Synthesis of tert-butyl hydroperoxide and tert-butyl peroxide and their optical investigation in relation to the problem of the structure of hydrogen peroxide

Meshcheryakov, A. P.; Batuev, M. I.; Matveeva, A. D.

doi:10.1007/bf01167351

Cited by 5 publications

(3 citation statements)

References 4 publications

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“…In a solvent of CCl 4 , the presence of an intramolecular hydroperoxide OH−π hydrogen bond has been observed in isopropylbenzene hydroperoxide based on the observation of two peaks in the OH-stretching region, and similarly, an intramolecular OH–O hydrogen bond has been reported in 2,4-dimethyl-2-hydroperoxy-3-pentanon. , In various solvents, the dimerization and formation of higher-order multimers of different hydroperoxides has been observed based on IR, Raman, and NMR spectroscopies. The hydroperoxides include tert -butyl hydroperoxide, deuterated tert -butyl hydroperoxide, isopropylbenzene hydroperoxide, tert -pentyl hydroperoxide, phenyl cyclohexane hydroperoxide, 3-phenylmethyl hydroperoxide, and two hydroperoxides from the oxidation of 2-methyltetrahydrofuran. − Similarly, on the basis of observed red shifts of the OH-stretching vibration in IR spectroscopy and changes in chemical shifts in NMR, complexes with various hydroperoxides as hydrogen-bond donors have been reported in different solvents with a wide range of hydrogen-bond acceptors: ketones, ethers, amines, alcohols, and various aromatic compounds. ,,− One of these studies comparing a number of different hydrogen-bond acceptors concludes that the hydrogen-bonding ability of hydroperoxides in the liquid phase is between that of alcohols and phenol…”

Section: Introductionmentioning

confidence: 99%

Side-by-Side Comparison of Hydroperoxide and Corresponding Alcohol as Hydrogen-Bond Donors

2017

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Hydroperoxides are formed in significant amounts in the atmosphere by oxidation of volatile organic compounds and are key in aerosol formation. In a room-temperature experiment, we detected the formation of bimolecular complexes of tert-butyl hydroperoxide (t-BuOOH) and the corresponding alcohol tert-butanol (t-BuOH), with dimethyl ether (DME) as the hydrogen-bond acceptor. Using a combination of Fourier-transform infrared spectroscopy and quantum chemical calculations, we compare the strength of the OH-O hydrogen bond and the total strength of complexation. We find that, both in terms of observed red shifts and determined equilibrium constants, t-BuOOH is a significantly better hydrogen-bond donor than t-BuOH, a result that is backed by a number of calculated parameters and can be explained by a weaker OH bond in the hydroperoxide. On the basis of combined experimental and theoretical results, we find that the hydroperoxide complex is stabilized by ∼4 kJ/mol (Gibbs free energy) more than the alcohol complex. Measured red shifts show the same trend in hydrogen-bond strength with trimethylamine (N acceptor atom) and dimethyl sulfide (S acceptor atom) as the hydrogen-bond acceptors.

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Section: Introductionmentioning

confidence: 99%

Side-by-Side Comparison of Hydroperoxide and Corresponding Alcohol as Hydrogen-Bond Donors

2017

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“…However, taking into account the high activity of HPS it is possible to assume that HPS also contains intermolecular hydrogen bonds in solution. If in the case of TBHP intermolecular hydrogen bonds are formed between the hydrogen atom of the peroxyl group of one hydroperoxide molecule and the oxygen atom of the peroxyl group of another molecule 24 , then in the case of HPS intermolecular hydrogen bonds are formed between the hydrogen atom of the peroxyl group of one hydroperoxide molecule and the oxygen atom of the non-peroxyl group of another molecule. This intermolecular hydrogen bond probably is more favourable to stabilization of the intermediate state of the epoxidation reaction and leads to a decreasing in O-H and O-O peroxyl group bond energy.…”

Section: Kinetic Studiesmentioning

confidence: 99%

Novel hydroperoxy sultam, 2-(6-bromo-pyrid-2-yl)-2,3,4,5,6,7-hexahydro-1,2-benzisothiazol-3-hydroperoxy 1,1-dioxide: synthesis, crystal structure and kinetics of catalytic interaction with cyclooctene

et al. 2008

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The novel hydroperoxy sultam, 2-(6-bromo-pyrid-2-yl)-2,3,4,5,6,7-hexahydro-1,2-benzisothiazol-3hydroperoxy 1,1-dioxide (HPS), was synthesized by the oxidation of the isothiazolium salt with hydrogen peroxide. As established by X-ray crystallography the unit cell of HPS in crystal state includes four molecules with a dimeric structure as a result of strong intermolecular hydrogen bond formation. The hydroperoxy sultam interacts with cyclooctene in the presence of molybdenum boride MoB as epoxidation catalyst at 40 1C. The additional consumption of HPS upon catalyst activation leads to an increase in the 1,2-epoxycyclooctane formation selectivity with increasing of HPS concentration. On the basis of the obtained results a kinetic reaction scheme was proposed. The equation for the reaction rate as well as the equation that connects the current concentration of hydroperoxide with reaction time and allows the calculation of the theoretical kinetic curves for HPS consumption were derived according to the kinetic scheme.

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“…tert -Butyl hydroperoxide (TBHP) is an important branch of alkyl hydroperoxides and is widely used as a catalyst, a cross-linking agent of unsaturated polyesters, a polymerization initiator, a rubber vulcanizing agent, etc. In the typical synthesis process, TBHP is generally obtained by the peroxidation of tert -butyl alcohol (TBA) with hydrogen peroxide (H 2 O 2 ) under the catalysis of sulfuric acid (H 2 SO 4 ). , However, since TBHP is produced, it would subsequently react with TBA and easily convert into di- tert -butyl peroxide (DTBP) as the byproduct . Besides, the oxidation of TBA is a strong exothermic reaction; overheating the reaction during the peroxidation process would lead to uncontrollable safety hazards.…”

Section: Introductionmentioning

confidence: 99%

Kinetics Study of the Peroxidation of tert-Butyl Alcohol to tert-Butyl Hydrogen Peroxide in a Microreactor

Zhu,

Yan,

Zhang

et al. 2023

Org. Process Res. Dev.

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tert-Butyl hydroperoxide (TBHP), an organic peroxide, is mainly used as a polymer initiator and is typically synthesized by the thermal reaction of tert-butyl alcohol (TBA) with hydrogen peroxide (H 2 O 2 ). In this study, we adopted sulfuric acid (H 2 SO 4 ) as the homogeneous catalyst to promote the peroxidation reaction of TBA in a microchannel reactor. The reaction conditions for the synthesis of TBHP were optimized, and the kinetic model of the synthesis was subsequently established. The results show that byproducts exist during the reaction as well, such as di-tert-butyl peroxide (DTBP). The reaction temperature was 50 °C, the optimum molar ratio of TBA to H 2 O 2 was determined to be 1:1, and the optimum molar ratio of H 2 SO 4 to TBA was determined to be 0.95. Kinetics studies showed that the pre-exponential factors for producing TBHP and DTBP were 1 × 10 19 and 3.12 × 10 25 , respectively, while the activation energies of the corresponding reactions were 131.72 and 179.33 kJ/mol, respectively. The calculation results of the kinetic model fit well with the concentration of the products measured during the microreactor experiments.

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Synthesis of tert-butyl hydroperoxide and tert-butyl peroxide and their optical investigation in relation to the problem of the structure of hydrogen peroxide

Cited by 5 publications

References 4 publications

Side-by-Side Comparison of Hydroperoxide and Corresponding Alcohol as Hydrogen-Bond Donors

Side-by-Side Comparison of Hydroperoxide and Corresponding Alcohol as Hydrogen-Bond Donors

Novel hydroperoxy sultam, 2-(6-bromo-pyrid-2-yl)-2,3,4,5,6,7-hexahydro-1,2-benzisothiazol-3-hydroperoxy 1,1-dioxide: synthesis, crystal structure and kinetics of catalytic interaction with cyclooctene

Kinetics Study of the Peroxidation of tert-Butyl Alcohol to tert-Butyl Hydrogen Peroxide in a Microreactor

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