1197-19-9Relevant academic research and scientific papers
Synthesis of Triazidochlorosilane (TACS). A NovelSilicon Mediated one pot Conversion of Aldehyde to Nitriles
Elmorsy, Saad S.,El-Ahi, Abdel-Aziz S.,Soliman, Hanan,Amer, Fathy A.
, p. 2639 - 2640 (1995)
Synthesis, structure elucidation of triazidochlorosilane (TACS) and a novel conversion of aldehydes to nitriles in one pot reaction on treatment with TACS (SiCl4-NaN3 in Situ) reagent in acetonitrile are described.
Kinetics and Mechanism of Oxygen Transfer in the Reaction of p-Cyano-N,N-dimethylaniline N-Oxide with Metalloporphyrin Salts. 5. The Influence of Imidazole Ligation of (meso-Tetrakis(2,6-dimethylphenyl)porphinato)manganese(III) Chloride on the Rates of Oxygen Transfer from N-Oxide to...
Wong, Wah-Hun,Ostovic, Drazen,Bruice, Thomas C.
, p. 3428 - 3436 (1987)
Equilibrium constants for mono- and bisligation of imidazole (ImH) with (meso-tetrakis(2,6-dimethylphenyl)porphinato)manganese(III) chloride ((Me8TPP)MnIIICl) have been determined so that the concentrations (dry CH2Cl2) of the three species (Me8TPP)MnIIICl, III(ImH)>Cl, and III(ImH)2>Cl may be calculated at different ImH concentrations.The equilibrium constants for ligation of the one and two imidazoles are K1 = 245 M-1 and β2 = 1.80 x 105 M-2.The reaction of p-cyano-N,N-dimethylaniline N-oxide (NO) with the manganese(III) porphyrin (under the pseudo-first-order conditions of i >> IIICl>i and in the presence and absence of ImH) is first order in both NO and manganese(III) porphyrin, and the rate-controlling step involves oxygen transfer with formation of higher valent manganese-oxo porphyrin species plus p-cyano-N,N-dimethylaniline (DA).From the dependence of the pseudo-first-order rate constants (kobsd) upon i, and a knowledge of the equilibrium constants for imidazole ligation there has been calculated the second-order-rate constants for the kinetic terms k1IIICl>, k2III(ImH)>Cl>, and k3III(ImH)2>Cl>.Comparison of the second-order rate constants (k1 = 3.4 X 10-2 M-1 s-1, k2 = 5.53 M-1 S-1, and k3 = 7.32 X 10-2 M-1 s-1) establishes that ligation by one imidazole increases the rate of reaction of the manganese(III)porphyrin with NO by ca. 166-fold.Bis-imidazole ligated species are blocked to reaction with NO.The higher valent manganese-oxo porphyrin species formed from the reaction of NO with III(ImH)>Cl has been shown to be the principal epoxidizing agent from the dependence of the percentage yield of epoxide upon the concentration of ImH in reactions with cis-cyclooctene using constant initial concentrations of (Me8TPP)MnIIICl and NO.Epoxidation reactions are not rate controlling, and epoxide is formed in competitive processes that involve the reaction of higher valent manganese-oxo porphyrin species with DA (and its oxidation products) and alkene.With exception of the sterically hindered trans-β-methylstyrene, the percentage yield of epoxide at 1.0 M alkene is essentially independent of the type of alkene.Increase in the concentration of alkene and the 1e- oxidizable 2,4,6-tri-tert-butylphenol fails to trap all higher valent manganese-oxo porphyrin species.This result is interpreted as being due to the initial formation of an intimate pair of oxo species and DA with competition between dissociation of DA and oxo species and oxidation of DA within the intimate pair.Epoxidation of alkene by the oxo species occurs after the latter dissociates from the intimate pair.
Laser flash photolysis study of the photoinduced oxidation of 4-(dimethylamino)benzonitrile (DMABN)
Leresche, Frank,Ludvíková, Lucie,Heger, Dominik,Klán, Petr,Von Gunten, Urs,Canonica, Silvio
, p. 534 - 545 (2019)
Aromatic amines are aquatic contaminants for which phototransformation in surface waters can be induced by excited triplet states of dissolved organic matter (3DOM*). The first reaction step is assumed to consist of a one-electron oxidation process of the amine to produce its radical cation. In this paper, we present laser flash photolysis investigations aimed at characterizing the photoinduced, aqueous phase one-electron oxidation of 4-(dimethylamino)benzonitrile (DMABN) as a representative of this contaminant class. The production of the radical cation of DMABN (DMABN+) after direct photoexcitation of DMABN at 266 nm was confirmed in accord with previous experimental results. Moreover, DMABN+ was shown to be produced from the reactions of several excited triplet photosensitizers (carbonyl compounds) with DMABN. Second-order rate constants for the quenching of the excited triplet states by DMABN were determined to fall in the range of 3 × 107-5 × 109 M?1 s?1, and their variation was interpreted in terms of electron transfer theory using a Rehm-Weller relationship. The decay kinetics of DMABN+ in the presence of oxygen was dominated by a second-order component attributed to its reaction with the superoxide radical anion (O2?). The first-order rate constant for the transformation of DMABN+ leading to photodegradation of DMABN was estimated not to exceed ≈5 × 103 s?1
Improved Substrate Scope in the Potassium Hexacyanoferrate(II)-Based Cyanation for the Synthesis of Benzonitriles and Their Heterocyclic Analogues
Richardson, Jeffery,Mutton, Simon P.
, p. 4922 - 4931 (2018)
The use of Pd(DPEPhos)Cl2 (P26) as a catalyst for the formation of benzonitriles and their heterocyclic analogues provides excellent complementarity to existing catalysts, allowing highly electron-deficient heterocyclic aryl halides to be effic
Kinetics and Mechanisms of Oxygen Transfer in the Reaction of p-Cyano-N,N-Dimethylaniline N-Oxide with Metalloporphyrin Salts. 3. Catalysis by iron(III) Chloride
Dicken, C. Michael,Woon, T. C.,Bruice, Thomas C.
, p. 1636 - 1643 (1986)
Decomposition of p-cyano-N,N-dimethylaniline N-oxide (NO) catalyzed by iron(III) chloride ((Cl8TPP)FeIIICl) yields as products p-cyano-N,N-dimethylaniline (DA), p-cyano-N-methylaniline (MA), and formaldehyde (CH2Cl2 solvent, 25 deg C, N2 atmosphere).Intermediate in the reaction are mono and bis NO complexes (Cl8TPP(Cl)FeIIINO and Cl8TPP(NO)FeIIINO, respectively).Oxygen transfer from the complexed NO species to the iron porphyrin is rate-limiting and provides the higher valent iron(IV) salts (IVO>+. and IVO>+.) and DA.The observed kinetics for reactions involving 10-100 turnovers of catalyst dictate that the catalyst is saturated in the formation of Cl8TPP(Cl)FeIIINO and that formation of Cl8TPP(NO)FeIIINO is unfavorable.The two iron(IV)-oxo porphyrin ?-cation radical species are converted back to the iron(III) porphyrin catalytic moieties by oxidation of DA -> MA + CH2O and oxidation of CH2O.Addition of 2,4,6-tri-tert-butylphenol (TBPH), 2,3-dimethyl-2-butene (TME), and cyclohexene results in the formation of TBP. and the respective epoxides, thus inhibiting the oxidation of DA and CH2O.The kinetics of the overall reaction and formation of each product may be simulated by employing the reactions of Scheme II and eq l-r, and from the simulations, the rates and equilibria, leading to the formation of the two iron(IV)-oxo porphyrin ?-cation radical species may be determined as can minimal rate constants for the oxidations of DA, CH2O, and TBPH and the epoxidation of TME and cyclohexene.The results obtained herein with the electron-deficient porphyrin, (Cl8TPP)Fe(III)Cl, are discussed and compared to those obtained previously when employing (TPP)FeIIICl as the catalyst.
FeCl3 mediated one-pot route to nitriles
Ghosh, Pranab,Subba, Raju
, p. 4885 - 4887 (2013)
A new and convenient protocol for the transformation of aldehydes into nitriles using hydroxylamine hydrochloride by iron III chloride is presented. The protocol offers a very simple, cost efficient, and environmentally benign procedure with good to excellent yield of nitrile.
The Kinetics and Mechanisms of Oxygen Transfer in the Reaction of p-Cyano-N,N-dimethylaniline N-Oxide with Metalloporphyrin Salts. 4. Catalysis by meso-(Tetrakis(2,6-dimethylphenyl)porphinato)iron(III) Chloride
Woon, T. C.,Dicken, C. Michael,Bruice, Thomas C.
, p. 7990 - 7995 (1986)
meso-(Tetrakis(2,6-dimethylphenyl)porphinato)iron(III) chloride ((Me8TPP)Fe(III)Cl) is a catalyst for the conversion of p-cyano-N,N-dimethylaniline N-oxide (NO) to p-cyano-N,N-dimethylaniline (DA), p-cyano-N-methylaniline (MA), p-cyano-N-formyl-N-methylaniline (FA), p-cyanoaniline (A), N,N'-dimethyl-N,N'-bis(p-cyanophenyl)hydrazine (H), N,N'-bis(p-cyanophenyl)-N-methylmethylenediamine (MD), and CH2O.All evidence supports these reactions to occur by equilibrium ligation of NO to iron(III) porphyrin followed by rate-detrmining oxygen transfer to yields as intermediate products DA and the iron(IV)-oxo porphyrin ?-cation radical.Stepwise oxidation of DA by the higher valent iron-oxo porphyrin species is responsible for the formation of the other products (i.e., DA-->-->FA, DA-->MA-->A, 2MA-->MD, and 2MA-->H).The oxidation potentials of (Me8TPP)Fe(III)OCH3 are comparable to those of the unsubstituted meso-(tetraphenylporphinato)iron(III) methoxide ((TPP)Fe(III)OCH3).The following results are, therfore, not surprising: (i) The second-order rate constant (kakb/k-a) for reaction of (Me8TPP)Fe(III)Cl with NO is but 3.3-fold smaller than in the case of the reaction of NO with (TPP)Fe(III)Cl; (ii) the percentage yields of products (DA, 53percent; MA, 24percent; A, 3percent; FA, 8percent; H, 7percent; MD, 5percent) are comparable to when (TPP)Fe(III)Cl is employed; and (iii) oxidation and epoxydation of added substrates are not rate-determining.Of considerable interest is the finding that epoxidation reactions using NO with (Me8TPP)Fe(III)Cl occur in much higher yield (80percent to 100percent) than when (TPP)Fe(III)Cl is used as the catalyst.
Dimethylanilinic N-Oxides and Their Oxygen Surrogacy Role in the Formation of a Putative High-Valent Copper-Oxygen Species
Diaz, Daniel E.,Bhadra, Mayukh,Karlin, Kenneth D.
, p. 13746 - 13750 (2019)
The reaction of p-cyano-N,N-dimethylaniline N-oxide, an O-atom donor, with different copper(I) complexes (at room temperature and in acetone) indicates the formation via O-atom transfer of a high-valent copper oxyl species, CuII-O?, a putative key intermediate in the catalytic cycle of copper-containing monooxygenases. The formation of p-cyano-N-hydroxymethyl-N-methylaniline and p-cyano-N-methylaniline as the main products of the reaction highlight the capability of this species to hydroxylate strong C-H bonds (bond dissociation energy ～90 kcal/mol). A plausible mechanism for the reactivity of this catalytic system is proposed.
Microwave activation in organic synthesis: Natural Indian clay, EPIC(R) EPZG(R) and EPZ10(R) as novel heterogenous catalysts for rapid synthesis of nitriles from aldoximes in absence of solvent
Bandgar,Sadavarte,Sabu
, p. 3409 - 3413 (1999)
The Conversion of aldoximes into nitriles was carried out in the absence of solvent under microwave irradiation using environmentally-friendly catalysts like natural kaolinitic clay, EPIC(R) EPZG(R) and EPZ10(R). Acceleration of reaction rate, simple work-up and formation of clean products are salient features of this method.
Convenient conversion of aldoximes into nitriles with N-chlorosuccinimide and pyridine
Gucma, Miroslaw,Golebiewski, W. Marek
, p. 1997 - 1999 (2008)
Benzaldehyde oximes substituted with electron-donating groups are dehydrated to the corresponding benzonitriles by N-chlorosuccinimide/pyridine in acetonitrile. Benzaldehyde oxime itself and alkanal oximes afford the corresponding aldehydes. Thieme Stuttgart.
