JPH0350751B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing special organic peroxides. More specifically, the present invention relates to a method for selectively producing a β-hydroxyperoxide compound, which is an industrially very useful intermediate material, by reacting an oxirane compound with hydrogen peroxide or an organic hydroperoxide in the presence of a catalyst. Until now, not much has been known about β-hydroxyperoxide compounds, and only a few publications describe these compounds. For example, the reaction between isobutylene oxide and t-butyl hydroperoxide using sulfuric acid as a catalyst (WHRichardson and RSSmith, J.Org.
CHEM., 10 , 3882 (1968)) or hydrogen peroxide and isobutylene oxide, α-methylstyrene oxide, at a concentration of 98% in ether without catalyst.
Synthesis of the corresponding β-hydroxy hydroperoxide compounds by reaction with oxirane compounds such as 1,1-diphenylethylene oxide (W.Adam and A.Rios, Chem.Comm.,
1971 822) have been reported. 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 industrially. The present inventors have conducted detailed studies on the reaction of β-hydroxyperoxide compounds, and as a result,
We have discovered that these can be converted into aldehyde compounds or ketone compounds by thermal or catalytic decomposition. For example, there is a proposal for a method for producing glutaraldehyde from a β-hydroxycyclopentyl peroxide compound and a compound having a 2,3,5-trioxabicyclo[4,3,0]nonane core (Patent Publication No. 1 -38773 and Japanese Patent Publication No. 2-7299). The present inventors recognized the industrial importance of such β-hydroxyperoxide compounds, and as a result of intensive research into inexpensive and efficient production methods for these compounds, the present invention was completed. . That is, the present invention provides a method in which 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 , R ₂ ,
The sum of the carbon numbers of 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 hydrogen peroxide or the general formula R ₅ OOH (R ₅ is a straight or branched aliphatic chain having 1 to 16 carbon atoms,
It is an alicyclic or aromatic organic group. ) A general formula characterized by reacting with an organic hydroperoxide represented by (R ₈ is hydrogen or R ₅ ). According to the method of the present invention, β-
It is characterized by the ability to selectively produce hydroxyperoxide compounds with good yield. That is, according to the method of the present invention, there is almost no 1,2-glycol, polymers, and other by-products, and the produced β-
Because hydroxyperoxide compounds are stable, they do not decompose or undergo further reactions and are not consumed. 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 ₈ is hydrogen or R _5. )
It is a hydroxyperoxide compound. To give specific examples of these compounds: [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [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 in a state of zero valence, or inorganic or organic compounds having 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-
Dicyano octane, styrene oxide, cyclopentene oxide (1,2), 3-chlorocyclopentene oxide (1,2), 4-phenylcyclopentene oxide (1,2), cyanocyclopentene oxide (1,2), Cyclohexene oxide-(1,2)-4-ethoxy-cyclohexene oxide-(1,2), cyclohexene oxide-
(1,2), cyclododecene oxide-(1,2),
3-oxatricyclo[3,21,0 ^2,4 ] octane,
5-oxatetracyclo[6,2,1,0 ^2,7 ,
0 ^4,6 ] Undecane. The peroxide used in the method of the present invention is hydrogen peroxide or has the general formula R ₅ OOH (R ₅ is a linear or branched aliphatic group having 1 to 16 carbon atoms,
Cycloaliphatic groups are aromatic organic groups. ) is an organic hydroperoxide represented by Specific examples of such organic hydroperoxides include [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula]. 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 to 16 carbon atoms.
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, and isoamyl acetate. , cyclohexyl acetate, butyl propionate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dimethyl formamide, dimethyl acetamide, triethyl phosphate, trihexyl phosphate, trioctyl phosphate, diethyl methanephosphonate, t-butyl alcohol, diethyl ether, anisole and so on. Preferably, the method is carried out in a non-aqueous system. Therefore, the hydrogen peroxide or organic hydroperoxide used is preferably dehydrated before the reaction. In particular, when using hydrogen peroxide, hydrogen peroxide is usually obtained as an aqueous solution, so it can be extracted with the above-mentioned organic solvent or used by adding the above-mentioned organic solvent to the aqueous solution and then azeotropic distillation. Alternatively, it is desirable to remove water by distillation under reduced pressure and use it as a non-aqueous solution. The concentration of hydrogen peroxide or organic hydroperoxide used in the present invention in the reaction solution is 1 to 50 wt%, preferably 3 to 50 wt%, in order to prevent heat generation and runaway due to rapid reaction.
It is desirable that it be 40wt%. In practicing this invention, the proportions of oxirane compound and hydrogen peroxide or organic hydroperoxide used can vary over a wide range. However, using excess hydrogen peroxide or organic hydroperoxide is not only uneconomical, but also requires a large amount of energy for recovery or post-treatment of unreacted hydrogen peroxide or organic hydroperoxide. Therefore, hydrogen peroxide or organic hydroperoxide is added per mole of oxirane compound.
0.05 mol to 3.0 mol, preferably 0.1 mol to 1.5 mol
It is preferable to use moles. When reacting an oxirane compound with hydrogen peroxide or 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 the amount of catalyst per mole of oxirane compound can be varied over a wide range. 10 ^-7 mole to 0.05
Preference is given to using amounts of moles, especially from 10 ^-5 moles to 0.01 moles. The temperature at which the method of the present invention is carried out is not preferably high enough to cause self-decomposition of hydrogen peroxide or organic hydroperoxide as a raw material and the β-hydroxyperoxide compound as a product; Economically unfavorable. Therefore, the method is preferably carried out in a temperature range of -20°C to 150°C, particularly preferably 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 Titanium oxide was placed in a 300 c.c. three-necked flask equipped with a stirrer, reflux condenser, and dropping funnel.
After adding 5 g of silica (supporting amount of titanium oxide, 5 wt%) and 120 g of t-butanol, the flask was kept at 30°C and was poured into the dropping funnel with stirring using a dropping funnel containing 42 g of cyclopentene oxide and 88 g of a t-butanol solution containing 20 wt% of anhydrous hydrogen peroxide. The mixture was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was further carried out at 30°C for 7 hours, and then the catalyst was filtered off. After removing t-butanol from the filtrate by vacuum distillation, the concentrated liquid was subjected to liquid chromatography using silica gel as the stationary phase and benzene:ethanol = 20:1 as the mobile phase. 53 g of liquid β-hydroxycyclopentyl hydroperoxide was obtained. The yield of hydroperoxide was 90%. Example 2 In a reaction vessel similar to Example 1, 1.9 g of H ₃ BO ₃ , 130 g of anisole, and 1,2-epoxyhexane were added.
Anhydrous hydrogen peroxide at 40℃ after adding 49g
92 g of a t-butanol solution containing 18 wt% was added dropwise over 0.5 hours. After the dropwise addition was completed, the reaction was carried out at 40°C for 9 hours.
After the reaction was completed, unreacted hydrogen peroxide was decomposed with catalase, and the amount of hydroperoxide produced was analyzed by iodometry, and it was found that the reaction solution contained 375 mmol of hydroperoxide.
In addition, after the generated hydroperoxide was purified by preparative liquid chromatography, ¹ H−
NHR, ¹³ C-NMR and elemental analysis revealed that this hydroperoxide was 1-hydroxy-2-hydroperoxyhexane. The yield of hydroperoxide was 77%. Example 3 In a reaction vessel similar to Example 1, 2.0 g of WO ₃ and t-
After 80 g of butanol and 47 g of t-butyl hydroperoxide were added, 49 g of cyclohexene oxide was added dropwise over 0.5 hours at 60°C. After the dropwise addition was completed, the reaction was further carried out at 60°C for 7 hours, and then analyzed using high performance liquid chromatography using silica gel as a packing material.
It was found that 70g of (β-hydroxycyclohexyl) peroxide was produced. The yield of peroxide was 74%. Examples 4 to 10 The oxirane compound was reacted with hydrogen peroxide or organic hydroperoxide in the presence of various catalysts in the same manner as in Examples 1 to 3. The results are shown in Table 1. [Table] [Table] 1) Indicates hydrogen peroxide or organic hydroperoxide. Dehydrated hydrogen peroxide was used.
2) Examples 5 and 9 represent the combined yield of two types of products.
3) Shows the yield based on the oxirane compound. If there are two products, the combined yield is shown.

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 , R ₂ ,
The sum of the carbon numbers of 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 hydrogen peroxide or the general formula R ₅ OOH (R ₅ is a straight or branched aliphatic chain having 1 to 16 carbon atoms,
Cycloaliphatic groups are aromatic organic groups. ) A general formula characterized by reacting with an organic hydroperoxide represented by (R ₈ is hydrogen or R _5. ) A method for producing an organic peroxide.