5809-08-5

Basic information

• Product Name: 1,1,3,3-Tetramethylbutyl hydroperoxide
• Synonyms: hydroperoxide, 1,1,3,3-tetramethylbutyl;Hydroperoxide,1,1,3,3-tetramethyl butyl;2-(Hydroperoxy)-2,4,4-trimethylpentane;1,1,3,3-tetramethylbutyl hydropereoxide;Einecs 227-369-2
• CAS NO: 5809-08-5
• Molecular Formula: C₈H₁₈O₂
• Molecular Weight: 146.23
• EINECS: 227-369-2
• Mol File: 5809-08-5.mol

Chemical Properties

• Boiling Point: 197.7°Cat760mmHg
• Flash Point: 73.4°C
• Appearance: /
• Density: 0.888g/cm³
• Vapor Pressure: 5.98E-17mmHg at 25°C
• Refractive Index: 1.758
• PKA: 12.71±0.50(Predicted)
• Water Solubility: 2.8g/L at 20℃
• CAS DataBase Reference: 1,1,3,3-Tetramethylbutyl hydroperoxide(CAS DataBase Reference)
• NIST Chemistry Reference: 1,1,3,3-Tetramethylbutyl hydroperoxide(5809-08-5)
• EPA Substance Registry System: 1,1,3,3-Tetramethylbutyl hydroperoxide(5809-08-5)

Safety Data

• RIDADR: 3105
• HazardClass: 5.2
• PackingGroup: II
• Hazardous Substances Data: 5809-08-5(Hazardous Substances Data)

Usage

General Description

1,1,3,3-Tetramethylbutyl hydroperoxide is heat and contamination sensitive.

Reactivity Profile

Most alkyl monohydroperoxides are liquid, the explosivity of the lower members (e.g., methyl hydroperoxide, or possibly due to traces of the dialkyl peroxides) decreasing with increasing chain length and branching [Bretherick 2nd ed. 1979 p.10].

InChI:InChI=1/C20H14N6O6S/c1-2-32-19(29)15(23-22-11-7-9-12(10-8-11)26(30)31)16(27)18-24-25-14-6-4-3-5-13(14)17(28)21-20(25)33-18/h3-10,22H,2H2,1H3/b23-15+

Synthetic route

2,4,4-trimethyl-2-pentanol (690-37-9) → 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5)

Conditions	Yield
With sulfuric acid; dihydrogen peroxide In water at 5 - 110℃; for 0.0533333h; Temperature; Flow reactor;	76.4%
With dihydrogen peroxide In water

2,2,4-trimethylpentane (540-84-1) → 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5)

Conditions	Yield
With sulfuric acid; dihydrogen peroxide In water

2,2,4-trimethylpentane (540-84-1) → 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) + 1-isopropyl-2,2-dimethyl-propyl hydroperoxide + 2,2,4-Trimethyl-pent-1-yl-hydroperoxide + 2,4,4-Trimethyl-pent-1-yl-hydroperoxide

Conditions	Yield
With dihydrogen peroxide; oxygen; [n-Bu4N]VO3; 2,3,4,5,6-pentachloroaniline In acetonitrile at 50℃; Product distribution; Further Variations:; Reagents; Temperatures;

2,2,4-trimethylpentane (540-84-1) → 2,2,4-trimethylpentanone (5857-36-3) + 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) + 1-isopropyl-2,2-dimethyl-propyl hydroperoxide + 2,4,4-Trimethyl-pent-1-yl-hydroperoxide

Conditions	Yield
With 2-pyrazylcarboxylic acid; dihydrogen peroxide; [(1,4,7-triazacyclononane-Fe(II))2(O)][(CH3COO)2] In acetonitrile Product distribution; Further Variations:; Catalysts; Reagents;

2,4,4-trimethyl-1-pentene (107-39-1) + pyridine-BH3 → 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 65percent H2O2 / H2O / 0 - 5 °C 2: 50percent H2O2 / H2O View Scheme

cycloxexanone dimethyl ketal (933-40-4) + 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) → 1,1-Bis-(1,1,3,3-tetramethyl-butylperoxy)-cyclohexane

Conditions	Yield
With toluene-4-sulfonic acid In dimethyl sulfoxide at 20℃; under 15 - 20 Torr;	88.3%

cycloxexanone dimethyl ketal (933-40-4) + 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) → 1-methoxy-1-(1,1,3,3-tetramethylbutylperoxy)cyclohexane

Conditions	Yield
With toluene-4-sulfonic acid In dimethyl sulfoxide at 20℃;	72.7%

1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) → 2,4,4-trimethyl-2-pentanol (690-37-9)

Conditions	Yield
With sulfuric acid; iron(II) sulfate
Multi-step reaction with 2 steps 1: Py / pyridine 2: CuBr / benzene View Scheme

1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) + acetyl chloride (75-36-5) → peroxyacetic acid 1,1,3,3-tetramethyl-butyl ester (926-13-6)

Conditions	Yield
With Py In pyridine

2-methyl-1,2-epoxypropane (558-30-5) + 1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) → 2-Methyl-2-(1,1,3,3-tetramethyl-butylperoxy)-propan-1-ol

Conditions	Yield
With trifluoroacetic acid In benzene at 35℃; for 0.5h;	62 % Chromat.

1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) + pivaloyl chloride (3282-30-2) → 2-neopentyl-2-propyl peroxypivalate (22288-41-1)

Conditions	Yield
With potassium hydroxide In water at 0 - 5℃; for 0.5h;
Acylation;

1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) + tert-butyl alcohol (75-65-0) → t-butyl 1,1,3,3-tetramethylbutyl peroxide (85153-88-4)

Conditions	Yield
With sulfuric acid 1.) 0 deg C, 20 min, 2.) 25 deg C, 2 h; Yield given. Multistep reaction;

1,1,3,3-tetramethylbutyl hydroperoxide (5809-08-5) + 2-Methylpropionic anhydride (97-72-3) → 1,1,3,3-tetramethylbutyl peroxy isobutyrate

Conditions	Yield
With sodium hydroxide at 20℃; for 2.16667h;

Upstream product

• 540-84-1 2,2,4-trimethylpentane 
• 107-39-1 2,4,4-trimethyl-1-pentene 
• 690-37-9 2,4,4-trimethyl-2-pentanol 

Downstream Products

• 690-37-9 2,4,4-trimethyl-2-pentanol 
• 22288-41-1 2-neopentyl-2-propyl peroxypivalate 
• 85153-88-4 t-butyl 1,1,3,3-tetramethylbutyl peroxide 

Relevant articles and documents

ONLINE CONTINUOUS FLOW PROCESS FOR THE SYNTHESIS OF ORGANIC PEROXIDES USING HYDROGEN PEROXIDE AS RAW MATERIAL

An online continuous flow production process for directly preparing organic peroxides by using hydrogen peroxide as a raw material. This production process uses hydrogen peroxide, catalyst, and an oxidation substrate as a raw material. Substrate will be turned to designated peroxides sequentially through oxidation and workup. This process is performed in a plug-and-produce integrated continuous flow reactor, and the raw materials are continuously fed to the reactor. So, specified peroxide can be continuously obtained at the outlet of the plug-and-produce integrated continuous flow reactor.

Lithographic printing method

A lithographic printing plate precursor comprising a support and an image-recording layer containing at least one infrared absorbing agent of a cyanine dye in which a HOMO energy level of each of substituents present on both terminal nitrogen atoms is -10.0 eV or higher. An infrared absorbing agent of a cyanide dye represented by formula (V) shown below: wherein Z 1 and Z 2 each independently represents an aromatic ring which may have a substituent or a hetero aromatic ring which may have a substituent; R 10 and R 20 each independently represents a phenyl group, a naphtyl group, an anthracenyl group, a carbazolyl group or a phenothiazinyl group each of which may have a substituent; A - represents an anion which exists in case of being necessary for neutralizing a charge and is selected from a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion and a sulfonate ion; and n represents 1 or 2.

Hydrogen peroxide oxygenation of alkanes including methane and ethane catalyzed by iron complexes in acetonitrile

This paper describes an investigation of the alkane oxidation with hydrogen peroxide in acetonitrile catalyzed by iron(III) perchlorate (1), iron(III) chloride (2), iron(III) acetate (3) and a binuclear iron(III) complex with 1,4,7-triazacyclononane (4). The corresponding alkyl hydroperoxides are the main products. Nevertheless in the kinetic study of cyclohexane oxidation, the concentrations of oxygenates (cyclohexanone and cyclohexanol) were measured after reduction of the reaction solution with triphenylphosphine (which converts the cyclohexyl hydroperoxide to the cyclohexanol). Methane and ethane can be also oxidized with TONs up to 30 and 70, respectively. Chloride anions added to the oxidation solution with 1 activate the perchlorate iron derivative in acetonitrile, whereas the water as additive inactivates 2 in the H 2O2 decomposition process. Pyrazine-2-carboxylic acid (PCA) added to the reaction mixture decreases the oxidation rate if 1 or 2 are used as catalysts, whereas compounds 3 and 4 are active as catalysts only in the presence of small amount of PCA. The investigation of kinetics and selectivities of the oxidations demonstrated that the mechanisms of the reactions are different. Thus, in the oxidations catalyzed by the 1, 3+PCA and 4+ PCA systems the main oxidizing species is hydroxyl radical, and the oxidation in the presence of 2 as a catalyst has been assumed to proceed (partially) with the formation of ferryl ion, (FeIV=O)2+. In the oxidation catalyzed by the 4+PCA system (TONs attain 240) hydroxyl radicals were generated in the rate-determining step of monomolecular decomposition of the iron diperoxo adduct containing one PCA molecule. A kinetic model of the process which satisfactorily describes the whole set of experimental data was suggested. The constants of supposed equilibriums and the rate constant for the decomposition of the iron diperoxo adduct with PCA were estimated.

Oxidations by the reagent "O2-H2O2-vanadium derivative-pyrazine-2-carboxylic acid". Part 12. Main features, kinetics and mechanism of alkane hydroperoxidation

Various combinations of vanadium derivatives (n-Bu4NVO3 is the best catalyst) with pyrazine-2-carboxylic acid (PCA) catalyse the oxidation of saturated hydrocarbons, RH, with hydrogen peroxide and air in acetonitrile solution to produce, at temperatures V(PCA)(H2O2) → VIV(PCA) + HOO. + H+. The VIV species thus formed reacts further with a second H2O2 molecule to generate the hydroxyl radical according to the equation VIV(PCA) + H2O2 → VV(PCA) + HO. + HO-. The concentration of the active species in the course of the catalytic process has been estimated to be as low as [V(PCA)H2O2] ≈ 3.3 × 10-6 mol dm-3. The effective rate constant for the cyclohexane oxidation (d[ROOH]/dt = keff[H2O2]0[V]0) is keff = 0.44 dm3 mol-1 s-1 at 40 °C, the effective activation energy is 17 ± 2 kcal mol-1. It is assumed that the accelerating role of PCA is due to its facilitating the proton transfer between the oxo and hydroxy ligands of the vanadium complex on the one hand and molecules of hydrogen peroxide and water on the other hand. For example: (pca)(O=)V ... H2O2 → (pca)(HO-)V-OOH. Such a "robot's arm mechanism" has analogies in enzyme catalysis.

Homolytic Decomposition of t-Alkyl 2,2-Dimethylperoxypropionates

Decomposition rates and products of t-alkyl 2,2-dimethylperoxypropionates were measured in cumene at several temperatures.The peroxyesters decomposed homolitycally, depending on the structure of the t-alkyl moiety.The relative rates of the t-alkyl moieties to the 1,1-dimethylethyl one were: 1,1-dimethylbutyl (1.14), 1,1-dimethylpropyl (1.19), 1,1,2-trimethylpropyl (1.85), 1,1,3,3-tetramethylbutyl (2.10), and 1,1-dimethyl-2-phenylethyl (2.34).The decomposition showed an isokinetic relationship and the importance of stabilization by hyperconjugation.Based on these data, the decomposition mechanism, which contains a slight stretching of the Cα-Cβ bond to the peroxyl oxygen at the transition state is, discussed.

Novel organic peroxides and their use in the preparation of epoxide groups containing (co)polymers

Novel organic peroxides of the general formula wherein p = 0 or 1 and n = 1, 2, 3 or 4 are described. These peroxides are excellently suitable for use in the preparation of epoxide groups-containing (co)polymers. Also described are shaped objects obtained by using (co)polymers thus modified.