Reaction Of Benzonitrile Research Articles

Dinuclear Zn(II) complexes with Schiff base ligands derived from 4-aminoantipyrine; crystal structure and catalytic activity in the synthesis of tetrazoles

Two new phenolato bridged dinucelar Zn(II) complexes, [Zn2(L1)2(N3)2] (1) and [Zn2(L2)2(N3)2] (2), were synthesized where HL1 and HL2 are tridentate Schiff base ligands obtained from the reaction of 4-aminoantipyrine with 5-bromo-2-hydroxybenzaldehyde and 2-hydroxybenzaldehyde, respectively. The ligands and complexes were characterized by elemental analysis and spectroscopic methods. Crystal structures of complexes 1 and 2 were determined by X-ray analysis which revealed the Zn(II) ions in both of these neutral dinuclear complexes are five coordinated and have distorted square pyramidal geometry. The equatorial plane of this geometry is filled by ONO-donor atoms of the ligands and the axial position is filled by azide co-ligand. Intermolecular interactions in the crystal structure of 1 and 2 were studied by Hirshfeld surface analysis. Due to the presence of azide ligand in the structure of these complexes, they were used as catalysts in the synthesis of 5-phenyl-1H-tetrazole from the reaction of benzonitrile and sodium azide. The results indicated that complexes 1 and 2 are active catalysts for the synthesis of tetrazoles from nitrile and azide cycloaddition reaction.

Reduced Arene Complexes of Hafnium Supported by a Triamidoamine Ligand.

A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy‐N3N)(arene)] (Xy‐N3N={(3,5‐Me2C6H3)NCH2CH2}3N3−, L=THF, 18‐crown‐6; arene=C10H8 2−, C14H10 2−) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy‐N3N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert‐butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2−) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2−) complex led to the selective protonation of the corresponding dianionic ligand.

Possible B-C bonding in the hydroboration of benzonitrile by an external electric field.

Generally, the hydroboration of benzonitrile produces B-N containing compounds. However, an unprecedented B-C bond may be formed in the presence of a suitable external electric field (EEF). In reactions of benzonitrile with borane, when the EEF is oriented parallel to the positive direction (N → C) of the N[triple bond, length as m-dash]C bond, the barriers to Markovnikov hydroboration are decreased gradually, meaning the pathway for generating B-C bonds becomes more favorable. Accordingly, hydroboration could be influenced and its selectivity could be controlled by changing the magnitude and direction of an applied EEF.

ChemInform Abstract: The Direct Synthesis of N‐Alkylated Amides via a Tandem Hydration/N‐Alkylation Reaction from Nitriles, Aldoximes and Alcohols.

AbstractThe iridium‐catalyzed reaction of benzonitrile (I) with n‐butylaldoxime followed by an addition of alcohol (III) and a base to the crude reaction mixture affords benzamides (IV) in high yields.

Reaction of Olefins with Nitriles under Solvent-Free Conditions Using Molecular Iodine as a Catalyst in the Presence of Water

The reaction of olefins with nitriles using iodine as a catalyst under solvent-free conditions was investigated. The reaction of cycloolefins, such as cyclopentene and cyclohexene, with benzonitrile using iodine as a catalyst produced both amide and heterocyclic compounds. The reaction of chiral (+)-camphene with benzonitrile produced racemic (±)-N-isobornylbenzamide (N-((1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)benzamide). This indicated that skeletal rearrangement of camphene as well as amidation occurred. The optimized conditions were determined to be as follows: temperature, 90°C; molar ratio of nitrile:alcohol:iodine:water, 1:5:0.2:1.0; and reaction time, 18 h. The yield was 87% under these conditions. The reaction of (+)-camphene also proceeded with the other aromatic and aliphatic nitriles to produce racemic isobornylamides. However, except for styrene, complex reactions occurred in the reactions of benzonitrile with other terpenic olefins.

Transformation of benzonitrile into benzyl alcohol and benzoate esters in supercritical alcohols

Abstract The reactions of benzonitrile in supercritical methanol, ethanol, and 2-propanol were investigated under non-catalytic conditions. In supercritical methanol, benzonitrile was converted to methyl benzoate in high yield. The esterification reaction also occurred in supercritical ethanol to afford ethyl benzoate in moderate yield. The esterification could occur via a route analogous to the Pinner reaction. On the other hand, benzonitrile in supercritical 2-propanol yielded no ester. Benzyl alcohol was the major product in supercritical 2-propanol. We investigated the reaction of the C N bond in supercritical 2-propanol. In supercritical 2-propanol, N -benzylideneaniline was transferred to the reduction product ( N -benzylaniline) and hydrolysis products (benzyl alcohol and aniline). The hydrolysis reaction was restricted when the reaction was carried out in supercritical 2-propanol with a low water content. This indicates that the water in the 2-propanol acts as a reagent for the hydrolysis of the C N bond. These results suggested the following reaction process: C 6 H 5 C N→C 6 H 5 CH NH→C 6 H 5 CHO→C 6 H 5 CH 2 OH.

Reactions of benzonitrile with diiodides of neodymium, dysprosium, and thulium

The reactions of LnI2 (Ln = Nd, Dy, Tm) with benzonitrile are accompanied by disproportionation, resulting in the formation of triiodides LnI3(PhCN)4 and an intractable mixture of monoiodine derivatives LnI(R)R". Hydrolysis of the mixture gives 2,4,6-triphenyl-1,3,5-tiazine, 2,3,5,6-thetraphenyl-1,4-pyrazine, and 2,4,5-triphenylimidazole. The reaction of dysprosium diiodide with acrylonitrile gives a metal-containing polymer with a molecular weight of 2700. Treatment of the polymer with water results in separation of DyI2(OH)(H2O) x to give metal-free polyacrylonitrile with a molecular weight of 2400.

D2 Complexes of tungsten containing p-toluonitrile as a four- or two-electron donor and oxidative addition giving the two-electron donor acylimido ligand NCOC6H4Me-4

A. J. Nielson, P. A. Hunt, C. E. F. Rickard and P. Schwerdtfeger, J. Chem. Soc., Dalton Trans., 1997, 3311 DOI: 10.1039/A702839C

Reactions of benzene derivatives containing C≡N and C≡CH groups with atomic chromium

Reactions of benzonitrile and phenylacetylene with atomic chromium were studied. Products of the trimerization and polymerization of the initial aromatic compounds form in considerable amounts along with bisarenechromium complexes. Mechanisms of the reactions were suggested. The possibility of increasing the yields of the bisarenechromium complexes was considered.

Die Kristallstruktur des Lithium-Benzamidinats {Li3[C6H5 - C(NSiMe3)2]3 · NC - C6H5} / The Crystal Structure of the Lithium Phenylamidinate {Li3[C6H5 - C(NSiMe3)2]3 · NC - C6H5}

Abstract Single crystals of the title compound have been prepared by the reaction of benzonitrile with LiN-(SiMe3)2 in hexane and subsequent evaporation of the solvent. Space group P21/n, Z = 4, structure solution with 7945 observed unique reflections. R = 0.052. Lattice dimensions at -70 °C: a = 1485.2(9); b = 2486.9(11); c = 1568.9(8) pm; β = 91.06(4)°. The compound forms a trimeric ion ensemble in which two of the lithium cations are coordinated by three nitrogen atoms of two phenylamidinate an ions, the other one by four nitrogen atoms of two chelating phenylaminidate anions and in addition by the nitrogen atom of a benzonitrile molecule.

ChemInform Abstract: Reaction of Benzonitrile N‐(p‐Nitrophenyl)imide with 5‐Substituted Tetrazoles: A New Route to Substituted 1,2,4‐Triazoles via N‐Hydrazonoyltetrazoles.

AbstractThe reaction of the tetrazoles (I) with benzonitrile N‐(p‐nitrophenyl)imide (generated in situ from the hydrazonoyl bromide (II)) gives rise to the regioisomeric hydrazonoyltetrazoles (III) and (IV).

Reaction of benzonitrile N-(p-nitrophenyl)imide with 5-substituted tetrazoles: a new route to substituted 1,2,4-triazoles via N-hydrazonoyltetrazoles

A wide range of phenyl 5-R-substituted (R = aryl, alkyl, amino, halo, H) 1- and 2-hydrazonoyltetrazoles has been synthesized. Substituent effects on the orientation of nitrite imide attack on 5-aryltetrazoles are reported. Thermolysis and fragmentation of the resulting hydrazonoyltetrazoles under different conditions gave high yields of a range of substituted 1,2,4-triazoles including aryl, alkyl, amino and azido derivatives. Interesting substituent effects including steric blocking of triazole formation from 5-aryltetrazoles by di-ortho-substitution of the 5-aryl ring are also noted.

Tetrazoles. 21. Reaction of benzonitrile with salts of hydrazoic acid

The reaction of benzonitrile with the ammonium, alkyl-, dialkyl-, and trialkylammonium salts of hydrazoic acid in DMF at 100‡C produces 5-phenyltetrazole. The yield of 5-phenyltetrazole is practically independent of the structure of the ammonium cation. Under the same conditions, the tetraalkylammonium salts of hydrazoic acid do not react with benzonitrile. It was proposed that the formation of 5-substituted tetrazoles from nitriles and the salts of hydrazoic acid proceeds by the mechanism of 1,3-dipolar cycloaddition.

Interaction of chromium vapour with benzonitrile and bromobenzene

Bis(benzonitrile)chromium was isolated from the reaction of benzonitrile with chromium vapour. The major process was accompanied by cyclotrimerization of benzonitrile to form 2,4,6-triphenyltriazine. Phenyl bromide reacted with chromium to give insignificant amounts of cationic bis(arene)chromium compounds containing bromobenzene, diphenyl and benzene as ligands.

The reactions of tetraalkylaluminoxanes with benzonitrile

The reactions of benzonitrile with tetraethylaluminoxane and with tetramethylaluminoxane in 1 : 1 molar ratio were studied. In the case of tetraethylaluminoxane 1,3,5-triphenyl-2,4-diaza-1-aminoheptadiene-1,4, Ph(Et)HCNC(Ph)NC(Ph)NH 2, was found to be the main product after hydrolysis, 1,3-dipheny-2-aza-1-aminopentene-1, Ph(Et)HCNC(Ph)NH 2,2,4,6-triphenylazine-1,3,5; 5-methyl-2,4,6-triphenylpyrimidine, propiophenone and benzaldehyde were also formed. A reaction scheme is proposed. In the case of Me 4Al 2O, acetophenone was formed as the main product after hydrolysis.

Reactions of benzonitrile with lithium amides

Reactions of benzonitrile with lithium amides

Catalytic Role of some Sulfur Compounds in the Reaction of Benzonitrile with Hydrazine Hydrate

The reacton of nitriles with hydrazine hydrate in the presence of sulfer compounds offers a convenient synthetic method of 3, 6-disubstituted-1, 2-dihydro-s-tetrazines. Sulfur, mercaptans, disulfides and polysulfides are effective catalysts for the reaction at temperatures in the range of about 20° to 80°C. Mercaptoacetic acid and mercaptoethanol were the most effective catalysts among them. Their catalytic ro1e is discussed in terms of neighboring group participation.The additions of large amounts of amines in the reaction mixture of benzonitrle, hydrazine hydrate and mercaptoacetic acid did not affect the yield of the product, but, when sodium hydroxide was added, none of the products was formed.On the basis of these observatlons, a mechanism of the reaction and also the catalytic role of some sulfur compounds were discussed.

ベンゾニトリルと2,3-ジメチルブタジエンとの光化学反応

ベンゾニトリルと2,3-ジメチルブタジエンとの光化学反応