61820-92-6

Upstream product

• 54079-72-0 N-(4-methoxybenzylidene)benzothiazol-2-amine 
• 86884-98-2 N-(4-methoxybenzyl)-N'-phenylthiourea 
• 136-95-8 2-amino-benzthiazole 
• 105-13-5 4-Methoxybenzyl alcohol 
• 615-20-3 2-chlorobenzo[d][1,3]thiazole 
• 2393-23-9 4-methoxy-benzylamine 
• 19350-72-2 N'-(4-methoxybenzylidene)-4-methylbenzenesulfonohydrazide 
• 123-11-5 4-methoxy-benzaldehyde 

Relevant academic research and scientific papers

Palladium(II) acetate as catalyst for the N-alkylation of aromatic amines, sulfonamides, and related nitrogenated compounds with alcohols by a hydrogen autotransfer process

Palladium(II) acetate is a versatile, inexpensive, and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, sulfonamides, and phosphazenes, using, in all cases, primary alcohols as the initial source of the electrophile, through a hydrogen autotransfer process. The regioselectivity of the benzothiazol-2-amine alkylation is contrary to that found using halogenated electrophiles.

Synthetic method for N-alkyl(benzo)thiazole

The invention provides a synthetic method for N-alkyl(benzo)thiazole. The synthetic method comprises the following steps: putting 0.4-0.8 mmol of a carbonyl compound, 0.4-0.8 mmol of p-toluenesulfonylhydrazide and 4-10 mL of a solvent in a flask and carrying out a reaction at 30 DEG C to 80 DEG C for 1 to 3 h; adding 0.4 mmol of 2-aminothiazole, 0.4-0.8 mmol of metal copper salt and 0.4-1.2 mmolof an alkali substance into the above reaction system, carrying out heating to 100 DEG C to 150 DEG C, and continuing the reaction for 2 h to 5 h; terminating the reaction to obtain a reaction productA; and subjecting the product A to purification and impurity separation so as to obtain pure N-alkyl(benzo)thiazole. According to the invention, the intermediate sulfonyl hydrazone is prepared from the carbonyl compound and sulfonyl hydrazide, and reacts with a 2-aminothiazole substance in the presence of a catalyst and under alkali conditions to obtain N-alkyl(benzo)thiazole. The synthetic method of the invention has the advantages of simple operation, low cost, high product yield and wide application range of a substrate. At the same time, the established method can also realize the synthesis of the anti-inflammatory drug fanetizole, and thus has high practical value.

Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1 H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol

The application of nontoxic, earth-abundant transition metals in place of costly noble metals is a paramount goal in catalysis and is especially interesting if the air- and moisture-stable ligand scaffold is used. Herein, we report the synthesis of amines/imines directly from alcohol and amines via hydrogen autotransfer or acceptorless dehydrogenation catalyzed by well-defined phosphine-free Mn complexes. Both imines and amines can be obtained from the same set of alcohols and amines using the same catalyst, only by tuning the reaction conditions. The amount and nature of the base are found to be a highly important aspect for the observed selectivity. Both the primary and secondary amines have been employed as substrates for the N-alkylation reaction. As a highlight, we showed the chemoselective synthesis of resveratrol derivatives. Furthermore, the Mn-catalyzed dehydrogenative synthesis of structurally important 2,3-dihydro-1H-perimidines has also been demonstrated. Density functional theory calculations were also carried out to model the reaction path and to calculate the reaction profile.

Copper-catalyzed one-pot coupling reactions of aldehydes (ketones), tosylhydrazide and 2-amino(benzo)thiazoles: An efficient strategy for the synthesis of N-alkylated (benzo)thiazoles

An efficient and practical C–N bond formation methodology for the synthesis of N-alkylated (benzo)thiazoles was developed, via the copper-catalyzed one-pot two-step reactions of 2-amino(benzo)thiazoles and aldehydes (ketones) with tosylhydrazide. This cross-coupling reaction proceeded smoothly and tolerated a broad range of functional groups (46 examples). A variety of functionalized N-alkylated (benzo)thiazoles were obtained in moderate to high yields. Notably, gram-scale synthesis of fanetizole (anti-inflammatory drug) was also realized through this protocol.

Method for synthesizing substituent miscellaneous aromatic amine through reaction between miscellaneous aromatic amine and amine

The invention discloses a method for synthesizing substituent miscellaneous aromatic amine through a reaction between miscellaneous aromatic amine and amine. Inorganic base serves as an accelerant. The miscellaneous aromatic amine and the amine are directly subjected to the de-ammonia gas alkylation reaction, N-substituent miscellaneous aromatic amine ramifications are obtained, the reaction temperature ranges from 130 DEG C to 200 DEG C, the reaction time ranges from 24 hours to 48 hours, and the by-product is ammonia gas. According to the technical scheme, the inorganic base serves as the accelerant, the amine low in price and easy to get serves as an alkylation reagent, under the solvent-free conditions of nitrogen protection and sealing, the miscellaneous aromatic amine and the amine are subjected to the de-ammonia gas N-alkylation reaction, and the N-substituent miscellaneous aromatic amine ramifications can be obtained through direct synthesizing. The reaction method is direct, conditions are simple, operation is easy, the by-product is ammonia gas, less pollution is caused, and the ammonia gas can be recycled.

An aerobic oxidative coupling approach for the synthesis of N-substituted 2-aminobenzothiazole derivatives using iron catalyst

A facile and convenient method was developed for the formation of novel N substituted 2-aminobenzothiazoles via an iron-catalysed condensation of 2-aminobenzothizole with different amines. This method is applicable for a wide range of aliphatic, aromatic and heterocyclic amines furnishing moderate yields of the corresponding products and thus rendering the methodology as a highly eco-friendly, inexpensive alternative to the existing methods.

Ruthenium(II) complexes containing a phosphine-functionalized thiosemicarbazone ligand: Synthesis, structures and catalytic C-N bond formation reactions via N-alkylation

A series of ruthenium(II) complexes incorporating a thiosemicarbazone chelate tethered with a diphenylphosphine pendant have been studied. Thus, [(PNS-Et)RuCl(CO)(PPh3)] (1), [N,S-(PNS-Et)RuH(CO)(PPh3)2] (2) and [(PNS-Et)RuCl(PPh3)] (3) were synthesized by reactions of various RuII precursors with 2-(2-(diphenylphosphino)benzylidene)-N-ethylthiosemicarbazone (PNS-Et). However, complexation of PNS-Et with an equimolar amount of [RuCl2(dmso)4] resulted in two different entities [(PNS-Et)RuCl(dmso)2] (4) and [(PNS-Et)2Ru] (5) with different structural features in a single reaction. All the RuII complexes have been characterized by analytical and various spectroscopic techniques. Compounds 1-5 were recrystallized, and the X-ray crystal structures have been reported for 1, 2 and 5. In the complexes 1 and 3-5 the ligand coordinated in a tridentate monobasic fashion by forming PNS five- and six-membered rings, whereas in 2, the ligand coordinated in a bidentate monobasic fashion by forming a strained NS four-membered ring. Furthermore, compounds 1-5 showed catalytic activity in N-alkylation of heteroaromatic amines. Notably, complexes 1-3 were found to be very efficient catalysts toward N-alkylation of a wide range of heterocyclic amines with alcohols. In the presence of a catalytic amount of 2 with 50 mol% of KOH, N1,C5-dialkylation of 4-phenylthiazol-2-amine has been investigated. Reaction of in situ generated aldehyde with amine yields the N1,C5-dialkylated products through the hydride ion transformation from alcohol. Complexes 1-3 also catalyzed a variety of coupling reactions of benzyl alcohols and sulfonamides, which were realized often with 99% isolated yields. Advantageously, only one equivalent of the primary alcohol was consumed in the process.

Structure-dependent tautomerization induced catalyst-free autocatalyzed N-alkylation of heteroaryl amines with alcohols

Catalyst-free autocatalyzed dehydrative N-alkylation reactions of 2-aminobenzothiazoles, 2-aminopyrimidines, and 2-aminopyrazine with primary and secondary alcohols have been achieved for efficient, practical, and green synthesis of the versatile heteroaryl amine derivatives. These reactions were interestingly induced by structure-dependent tautomeric equilibria of the heteroaryl amines via MPV-O transfer hydrogenation of the imino tautomers by alcohols to give aldehydes as the key initiating step.

Efficient and versatile catalysis of N-alkylation of heterocyclic amines with alcohols and one-pot synthesis of 2-aryl substituted benzazoles with newly designed ruthenium(ii) complexes of PNS thiosemicarbazones

Ruthenium(ii) carbonyl complexes with phosphine-functionalized PNS type thiosemicarbazone ligands [RuCl(CO)(EPh3)(L)] (1-6) (E = P or As, L = 2-(2-(diphenylphosphino)benzylidene) thiosemicarbazone (PNS-H), 2-(2-(diphenylphosphino)benzylidene)-N-methylthiosemicarbazone (PNS-Me), 2-(2-(diphenylphosphino)benzylidene)-N-phenylthiosemicarbazone (PNS-Ph)) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-Vis, 1H, 13C, 31P-NMR) as well as ESI mass spectrometry. The molecular structures of complexes 1, 2 and 6 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that all the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate PNS fashion. All the ruthenium complexes (1-6) were tested as catalyst for N-alkylation of heteroaromatic amines with alcohols. Notably, complex 2 was found to be a very efficient and versatile catalyst towards N-alkylation of a wide range of heterocyclic amines with alcohols. Complex 2 can also catalyze the direct amination of 2-nitropyridine with benzyl alcohol to the corresponding secondary amine. Furthermore, a preliminary examination of performance for N,N-dialkylation of diamine showed promising results, giving good conversion and high selectivity. In addition, N-alkylation of ortho-substituted anilines (-NH2, -OH and -SH) led to the one-pot synthesis of 2-aryl substituted benzimidazoles, benzoxazoles and benzothiazoles, also revealing the catalytic activity of complex 2. This journal is the Partner Organisations 2014.

Convenient and reliable routes towards 2-aminothiazoles: Palladium-catalyzed versus copper-catalyzed aminations of halothiazoles

Two efficient methods for the amination of 2-halothiazoles are presented here. A first protocol requires a Pd/L system. Several 2-aminothiazoles were synthesized under optimized conditions and isolated in good yields. The first palladium-catalyzed C-N coupling reactions between 2-halothiazoles and primary alkylamines are presented. In a second part, ligand-free copper-catalyzed aminations of 2-halothiazoles by alkylamines and aniline in a green solvent have been developed. The protocol is very effective for primary and secondary amines and perfectly tolerates the presence of another halide moiety on the 2-halothiazole. The reaction occurs under the assistance of microwave irradiation, which drastically decreases the reaction time. The reaction leads to the formation of 2-aminothiazoles, key molecules in pharmaceutical research. Copyright