Poly(N-bromobenzene-1,3-disulfonamide) and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide as novel catalytic reagents for silylation of alcohols, phenols, and thiols using hexamethyldisilazane

Poly(N-bromobenzene-1,3-disulfonamide) [PBBS] and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide [TBBDA] are effective catalysts for the silylation of alcohols, phenols, and thiols in the presence of hexamethyldisilazane with, or without solvent, and also under microwave irradiation.     

Poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide), N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide and novel poly(N,N′-dibromo-N-phenylbenzene-1,3-disulfonamide) as powerful reagents for benzylic bromination

N,N,N′,N′-Tetrabromobenzene-1,3-disulfonamide [TBBDA], poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS], and novel poly(N,N′-dibromo-N-phenylbenzene-1,3-disulfonamide) [PBPS] can be used for bromination of benzylic positions in solvent.     

Poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide), N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide as new reagents for conjugate addition of indole, pyrrole with α,β-unsaturated ketones

Poly(N,N??-dibromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS] and N,N,N??,N??-tetrabromobenzene-1,3-disulfonamide[TBBDA] were used as efficient reagents for conjugate addition of indole and pyrrole with ??,??-unsaturated ketones and also, double-conjugate 1,4-addition of indoles to dibenzylidenacetones.     

Highly efficient one-pot synthesis of tetrahydropyridines

The combination of aromatic aldehydes, and 1,3-dicarbonyl compounds in the presence of a catalytic amount of poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS] and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide [TBBDA] leads to the formation of highly substituted tetrahydropyridines. In this way, a series of pharmacologically interesting substituted piperidine derivatives were obtained in moderate to high yields at room temperature.     

One-pot synthesis of 2-amino-3-cyanopyridine derivatives under solvent-free conditions

A series of 2-amino-3-cyanopyridines were obtained from aryl aldehydes, substituted acetophenones, malononitrile and ammonium acetate in good to excellent yields by proceeding through a simple, mild and efficient procedure utilizing N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide [TBBDA] and poly(N-bromo-N-ethylbenzene-1,3-disulfonamide) [PBBS] as catalysts.     

A novel method for the reduction of sulfoxides with the N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide (TBBDA)/PPh3 system

A new method is described for the reduction of sulfoxides to sulfides using N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide [TBBDA] in combination with triphenylphosphine. Good to excellent yields, short reaction times, high efficiency and facile isolation of the desired products are the advantages of this method.     

One-pot synthesis of aliphatic and aromatic 2H-indazolo[2,1-b]phthalazine-triones catalyzed by N-halosulfonamides under solvent-free conditions

N, N, N′, N′-Tetrabromobenzene-1,3-disulfonamide and poly(N-bromo-N-ethylbenzene-1,3-disulfonamide) were used as efficient catalysts for the one-pot synthesis of aliphatic and aromatic 2H-indazolo[2,1-b]phthalazine-triones in excellent yields from aldehydes, phthalhydrazide, and dimedone at 80-100 °C under solvent-free conditions.     

On the oxidative coupling of N,N-disubstituted 2-aminothiophenes—synthesis of N,N′-persubstituted 5,5′-diamino-2,2′-bithiophenes

The oxidative coupling of N,N-disubstituted 2-aminothiophenes performed by several heavy-metal free oxidizing agents gives rise to the formation of N,N′-persubstituted 5,5′-diamino-2,2′-bithiophenes which are of interest as hole-transport materials for optoelectronic applications.     

Poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) and N,N,N′,N′- tetrabromobenzene-1,3-disulfonamide as effective catalysts for conversion of aldehydes to 1,1-diacetates and acetals

Poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS] and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide [TBBDA] are effective catalysts for easy preparation of 1,1-diacetates from aldehydes and acetic anhydride, and for easy preparation of acetals using diols under microwave irradiation in the presence of SiO₂.     

Solid-state synthesis of novel 3-substituted indoles

Poly(N-bromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS] and N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide [TBBDA] were used as efficient catalysts for the one-pot synthesis of 3-substituted indoles in good to high yields from indole, aldehydes, and arylamines under solid-state conditions at room temperature.     

Ni-catalyzed arylation of bromomagnesium diarylamides with aryl N,N-dimethylsulfamates

The combination use of Ni(cod)₂ and N,N-1,3-bis(2,6-diisopropylphenyl)-4-imidazoline-2-ylidene as a catalyst successfully gave unsymmetrical N,N-diaryl-N′,N′-diphenyl-1,1′-biphenyl-4,4′-diamines through the arylation of bromomagnesium diarylamide with 1-(4′-diphenylamino-1,1′-biphenylyl) N,N-dimethylsulfamate. This Ni catalyst and Grignard reagents of diaryl or monoarylamides were also useful in the syntheses of various triarylamines and diarylamines from corresponding aryl N,N-dimethylsulfamates.     

1,n-Diamines. Part 3: Microwave-assisted synthesis of N-acyl-N′-arylhexahydropyrimidines and hexahydro-1,3-diazepines

In this Letter we present a method for the synthesis of N-acyl-N′-arylhexahydropyrimidines 1, by ring closure of N-acyl-N′-aryl-1,3-propanediamines 3 with formaldehyde. Cyclodehydrations were performed in aqueous medium under microwave irradiation, and led to high yields of the desired compounds in remarkably short reaction times. The method also allowed for the synthesis of hitherto unreported N-acyl-N′-arylhexahydro-1,3-diazepines 2. The acyclic tetramethylenic precursors 4 were synthesized by selective functionalization of N-arylputrescines.     

Poly(N-bromo-N-ethyl-benzene-1,3-disulfonamide), N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide as new efficient reagents for conversion of alcohols to THP ethers and aldehydes to oxazoline compounds

This paper is concerned with an easy preparation of THP ethers from primary, secondary and tertiary alcohols and oxazoline compounds from various aldehydes using poly(N-bromo-N-ethyl-benzene-1,3-disulfonamide), N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide [TBBDA] as new and efficient reagents under ambient conditions without over-oxidation.     

Mild and regioselective iodination of aromatic compounds with N,N′-diiodo-N,N′-1,2-ethanediylbis(p-toluenesulphonamide)

N,N′-Diiodo-N,N′-1,2-ethanediylbis(p-tolouenesulphonamide) [NIBTS] and catalytic trifluoroacetic acid can be used for the regioselective iodination of aromatic compounds in acetonitrile under mild conditions in excellent yields.     

Crystal structure and conformation of N,N′-bis (3,5-dichlorosalicylidene)-2-hydroxy 1,3 diamino-2-propan

N,N′-bis(3,5-dichlorosalicylidene)-2-hydroxy-1,3-diamino-2-propan (C₁₇H₁₄Cl₄N₂O₃) was synthesized and its crystal structure determined. It crystallizes in the monoclinic space group, C2/c, with a=29.734(8), b=4.541(1), c=14.694(2) Å, β=115.85(2), R(F²)=0.048 for 1704 independent reflections. The title compound has a twofold axis passing through the central C9 atom. The intramolecular hydrogen bond occurs between the pairs of atoms N1 and O1 [2.648(5) Å] and the hydrogen atom is essentially being bonded to the nitrogen atom. There is no intermolecular proximity between molecules. Conformations of the title compound were investigated by semi-empirical quantum mechanical AM1 calculations. The optimized geometry of the molecular structure corresponding to the non-planar conformation is the most stable conformation in the theoretical calculations. The results strongly indicate that the minimum energy conformation is primarily determined by non-bonded steric interactions.     

Synthesis and properties of N,N,N′,N′-tetrasubstituted 1,3-bis(5-aminothien-2-yl)azulenes and their application as a hole-injecting material in organic light-emitting devices

Two title compounds, N,N,N′,N′-tetraphenyl-1,3-bis(5-aminothien-2-yl)azulene (3a) and 1,3-bis{5-(9-carbazolyl)thien-2-yl}azulene (3b), were synthesized from 1,3-di(2-thienyl)azulene (4) by a two-step sequence involving bromination and subsequent Pd-catalyzed amination. These compounds were characterized by spectroscopic analyses and the structure of 3a was determined by X-ray crystallographic analysis. Their HOMO energy levels were estimated using their electrochemical oxidation potentials, and these compounds were used as a hole-injecting material in organic light-emitting devices. The device with 3a showed greater durability than that with copper phthalocyanine.     

Poly(N,N′-dichloro-N-ethyl-benzene-1,3-disulfonamide, N,N,N′,N′-tetrachlorobenzene-1,3-disulfonamide, poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide, and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide catalyzed formylation of amines and alcohols using ethyl formate under microwave irradiation

A simple, rapid, and efficient procedure for formylation of primary and secondary amines and alcohols using ethyl formate catalyzed with poly(N,N′-dichloro-N-ethyl-benzene-1,3-disulfonamide (PCBS), N,N,N′,N′-tetrachlorobenzene-1,3-disulfonamide (TCBDA), poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide (PBBS) and also N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide (TBBDA) was adopted. The reactions were performed under microwave irradiation with high yields.     

Novel dinuclear and polynuclear copper(II)-pyrazine-2,3-dicarboxylate supramolecular complexes with 1,3-propanediamine, N,N,N′,N′-tetramethylethylenediamine and 2,2′-bipyridine

Three novel Cu(II)-pyrazine-2,3-dicarboxylate complexes with 1,3-propanediamine (pen), [Cu₂(μ-pzdc)₂(pen)₂] · 2H₂O (1), N,N,N′,N′-tetramethylethylenediamine (tmen), {[Cu(μ-pzdc)(tmen)] · H₂O}_n(2), and 2,2′-bipyridine (bipy), {[Cu(μ-pzdc)(bipy)]·H₂O}_n(3) have been synthesized and characterized by means of elemental and thermal analyses, magnetic susceptibilities, IR and UV/vis spectroscopic studies. The molecular structures of dinuclear (1) and polynuclear (2 and 3) complexes have been determined by the single crystal X-ray diffraction technique. The pyrazine-2,3-dicarboxylate acts as a bridging ligand through oxygen atom of carboxylate group and N atom of pyrazine ring and one oxygen atom of neighboring carboxylate. It links the Cu(II) ions to generate a distorted square pyramidal geometry forming a one-dimensional (1D) chain. Adjacent chains of 1 and 2 are then mutually linked via hydrogen bonding interactions, which are further assembled to form a two and three-dimensional network, respectively. The chains of complex 3 are further constructed to form three-dimensional framework by hydrogen bonding, C–H?π and ring?ring stacking interactions. In the complexes, Cu(II) ions have distorted square pyramidal geometry. Thermal analyses properties and thermal decomposition mechanism of complexes have been investigated by using thermal analyses techniques (TG, DTG and DTA).     

Synthesis of B-trisubstituted borazines via the rhodium-catalyzed hydroboration of alkenes with N,N′,N″-trimethyl or N,N′,N″-triethylborazine

Hydroboration of terminal and internal alkenes with N,N′,N″-trimethyl- and N,N′,N″-triethylborazine was carried out at 50 °C in the presence of a rhodium(I) catalyst. Addition of dppb or DPEphos (1 equiv.) to RhH(CO)(PPh₃)₃ gave the best catalyst for hydroboration of ethylene at 50 °C, resulting in a quantitative yield of B,B′,B″-triethyl-N,N′,N″-trimethylborazine. On the other hand, a complex prepared from (t-Bu)₃P (4 equiv.) and [Rh(coe)₂Cl]₂ gave the best yield for hydroboration of terminal or internal alkenes.     

Pyrazolo[2′,3′:3,4][1,3]oxazino[5,6-b]quinoxaline, a novel tetracyclic ring system

Reaction of 2-chloro-3-(3-chloro-1H-pyrazol-5-yl)quinoxaline and aldehydes does not afford the corresponding N-(α-hydroxyalkylated) derivatives but results in a cyclisation reaction to give a derivative bearing the hitherto undescribed pyrazolo[2′,3′:3,4][1,3]oxazino[5,6-b]quinoxaline system.