Reaction of primary amines with Pt/C catalyst in water under microwave irradiation: a convenient synthesis of secondary amines from primary amines

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

Efficient conversion of primary and secondary alcohols to primary amines

A convenient single-vessel conversion of primary and secondary alcohols to primary amines is reported. Use of this method results in substantially cleaner crude products than similar procedures reported in the literature. A simple work-up also makes this procedure ideal for parallel synthesis.     

Protection of primary and secondary amines in the hydroboration reaction

Trimethylsilyl groups are efficient to protect the NH bonds of olefinic amines in the hydroboration reaction with BMS; deprotection is easily run with methanol and affords aminoorganoboranes which can be used without any oxydation.     

Glycoconjugates of amines: alkylation of primary and secondary amines withN-chloroacetyl-β-glycopyranosylamines

Efficient monoalkylation of a series of primary and secondary amines was demonstrated with the use ofN-chloroacetylglycosylamines derived fromd-glucose,d-galactose,d-mannose,N-acetyl-d-glucosamine, and lactose. The reaction was shown to be useful for incorporation of carbohydrate residues into physiologically active compounds. Glycoconjugates of some derivatives of piperazine, 2-phenylethylamine, tryptamine, and important biogenic amines (norephedrine, octopamine, dopamine) were prepared. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 6, pp. 1244–1247, June, 1998.     

Aldehyde cruciforms: dosimeters for primary and secondary amines

We demonstrate that aldehyde-substituted donor-acceptor cruciforms [1,4-bis(arylethynyl)-2,5-distyrylbenzenes] are useful dosimeters for primary amines, primary diamines, and secondary amines. The 1,n-diamines are particularly reactive towards this dosimeter and can be detected in less than 100 ppm concentration. Using a single aldehyde-functionalized cruciform in seven different solvents allowed us to discern fourteen different amines by digital photography and statistical evaluation of the response patterns extracted as red, green, blue (RGB) values.     

N-arylation of primary and secondary aliphatic amines on solid supports

A general and mild method for the N-arylation of primary and secondary aliphatic amines is reported. Copper acetate, triethylamine mediated C/N cross-coupling reaction of arylboronic acids at room temperature to solid-supported primary and secondary amines gave good to excellent yields of the desired N-arylated products.     

Interaction of the diethylacetal of epoxybutyraldehyde with primary and secondary amines

Conclusions The reaction of the diethylacetal of trans-2-3-epoxybutyraldehyde with primary amines proceeds structurally and sterically selectively and leads to-hydroxy--amino compounds of the erythro series. Under the action of secondary amines, the reaction also proceeds structurally selectively; however, in the case of diethylarnine, a small amount of the corresponding threo-isomer could be isolated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1669–1671, September, 1966.     

Chemoselective organocatalytic aerobic oxidation of primary amines to secondary imines

Biomimetic aerobic oxidation of primary benzylic amines has been achieved by using a quinone catalyst. Excellent selectivity is observed for primary, unbranched benzylic amines relative to secondary/tertiary amines, branched benzylic amines, and aliphatic amines. The exquisite selectivity for benzylic amines enables oxidative self-sorting within dynamic mixtures of amines and imines to afford high yields of cross-coupled imine products.     

Iridium-catalyzed coupling of simple primary or secondary amines, aldehydes and trimethylsilylacetylene: preparation of propargylic amines

The coupling of amines, aldehydes and trimethylsilylacetylene was found to be promoted in the presence of a catalytic amount of [IrCl(cod)]2; 1 : 1 : 1 or 1 : 2 : 2 coupling products were obtained by allowing primary amine to react with aldehyde and trimethylsilylacetylene.     

Spectrophotometric determination of aliphatic primary and secondary amines by reaction with p-benzoquinone

A simple, sensitive and selective spectrophotometric method has been developed for determination of aliphatic primary and secondary amines. It is based on a reaction with excess of p-benzoquinone in ethanol whereby 1:1 (amine:quinone) coloured products are obtained, which have maximum absorption at 510 nm and E(1cm)(1%) in the range 400-650. The effect of solvent, temperature, concentration of quinone and the presence of water have been kinetically investigated by the initial rate method. The conditions for monitoring amine concentrations as low as 0.1 microg/ml are optimized in the light of the kinetic data. Results with an average recovery of 98.5% and mean standard deviation of 1.9% are obtained with 9 different amines without interference from tertiary amines, ammonia, amides, imides, anilides, hydrazines and alpha-amino-acids.     

Michael additions of primary and secondary amines to acrylonitrile catalyzed by lipases

The present Letter details our findings on the lipase-catalyzed Michael reactions between primary or secondary amines and acrylonitrile. Several lipases were evaluated, and good results were obtained leading to the formation of Michael adducts in shorter reaction times than the uncatalyzed reactions.     

Nucleophilicities of nitroalkyl anions

The kinetics of the reactions of eight nitroalkyl anions (nitronate anions) with benzhydrylium ions and quinone methides in DMSO and water were investigated photometrically. The second-order rate constants were found to follow a Ritchie constant selectivity relationship with slightly smaller selectivities than those observed previously for other carbanions and O or N nucleophiles. Evaluation of the kinetic data by the correlation equation log k (20 degrees C) = s(N + E) yields the nucleophilicity parameters (N), which allow a comparison of the nucleophilicities of nitronates with those of other classes of compounds. Although the aliphatic nitronates 1a-c are more nucleophilic than the aromatic representatives 1d-h in DMSO, hydration reduces the nucleophilicities of aliphatic nitronates by a factor of 1 million, which is considerably greater than the reduction of the reactivities of the aromatic nitronates with the consequence that aromatic nitronates are more nucleophilic in water than aliphatic ones. The nucleophilic reactivities of nitronates are only slightly affected by substituent variation in DMSO and even less so in aqueous solution, which is considered to be the reason for the unusual rate equilibrium relationships, the so-called nitroalkane anomaly. Outer-sphere electron transfer does not occur in any of the reactions that were investigated.     

Detection of primary and secondary amines in energy-related materials using an element-selective glow-discharge detector

Mutagenic primary polycyclic aromatic amines present in shale oil and synthetic crudes may be readily detected by a simple derivatization and Chromatographic procedure. Nitrogenous bases and amines are extracted from the sample with dilute mineral acid and derivatized with trifluoroacetic anhydride. The derivatized amines are separated by gas chromatography and specifically detected using a glow-discharge detector tuned to an emission wavelength of fluorine. Under these conditions, the aromatic nitrogenous bases, such as acridine, are not detected even though they are present in the sample. As little as 14 ng of fluorine, arising from the derivative of 33 ng of 2,4,6-trimethylaniline, can be detected. The selectivity of the glow-discharge detector for derivatized amines vs. nonderivatized aromatic nitrogenous bases was estimated to be a minimum of 200:1.