Thermal runaway hazards of <Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide by calorimetric studies

Thermal runaway reactions associated with exothermic behaviors of tert-butyl hydroperoxide (TBHP) solutions and TBHP reacting with alkaline contaminants were studied. A differential scanning calorimetry (DSC) was used to characterize these inherent behaviors of TBHP solutions with KOH, NaOH, LiOH and NH₄OH. The exothermic peak in thermal curves of TBHP solutions with different alkali were detected by DSC thermal analysis. By thermal analysis, we compared various heats of decomposition of TBHP solutions with alkaline impurities, and determined the incompatible hazards of various TBHP solutions with alkaline contaminants. Comparing with TBHP in various diluents, the adiabatic runaway reaction via vent sizing package 2 (VSP2) indicated that aqueous TBHP intrinsically possesses the phenomena of thermal explosion with dramatic self-reactive rate and pressure rise under adiabatic conditions. Many commercial organic peroxides may have different hazard behaviors. Therefore, using thermal method to classify the hazards is an important subject.     

Specific features of the reaction of vanadyl acetylacetonate with <Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide

Reaction of vanadyl acetylacetonate with tert-butyl hydroperoxide (benzene, 20°C) at any molar ratio leads to the elimination of ligand and its oxidation mainly to CO₂ and acetic acid. At the (acac)₂VO: t-BuOOH ratio above 1:10 liberation of oxygen partially in the singlet state takes place.     

Mono-<Emphasis Type="Italic">meso</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-butylporphyrin

Summary. Treatment of meso-tetra(tert-butyl)porphyrin with sulfuric acid/n-butanol affords a mixture of porphyrin and mono-tert-butylporphyrin in relatively high yield.     

Alkylation of pyrocatechol in <Emphasis Type="Italic">tert</Emphasis>-butyl alcohol-sulfuric acid-benzene

Alkylation of pyrocatechol with tert-butyl alcohol in benzene in the presence of sulfuric acid gave 3,5-di-tert-butylbenzene-1,2-diol in a higher yield than in analogous reaction with tert-butyl alcohol. This result was rationalized by reduction of inhibitory effect of liberated water, formation of heterogeneous system, and occurrence of the alkylation process in nonpolar organic phase. Intermediate products were identified and found to undergo intra- and intermolecular tert-butyl group transfer with formation of more stable 3,5-di-tertbutylbenzene-1,2-diol. The formation of p-di-tert-butylbenzene indicated participation of benzene in crossalkylation processes.     

Heat capacities and thermodynamic properties of (<Emphasis Type="Italic">S</Emphasis>)-<Emphasis Type="Italic">tert</Emphasis>-butyl 1-phenylethylcarbamate

An N-tert-butyloxycarbonylated organic synthesis intermediate, (S)-tert-butyl 1-phenylethylcarbamate, was prepared and investigated by means of differential scanning calorimetry (DSC) and thermogravimetry (TG). The molar heat capacities of (S)-tert-butyl 1-phenylethylcarbamate were precisely determined by means of adiabatic calorimetry over the temperature range of 80-380 K. There was a solid–liquid phase transition exhibited during the heating process with the melting point of 359.53 K. The molar enthalpy and entropy of this transition were determined to be 29.73 kJ mol⁻¹ and 82.68 J K⁻¹ mol⁻¹ based on the experimental C _p–T curve, respectively. The thermodynamic functions, [H_T⁰ - H_298.15⁰ H_{T}^{0} - H_{298.15}^{0} ] and [S_T⁰ - S_298.15⁰ S_{T}^{0} - S_{298.15}^{0} ], were calculated from the heat capacity data in the temperature range of 80–380 K with an interval of 5 K. TG experiment showed that the pyrolysis of the compound was started at the temperature of 385 K and terminated at 510 K within one step.     

Runaway reaction on <Emphasis Type="Italic">tert</Emphasis>-butyl peroxybenzoate by DSC tests

Tert-butyl peroxybenzoate (TBPB) is one of the sensitive and hazardous chemicals which have been popularly employed in petrifaction industries in the past. This study attempted to elucidate its unsafe characteristics and thermally sensitive structure so as to help prevent runaway reactions, fires or explosions in the process environment. We employed differential scanning calorimetry (DSC) to assess the kinetic parameters (such as exothermic onset temperature (T ₀), heat of reaction (ΔH), frequency factor (A)), and the other safety parameters using four different scanning rates (1, 2, 4 and 10°C min⁻¹) combined with curve-fitting method. The results indicated that TBPB becomes very dangerous during decomposition reactions; the onset temperature and reaction heat were about 100°C and 1300 J g⁻¹, respectively. Through this study, TBPB accidents could be reduced to an accepted level with safety parameters under control. According to the findings in the study and the concept of inherent safety, TBPB runaway reactions could be thoroughly prevented in the relevant plants.     

Synthesis and cytotoxic activity of derivatives of 6<Emphasis Type="Italic">Z</Emphasis>-acetylmethylenepenicillanic acid <Emphasis Type="Italic">tert</Emphasis>-butyl ester

The sulfoxide of 6Z-[2-(methoxyimino)propylidene]penicillanic acid tert-butyl ester and the sulfones of 6Z-[2-(hydroxyimino-, methoxyimino-, benzyloxyimino-, 2-bromo- and 4-bromobenzyloxyimino)-propylidene]penicillanic acid in the syn and anti forms have been synthesized by the condensation of the sulfoxide and sulfone of 6Z-acetylmethylenepenicillanic acid tert-butyl ester with hydroxylamine, methoxyamine, benzyloxyamine, 2-bromo- and 4-bromobenzyloxyamines. The syn and anti isomers of 3Z-(2-methoxyiminopropylidene)-4R-(benzothiazolyl-2-dithio)-2-oxoazetidinyl-1R-(2-propenyl)acetic acid tert-butyl ester were obtained by opening of the thiazolidine ring in 6Z-[2-(methoxy-imino)propylidene]-1-oxopenicillanic acid tert-butyl ester with 2-mercaptobenzothiazole. The 3Z-(2-methoxyiminopropylidene)-4R-(methylsulfonyl)-2-oxoazetidinyl-1-(2-propylidene)acetic acid tert-butyl ester was synthesized by the interaction of 1,8-diazobicyclo[5.4.0]undec-7-ene and methyl iodide with 6Z-[2-(methoxyimino)propylidene]-1,1-dioxopenicillanic acid tert-butyl ester. A dependence of the cytotoxic effect in relation to cancer and normal cells in vitro on the structure of the substituent in position 6 and the syn and anti isomerism of the oxyimino group was established for the synthesized compounds.     

Geometrical and energetical aspects of structure of 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-<Emphasis Type="Italic">o-</Emphasis>benzoquinones

From the geometrical point of view, all observed conformations of the 3,6-di-tert-butyl-o-benzoquinone fragments are determined by the inequivalent positions of the Me groups of the tBu substitutes relative to the carbonyl oxygen atoms. The geometrical inequivalence is believed to cause the energetic inequivalence of the Me groups. The relevant quantum mechanical computations revealed intramolecular contacts of the C=O···H-(tBu)-type (2.37–3.83 kcal/mole) that can be interpreted to be hydrogen bonding interactions.     

The effect of reaction conditions on MoB activation in 1-octene epoxidation with <Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide

The change in the surface composition of a MoB catalyst in the epoxidation of 1-octene with tert-butyl hydroperoxide and the effects of the reactant concentrations and reaction products (tert-butanol and 1,2-epoxyoctane) on this process have been studied.     

System vanadium alkoxy compound-<Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide-oxidant of hydrocarbon C-H bonds

Vanadium alkoxy compounds [(t-BuO)₄V, (t-BuO)₃VO] react with tert-butyl hydroperoxide (C₆H₆, 20°C) to liberate oxygen, partly in the singlet form, and to form alkoxyl and peroxyl radicals via the intermediacy of vanadium peroxides and trioxide. These systems are capable of oxidizing hydrocarbon C-H bonds. The process is radical in nature and involves formation of carbon-centered radicals and their reaction with oxygen generated in the systems. Vanadium-containing peroxides, too, take part in the oxidation reaction.     

Interaction of 9-substituted anthracenes with oxidation systems <Emphasis Type="Italic">tert</Emphasis>-butylhydroperoxide-metal <Emphasis Type="Italic">tert</Emphasis>-butoxide

9-R-Anthracenes (R = Me, Ph) are effective acceptors of peroxyl and metalalkoxyl radicals in the systems tert-butylhydroperoxide-metal tert-butoxide (M = Al, V, Cr; C₆H₆, 20°C). Isolation of 9-R-9,10-dihydro-9,10-di-tert-butylperoxyanthracenes, 10-R-10-tert-butylperoxy-9-anthrones as major products reliably confirms the formation of tert-butylperoxy radicals and can be used for quantitative assessment of their content.     

Interaction of zinc(II) tetra-<Emphasis Type="Italic">tert</Emphasis>-butyl-phthalocyaninate with organic ligands in solution

Calorimetric titration was used to obtain standard thermodynamic characteristics of zinc(II) tetra-tert-butyl-phthalocyaninate interaction with electron-donor ligands in benzene. The formation of molecular complexes of Zn(t-Bu)₄Pc with ligands (hexamethylphosphoramide, pyridine, piperidine, and morpholine) was found to be greatly affected both by the electron-donor and polarization properties of the coordinated ligands, as well as by the solvation effect of a medium. It was shown that the formation of thermodynamically stable molecular complexes of zinc(II) tetra-tert-butyl-phthalocyaninate with the electron-donor solvents (with stability constant K_s > 10⁴) favors the formation of -polymorphic modification of a metal phthalocyaninate during its crystallization from a given solvent.Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 915–918.Original Russian Text Copyright © 2004 by Lebedeva, Malkova, Pavlycheva, Vugin.     

Properties of single-component acrylic pressure-sensitive adhesives synthesized using <Emphasis Type="Italic">tert</Emphasis>-butyl peroxypivalate initiator

In this work, tert-butyl peroxypivalate initiator was newly used in the solution polymerization of acrylic copolymers with 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate and acrylic acid monomers for application of pressure-sensitive adhesives (PSAs). Its proper dosage was determined to vary from 0.6 to 1.2 wt % when a high monomer conversion (>99%) was ensured. In this amount range, polymer properties and adhesive performance of the PSAs were investigated. The results indicated that with the amount of tert-butyl peroxypivalate increased, the molecular weights of the polymer decreased and the molecular weight distribution became wider. It was also observed that the synthesized PSAs had high interfacial adhesion and low cohesion strength, and thus exhibited cohesive failure during the peel test. So cross-linking agent was employed to improve the shear strength of the PSAs and to eliminate the adhesive residue while at the sacrifice of loop tack and peel strength. As a whole, the optimal performance was obtained by using 1.2 wt % amount of initiator and 0.5 wt % concentration of cross-linker. In this case, the peel and shear strength have achieved the best balance. In addition, for the cross-linked PSA tapes, the peel strength slightly decreased with the dwell time.     

New synthetic approach to aminoethoxy derivatives of <Emphasis Type="Italic">p</Emphasis>-(<Emphasis Type="Italic">tert</Emphasis>-butyl)calix[4]arene

A new procedure has been proposed for the synthesis of mono- and bis(2-aminoethoxy)-p-(tertbutyl) calix[4]arenes from the corresponding mono- and bis[2-(1,3-dioxoisoindol-2-yl)ethoxy]-p-(tert-butyl)-calix[4]arenes.     

About selective methods of synthesis of 6-<Emphasis Type="Italic">tert</Emphasis>-butyl-2-methylphenol and 6-<Emphasis Type="Italic">tert</Emphasis>-butyl-2,4-dimethylphenol

Vapor phase catalytic methylation with methanol of 2-tert-butylphenol at the temperature 280–300°C proceeds selectively with formation of 6-tert-butyl-2-methylphenol. Elevating reaction temperature above 300°C leads to formation of 2,6-dimethylphenol. Reaction of 2-tert-butylphenol with methanol in alkaline medium in the presence of zinc oxide is shown to lead initially to formation of a mixture of calixarenes and methylenebisphenols that at elevated temperature exert splitting leading in future to 6-tert-butyl-2,4-dimethylphenol. Obtaining it in this reaction from 2,2′-methylenebis-(6-tert-butyl-4-methylphenol) proceeds selectively. Pathways of the reductive methylation of methylenebisphenols with methanol in alkaline medium is considered.     

Development of a one-stage synthesis of 2,6-di-<Emphasis Type="Italic">tert</Emphasis>-4-ethylbutylphenol from 2,6-di-<Emphasis Type="Italic">tert</Emphasis>-butylphenol

Investigation of the catalyzed reaction of 2,6-di-tert-butylphenol with ethanol, ethylene glycol, oligomeric glycols, and paraldehyde in a strongly basic medium permitted to develop a technologically suitable procedure for manufacture of 2,6-di-tert-4-ethyl-butylphenol, used in the synthesis of Antioxidant-425.     

Heterospin biradicals based on new piperidineoxyl-substituted 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-<Emphasis Type="Italic">o</Emphasis>-benzoquinone

A nucleophilic addition reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (OH-TEMPO) to 3,6-di-tert-butyl-o-benzoquinone was used to obtain a new sterically hindered o-benzoquinone (1) containing 2,2,6,6-tetramethylpiperidineoxyl functional group, which was characterized by IR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction. A one-electron reduction of 1 with potassium and thallium is an efficient method for the generation of earlier unknown heterospin biradicals 5a and 5b, respectively, containing nitroxide and o-semiquinone radical centers. Analysis of the hyperfine structure of the ESR spectra of biradicals 5a and 5b in solution showed that they belong to the group of heterospin biradicals with strong (J >> a) and fast exchange interaction between the radical centers.     

Chemoselective acylation of monosubstituted thiacalix[4]arene with di-<Emphasis Type="Italic">tert</Emphasis>-butyl dicarbonate

Mono-, di-, and tetrasubstituted derivatives of p-tert-butylthiacalix[4]arene containing tert-butylcarbamate, tert-butylcarbonate, and tert-butyl fragments have been prepared for the first time. Depending on the reaction conditions (reagents ratio, temperature, and the presence of a base), the interaction of the monoamine derivative of p-tert-butylthiacalix[4]arene with di-tert-butyl dicarbonate can lead to the formation of mono-, di-, and tetrasubstituted products.