1122-59-4

Usage

Uses

Aniline-N,N-d2 (CAS# 1122-59-4) is a useful isotopically labeled research compound.

Upstream product

• 62-53-3 aniline 
• 7789-20-0 water-d2 
• 98-95-3 nitrobenzene 

Downstream Products

• 108959-52-0 C₁₂H₁₀⁽²⁾HF₄NS 

Relevant academic research and scientific papers

Hydrogen bond formation and molecular motion in solutions of aniline with nitroxide free radicals

1H NMR spin-lattice relaxation rates and paramagnetic contact shifts have been measured at various temperatures and frequencies in solutions of aniline, aniline-d2, and aniline-d5 containing nitroxide free radicals. The data can be explained in terms of transient hydrogen bond formation between the amino protons and the NO groups of the radical. Detailed information about the intermolecular transfer of electron spin density and the steric arrangement of the complex have been obtained. Molecular motions and interactions have been probed by relaxation measurements over a large frequency range between 100 kHz and 300 MHz. The results are compared with other hydrogen-bonded complexes of nitroxide radicals and proton donor solvent molecules.

Concerted pathway to the mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic chloride in Acetonitrile

The kinetics of the nucleophilic substitution reactions of bis(N,N-diethylamino)phosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated in MeCN at 65.0°C. The deuterium kinetic isotope effects (DKIEs) are secondary inverse (kH/kD1: 0.706-0.947) and the magnitudes of the secondary inverse DKIEs (kH/kD) increase constantly as the nucleophiles are changed from weakly basic to strongly basic anilines. The magnitudes of the selectivity parameters are ρX(H)≤-6.34, and βX(H)≤2.24 with substituted anilines and ρX(D)≤-6.13 and βX(D)≤2.17 with deuterated anilines. A concerted SN2 mechanism involving predominant backside attack is proposed based on the kH/kD values with substituent X.

Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy

Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C= O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm-1, which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τET1 = 500 fs, τET 2 = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.

Application of Silicon-Initiated Water Splitting for the Reduction of Organic Substrates

The use of water as a donor for hydrogen suitable for the reduction of several important classes of organic compounds is described. It is found that the reductive water splitting can be promoted by several metalloids among which silicon shows the best efficiency. The developed methodologies were applied for the reduction of nitro compounds, N-oxides, sulfoxides, alkenes, alkynes, hydrodehalogenation as well as for the gram-scale synthesis of several substrates of industrial importance.

Visible light-driven selective hydrogenation of unsaturated aromatics in an aqueous solution by direct photocatalysis of Au nanoparticles

Selective hydrogenation of various chemical bonds, such as CC, CC, CO, NO, and CN, is efficiently driven by visible light over a supported gold nanoparticle (AuNP) photocatalyst under mild reaction conditions. The reaction system exhibits high substituent tolerance and tunable selectivity by light wavelength. Density functional theory (DFT) calculations demonstrated a strong chemisorption between the reactant molecule and metal resulting in hybridized orbitals. It is proposed that direct photoexcitation between hybridized orbitals is the main driving force of the hydrogenation reaction. The hydrogenation pathway is investigated by the isotope tracking technique. We revealed the cooperation of water and formic acid (FA) as a hydrogen source and the hydrogenation route through Au-H species on the AuNP surface.

Anilinolysis of O-butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis, characterization, kinetic study, and reaction mechanism

This paper describes a simple optimized method for the synthesis of O-butyl phenyl phosphonochloridothioate (4) under mild conditions. The target compounds were characterized by 1H-nuclear magnetic resonance (NMR), 13C-NMR, and 31P-NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6-311?+?G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X-anilines (XC6H4NH2) and deuterated X-anilines (XC6H4ND2) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X?=?H and X?=?3-MeO, giving large negative ρX and small positive βX values. The deuterium kinetic isotope effects were secondary inverse (kH/kD?H/kD), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted SN2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.

Mechanistic insights into the Pd-catalyzed direct amination of allyl alcohols: Evidence for an outer-sphere mechanism involving a palladium hydride intermediate

The mechanism of direct amination of allyl alcohol by a palladium triphenylphosphite complex has been explored. Labelling studies show that the reaction proceeds through a π-allylpalladium intermediate. A second-order dependence of reaction rate on allyl alcohol concentration was observed. Kinetic isotope effect studies and ESI-MS studies are in agreement with a reaction proceeding through a palladium hydride intermediate in which both O-H bond and C-O bond cleavages are involved in rate-determining steps. A stereochemical study supports an outer-sphere nucleophilic attack of the π-allylpalladium intermediate giving complete chiral transfer from starting material to product. Two cleavages: The mechanism of the direct amination of allyl alcohol by palladium complexes bearing triphenylphosphite ligands has been explored. Kinetic isotope and ESI-MS studies are in good agreement with that both Oi￡H bond and Ci￡O bond cleavages are involved in rate-determining steps. Furthermore, stereochemical studies support an outer-sphere nucleophilic attack of the π-allylpalladium intermediate. Copyright

Iridium porphyrin catalyzed N-H insertion reactions: Scope and mechanism

Ir(TTP)CH3 catalyzed N-H insertion reactions between ethyl diazoacetate (EDA) or methyl phenyldiazoacetate (MPDA) and a variety of aryl, aliphatic, primary, and secondary amines to generate substituted glycine esters with modest to high yields. Aniline substrates generally gave yields above 80%, with up to 105 catalyst turnovers, and without slow addition of the diazo reagent. Good yields were also achieved with aliphatic amines, though higher catalyst loadings and slow addition of the amine were necessary in some cases. Primary amines reacted with EDA to generate both single- and double-insertion products, either of which could be produced selectively in high yield with the proper choice of stoichiometric ratios and reaction temperature. Notably, mixed trisubstituted amines, RN(CH2CO2Et) (CHPhCO2Me), were generated from the insertion of 1 equiv of EDA and 1 equiv of MPDA into primary amines. The N-H insertion mechanism was examined using substrate competition studies, trapping experiments, and multiple spectroscopic techniques. Substrate competition studies using pairs of amines with EDA or MPDA revealed Hammett correlations with respective slopes of ρ = 0.15 and ρ+ = -0.56 as well as kinetic isotope ratios of k H/kD = 1.0 ± 0.2 and 2.7 ± 0.2. Competitive amine binding to the iridium center was demonstrated by kinetics and equilibrium binding studies. Equilibrium binding constants ranged from 102 to 105. Monitoring the reaction by absorption spectroscopy revealed a transient metalloporphyrin complex. The lifetime of this species was dependent on the nature of the amine substrate, which suggests that the catalytic cycle proceeds through a metal-ylide intermediate.

Kinetics and mechanism of anilinolyses of ethyl methyl, ethyl propyl and diisopropyl chlorothiophosphates in acetonitrile

Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 oC. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.66-0.99) with 2, primary normal and secondary inverse (kH/ kD = 0.78-1.19) with 4, and primary normal (kH/kD = 1.06-1.21) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transitionstate, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reactionmechanism, DKIE and activation parameter.

Kinetics and mechanism of the anilinolysis of (2R,4R,5S)-(+)-2-chloro-3,4- dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide in acetonitrile

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4- dimethyl-5-phenyl-1,3,2-oxazapho-spholidine 2-sulfide (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 5.0 °C. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (ΔS≠ = -2 cal mol-1 K -1) over considerably unfavorable enthalpy of activation (ΔH≠ = 18.0 kcal mol-1). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted S N2 mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, k H/kD 1.