KR20030005295A - Method for producing ketal and/or acetal - Google Patents

Abstract

It is an object of the present invention to prepare ketals and / or acetals from olefins with high conversion and high selectivity. The present invention provides a process for the preparation of ketals and / or acetals by reacting olefins having at least one ethylenic double bond with oxygen and polyhydric alcohols in the presence of a catalyst, wherein (a) palladium as catalyst, (b) 8, 9 of the periodic table , A process comprising carrying out the reaction in the presence of at least one metal other than palladium, belonging to groups 10 and 14 and (c) halogen, and the ketals and / or acetals obtained by the process in the presence of an acid catalyst It provides a process for producing ketones and / or aldehydes by decomposition.

Description

Process for preparing ketals and / or acetals {METHOD FOR PRODUCING KETAL AND / OR ACETAL}

Corresponding aldehydes or ketones obtained by oxidizing olefins with molecular oxygen are industrially useful compounds, and their synthesis by catalysis has been carried out for a long time. Particularly useful methods of these are reactions generally known as Wacker reactions. That is, a method of producing acetaldehyde from ethylene and acetone from propylene by molecular oxygen using an aqueous solution containing PdCl ₂ and CuCl ₂ as a catalyst has been industrially used. However, in this conventional Wacker reaction, because the aqueous solution is under strong acidic conditions and highly corrosive hydrochloric acid is present, high grade materials are required in the reactor and peripherals and reactive substrates are limited to lower hydrocarbons such as ethylene and propylene. From the point of view of this, this is not always an industrially advantageous way.

As a reaction similar to the conventional Wacker reaction, the ketone formation reaction of olefins with hydrogen peroxide complex of Pd (Pd-OOH species) has also been examined (JP-A-57-156428 (corresponding to US Pat. No. 4,400,544), JP-A) -60-92236, JP-A-61-60621; the term "JP-A" as used herein means "unexamined Japanese patent application". In this reaction, monohydric alcohols such as methanol or ethanol are used as the reaction medium instead of water used in conventional Wacker reactions and metal salts of Pd and Cu and / or Fe are used as catalysts, but as an industrial method, this reaction is Low selectivity of ketones or aldehydes as products, and fatal disadvantages such as precipitation of Pd metal when the reaction conditions shift towards higher temperatures. This document describes that cocatalysts Cu and Fe have equivalent effects.

In addition, J. Org. Chem. , vol. 34, 3949 (1969), which uses polyhydric alcohols such as PdCl ₂ and CuCl ₂ as catalysts and ethylene glycol or glycerol as reaction solvents, yields 1,4-dioxopyro [4,5] decane from cyclohexene in high yield Although obtaining is described, details such as exemplary yields are not described. This document does not describe the use of iron salts as catalyst components, nor does it describe a solution for Pd precipitation which is a fatal disadvantage as an industrial method.

As described above, it is currently present that no industrially effective method of synthesizing the corresponding aldehydes or ketones from olefins has yet been found.

In particular, cyclohexanone useful as a precursor of caprolactam is a process in which cyclohexane is oxidized, if necessary, in the presence of a catalyst, and the cyclohexanone-cyclohexanol mixture is dehydrogenated, or cyclohexan obtained by hydrating cyclohexene. It is produced by the method of dehydrogenation of knol. However, since the product formed in the former method is susceptible to successful oxidation during the oxidation of cyclohexane, it is necessary to control the conversion to a fairly low level and circulate excess unreacted cyclohexane, resulting in low energy. It becomes a method with efficiency. In addition, the latter method is not sufficient yield of the hydration reaction, when extracting and separating cyclohexene from the benzene-cyclohexane mixture, which is significantly close to the boiling point, or high boiling point, approximately equimolar cyclohexanone-cyclohexanol mixture There is a problem in that a large amount of energy is consumed when separating cyclohexanone from

As a result, if there is a selective and efficient method for the synthesis of aldehydes or ketones, in particular cyclohexanone from the corresponding olefins such as cyclohexene, the meaning is quite significant.

In order to solve this problem associated with the oxidation of olefins, the present inventors have conducted intensive studies and, in the production of ketals and / or acetals by reacting olefins with oxygen and polyhydric alcohols, (a) palladium and ( c) In addition to halogens, when (b) one or more metals other than palladium, belonging to groups 8, 9, 10 and 14 of the periodic table, are used as catalysts, industrially fatal Pd precipitation can be prevented and catalyst activity reduced It has been found that can be suppressed, thus completing the present invention.

The present invention relates to a process for the preparation of ketals and / or acetals by oxidizing olefins with molecular oxygen.

Therefore, the gist of the present invention lies in the following aspects.

(1) A process for preparing ketals and / or acetals by reacting olefins having at least one ethylenic double bond with oxygen and polyhydric alcohols in the presence of a catalyst, wherein (a) palladium as catalyst, (b) 8, 9 of the periodic table , At least one metal other than palladium belonging to groups 10 and 14 and (c) a reaction in the presence of a halogen.

(2) The process for producing ketal and / or acetal according to (1), wherein the reaction is carried out in a liquid phase in which the catalyst is dissolved.

(3) The method for producing ketal and / or acetal according to (1) or (2), wherein copper is further included as a catalyst.

(4) The process for producing ketal and / or acetal according to (3), wherein the catalyst compound used as the copper source is at least one copper chloride (I) and copper chloride (II).

(5) The copper according to (3) or (4), wherein (b) uses copper in an amount of 0.1 to 100 molar times based on one or more metals other than palladium belonging to groups 8, 9, 10 and 14 of the periodic table. Process for preparing ketals and / or acetals.

(6) The metal according to any one of (1) to (5), wherein (b) at least one metal other than palladium belonging to groups 8, 9, 10 and 14 of the periodic table is selected from iron, cobalt, nickel and tin Process for preparing phosphorus ketal and / or acetal.

(7) The method for producing ketal and / or acetal according to (6), wherein (b) at least one metal other than palladium belonging to groups 8, 9, 10 and 14 of the periodic table is iron.

(8) The method for producing ketal and / or acetal according to any one of (1) to (7), wherein (c) halogen is chlorine (Cl).

(9) The method for producing ketal and / or acetal according to any one of (1) to (8), wherein the concentration of palladium in the reaction solution is 0.001 to 10% by weight.

(10) The molar ratio of at least one metal other than palladium to palladium, other than palladium, according to any one of (1) to (9), belonging to groups 8, 9, 10 and 14 of the (b) Periodic Table in the reaction solution. Process for preparing ketals and / or acetals.

(11) The process for producing ketal and / or acetal according to any one of (1) to (10), wherein the molar ratio of (c) halogen to palladium in the reaction solution is 0.1 to 100.

(12) The method for producing ketal and / or acetal according to any one of (1) to (11), wherein (a) the catalyst compound used as the source of palladium is palladium chloride.

(13) The method for producing ketal and / or acetal according to any one of (1) to (12), wherein (a) the catalyst compound used as the source of palladium is a divalent palladium compound.

(14) The method for producing ketal and / or acetal according to any one of (1) to (13), wherein (a) the catalyst compound used as the source of palladium is a nitrile compound-coordination compound.

(15) The ketal according to any one of (1) to (14), wherein (b) the catalyst compound used as a source of at least one metal other than palladium belonging to groups 8, 9, 10 and 14 of the periodic table is chloride; and And / or a process for producing acetal.

(16) The process for producing ketal and / or acetal according to any one of (1) to (15), wherein (c) chlorine as halogen is used as the chloride of (a) or (b).

(17) The method for producing ketal and / or acetal according to any one of (1) to (16), wherein the olefin is a cyclic olefin having 4 to 10 carbon atoms.

(18) The method for producing ketal and / or acetal according to (17), wherein the olefin is cyclohexene.

(19) The method for producing ketal and / or acetal according to any one of (1) to (16), wherein the olefin is a terminal olefin having 2 to 25 carbon atoms.

(20) The process for producing ketal and / or acetal according to any one of (1) to (16), wherein the olefin is an internal olefin having 4 to 25 carbon atoms.

(21) The process for producing ketal and / or acetal according to any one of (1) to (20), wherein the polyhydric alcohol is an aliphatic or alicyclic diol.

(22) The process for producing ketal and / or acetal according to any one of (1) to (21), wherein the polyhydric alcohol is used in an amount of 1 to 100 molar times based on the olefin.

(23) A method for producing a ketone and / or aldehyde by hydrolyzing the ketal and / or acetal obtained by the method according to any one of (1) to (22) in the presence of an acid catalyst.

Best Embodiments for Carrying Out the Invention

(catalyst)

The catalyst of the present invention consists of (a) palladium, (b) at least one metal other than palladium and (c) halogen, belonging to groups 8, 9, 10 and 14 of the periodic table. In this case, the components of (a) to (c) may be present in any form in the reaction system, such as dissociation ions, salts or molecules.

(a) Palladium may be in divalent to tetravalent form and may be optionally selected from known and commercially available compounds. Examples thereof include palladium halides such as palladium chloride and palladium bromide, palladium salts of palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate and palladium acetylacetonate and inorganic acids such as palladium oxide and palladium hydroxide Palladium is included. In addition, base-coordination compounds derived from such metal salts, such as [Pd (en) ₂ ] Cl ₂ , [Pd (phen) ₂ ] Cl ₂ , [Pd (CH ₃ CN) ₂ ] Cl ₂ , [Pd (C ₆ H ₅ CN) ₂ ] Cl ₂ , [Pd (C ₂ O ₄ ) ₂ ] ₂ , [PdCl ₂ (NH ₃ ) ₂ ] and [Pd (NO ₂ ) ₂ (NH ₃ ) ₂ ] are useful, but here It is not limited to (wherein en represents ethylenediamine and phen represents 1,10-phenanthroline). Of these palladium sources, preference is given to using divalent palladium sources, in particular as chlorides or nitrile compound-coordination compounds.

The role of palladium in the catalyst system is manifested in the interaction with iron ions and polyhydric alcohols, but the operating conditions are not always clear. Since the essence is that palladium is active by constituting the active species with other catalyst components, it is sufficient if there are enough palladium sources present in the system to induce the essence.

(b) Iron, cobalt, nickel, ruthenium and tin can be cited as one or more metals other than palladium, belonging to groups 8, 9, 10 and 14 of the periodic table, of which iron is preferred.

The catalyst compound used as the iron source may be in divalent or trivalent form. For example, chlorides such as iron (II) and iron (III) chloride, bromide such as iron (II) bromide and iron (III) bromide, iron (II) sulfate, iron (III) sulfate, iron nitrate (II) And various salts including inorganic acid salts such as iron (III) and salts such as iron (II) acetate, iron (III) acetate, iron (II) oxalate, iron (III) oxalate, iron formate and iron acetylacetone. Or in the form of their coordination compounds. Similar to the case of palladium, the essence is that iron is active by constituting the active species with other catalyst components, so that there is enough iron source present in the system to induce the essence.

The catalytic compound used as the source of cobalt, nickel, ruthenium or tin may be in divalent, trivalent or tetravalent form. Illustratively, various salts, or coordination compounds thereof, may be used, including halides such as chlorides and bromide, inorganic acid salts such as sulfuric acid and nitric acid, and salts such as acetic acid, oxalic acid, formic acid and acetylacetonate salts. have. If component (b) is cobalt, nickel, ruthenium or tin, it is further preferred to combine with copper.

The main effect of the present invention is that the precipitation of Pd is remarkably suppressed by the addition of component (b), but further addition of copper compounds such as CuCl or CuCl ₂ improves the reaction rate and the by-products such as halides Another advantageous result as a reducing, industrial method is shown.

Halogen (c) is chlorine (Cl) and / or bromine (Br), but chlorine (Cl) is particularly preferred. Halogen may be present as a counter anion of Pd and / or Fe in the reaction system. It may also be supplied to the reaction system as halides of other catalyst components or in certain forms such as HCl or HBr, but such compounds exist in the form of ions in the case of ethers in the reaction system.

According to the invention, ketals and / or acetals are produced by reacting olefins with oxygen and polyhydric alcohols in the liquid phase in which the catalyst described above is dissolved.

(Olefin)

The olefins used in the present invention are aliphatic or alicyclic organic compounds containing at least one ethylenic double bond. As the chain olefins, olefins generally having at least 2, preferably 2 to 25, more preferably 3 to 10 carbon atoms can be cited, such as ethylene, propylene, butene, pentene, hexene and octene. In this case, the position of the double bond can be terminal or internal, in the case of terminal olefins, mainly acetals or ketals of methyl ketones are formed, and in the case of internal olefins the corresponding ketals are mainly obtained.

Examples of cyclic olefins include compounds having 4 to 10, preferably 5 to 8, carbon atoms and containing at least one ethylenic double bond, such as cyclopentene, cyclohexene, cyclohexadiene, cycloheptene and cyclooctene; Of these, cyclopentene and cyclohexene are particularly industrially useful compounds. When cyclohexene is used as the olefin, 1,4-dioxopyro [4,5] decane (hereinafter referred to as cyclohexanone ketal) is formed as the product.

One or more substituents such as alkyl groups, alkoxy groups, aryl groups, phenyl groups, carboxyl groups, halogen atoms or nitro groups may be present at any position in the main chain of such olefins. For example, an olefin having a functional group such as acrylonitrile, acrolein, acrylic acid or vinyl chloride in the 2 position, or styrene or methyl styrene, suitably performs the reaction. In addition, if there is an ethylene-based double bond, a compound having a condensed ring may also be used, such as 3,4-dihydronaphthalene.

(Poly alcohol)

Polyhydric alcohols are generally divalent to tetravalent, with diols being particularly preferred. In the case of diols, they generally have two or more carbon atoms, but considering the cost, stability and easy formation of acetal or ketal, they are preferably from 2 to 10, more preferably from 3 to 8, preferred examples of such diols Examples are ethylene glycol, 1,3-propanediol, 1,2-dihydroxybutane, 1,2-dihydroxypropane, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,2- Cyclohexanedimethanol, diethylene glycol, 1,2-trans-cyclopentanediol, 2,4-pentanediol, styrene glycol, 1,5-dihydroxycyclooctane, 1,4-dihydroxycyclooctane, 2 , 5-dihydroxynorbornane, 2,6-dihydroxynorbornane, 1,4-dihydroxy-2,3-dimethylbutane, 1,5-dihydroxy-2,4-dimethylpentane, cyclo Butane-1,2-dimethanol, cyclohexane-1,3-dimethanol, 1,4-dihydroxy-2,3-dichlorobutane and 2,5-dihydroxyhexane, ethylene glycol, 1 , 3-propanediol, 1,2 -Dihydroxybutane, 1,2-dihydroxypropane, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, diethylene glycol, 1,2-transcyclopentane More preferred are diols, 2,4-pentanediol and styrene glycol. Two or more of these can be used in combination.

While it is not clear why polyhydric alcohols are necessary for the present invention, palladium starts in a divalent form, such as chloride, at which time it is considered to form a divalent peracid complex as a novel active ingredient, and alcohols inducing this active species It is considered that this plays an effective role. In addition to this role, it reacts with the formed aldehyde or ketone to form the corresponding acetal or ketal, thereby ensuring a significantly higher stability to oxygen oxidation compared to free aldehyde and ketone. Thus, it becomes possible to maintain the selectivity of the intended product at a remarkably high level.

When monohydric alcohols such as methanol, ethanol or propanol are used in place of polyhydric alcohols, the product is mainly aldehyde or ketone compounds and the formation of the corresponding acetals or ketals is extremely small. Since these free aldehydes and ketones are unstable in the presence of oxygen, they are oxidized continuously so that the yield of the desired aldehyde or ketone is not always high. In contrast, when using polyhydric alcohols comprising dihydric diols such as ethylene glycol, propylene glycol and butanediol, the corresponding acetals or ketals can be obtained as main products. Since the acetals or ketals thus obtained are hardly oxidized continuously under oxygen reaction conditions, the yield of aldehydes or ketones obtained by hydrolysis of electrons is remarkably high.

(Reaction conditions)

According to the present invention, the use of an oxygen containing gas is a prerequisite, but the above risk must be avoided because oxygen and organic compounds can form explosive mixtures at certain temperatures, at certain pressure ranges and at certain compositional ranges. If the partial pressure of oxygen is 0.001 MPa or more, the reaction will proceed but the reaction rate will be slow, and if the oxygen partial pressure is too low, the catalyst tends to be deactivated. In the present invention, preferably 0.01 to 10 MPa, more preferably 0.05 to 5 MPa, but the most preferred pressure is selected from the viewpoint of safety and economics.

The reaction will proceed when the reaction temperature is above 0 ° C., but a higher temperature is preferred because of the large temperature dependence of the reaction of the present invention. The reaction temperature is selected in consideration of the formation conditions of the explosive mixture and the increase in by-products due to radical autooxidation, but in general, the reaction rate is economically effective within the temperature range of 20 to 200 ℃, preferably 40 to 180 ℃ Can be obtained. The total pressure of the reaction may be above the liquid phase holding pressure, but is generally 0.1 MPa to 20 MPa, preferably 0.1 MPa to 15 MPa. In addition, the reaction time (retention time) is generally 5 seconds to 20 hours, preferably 10 seconds to 10 hours.

The concentration of (a) palladium as catalyst is [Pd ²⁺ ] based on the total weight of the reaction solution and is in the range of 0.001 to 10% by weight, preferably 0.01 to 5% by weight. Under high concentration conditions, the reaction rate shows a different concentration dependency than under low concentration conditions, and the catalyst efficiency tends to deteriorate, so the effective concentration is selected from an economic point of view.

(b) The concentration of at least one metal M other than palladium, belonging to groups 8, 9, 10 and 14 of the periodic table, may be described as (a) relative concentration to palladium. That is, in general, it can be selected in the range of 0.1 <[M] / [Pd] <100 (molar ratio), preferably 0.1 <[M] / [Pd] <10 (molar ratio). Lower concentrations involve a tendency to reduce the reaction rate and also a decrease in the effect of inhibiting Pd precipitation as the main effect of the metal (b). In addition, too large a quantity cannot inhibit the reaction itself, but will cause a tendency to limit the amount of dissolution in the reaction system.

The relative concentration of halogen (c) relative to Pd is generally 1 <[Cl and / or Br] / [Pd] <100 (molar ratio), preferably 0.3 <[Cl and / or Br] / [Pd] <50 (Molar ratio). Since there is a possibility of causing corrosion of the reactor material by water in the reactor under halogen high concentration conditions, it is preferable to select the concentration of halogen to a level such that the catalyst system operates at the lowest possible level. In addition, the component containing the catalytically derived halogen may in some cases be formed as part of the byproduct, in which case it is preferred to continuously or periodically supply the consumed halogen, for example in the form of a metal salt.

The amount of polyhydric alcohol present in the reaction system may be a theoretical amount (1 mole) based on olefins, but according to the present invention, it is also preferably used as the reaction solvent. Based on the total reaction volume, it is generally in the range of 1 to 99% by volume, preferably 5 to 99% by volume. In addition, the amount of polyhydric alcohols is generally 1 to 100 moles, preferably 2 to 50 moles, based on the olefin. The amount of olefin present in the reaction system may generally be selected in the range of 1 to 99% by volume, preferably 1 to 50% by volume.

If the concentration of polyhydric alcohols is relatively low, that is, if the relative concentration of olefins is too high, it will entail a tendency to readily cause precipitation of palladium due to the distribution of some of the catalyst components onto the olefins. On the other hand, when the polyhydric alcohol concentration is too large, the concentration of the supplied olefin becomes relatively small and tends to involve low productivity and difficulty in carrying out phase separation after the reaction. In such cases, the relative concentrations of polyhydric alcohols and olefins can be adjusted, and an oxidatively inert third component can be added to the reaction system to further improve phase separation properties.

According to the invention, further components may be added to increase activity and reactivity. For example, additives which have the effect of enhancing the oxidation reaction, such as copper compounds or alkali, alkaline earth metals or rare earth metals, can be added. In addition, a method of suppressing side reactions by adding a radical trapping agent may be applied.

Among the reactions of the present invention, particularly in mass production processes, such as the cyclohexanone production process from cyclohexene, it is required to efficiently separate traces of specific impurities when considering the balance of materials in the total process. For example, the formation of impurities that are particularly difficult to separate and likely to adversely affect products such as cyclohexenone, cyclohexenol, chlorocyclohexanone and cyclohexenone ketal should be controlled to be as small as possible.

The reaction of the present invention can be carried out according to a general oxidation reaction. When each catalyst component is present in solution, the oxidation reaction is carried out using a batch reactor and reacting the oxygen-containing gas and the olefin for a certain period of reaction time, or using a continuous phase reactor and continuously Can be achieved by feeding. On the other hand, when the catalyst component of the present invention is immobilized, a liquid phase reaction can be used, or a so-called trickle bed system can be employed in which the catalyst is filled in a fixed bed and the corresponding olefin and oxygen are supplied in the liquid phase. Can be.

Taking into account the supply of oxygen, techniques that are effective in dissolving oxygen in the reaction solution system, such as the use of mixing blades to make oxygen-containing gas into fine bubbles, the technique to make oxygen gas into fine bubbles by means of anti-arrangement plates in the reactor, or Techniques for spraying gases into the system at high velocity from the nozzle can be applied.

(Process after oxidation reaction)

The reaction product solution after the oxidation reaction contains the substance olefin, ketal and / or acetal as product, catalyst component and polyhydric alcohol. If the reaction product solution is under pressurized conditions, the pressure can be reduced by releasing to a certain degree. The boiling points of olefins and ketals and / or acetals in the reaction product solution are very different from those of polyhydric alcohol solvents, and these low boiling components (olefins and ketals and / or acetals) can be separated directly from the reaction product solution by distillation. . The polyhydric alcohol solution containing the catalyst component, obtained from the bottom of the distillation, can be recycled to the oxidation reaction step.

In addition, when the boiling point of the olefin and the ketal and / or acetal is higher than the boiling point of the polyhydric alcohol solvent, an extraction solvent such as an organic solvent, which forms two phases with the polyhydric alcohol, is added, and two phase separation is performed by extraction. The extraction solvent phase containing olefins and ketals and / or acetals is separated from the polyhydric alcohol phase containing the catalyst component. The olefins and ketals and / or acetals can then be recovered from the extraction solvent phase and then the ketals and / or acetals can be taken by distillation separation. The polyhydric alcohol phase containing the catalyst component can be recycled to the oxidation reaction step. In two phase separations, the extraction solvent containing olefins and ketals and / or acetals is contaminated with trace amounts of catalyst components and the residual amount of catalyst components in the extraction phase is subjected to two or more times of extraction with a polyhydric alcohol solvent. Can be reduced to a negligible level. Also, after the first two phase separations, the technique of increasing the residual catalyst concentration in the extraction solvent phase to a certain degree by distillation to separate olefins and ketals and / or acetals from the extraction solvent phase, and then applying the extraction again can be applied. have.

In addition, during the formation of the ketal by continuous oxidation, some water is formed in the reactor. It is desirable to remove the water thus formed from the reaction system as much as possible, but even at this time, if a halogen component such as Cl remains in the system, the possibility of its precipitation upon corrosion of the reactor is great. As a result, it is necessary to use materials that are highly resistant to corrosive acids, such as hydrogen chloride, in essential parts.

Materials such as glass, ceramics and Teflon can be used in areas where the reaction pressure is not too high, but when the reaction pressure is high, a vessel commonly used as a corrosion resistant reactor, i.e. an alloy such as a stainless alloy, in particular commonly referred to as Hastelloy It is preferable to use a container made of an alloy containing titanium or an alloy containing zirconium, or a container in which such alloy is coated and adhered to the surface by compression. The corrosion potential of the reactor is particularly high, but when further arranging the standing vessel and the separation vessel, these parts are also highly likely to corrode. In addition, in the oily phase distillation containing the product, when the catalyst component remains, there is a possibility that the halogen component is concentrated, and therefore also highly corrosive. Depending on the degree of corrosion potential in these main vessels and the pipes attached thereto, it is desirable to use corrosion resistant materials in an economically acceptable range.

The polyhydric alcohols present in the reaction system as essential components are not completely inert to the oxidation reaction. In addition, even in very small amounts, some compounds formed by the continuous oxidation of olefins have a similar polarity to polyhydric alcohols. Thus, when the batch reaction is repeated for extended periods or in the case of continuous reactions, certain components which are derived from polyhydric alcohols and olefins, but which are not necessarily desirable for the reaction, accumulate in the alcohol phase containing the catalyst component. In order to operate the process stably, it is necessary to properly adjust the total material balance. As a result, for the rate of formation of such impurities and the rate of formation of continuously oxidized components, it is necessary to supply a fresh catalyst material solution by removing a portion of the catalyst-containing polyhydric alcohol phase from the system. In this case, when the removal ratio of the catalyst component removed from the system is large, and thus the economic burden is large, it is necessary to recover the catalyst component. This method is not limited, but techniques including removal of organic matter, washing and recovery of metal components are effective.

In addition, when an extraction solvent such as an organic solvent is removed by distillation from an extraction solvent phase containing two phase separation products (ketal and / or acetal), accumulation of impurities may also occur in the same way, in which case too By removing some of the previous extraction solvent, a fresh extraction solvent can be supplied.

The ketals and / or acetals obtained by the present invention are converted to the corresponding ketones and / or aldehydes by carrying out hydrolysis in the presence of water and acid. Examples of acids that can be used in this case include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, polyacids such as heteropolyacids, and solid acids such as ion exchange resins, zeolites and clays. The aldehydes and ketones of interest can be efficiently obtained by removing water and polyhydric alcohols from the reaction product solutions thus rich in aldehydes and / or ketones, followed by separating and purifying the aldehydes and ketones as the desired compound.

In addition, the ketals and / or acetals obtained by the present invention can be efficiently converted to the corresponding alcohols by carrying out hydrogenation in the presence of water, a hydrogen source and a hydrogenation catalyst. Examples of hydrogen sources include hydrogen, formalin and disodium borohydride (NaBH ₄ ), and examples of hydrogenation catalysts include oxides containing Raney Ni, Raney Co, Cu—Cr, Pd, Pt or Ru; Catalysts in which the same Group 8 metal is carried by the carrier and complex catalysts using Group 8 metals such as Ru, Pt or Pd as the center metal are included. The alcohol of interest is obtained by hydrogenation and is efficiently obtained by recovering water and acetal and / or ketal-forming alcohols from the alcohol-rich reaction product solution and then separating and purifying the alcohol as the desired compound.

The invention is further illustrated by way of the following examples, although the invention is not limited to these examples.

Example 1

In a drum-shaped Pyrex reactor with an internal diameter of 40 mm and a height of 12 mm, equipped with a magnetic bar and a gas introduction tube, 0.1 mmol of Pd (CH ₃ CN) ₂ Cl ₂ , 0.1 mmol of CuCl ₂ , 0.1 mmol FeCl ₃ , 10 mL of ethylene glycol and 20 mmol of cyclohexene were charged and air was replaced with pure oxygen, then the reaction was carried out at 40 ° C. for 5 hours with stirring. The product was analyzed by gas chromatography by adding an internal standard compound to the reaction solution. As a result, the cyclohexene conversion was 2.5% and cyclohexanone ketal was obtained with a yield of 2.5%. TOF = 1.0 / hour. TOF means the rate of formation of cyclohexanone and cyclohexanone ketal (moles) per mole of Pd per hour. In this case, only cyclohexanone ketal was formed. No precipitation of palladium was found in the solution after the reaction. In addition, chlorocyclohexane was not formed.

Example 2

The reaction was carried out according to the procedure of Example 1, except that CuCl ₂ was not added. As a result, the cyclohexene conversion was 2.5% and cyclohexanone ketal was obtained with a yield of 2.5%. TOF was 1.0 / hour. A byproduct of 1.0 mol% chlorocyclohexane based on cyclohexanone ketal was found. No precipitation of palladium was found in the solution after the reaction.

Comparative Example 1

The reaction was carried out in the same manner as described in Example 1 except that FeCl ₃ was not added. As a result, the cyclohexene conversion was 2.3%, the cyclohexanone ketal yield was 2.3%, and the TOF was 0.92 / hour. After the reaction, the reaction solution became turbid with fine black powder of Pd-black and precipitation of palladium was found at the bottom and inner wall of the reactor.

Pd compound Fe compound Cu compound CHE conversion rate ^* Ketal yield ^** TOF ^*** Observation Example 1 0.1 mmol 0.1 mmol 0.1 mmol 2.5% 2.5% 1.0 / hour Pd non-precipitated, chlorocyclohexane non-forming Example 2 0.1 mmol 0.1 mmol Not used 2.5% 2.5% 1.0 / hour Pd non-precipitated, chlorocyclohexane formation Comparative Example 1 0.1 mmol Not used 0.1 mmol 2.3% 2.3% 0.92 / hour Pd sedimentation *: Cyclohexene conversion **: cyclohexanone ketal yield ***: rate of formation of cyclohexanone and cyclohexanone ketal per mole of Pd per hour

Comparing Examples 1 and 2 with Comparative Example 1, it was found that precipitation of Pd was suppressed by the addition of Fe. It was also seen that the formation of chlorocyclohexane is further inhibited by adding copper compounds.

Example 3

A cylinder-type Teflon beaker of 40 mm inner diameter and 15 mm height, equipped with a magnetic bar, was inserted into a SUS-316 autoclave with an internal pressure of 100 kG and a size suitable for the beaker, using the same fill composition of Example 1 The reaction was carried out under an oxygen pressure of 7 kG for 1 hour at a reaction temperature of 80 ℃. As a result, a reaction product ratio of cyclohexanone ketal / cyclohexanone = 24.8 and cyclohexanone ketal / cyclohexenone = 26.1 was obtained with a cyclohexene conversion of 30% and a TOF of 60 / hour. After completion of the reaction, no precipitation of Pd was found.

Example 4

The reaction was carried out in the same manner as described in Example 3, except that CuCl was not used. As a result, the cyclohexene conversion was 34% and TOF was 67 / hour. Chlorocyclohexane was formed in an amount of 1 mol% based on ketal. After completion of the reaction, no precipitation of Pd was found.

Comparative Example 2

The reaction was carried out in the same manner as described in Example 4, without using FeCl ₃ and using a predetermined amount of CuCl ₂ or CuCl. The results are shown in Table 2. Precipitation of Pd was found in all cases.

Copper compound Cyclohexene conversion TOF ^* (/ hour) CuCl (0.1 mmol) CuCl ₂ (0.1 mmol) CuCl ₂ (0.2 mmol) 13.5% 21.0% 45.0% 274290 *: Rate of formation of cyclohexanone and cyclohexanone ketal per mole of Pd per hour

From the above results, it can be seen that when Fe is present in the system, even if the oxygen concentration increases and the cyclohexene conversion reaches a high level, precipitation of Pd does not occur and the catalyst works effectively.

Example 5

The reaction was carried out in the same manner as described in Example 1 except for using a mixed solution of 5 ml of ethanol + 2.5 g of ethylene glycol instead of ethylene glycol. As a result, the cyclohexene conversion was 22%, the yield (cyclohexanone + cyclohexanone ketal) was 21.0%, the selectivity (cyclohexanone ketal + cyclohexanone) was 95%, and the TOF was 8.4 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 6

The reaction was carried out in the same manner as described in Example 1 except for using a mixed solution of 5 ml of methanol + 2.5 g of ethylene glycol instead of ethylene glycol. As a result, cyclohexanone ketal and cyclohexanone were obtained at a ratio of 17.6 by 10.0% cyclohexene conversion, 10.0% (cyclohexanone + cyclohexanone ketal) yield and 4.0 / hour TOF. No precipitation of Pd was found in the solution after the reaction.

Example 7

The reaction was carried out in the same manner as described in Example 1 except for using a mixed solution of 7.5 g of 1,4-butanediol + 2.5 g of ethylene glycol instead of ethylene glycol. As a result, the cyclohexene conversion was 22% and TOF was 8.0 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 8

The reaction was carried out in the same manner as described in Example 1, except that 1,3-propanediol was used instead of ethylene glycol. As a result, a reaction product of cyclohexanone ketal / cyclohexanone = 2.87 and cyclohexanone ketal / cyclohexenone = 16.1 was obtained with a cyclohexene conversion of 16%. Considering the rate of (cyclohexanone + ketal) formation, the TOF was 6.4 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 9

The reaction was carried out in the same manner as described in Example 1, except that 1,4-butanediol was used instead of ethylene glycol. As a result, a reaction product of cyclohexanone ketal / cyclohexanone = 0.41 and cyclohexanone ketal / cyclohexenone = 4.93 was obtained with a cyclohexenone conversion of 27%. (Cyclohexanone + ketal) selectivity was 79% and TOF was 8.5 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 10

The reaction was carried out in the same manner as described in Example 1, except that 2,3-butanediol was used instead of ethylene glycol. As a result, the cyclohexene conversion was 7%, the selectivity (cyclohexanone ketal + cyclohexanone) was 91.5%, and the TOF was 2.6 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 11

The reaction was carried out in the same manner as described in Example 1, except that 1,2-cyclohexanediol was used instead of ethylene glycol. As a result, the cyclohexene conversion was 12%, the cyclohexanone ketal / cyclohexanone was 3.7, the (cyclohexanone ketal + cyclohexanone) selectivity was 90%, and the TOF was 4.3 / hour. No precipitation of Pd was found in the solution after the reaction.

Comparative Example 3

The reaction was carried out in the same manner as described in Example 1, except using ethanol instead of ethylene glycol. As a result, the cyclohexene conversion was 35% and the cyclohexanone yield was 17%. The selectivity of cyclohexanone was 51%. No precipitation of palladium was found on the inner wall of the reactor. Cyclohexanone acetal was not formed.

The results of Examples 5 to 11 and Comparative Example 3 are shown together with the results of Example 1 in Table 3 below.

Alcohol CHN ketal / CHN ^* TOF ^** Observation Example 1 10 ml of ethylene glycol (EG) 100 1.0 / hour Pd non-precipitated, without chlorocyclohexane Example 5 Ethanol 5 ml + EG 2.5 g > 10 8.4 / hour Pd non-precipitated Example 6 Methanol 5 ml + EG 2.5 g 17.6 4.0 / hour Pd non-precipitated Example 7 1,4-butanediol (BG) 7.5 g + EG 2.5 g > 10 8.0 / hour Pd non-precipitated Example 8 10 ml of 1,3-propanediol 2.87 6.4 / hour Pd non-precipitated Example 9 10 ml of 1,4-butanediol (BG) 0.41 8.5 / hour Pd non-precipitated Example 10 10 ml of 2,3-butanediol 5-10 2.6 / hour Pd non-precipitated Example 11 10 ml of 1,2-cyclohexanediol 3.7 4.3 / hour Pd non-precipitated Comparative Example 3 10 ml of ethanol 0 6.8 / hour Pd non-precipitated, no ketal formation *: Cyclohexanone ketal / cyclohexanone **: rate of formation of cyclohexanone and cyclohexanone ketal per mole of Pd per hour

Comparing Examples 1 and 5-11 with Comparative Example 3, it can be seen that CHN ketals are formed when polyhydric alcohols are present. As compared to CHN, since CHN ketals undergo little successive oxidation in the reaction system, for (CHN + CHN ketal) selectivity, it is desirable to obtain products with large CHN ketal / CHN ratios.

Example 12

The reaction was carried out in the same manner as described in Example 7, except that Pd (BzCN) ₂ Cl ₂ was used instead of Pd (CH ₃ CN) ₂ Cl ₂ . As a result, the cyclohexene conversion was 5% and TOF was 2 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 13

The reaction was carried out in the same manner as described in Example 7, except that PdCl ₂ was used instead of Pd (CH ₃ CN) ₂ Cl ₂ . As a result, the cyclohexene conversion was 4% and the TOF was 1.6 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 14

A cylinder-type Teflon beaker with an inner diameter of 40 mm and a height of 15 mm, equipped with a magnetic bar, was inserted into a SUS-316 autoclave with an internal pressure of 100 kG and a snug fit to the beaker, using the same fill composition of Example 1 The reaction was carried out under an oxygen pressure of 7 kG for 1 hour at a reaction temperature of 70, 80, 90 or 100 ℃. No precipitation of Pd was found in the solution after the reaction. The results are shown in Table 4. It can be seen that the reaction rate is highly dependent on the reaction temperature and the oxygen pressure.

Reaction temperature (℃) Cyclohexene conversion TOF ^* Ketal / cyclohexanone Ketal / cyclohexenone 708090100 21% 30% 50% 58% 425893110 > 4024.828.518.3 > 100026.112.315.7 *: Rate of formation of cyclohexanone and cyclohexanone ketal per mole of Pd per hour

Example 15

The reaction is carried out in the same manner as described in Example 14 except that a mixture of 2.5 g of ethylene glycol 2.5 g + 1,4-butanediol is used as the reaction solvent and the reaction temperature is 40, 60, 80 or 90 ° C. It was. No precipitation of Pd was found in the solution after the reaction. The results are shown in Table 5.

Reaction temperature (℃) Cyclohexene conversion TOF ^* Ketal / cyclohexanone Ketal / cyclohexenone 40608090 4% 13% 46% 87% 82484154 5.32.62.31.1 12.58.07.23.7 *: Rate of formation of cyclohexanone and cyclohexanone ketal per mole of Pd per hour

It can be seen that the reaction rate increases rapidly as the reaction temperature increases.

Example 16

The reaction of Example 14 was carried out except that the reaction temperature was fixed at 80 ° C. and the amount of cyclohexene charged was changed. No precipitation of Pd was found in the solution after the reaction. The results are shown in Table 6.

Cyclohexene / Pd Reaction time Cyclohexene conversion TOF ^* (/ hour) Ketal / cyclohexanone Ketal / cyclohexenone 200400 1.03.01.03.0 26% 70.5% 37% 60% 50434737 24.811.727.617.2 26.110.419.011.9 *: Rate of formation of cyclohexanone and cyclohexenone ketals per mole of Pd per hour

Example 17

The reaction of Example 15 was carried out except that the reaction temperature was fixed at 90 ° C. and the charge amount of each of Pd, Cu and Fe was fixed at 0.025 mmol. As a result, the cyclohexene conversion was 58%, the TOF value was 425 / hour, the cyclohexanone ketal / cyclohexanone ratio was 4.4 and the cyclohexanone ketal / cyclohexenone ratio was 8.5. No precipitation of Pd was found in the solution after the reaction.

Example 18

The same oxidation reaction of Example 3 was carried out except that FeCl ₃ was changed to the cocatalyst shown in Table 7. As a result, the product was almost cyclohexanone ketal. The TOF values are shown in Table 7.

Cocatalyst TOF / hour Pd black precipitate Example 3 FeCl ₃ 60 none Example 18 RuCl ₃ 70 slightly CoCl ₃ 57 slightly Sn (acac) ₂ Br ₂ 27 none Ni (acac) ₂ 4 none acac: acetylacetonate

Example 19

A cylinder-type Teflon beaker with an inner diameter of 40 mm and a height of 15 mm, equipped with a magnetic bar, was inserted into a SUS-316 autoclave with an internal pressure of 100 kG and a snug fit to the beaker, using the same fill composition of Example 1 20 mmol of styrene was added thereto, and the reaction was performed at an oxygen temperature of 7 kG at a reaction temperature of 80 ° C. After 1 hour of reaction, the contents were taken and analyzed by GC. As a result, the TOF value was 154 / hour, the EG acetal compound selectivity of phenylacetaldehyde was 54%, the EG ketal compound selectivity of acetophenone was 11%, and the (phenylacetaldehyde + acetophenone) selectivity was 25%. No precipitation of Pd was found in the solution after the reaction.

Example 20

The reaction was carried out in the same manner as described in Example 19, except that α-methylstyrene was used instead of styrene. As a result, the TOF value was 54 / hour, and only 2-phenylpropylaldehyde and its EG acetal compound were formed. Acetal / aldehyde ratio was 2.5. No precipitation of Pd was found in the solution after the reaction.

Example 21

The reaction was carried out in the same manner as described in Example 19, except that 3,4-dihydronaphthalene was used instead of styrene. As a result, the TOF value was 90 / hour. No precipitation of Pd was found in the solution after the reaction.

Example 22

The reaction was carried out in the same manner as described in Example 19, except that 1-octene was used instead of styrene. As a result, the TOF value was 46 / hour, the (ketal compound + acetal compound) selectivity was 70%, and the ketal compound of the corresponding ketone compound of octene, with the double bond shifted, was mainly obtained. No precipitation of Pd was found in the solution after the reaction.

Example 23

The reaction was carried out in the same manner as described in Example 22, except for using 2-octene instead of 1-octene. As a result, the TOF value was 40 / hour and the (ketal compound + acetal compound) selectivity was 84%. The distribution of the formed product was the same as in Example 22. No precipitation of Pd was found in the solution after the reaction.

(Examples of Use of Mixed Material of Cyclohexene and Benzene)

Example 24

Assume that a cylinder-type Teflon beaker with a magnetic bar with an internal diameter of 40 mm and a height of 15 mm is inserted into a SUS-316 autoclave with an internal pressure of 100 kG and fits into a beaker, with benzene coexisting, 2.2 g of benzene, 2 g of cyclohexene, 0.3 mmol of Pd (CH ₃ CN) ₂ Cl ₂ , 0.3 mmol of CuCl ₂ , 0.3 mmol of FeCl ₃ and 6.2 g of 1,4-butanediol were charged. The reaction was carried out under a reaction temperature of 70 ° C. and various oxygen pressures described in the table below. The main products other than cyclohexanone and cyclohexanone ketal were cyclohexenone. The results are shown in Table 8.

Oxygen pressure (kG) Reaction time (min) Cyclohexene conversion (%) Selectivity (%) 456789 24202224911 636768627285 717277847074 Selectivity = cyclohexanone + cyclohexanone ketal

Example 25

Using the same reaction apparatus of Example 24, assuming benzene coexists, 2.2 g benzene, 2 g cyclohexene, 0.6 mmol Pd (CH ₃ CN) ₂ Cl ₂ , 0.6 mmol CuCl ₂ , 0.6 mmol of FeCl ₃ and 6.2 g of 1,4-butanediol were charged. The reaction was carried out under various reaction temperatures and oxygen pressure of 7 kG described in the table below. The main products other than cyclohexanone and cyclohexanone ketal were cyclohexenone. The results are shown in Table 9.

Reaction temperature (℃) Reaction time (min) Cyclohexene conversion (%) Selectivity (%) 706560 81128 807572 707679 Selectivity = cyclohexanone + cyclohexanone ketal

Example 26

Using the same reaction apparatus of Example 24, assuming benzene coexists, 1.1 g of benzene, 1 g of cyclohexene, 0.3 mmol of Pd (CH ₃ CN) ₂ Cl ₂ , 0.3 mmol of CuCl ₂ , 0.3 mmol of FeCl ₃ and 6.2 g of 1,4-butanediol were charged. The reaction was carried out for 3.5 minutes at a reaction temperature of 80 ° C. under an oxygen pressure of 7 kG. As a result, the cyclohexanone conversion was 92%, and the selectivity of cyclohexanone and cyclohexanone ketal was 70%. The main products other than cyclohexanone and cyclohexanone ketal were cyclohexenone.

Example 27

The materials and catalyst components were charged to the reaction apparatus in the same manner as described in Example 24 except that 1,2-cyclohexanedimethanol was used instead of 1,4-butanediol. The reaction was carried out for 32 minutes at a reaction temperature of 70 ° C. under an oxygen pressure of 7 kG. As a result, the conversion rate of cyclohexene was 52%, and the selectivity of cyclohexanone and cyclohexanone ketal was 84%. The cyclohexanone ketal / cyclohexanone ratio was 3.

Example 28

Except for using 2.3 g 1,2-cyclohexanedimethanol and 3.9 g 1,4-cyclohexanedimethanol instead of 6.2 g 1,2-cyclohexanedimethanol, In the same way the material and catalyst components were charged to the reaction apparatus. The reaction was carried out for 20 minutes at a reaction temperature of 70 ° C. under an oxygen pressure of 7 kG. As a result, the conversion rate of cyclohexene was 70%, and the selectivity of cyclohexanone and cyclohexanone ketal was 63%. The cyclohexanone ketal / cyclohexanone ratio was 1.

According to the present invention, ketals and / or acetals can be produced from olefins with high conversion and high selectivity while suppressing precipitation of the Pd component, which has high industrial potential.

While the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope thereof.

This application is based on Japanese Patent Application No. 2000-125535 for which it applied on April 26, 2000, The whole content is taken in here as a reference.

Claims (23)

A process for the preparation of ketals and / or acetals by reacting olefins having at least one ethylenic double bond with oxygen and polyhydric alcohols in the presence of a catalyst, comprising (a) palladium as catalyst, (b) 8, 9, 10 and And performing the reaction in the presence of at least one metal other than palladium and (c) halogen belonging to group 14. The process for producing ketal and / or acetal according to claim 1, wherein the reaction is carried out in a liquid phase in which the catalyst is dissolved. The process for producing ketal and / or acetal according to claim 1 or 2, wherein copper is further included as a catalyst. 4. The process of claim 3 wherein the catalyst compound used as the copper source is at least one copper chloride (I) and copper chloride (II). The ketal according to claim 3 or 4, wherein (b) uses copper in an amount of 0.1 to 100 mole times based on one or more metals other than palladium belonging to groups 8, 9, 10 and 14 of the periodic table; Or acetal production method. The ketal according to any one of claims 1 to 5, wherein (b) at least one metal other than palladium, belonging to groups 8, 9, 10 and 14 of the periodic table is a metal selected from iron, cobalt, nickel and tin. And / or a process for producing acetal. The process for producing ketal and / or acetal according to claim 6, wherein (b) at least one metal other than palladium belonging to groups 8, 9, 10 and 14 of the periodic table is iron. The process for producing ketal and / or acetal according to any one of claims 1 to 7, wherein (c) halogen is chlorine (Cl). The process for producing ketal and / or acetal according to any one of claims 1 to 8, wherein the concentration of palladium in the reaction solution is 0.001 to 10% by weight. The ketal according to any one of claims 1 to 9, wherein the molar ratio of at least one metal other than palladium to palladium belonging to groups 8, 9, 10 and 14 of the (b) periodic table in the reaction solution is from 0.1 to 100 and And / or a process for producing acetal. The process for producing ketal and / or acetal according to any one of claims 1 to 10, wherein the molar ratio of (c) halogen to palladium in the reaction solution is from 0.1 to 100. The process for producing ketal and / or acetal according to any one of claims 1 to 11, wherein (a) the catalyst compound used as the source of palladium is palladium chloride. The process for producing ketal and / or acetal according to any one of claims 1 to 12, wherein (a) the catalyst compound used as the source of palladium is a divalent palladium compound. The process for producing ketal and / or acetal according to any one of claims 1 to 13, wherein (a) the catalyst compound used as the source of palladium is a nitrile compound-coordination compound. 15. The catalyst according to any one of claims 1 to 14, wherein (b) the catalyst compound used as a source of one or more metals other than palladium, belonging to groups 8, 9, 10 and 14 of the periodic table, is a chloride and / or Process for the preparation of acetal. The process for producing ketal and / or acetal according to any one of claims 1 to 15, wherein (c) chlorine as halogen is used as chloride of (a) or (b). The process for producing ketal and / or acetal according to any one of claims 1 to 16, wherein the olefin is a cyclic olefin having 4 to 10 carbon atoms. 18. The process for producing ketal and / or acetal according to claim 17, wherein the olefin is cyclohexene. The process for producing ketal and / or acetal according to any one of claims 1 to 16, wherein the olefin is a terminal olefin having 2 to 25 carbon atoms. The process for producing ketal and / or acetal according to any one of claims 1 to 16, wherein the olefin is an internal olefin having 4 to 25 carbon atoms. The process for producing ketal and / or acetal according to any one of claims 1 to 20, wherein the polyhydric alcohol is an aliphatic or alicyclic diol. 22. The process for producing ketal and / or acetal according to any one of claims 1 to 21, wherein the polyhydric alcohol is used in an amount of 1 to 100 molar times based on the olefin. 23. A process for the preparation of ketones and / or aldehydes by hydrolysis of the ketals and / or acetals obtained by the process of any one of claims 1 to 22 in the presence of an acid catalyst.