Trinitromethane Research Articles

Photochemical Reactions of Nitrocobalt(III) Tetraphenylporphyrin and Its Pyridine Complex Studied by Laser Flash Photolysis

The photochemical reactions of nitrocobalt(III) tetraphenylporphyrin, (NO2)CoIIITPP, and its six-coordinated complex with 4-(dimethylamino)pyridine, (NO2)CoIIITPP(DMAPy), in benzene were studied by using a laser flash technique. The structures solved by X-ray analysis show that both compounds are the nitro form (O2N−CoIII) instead of the nitrito form (ONO−CoIII). The transient absorption spectrum observed 50 ns after laser excitation of (NO2)CoIIITPP(DMAPy) in benzene revealed that the pyridinate complex undergoes photodissociation of the N−CoIII bond to yield NO2 and CoIITPP(DMAPy). These products recombine and regenerate the original complex with a second-order rate constant of 2.5 × 109 dm3 mol-1 s-1. In the case of (NO2)CoIIITPP, the transient absorption spectrum detected 50 ns after the laser flash changes to another spectrum which has a longer lifetime and decays according to first-order kinetics with the rate constant of 3.0 × 102 s-1. The former spectrum corresponds to formation of CoIITPP from the photodissociation of the N−CoIII bond. The change from the former to latter spectrum is found to follow second-order kinetics with the rate constant of 3.6 × 109 dm3 mol-1 s-1. On the basis of the results obtained, it was concluded that the metastable transient giving the latter spectrum is the nitrito species, (ONO)CoIIITPP, which undergoes a nitrito → nitro linkage isomerization.

Phase transfer catalysis in the chemistry of aliphatic nitrocompounds

The methylation of trinitromethane (TNM) Na-salt under phase transfer catalysis (PTC) conditions was studied in a two-phase system (aqueous solution of TNM Na-salt-CH3I). The obtained data revealed a relationship between the yield of the methylation product (1,1,1-trinitroethane) and the nature of the phase transfer catalyst and the degree of TNM anion transfer to the organic phase. The kinetic measurements showed that higher efficiency of methylation was achieved under PTC conditions than occurs in a homogeneous reaction due to the fact that the reaction proceeded in the CH3I medium.

Improved Synthesis of 2,2,2-Trinitroethyl Ethers

Abstract An improved synthesis of 2,2,2-trinitroethyl ethers (from iodomethyl ethers and trinitromethane) that avoids the use of unstable potassium trinitromethide is described.

Nitrogen source effects on rabbiteye blueberry plant‐soil interactions

Abstract The acidity of alfisols and ultisols may be unfavorably increased for blueberry production by the use of specific nitrogen (N) fertilizers. Several ammonium containing fertilizers were evaluated for their effects on rabbiteye blueberries (Vaccinium ashei Reade). Rooted ‘Tifblue’ cuttings were grown in a 1: 1 peat: Lilbert loamy fine sand mix for 90 days. After establishment, plants were moved into the glasshouse and fertilized four times at 90‐day intervals with one of six N sources at one of four rates. Nitrogen sources were (NH4)2SO4 (AS), NH4NO3 (AN), urea, urea‐NH4NO3 (UAN), Nitro‐form (NF) and sulfur coated urea (SCU). Rates of N per application were equivalent to 0, 112, 224, or 336 kg/ha. The application of the high rate of each N source reduced plant growth. The 112 and 224 kg/ha N treatments increased growth compared to no nitrogen treatments. When comparing N sources, SCU treatments produced the greatest plant growth and AS treatments the lowest. Sulfur coated urea had less effect on so...

ChemInform Abstract: A Theoretical Study of the Nitration of Ethylene and Benzene with the Nitronium Ion

Ab initio and semi-empirical (MNDO, MINDO/3) studies of the interaction of NO2+ with ethylene and benzene are reported. 6-31G**//4-31G Calculations have been performed at selected points of the ethylene–nitrnium ion energy hypersurface, as well as RMP2 4-31G//4-31 G calculations, from which it is found that the non-classical π-complex is more stable than the classical nitro complex. Fully optimised STO-3G calculations are described for 5 stationary points of the benzene–NO2+ hypersurface; 3-21G calculations at these geometries show that the nitrito σ-complex and a 5-membered-ring structure have similar energies. 4-31G//STO-3G Calculations however show the nitro from to be the next most stable to the nitrito form. Geometry optimisation at the 3-21G level of the nitrito and nitro forms shows this finding to persist at both the 3-21G and 4-31G levels. If correlation is introduced via GVB/1 calculations both nitro compounds are shown to possess incipient biradicaloid character. Finally semi-empirical MINDO/3-solvaton calculations of solvation effects show that the nitro form is the most stabilised in both systems.

A theoretical study of the nitration of ethylene and benzene with the nitronium ion

Ab initio and semi-empirical (MNDO, MINDO/3) studies of the interaction of NO2+ with ethylene and benzene are reported. 6-31G**//4-31G Calculations have been performed at selected points of the ethylene–nitrnium ion energy hypersurface, as well as RMP2 4-31G//4-31 G calculations, from which it is found that the non-classical π-complex is more stable than the classical nitro complex. Fully optimised STO-3G calculations are described for 5 stationary points of the benzene–NO2+ hypersurface; 3-21G calculations at these geometries show that the nitrito σ-complex and a 5-membered-ring structure have similar energies. 4-31G//STO-3G Calculations however show the nitro from to be the next most stable to the nitrito form. Geometry optimisation at the 3-21G level of the nitrito and nitro forms shows this finding to persist at both the 3-21G and 4-31G levels. If correlation is introduced via GVB/1 calculations both nitro compounds are shown to possess incipient biradicaloid character. Finally semi-empirical MINDO/3-solvaton calculations of solvation effects show that the nitro form is the most stabilised in both systems.

Japanese holly growth and release pattern of ammonium and nitrate from controlled-release fertilizers

Applications of 0.85, 1.70 or 2.55 kg N m −3 were made to Ilex crenata Thunb. Hetzi. Nitrogen sources included weekly applications of liquid fertilizer (NH 4NO 3) and single application of TVA's Sulfur coated urea (SCUT), Gold N (SCUG), Nitroform (NITR), isobutylidene diurea (IBDU), and an experimental N-containing Osmocote (OSCN). Shoot dry matter and leaf N from recently matured leaves were determined. Analyses of NH 4-N and NO 3-N were also conducted on the monthly leachates collected from the containers. Most controlled-release fertilizers (CRFs) produced greater dry weights at 1.70 kg N, while NH 4NO 3 produced more dry weight than CRF's at 0.85 or 2.55 kg N. Initially, for CRF's ammonium was more abundant than nitrate in the leachate; subsequently, nitrate became the dominant N form for most of the growing-season. All urea-based fertilizers had higher NH 4 levels in the leachate when compared with NH 4NO 3-based fertilizers.

Contribution of the pyrylium structure to the electrochemical properties of nitroflavones

The polarographic behavior of 3- and 4′-nitroflavones on a dropping mercury electrode in Britton-Robinson buffer solutions was investigated. It Is shown that, depending on its position, the nitro group displays properties that are typical only for aromatic nitro compounds or a combination of properties of aromatic and aliphatic α-unsaturated nitro compounds. The deciding factor is the realization of pyrylium and pyrone structures, depending on the pH of the medium. The kinetic parameters of the chemical transformation of the nitro form to the aci form of 3-nitroflavone in an alkaline medium are presented.

Linkage isomerization of [Co(NH 3) 5ONO] 2+ in poly(vinyl alcohol)

The rate of linkage isomerization of nitritopentaamminecobalt (III) to the nitro form was measured spectrophotometrically in poly(vinyl alcohol) sheets at three temperatures. The nitrito complex was generated photochemically.

The reaction of trinitro methane salts with ?-halofunctional derivatives

The reaction of the ambident trinitromethane anion withα-halofunctional derivatives — bromoacetone and ethyl bromoacetate — involves only O-alkylation.

A study of the electronic structure of nitrotoluenes in their nitro and aci-nitro forms and of the mechanism of their ground state interconversions using the CNDO/2 method

The CNDO/2 method (complete neglect of differential overlap for valence electrons) [1] was used to calculate the models of molecules of toluene (I), nitrobenzene (II), o-nitrotoluene (III), and 2,4-dinitrotoluene (IV). The π- and σ-electronic structure of these molecules was discussed in the ground electronic state. A comparison of the total energies of various forms of III and IV molecules was used to determine the most likely pathway of conversion of the aci-nitro form into the nitro form and to estimate the activation energy of this process.

Structure of nitroform in various solvents

Structure of nitroform in various solvents

Reaction of trinitromethane with ketenes

The reaction of trinitromethane with ketene (prepared in a ketene lamp) proceeds with the formation of 1,1,1-trinitro-tert-butyl acetate.

The silver salt of trinitrometh ane in complex-forming reactions

1. The silver salt of trinitromethane forms complexes with a 1∶1 composition with a wide range of organic electron-donating compounds. 2. The complexes have an ionic structure.

Trinitromethane adducts of .alpha.,.beta.-unsaturated aldehydes and acylals

Trinitromethane adducts of .alpha.,.beta.-unsaturated aldehydes and acylals

CONTROLLED POTENTIAL ELECTROLYSIS. X. POLAROGRAPHIC BEHAVIOR AND ELECTROLYTIC REDUCTION PROCESS OF ESTERS OF ALIPHATIC ALPHA-NITROCARBOXYLIC ACIDS.

Polarographic reduction mechanism of aliphatic ethyl nitrocarboxylates was investigated. The decrease of the wave height in alkaline region was ascribed to the conversion of the nitro form to aci-nitro anion rather than the ester hydrolysis. Only ethyl nitroacetate developed a wave for the aci-nitro anion. The coulometric n values and the products obtained, combined with the polarographic results, suggest the scheme (1) as the most probable reduction mechanism. The production of amine is only possible through C=N double bond formation, but not through hydroxyamino derivatives as usually suggested.

High-reliability computers using duplex redundancy : R. W. Lowrie, Electron. Ind., p. 116 (Aug. 1963)

The low-melting isomers of 2,5-dinitro-1,6-hexanediol (IB) and 2,6-dinitro-l,7-heptanediol (IIB) undergo facile acid-catalyzed epimerization to form the respective high-melting isomers (IA and IIA) in water or in aprotic solvents. The dimethyl ether and bis-phenylurethan derivatives of IB are not epimerized by acid catalysts under the same conditions. The rate of the isomerization, IB → IA, has been determined in n hydrochloric acid at 60° and compared with rates of other acid-catalyzed reactions occurring in this medium. The rates of tautomerization to the nitro form, of the mono and bis-nitronic acids derived from I, have been measured and found to be very rapid relative to the isomerization reaction. Mechanisms for the epimerization and related acid-catalyzed reactions of nitroalkanes are presented and discussed.

General Acid Catalysis of the Fading of Photoisomerized 2,4-Dinitrotoluene

Short-lived colored species are formed when a water solution of 2,4-dinitrotoluene is exposed to ultraviolet light. The colored species displayed an acid—base equilibrium and the absorption spectra of the acid form and the base form were measured. The half-life time for the first-order fading reaction was varied over a 105-fold range (20 μsec to 1 sec) by changing the acidity and temperature. The fading reaction was found to be general acid-catalyzed over the pH region 2–13. The experiment supports a mechanism having the following essential features. The nitro form is photochemically isomerized to an aci-nitro form which is in equilibrium with the anion. The rate-determining step in the fading reaction is the neutralization of this anion. The rate constants for the neutralization by various acids have been measured at 30°C to be 1.8×10—2 (H2O), 4.8×103 (HAc), 2.4×104 (+NH3CH2COOH), 7.4×104 (H+) liter sec—1 mole—1.

Acid-catalyzed aci-nitro tautomerism epimerization of α, ω-bis-hydroxymethyl- α, ω-dinitroalkanes

The low-melting isomers of 2,5-dinitro-1,6-hexanediol (IB) and 2,6-dinitro-l,7-heptanediol (IIB) undergo facile acid-catalyzed epimerization to form the respective high-melting isomers (IA and IIA) in water or in aprotic solvents. The dimethyl ether and bis-phenylurethan derivatives of IB are not epimerized by acid catalysts under the same conditions. The rate of the isomerization, IB → IA, has been determined in n hydrochloric acid at 60° and compared with rates of other acid-catalyzed reactions occurring in this medium. The rates of tautomerization to the nitro form, of the mono and bis-nitronic acids derived from I, have been measured and found to be very rapid relative to the isomerization reaction. Mechanisms for the epimerization and related acid-catalyzed reactions of nitroalkanes are presented and discussed.

Notes. The Chemistry of Trinitromethane. II. Reactions with Esters of Unsaturated N-Methylolamides.

Notes. The Chemistry of Trinitromethane. II. Reactions with Esters of Unsaturated N-Methylolamides.