3006-86-8

Basic information

• Product Name: 1,1-Di(tert-butylperoxy)cyclohexane
• Synonyms: 1,1-BIS(T-BUPEROXY)CYCLOHEXANE, 80 WT. %;1 1-BIS(T-BUTYLPEROXY)CYCLOHEXANE TECH&;50%solutioninmineraloil;1,1-Di(tert-butylperoxy)cyclohexane, 50% solution in mineral oil;1,1-Di-(tert.-butylperoxy)-cyclohexan;Cyclohexylidenebis[(1,1-dimethylethyl)peroxide];Luperox(R) 331P80;1,1-Bis(tert-butylperoxy)cyclohexane (Luperox(R) 331M80) solution
• CAS NO: 3006-86-8
• Molecular Formula: C₁₄H₂₈O₄
• Molecular Weight: 260.37
• EINECS: 221-111-2
• Product Categories: Industrial/Fine Chemicals
• Mol File: 3006-86-8.mol

Chemical Properties

• Melting Point: 65 °C (SADT)
• Boiling Point: 52-54 °C (0.1 mmHg)
• Flash Point: 155 °F
• Appearance: Clear/Liquid
• Density: 0.891 g/mL at 25 °C
• Vapor Pressure: 0.00705mmHg at 25°C
• Refractive Index: n20/D 1.435
• Storage Temp.: Refrigerator (+4°C)
• Water Solubility: miscible
• CAS DataBase Reference: 1,1-Di(tert-butylperoxy)cyclohexane(CAS DataBase Reference)
• NIST Chemistry Reference: 1,1-Di(tert-butylperoxy)cyclohexane(3006-86-8)
• EPA Substance Registry System: 1,1-Di(tert-butylperoxy)cyclohexane(3006-86-8)

Safety Data

• Hazard Codes: O,N,T
• Statements: 7-62-50/53-36/37/38-61-65-45-51/53
• Safety Statements: 17-36/37/39-3/7-14A-61-60-45-26-14-53-62
• RIDADR: UN 3103 5.2
• WGK Germany: 2
• HazardClass: 5.2
• PackingGroup: II
• Hazardous Substances Data: 3006-86-8(Hazardous Substances Data)

Usage

Chemical Properties

clear liquid

Uses

Polymerization initiator.

Reactivity Profile

The explosive instability of the lower dialkyl peroxides (e.g., dimethyl peroxide) and 1,1-bis-peroxides decreases rapidly with increasing chain length and degree of branching, the di-tert-alkyl derivatives being amongst the most stable class of peroxides. Though many 1,1-bis-peroxides have been reported, few have been purified because of the higher explosion hazards compared with the monofunctional peroxides. 1,1-Di(tert-butylperoxy)cyclohexane is unlikely that this derivative would be particularly unstable compared to other peroxides in it's class, Bretherick 2nd ed., p 44 1979.

Flammability and Explosibility

Notclassified

InChI:InChI=1/C14H28O4/c1-12(2,3)15-17-14(10-8-7-9-11-14)18-16-13(4,5)6/h7-11H2,1-6H3

Synthetic route

tert.-butylhydroperoxide (75-91-2) + cycloxexanone dimethyl ketal (933-40-4) → 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8)

Conditions	Yield
With tetrafluoroboric acid In diethyl ether; Petroleum ether at 20℃; for 3h;	92%

tert.-butylhydroperoxide (75-91-2) + 1-methoxy-cyclohex-1-ene (931-57-7) → 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8)

Conditions	Yield
With tetrafluoroboric acid In Petroleum ether at 20℃; for 3h;	91%

tert.-butylhydroperoxide (75-91-2) + cyclohexanone (108-94-1) → 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8)

Conditions	Yield
With sulfuric acid at 15℃; for 2h;	89%
With sulfuric acid In toluene at 0 - 12℃; for 0.75h;	58%
With sulfuric acid In various solvent(s) at 10℃; for 0.5h;	43%

tert.-butylhydroperoxide (75-91-2) + 1-tert-butylperoxycylohexanol (25813-15-4) → 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8)

Conditions	Yield
With sulfuric acid In 1,4-dioxane at 25℃; Equilibrium constant; Rate constant;

1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) + ethyl 3-hydroperoxy-2-methylenebutanoate (100841-11-0) → ethyl 2-<1-<<1-(tert-butylperoxy)-1-cyclohexyl>peroxy>ethyl>propenoate

Conditions	Yield
With toluene-4-sulfonic acid	74%

styrene (100-42-5) + 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) → 2-(2-(tert-butylperoxy)-2-phenylethyl)cyclohexan-1-one

Conditions	Yield
With methanesulfonic acid; toluene-4-sulfonic acid In acetonitrile at 20℃; for 4h; Schlenk technique;	65%

pyridine N-oxide (694-59-7) + 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) → 2-methylpyridine N-oxide (931-19-1) + 2,6-lutidine N-oxide (1073-23-0)

Conditions	Yield
In neat (no solvent) at 120℃; for 24h; Sealed tube; Inert atmosphere; Schlenk technique;	A 38% B 13%

1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) → tert.-butylhydroperoxide (75-91-2) + 1-tert-butylperoxycylohexanol (25813-15-4)

Conditions	Yield
With sulfuric acid; water In 1,4-dioxane at 25℃; Equilibrium constant;

1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) → dicumene (1889-67-4) + tert-butyl peroxyhexanoate (10100-94-4) + acetone (67-64-1) + tert-butyl alcohol (75-65-0) + pentane (109-66-0)

Conditions	Yield
In various solvent(s) at 80℃; for 40h; Mechanism; Product distribution;	A 71 % Chromat. B 42 % Chromat. C 8 % Chromat. D 139 % Chromat. E 2 % Chromat.
In nonane at 100℃; Rate constant;
In dodecane at 100℃; Rate constant; n-hexadecane as solvent;
In hexane at 100℃; Rate constant;

Isopropylbenzene (98-82-8) + 1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) → dicumene (1889-67-4) + tert-butyl peroxyhexanoate (10100-94-4) + tert-butyl cumyl peroxide (3457-61-2) + cyclohexanone (108-94-1) + acetone (67-64-1) + tert-butyl alcohol (75-65-0) + polyester of 2-hydroxyhexanoic acid

Conditions	Yield
at 80℃; Kinetics; Rate constant; Thermodynamic data; ΔH(excit.), ΔS(excit.); mechanism; var. temperat.;

...Expand

1,1-bis(tert-butylperoxy)cyclohexane (3006-86-8) → tert-butyl 8,9-epoxy-8-(ethoxycarbonyl)perdecanoate

Conditions	Yield
Multi-step reaction with 2 steps 1: 74 percent / p-toluenesulfonic acid monohydrate 2: 90 percent / Et3B, O2 / benzene; hexane / 0.5 h / 20 °C View Scheme

Upstream product

• 75-91-2 tert.-butylhydroperoxide 
• 108-94-1 cyclohexanone 
• 25813-15-4 1-tert-butylperoxycylohexanol 
• 933-40-4 cycloxexanone dimethyl ketal 
• 931-57-7 1-methoxy-cyclohex-1-ene 

Downstream Products

• 75-91-2 tert.-butylhydroperoxide 
• 25813-15-4 1-tert-butylperoxycylohexanol 
• 1889-67-4 dicumene 
• 10100-94-4 tert-butyl peroxyhexanoate 
• 67-64-1 acetone 
• 75-65-0 tert-butyl alcohol 
• 109-66-0 pentane 
• 3457-61-2 tert-butyl cumyl peroxide 
• 108-94-1 cyclohexanone 
• 931-19-1 2-methylpyridine N-oxide 
• 1073-23-0 2,6-lutidine N-oxide 

Relevant articles and documents

Neutral Organic Super Electron Donors Made Catalytic

Neutral organic super electron donors (SEDs) display impressive reducing power but, until now, it has not been possible to use them catalytically in radical chain reactions. This is because, following electron transfer, these donors form persistent radical cations that trap substrate-derived radicals. This paper unlocks a conceptually new approach to super electron donors that overcomes this issue, leading to the first catalytic neutral organic super electron donor.

Lithographic printing method

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Synthesis of geminal bisperoxides by acid-catalyzed reaction of acetals and enol ethers with tert-butyl hydroperoxide

A new efficient procedure was developed for the synthesis of geminal bisperoxides by reaction of ketals and enol ethers with tert-butyl hydroperoxide catalyzed by protic or Lewis acids. Georg Thieme Verlag Stuttgart.

Substituent Effects on the Decomposition of Bis(tert-butylperoxy)cycloalkanes

Decompositions of bis(tert-butylperoxy)cycloalkanes have been carried out in cumene and n-alkanes at temperatures of 80-120 deg C and have been compared mainly with the decomposition of tert-alkyl tert-butyl peroxides in order to investigate substituent effects on the homolytic scission of one O-O bond in gem-diperoxides.The decomposition rates of bis(tert-butylperoxy)cycloalkanes are much faster than those of tert-alkyl tert-butyl peroxides; the decomposition rates of the cycloalkanes decrease in the following order: cyclopentane > 3,5,5-trimethylcyclohexane > cyclohexane > cyclooctane > cyclododecane.The effect of ring size on the decomposition and the isokinetic relationships between the activation parameters suggest that stabilization of the transition state by electron donation from the cycloalkyl substituents and repulsion between lone-pair electrons on different peroxy oxygen atoms in the ground state are important factors in the decomposition of gem-diperoxides.

Radical Intermediates in the Thermal Decomposition of 1,1-Bis(t-butyldioxy)cyclohexane

The thermolysis mechanism of 1,1-bis(t-butyldioxy)cyclohexane (6) has been studied in solutions.The activation parameters obtained in cumene are ΔH=139.5 kJ mol-1 and ΔS=44.8 J K-1 mol-1, and the volatile products are t-butyl alcohol, t-butyl peroxyhexanoate, and 2,3-dimethyl-2,3-diphenylbutane along with minor products of acetone, cyclohexanone, and t-butyl 1-methyl-1-phenylethyl peroxide.The thermolysis of 6 in benzene gave acetone and t-butyl alcohol as major volatile products.The polyester of 2-hydroxyhexanoic acid was obtained both in cumene and benzene as a non-volatile product, and the yield was as high as 76percent in benzene.These facts indicate that oxyl radical (7) undergoes a facile ring-opening reaction yielding 5-(t-butyldioxycarbonyl)pentyl radical (8).The resulting radicals abstract hydrogen atoms either intra- or intermolecularly.The former reaction is predominant in the absence of good hydrogen donors, affording 2-hexanolide and ultimately the corresponding polyesters.

2-Hydrocarbyl ethers of cycloaliphatic ketones and process for their preparation

Compounds of the formula EQU1 WHEREIN R is a hydrocarbyl radical selected from the group consisting of alkyl, aralkyl and cycloalkyl having from 3 to 12 carbon atoms and n is an integer from 1 to 9 are prepared by reacting a 1,1-bis (hydrocarbyl peroxy) cycloalkane with cycloaliphatic ketones in the presence of a molybdenum containing catalyst. The 1,1-bis (hydrocarbyl peroxy) cycloalkane can be prepared in situ from an organic hydroperoxide and a cycloalkanone. The compounds have utility as solvents and certain specific members of the class have utility as intermediates to adipic acid by further oxidation or as an intermediate to 2-t-butoxyphenol by known dehydrogenation methods.