also relates to use as polymerization initiators and to the use of known hydroxylamine esters selected from the group consisting of HALS compounds and the novel hydroxylamine esters for the controlled degradation of polypropylene and for achieving a controlled increase in the molecular weight of polyethylene.