Direct amination of pyrimidin-2-yl tosylates with aqueous ammonia under metal-free and mild conditions

Ametal-free synthesis of pyrimidine functionalized primary amines via direct amination of pyrimidin-2-yl tosylate with aqueous ammonia has been developed under mild conditions. The desired products pyrimidin-2-amines can be generated in excellent yields in PEG-400, without any catalysts or other additives.     

Direct aromatic-ring amination by aqueous ammonia with a platinum loaded titanium oxide photocatalyst

Active species generated from aqueous ammonia with a platinum-loaded titanium oxide photocatalyst can selectively aminate the aromatic ring of benzene and some substituted benzenes.     

Reductive amination of 2, 2′-methylenebiscyclohexanone and its analogs with potassium borohydride and ammonia (or amines)

Treatment of 2, 2-methylenebiscyclohexanone and its analogs with potassium borohydride and ammonia or amines gives perhydroacridines. The reaction is stereospecific.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1236–1238, September, 1970.     

Direct amination of ceramidonines

Direct amination of ceramidonine, 2-methylceramidonine, and 2-methyl-7-chloroceramidonine is investigated. It is shown that aromatic amines react with ceramidonines at 120°–150° C, to give 6- and 8-arylaminoceramidonines, the amino group entering preferentially at position 6. Strongly basic amines, (cyclohexylamine, methylamine) react with 2-methylceramidonines under mild conditions, giving mainly 8 -aminoceramidonines.The nomenclature used is that of the Ring Index, Patterson and Capell, 1960.     

Enantioselective iridium-catalyzed allylic amination of ammonia and convenient ammonia surrogates

Iridium-catalyzed, asymmetric allylation of ammonia as a nucleophile occurs with stereoselectivity to form a symmetric diallylamine, and related allylation of the inexpensive ammonia equivalent potassium trifluoroacetamide or the highly reactive ammonia equivalent lithium di-tert-butyliminodicarboxylate forms a range of conveniently protected, primary, alpha-branched allylic amines in high yields, high branched-to-linear regioselectivities, and high enantiomeric excess. The reactions of ammonia equivalents were conducted with a catalyst generated from a phosphoramidite containing a single stereochemical element.     

Redox-photosensitized amination of alkenes and alkadienes with ammonia and alkylamines

Using 1,2,4-triphenylbenzene as a photosensitizer, the photoamination of alkenes and alkadienes (1), which had no absorption at >300 nm proceeded efficiently in the presence of p-dicyanobenzene to give addition products by incorporating both amino and p-cyanophenyl groups. The reaction efficiency was discussed in terms of the relationships between 1 and the photosensitizer in their oxidation potentials and the distribution of positive charge on the reaction site of the cation radical of 1 (1⁺).     

Direct amination of 3-phenothiazone

3-Phenothiazone reacts with primary and secondary aliphatic and aromatic amines to give 2- and 7-monoamino derivatives. Replacement of the bridge oxygen atom of 3-phenoxazinone by a sulfur atom leads to an increase in the reactivity of the 7 position and to a bathochromic shift of the long-wave absorption band in the electronic spectrum.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 353–357, March, 1975.     

Nucleophilic substitution reactions of 1-methyl-4,5-dinitroimidazole with aqueous ammonia or sodium azide

Chemistry of Heterocyclic Compounds - In this work, 5-amino-1-methyl-4-nitroimidazole was synthesized by amination reaction of 1-methyl-4,5-dinitroimidazole with aqueous ammonia in 95% yield....     

Direct amination of naphthopurpurin and mompain,sea urchin pigments,and their O-methyl ethers by the reaction with ammonia

Russian Chemical Bulletin - The regiochemistry of direct amination of 2-hydroxynaphthazarin (naphthopurpurin) and 2,7-dihydroxynaphthazarin (mompain), sea urchin pigments, and their O-methyl ethers...     

Reductive amination of 1,6-hexanediol with Ru/Al_2O_3 catalyst in supercritical ammonia

Hexamethylenediamine(HMDA) is an important reagent for the synthesis of Nylon-6,6, and it is usually produced by the hydrogenation of adiponitrile using a toxic reagent of hydrocyanic acid. Herein, we developed an environmental friendly route to produce HMDA via catalytic reductive amination of 1,6-hexanediol(HDO) in the presence of hydrogen. The activities of several heterogeneous metal catalysts such as supported Ni, Co, Ru, Pt, Pd catalysts were screened for the present reaction in supercritical ammonia without any additives. Among the catalysts examined, Ru/Al_2O_3 presented a high catalytic activity and highest selectivity for the desired product of HMDA. The high performance of Ru/Al_2O_3 was discussed based on the Ru dispersion and the surface properties like the acid-basicity. In addition, the reaction parameters such as reaction temperature,time, H_2 and NH_3 pressure were examined, and the reaction processes were discussed in detail.     

Synthesis of primary amines: first homogeneously catalyzed reductive amination with ammonia

[reaction: see text] The synthesis of primary amines via reductive amination of the corresponding carbonyl compounds with aqueous ammonia is achieved for the first time with soluble transition metal complexes. Up to an 86% yield and a 97% selectivity for benzylamines were obtained in the case of various benzaldehydes by using a Rh-catalyst together with water-soluble phosphine and ammonium acetate. In the case of aliphatic aldehydes, a bimetallic catalyst based on Rh/Ir gave improved results.     

Copper-catalyzed amination of potassium aryl trifluoroborates using aqueous ammonia

The conversion of potassium aryl trifluoroborates containing different functionalities into the corresponding aryl amines using a catalytic amount of CuSO₄·5H₂O is described. The methodology uses water as a solvent under aerobic conditions to give the products in good yields.     

Direct amination of uracils and similar compounds

Conclusions A direct amination of uracils and similar compounds to aminopyrimidine derivatives was carried out using amides of phosphoric acid or phosphorous acid as animating agents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 655–662, March, 1969.The authors wish to thank L. A. Nikitina for the spectral investigations.     

Direct amination of benzene to aniline with several typical vanadium complexes

The liquid-phase direct catalytic amination of benzene to aniline was performed in acetic acid water solvent using a series of vanadium(Ⅲ,Ⅳ,Ⅴ)complexes with N,O-or O,O-ligands as catalysts and hydroxylamine hydrochloride as the aminating agent. The vanadium complexes exhibited much higher selectivity towards the production of aniline than NaVO_3 or VOSO_4.Under the optimized conditions,an aniline yield of 42.5%and a TON of 48 with a high selectivity of above 99.9%was obtained using 0.2 mmol of[VO(OAc)_2]...     

Synthesis of 7-methoxy-2-methyl-3,5,8-isoquinolinetrione

Synthesis of 7-methoxy-2-methyl-3,5,8-isoquinolinetrione from either 7- or 8-isoquinolinol is described. 3,5,8-Isoquinolinetrione is a novel heteroeyelic quinune which constitutes the aromatic carbon skeleton of mimosamycin.     

Ready synthesis of free N-H 2-arylindoles via the copper-catalyzed amination of 2-bromo-arylacetylenes with aqueous ammonia and sequential intramolecular cyclization

A wide range of free N-H 2-arylindoles were synthesised via the copper(II)-catalyzed amination of 2-bromo-arylacetylenes with aqueous ammonia and sequential intramolecular cyclization. The convenience and atom economy of aqueous ammonia, and the low cost of the copper catalytic system make this protocol readily superior in practical application.     

Direct amination of homoenolates catalyzed by N-heterocyclic carbenes

N-Heterocyclic carbenes derived from N-mesityl-N-methyltriazolium salts are effective catalysts for generating homoenolate species from alpha,beta-unsaturated aldehydes. The unique intermediate adds to the electrophilic nitrogen of 1-acyl-2-aryldiazenes, and the resulting activated carbonyl unit undergoes an intramolecular acylation event. This formal [3+2] cycloaddition between alpha,beta-unsaturated aldehydes and acylaryldiazenes, catalyzed by an N-heterocyclic carbene, produces substituted pyrazolidinones in good yields. This new NHC-catalyzed reaction accommodates aromatic and alkyl alpha,beta-unsaturated aldehydes and various aromatic diazenes. A chiral triazolium salt catalyzes the formation of the pyrazolidinone product in moderate yield and good enantioselectivity. The pyrazolidinones can undergo reductive N-N bond cleavage to give beta-amino acid derivatives.     

New ammonia equivalents for the Pd-catalyzed amination of aryl halides

[reaction: see text]. LiN(SiMe3)2, Ph3SiNH2, and LiNH2 can be be used as ammonia equivalents for the Pd-catalyzed coupling of aryl halides. Using these amine derivatives, simple anilines, including ortho-substituted ones, as well as di- and triarylamines can be readily prepared.