JPH0369900B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing special organic peroxides. More specifically, it relates to a method for selectively producing β-hydroxyperoxide compounds and/or cyclic peroxyketal compounds, which are industrially very useful intermediate raw materials, by reacting an oxirane compound and an organic hydroperoxide in the presence of a catalyst. . Until now, not much has been known about β-hydroxyperoxide compounds and cyclic peroxyketal compounds, and only a few publications describe these compounds. For example, isobutylene oxide using sulfuric acid as a catalyst and t-
Reaction with butyl hydroperoxide (WH
Richardson and RSSmith.J.Org.CHEW., 10 ,
3882 (1968)) or 98 in ether without catalyst.
% concentration of hydrogen peroxide and isobutylene oxide,
Synthesis of the corresponding β-hydroxy hydroperoxide compounds by reaction with oxirane compounds such as α-methylstyrene oxide and 1,1-diphenylethylene oxide (W.
Adam and A. Rios, Chem.Comm., 1971 822)
etc. have been reported. Incidentally, the latter document also shows a synthesis example of a cyclic peroxyketal compound by a method different from the method of the present invention. Furthermore, examples using strong acids or strong bases such as trifluoroacetic acid or potassium hydroxide as catalysts are also known (Y. Ogata, Y. Sawaki and H.
Shimizu, J.Org.Chem., 43 , 1760 (1978)). However, in these examples, since strong acids or strong bases are used as catalysts, the oxirane compound is consumed by side reactions, and the generated β-hydroxyperoxide compound is decomposed, resulting in a decrease in the yield of the desired organic peroxide. Since the reaction time is low and there is no catalyst, the reaction time is extremely long, sometimes taking up to two weeks. From the above facts, it can be said that it was natural that it was completely unthinkable to utilize these β-hydroxyperoxide compounds and/or cyclic peroxyketal compounds industrially. The present inventors have conducted detailed studies on the reaction of β-hydroxyperoxide compounds and cyclic peroxyketal compounds, and have found that these can be converted into aldehyde compounds or ketone compounds by thermal or catalytic decomposition. I found out. For example, β-hydroxycyclopentyl peroxide compounds and 2,3,5-trioxabicyclo[4,3,0]
An example of this is a proposal for a method for producing glutaraldehyde from a compound having a nonane bone core (Japanese Patent Publication No. 1-38773 and Japanese Patent Publication No. 1-38773).
-7299 Publication). The present inventors recognized the industrial importance of such β-hydroxyperoxide compounds and cyclic peroxyketal compounds, and as a result of intensive research into inexpensive and efficient production methods for these compounds, the present invention was developed. It was completed. In other words, the present invention is directed to a compound of the general formula (R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen or a linear or branched aliphatic, alicyclic or aromatic organic group having 1 to 30 carbon atoms. However, R ₁ ,
The sum of the carbon numbers of R ₂ , R ₃ and R ₄ is 3 or more.
R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may be linked to form a ring. ) and the general formula (R ₆ and R ₇ are each an organic group having 1 to 10 carbon atoms. _{R 6} and R ₇ may be connected to form a ring.) Featured general formula (R ₈ is hydrogen or

[Formula]. ) and/or general formula The present invention relates to a method for producing an organic peroxide shown in the following. The method of the present invention is characterized in that a β-hydroxyperoxide compound and/or a cyclic peroxyketal compound can be selectively produced in good yield from an oxirane compound and an organic hydroperoxide. That is, according to the method of the present invention, 1,2
- There are almost no glycols, polymers and other by-products, and the resulting β-hydroxyperoxide compounds and/or cyclic peroxyketal compounds are stable and will not decompose or be consumed through further reactions. Therefore, it has the characteristic that the produced organic peroxide can be easily purified. The organic peroxide produced by the method of the present invention has the general formula (R ₆ is hydrogen or

[Formula]. ) β-hydroxyperoxide compound and/or general formula represented by This is a cyclic peroxyketal compound represented by To give specific examples of these compounds:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. The catalyst used in the process of the invention is a mixture of at least one or more elements and compounds selected from the group consisting of boron, titanium, zirconium, vanadium, chromium, molybdenum and tungsten. These compounds are used in the form of complexes of elements with zero valence, or inorganic or organic compounds with various valences. Compounds of these elements include oxides, mixed oxides, hydroxides, oxyacids, heteropolyacids, salts and esters thereof. These include those derived from inorganic hydroacids, oxyacids, and organic carboxylic acids or sulfonic acids having 40 or less carbon atoms. Complexes of these elements are mainly called organometallic complexes, which are coordinated by organic groups and/or inorganic groups. Examples of catalysts that can be used in the present invention are as follows. namely, the elemental metals titanium, zirconium, vanadium, chromium, molybdenum, and tungsten; oxides of boron, titanium, zirconium, vanadium, chromium, molybdenum, and tungsten (H ₃ BO ₃ , HBO ₂ , B ₂ O ₃ , TiO ₂ ,
_{ZrO2 , VO2} , _V2O5 , _CrO2 , _Cr2O3 , _{CrO3 ,}
MoO ₂ , Mo ₂ O ₅ , MoO ₃ , WO ₂ , W ₂ O ₅ , WO ₆ , etc.); oxychlorides, fluorides, chlorides, bromides, iodides of these elements; nitrates, pyrophosphates of these elements , polyphosphates, borates, carbonates,
Formate, acetate, propionate, butyrate, isobutyrate, caproate, laurate, stearate, oxalate, succinate, adipate, benzoate, phthalate, etc. Organic acid salts, benzenesulfonates; acetylacetonates and phthalocyanine complexes of these elements; metal carbonyls of these elements [V(CO) ₆ , Cr(CO) ₆ , Mo(CO) ₆ ,
W(CO) ₆ etc.]; oxyacids such as molybdic acid, chromic acid, tungstic acid, corresponding heteropolyacids, and alkali metal salts or alkaline earth metal salts of the above acids. There is no problem in using a mixture of one or more of the above-mentioned single substances and compounds. Furthermore, it is also possible to use one or more of the above-mentioned simple substances and compounds by supporting them on a carrier such as alumina, silica, silica-alumina, zeolite, etc., or in some cases, an organic polymer, according to a known method. In the present invention, an oxirane compound represented by the following general formula is used. Here, R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen, a linear or branched aliphatic group having 1 to 30 carbon atoms,
It is an alicyclic or aromatic organic group. however,
The sum of the carbon numbers of R ₁ , R ₂ , R ₃ and R ₄ is 3 or more. R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may be linked to form a ring. Any of these oxirane compounds can be synthesized by epoxidizing a compound having an olefinic carbon-carbon double bond according to a known method. Specific examples of these oxirane compounds are as follows. 1,2-epoxypentane, 2,3-epoxypentane, 3,4-epoxyhexane, 1,2-epoxyheptane, 2,3
-Epoxyheptane, 3,4-epoxyoctane, 1,2-epoxynonane, 4,5-epoxynonane, 2,3-epoxydecane, 5,6-epoxydecane, 1,2-epoxyundecane, 3,
4-Epoxytetradecane, 1,2-epoxyoctadecane, 3,4-epoxy-2,5-dimethylhexane, 3,4-epoxy-1,6-dichlorohexane, 3,4-epoxy-1,6-dihydroxy Hexane, 3,4-epoxy-1,7-dimethoxyheptane, 4,5-epoxy-1,8-
Dicyanooctane, styrene oxide, cyclopentene oxide (1,2), 3-chlorocyclopentene oxide (1,2), 4-phenylcyclopentene oxide (1,2), 4-cyanocyclopentene oxide (1,2) ), cyclohexene oxide-(1,2), 4-ethoxy-cyclohexene oxide-(1,2), cycloheptenoxide-(1,2), cyclododecene oxide-(1,
2), 3-oxatricyclo[3,2,1,0 ^2,4 ]
Octane, 5-oxatetracyclo[6,2,
1,0 ^2,7 ,0 ^4,6 ] undecane. The peroxide used in the method of the invention has the general formula (R ₆ and R ₇ are each an organic group having 1 to 10 carbon atoms. R ₆ and R ₇ may be connected to form a ring.) It is an organic hydroperoxide represented by the following. Specific examples of such organic hydroperoxides include

【formula】 【formula】

and so on. Next, the solvent used in carrying out the method of the present invention is a hydrocarbon having 3 to 16 carbon atoms, or a hydrocarbon having 1 carbon number.
These include carboxylic acid esters, phosphoric acid esters, sulfonic acid esters, carboxylic acid amides, tertiary alcohols, and ethers containing ~12 organic groups. Specific examples of these solvents include n-pentane, isopentane, cyclopentane, cyclopentene, n-hexane, isohexane, cyclohexane, octane, dodecane, benzene, toluene, xylene, ethylbenzene, ethyl acetate,
Butyl acetate, isoamyl acetate, cyclohexyl acetate, butyl propionate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dimethylformamide, dimethylacetamide, triethyl phosphate, trihexyl phosphate, trioctyl phosphate, dimethyl methanephosphonate, t-butyl alcohol , diethyl ether, anisole, etc. Preferably, the method is carried out in a non-aqueous system. Therefore, the organic hydroperoxide used is preferably dehydrated before the reaction. The concentration of the organic hydroperoxide used in the present invention in the reaction solution is 1 to 1 to prevent heat generation and runaway due to rapid reaction.
It is desirable that the amount is 50 wt%, preferably 3 to 40 wt%. The proportions of oxirane compound and organic hydroperoxide used in the practice of this invention can vary over a wide range. However, the use of residual organic hydroperoxide is not only uneconomical, but also requires a large amount of energy for recovery or post-treatment of unreacted organic hydroperoxide. Therefore, the organic hydroperoxide is preferably used in an amount of 0.05 to 3.0 mol, preferably 0.1 to 1.5 mol, per 1 mol of the oxirane compound. When reacting an oxirane compound with an organic hydroperoxide according to the method of the present invention, the amount of catalyst can be varied over a wide range depending on its activity, but is generally 10 ^-7 mol per mol of oxirane compound. It is preferred to use an amount of from 10 -5 mol to 0.05 mol, especially from 10 ^-5 mol to 0.01 mol. The temperature at which the method of the present invention is carried out is not preferably high enough to cause self-decomposition of the organic hydroperoxide as a raw material and the β-hydroxyperoxide compound or cyclic peroxyketal compound as a product; It is economically unfavorable. Therefore, this method is −
A temperature range of 20°C to 150°C is preferred, and it is particularly desirable to carry out the process in a temperature range of 0°C to 100°C. This reaction can be carried out either batchwise or continuously, and the reaction time varies depending on the reaction temperature and the composition of the reaction system, but it is usually sufficient to carry out the reaction for 10 hours. Example 1 MoO ₂ in a 300 c.c. capacity three-necked flask equipped with a stirrer, reflux condenser, and addition funnel.
( _C5H7O2 ) _{2 0.5g} and _dimethyl phthalate 150g
A mixture of 41 g of cyclopentene oxide and 140 g of a dimethyl phthalate solution containing 20 wt % of methyl ethyl ketone peroxide was added dropwise to the flask over 1.5 hours using a dropping funnel while stirring while keeping the flask at 35°C. After the completion of the dropwise addition, the reaction was further carried out at 35°C for 5 hours, and then the catalyst was filtered off. After removing dimethyl phthalate from the filtrate by vacuum distillation, the concentrated solution was subjected to liquid chromatography using silica gel as the stationary phase and benzene:ethanol = 20:1 as the mobile phase. 2,4,5-
Trioxabicyclo[4,3,0]nonane 35g
and 18 g of β-hydroxycyclopentyl hydroperoxide were obtained. The yields of peroxide and peroxide were 41% and 31%, respectively. Example 2 A dimethyl phthalate solution containing 55 g of norbornane oxide and 40 g of methyl isobutyl ketone peroxide at 44° C. in a solution of 0.4 g of MoO ₃ and 80 g of dimethyl phthalate as in Example 1.
A mixture consisting of 150 g was added dropwise over a period of 1.5 hours. After completion of the dropwise addition, the reaction was further carried out at 44°C for 6 hours, and then subjected to liquid chromatography in the same manner as in Example 1, yielding 23.5 g of the above product.

Claims (1)

[Claims] 1. In the presence of a catalyst containing at least one element selected from the group consisting of boron, titanium, zirconium, vanadium, chromium, molybdenum and tungsten and/or a compound thereof, the general formula (R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen or a linear or branched aliphatic, alicyclic or aromatic organic group having 1 to 30 carbon atoms. However, R ₁ ,
The sum of the carbon numbers of R ₂ , R ₃ and R ₄ is 3 or more.
R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may be linked to form a ring. ) and the general formula (R ₆ and R ₇ are each an organic group having 1 to 10 carbon atoms. _{R 6} and R ₇ may be connected to form a ring.) Featured general formula (R ₈ is hydrogen or [formula].) and/or general formula A method for producing an organic peroxide shown in