TWI294423B - Method for producing ketal and/or acetal - Google Patents

Abstract

The object of the present invention is to produce ketal and/or acetal from olefins with a high conversion rate and a high selectivity. The present invention provides a method for producing a ketal and/or acetal by allowing olefins having at least one ethylenic double bond to react with oxygen and a polyhydric alcohol in the presence of a catalyst, which comprises carrying out the reaction in the presence of (a) palladium, (b) at least one metal other than palladium belonging to the groups 8, 9, 10 and 14 of the periodic table and (c) a halogen as the catalyst and a method for producing a ketone and/or aldehyde by hydrolyzing the ketal and/or acetal obtained by the above method in the presence of an acid catalyst.

Description

1294423 V. INSTRUCTIONS (1) TECHNICAL FIELD The present invention relates to a method of using a pound and/or an acetal. Manufacture of ketal by oxidation of oxyalkylenes Technical Background The compounds used in the oxidation of olefins by using molecular oxygen are industrially supported by catalytic reactions or ketones.

between. A particularly useful method;: Weighing: 亍...L reaction. In other words, a calving has been: Wacker's reaction

PdCl is used as a catalyst for the use of rhauh and CuC 12 aqueous solutions from the U-foods, and is used as a catalyst for the production of acetaldehyde u from ethylene and acetone from propylene. The method. From & a, scorpion in this conventional Wake reaction, the water bath is under strong acid conditions, g 6 + plant, ^ dry and there is a southern corrosive hydrochloric acid, so the reactor and Peripheral devices, such as 亜 Α Α 要 要 要 要 要 要 要 要 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ , , , , , , , , , , , , , , , , , , , , , , , , , , , This method is not always an industrially advantageous method. As for the reaction similar to the conventional Wacker reaction, a p-hydroperoxide complex of palladium (Pd-00H species) has been examined for the ketone formation reaction of olefins (JP-A-57-156428 (corresponding to U.S. Patent No. 4) 4〇〇544), JP-A-60-92236, JP-A-6 1 -60 62 1 ; The term "JP-A" is used herein to describe the "Japanese Patent Application". In the case where a monohydric alcohol such as methanol or ethanol is used as a reaction medium instead of the water used in the conventional Wick reaction, and a metal salt of copper and/or iron is used as a catalyst; however, as an industrial method, the reaction has Fatal disadvantages, such as low selectivity of the ketone or aldehyde as a product and precipitation of palladium metal when the reaction conditions are moved to the high temperature side. These documents show that the cocatalyst copper and iron also have the same effect.

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1294423 V. Description of invention (2)

Pdrl^ Journal of Organic Chemistry 34, 3949 (1 969) Jieyi ACuch # ^ ^ ^ - ^ ^ ^" Oil as a reaction solvent and such as ethylene glycol or glycan [4, 5] decane No: 'Hexene obtained 丨, 4~ dioxy snail did not explain the relevant - use iron to solve 祚幺; ί I is now used as a catalyst component, but also did not start the _ _ Gu Guan solution for the industrial method is a fatal shortcoming: : Not relevant, as this is the case, this is an effective method that has not been found in any industry that can be used in the temple. / 田 焱 焱 对应 对应 对应 对应 对应 对应 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛 醛Needed, cyclohexanthene is based on catalyst: < hexanyl-cyclohexanol mixture, and the cyclohexanol obtained by hydration of the ring is condensed, and the stalking method is used to form The product is in the heart of -P stomach, but because of the method of description, it is easy to continuously oxidize the conversion rate, so it is necessary to be strict with P, the degree of ridge is low, and the circulation is excessively excessive and imaginary.

ί ϋ The result is that this method becomes a process with low energy efficiency. I 接 Γ Γ 合 合 合 合 , , , , , 合 合 合 合 合 合 合 合 合 合 Γ , , , , , , , , , , , , , , , , , , , , , , , , , The ketone-'self" complex consumes a lot of energy. It is known that this is the second, if it is enough to have a selective olefin such as cyclohexene and a method of aldehyde or _, especially cyclohexyl, the meaning is quite heavy. The problem of olefin oxidation reaction, the inventors went to the bottom of the lamp and found that when reacting with olefins and oxygen and polyhydric alcohols, page 6 C:\2D-CODE\90-07\90109988.ptd 1294423 V. Description of the invention ( 3) In the deflation_and/or acetal, in addition to the metal other than (a), the industry can be prevented from being reduced in catalytic activity, thus leading to the completion of the present invention and suppressing the invention. The following characteristics. (1) A method for producing a condensed and/or condensed acid by reacting an olefin fish having at least one ethylenic double bond with a base alcohol in the presence of a catalyst, the method comprising: (a) palladium, (b) at least A metal other than palladium belonging to Groups 8, 9, 1 and 14 of the periodic table and (c) a halogen are reacted as a catalyst. (2) A method for producing a ketal and/or an acid reduction as described in (1), wherein the reaction is carried out in a liquid phase in which the catalyst is dissolved. (3) A method of producing a ketal and/or an acid reduction according to (1) or (2), further comprising copper as a catalyst. (4) A method for producing a ketal and/or an acetal according to (3), wherein the catalyst compound to be used as the copper source is at least one of copper (I) chloride and copper (I I ) . (5) The method for producing a ketal and/or an acetal according to (3) or (4), wherein (b) at least one gold other than palladium belonging to Groups 8, 9, 1 and 14 Based on the genus, the amount of copper used is 0.1 to 100 moles. (6) The method for producing a ketal and/or an acid reduction according to any one of (1) to (5), wherein (b) at least one of palladium belonging to Groups 8, 9, 10 and 14 of the periodic table The metal is a metal selected from the group consisting of iron, cobalt, nickel and tin.

C:\2D-roDE\90-07\90109988.ptd Page 7 1294423 V. Description of Invention (4) ' '--- (7) Method for producing ketal and/or acetal as described in (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) A method of producing a ketal and/or an acetal according to any one of (1) to (7), wherein (c) the halogen is chlorine (c 1 ). (9) A method for producing a ketal and/or an acetal as described in any one of (1) to (8) wherein the concentration of the reaction solution is from 〇·〇 〇丨 to 丨〇% by weight. (10) The method for producing a shrinkage and/or an acid reduction according to any one of (1) to (9), wherein (b) at least one of the groups belonging to Groups 8, 9, 1 and 14 of the periodic table The molar ratio of the metal other than the bar to the palladium of the reaction solution is 〇·1 to 丨〇〇. (11) The method for producing a shrinkage j and/or a shrinkage as described in any one of (1) to (10) wherein (c) the molar ratio of the halogen to the palladium of the reaction solution is 〇·1 to 100 ° (12) A method for producing a shrinkage and/or shrinkage according to any one of (1) to (11), wherein the catalyst compound to be used as the source of (a) palladium is palladium chloride. (13) A method for producing a ketal and/or a reduced age as described in any one of (1) to (12), wherein the catalyst compound to be used as the source of (a) palladium is a divalent I bar compound. (14) A method for producing a ketal and/or a reduced age as described in any one of (1) to (13), wherein the catalyst compound to be used as the source of (a) palladium is a nitrile compound-coordination compound. (15) A method of producing a ketal and/or an acetal according to any one of (1) to (14), wherein the (b) at least one of the periodic table 8, 9, 1 and The metal-derived catalyst compound other than the Group 4 palladium is a chloride.

\\312\2d-code\90-07\90109988.ptd Page 8 1294423 V. Description of Invention (5) (1) A ketal as described in any one of (1) to (1) And/or a method of acetal, wherein chlorine as the (C) halogen is used as the chloride of (a) or (b). (17) A process for producing a shrinkage and/or shrinkage according to any one of (1) to (16) wherein the olefin is a cyclic olefin having 4 to 1 carbon atoms. (1) A process for producing a ketal and/or an acetal according to (17), wherein the olefin is cyclohexene. (19) A process for producing a ketal and/or an acetal according to any one of (1) to (16) wherein the olefin is a terminal olefin having 2 to 25 carbon atoms. (20) A process for producing a ketal and/or an acetal according to any one of (1) to (16) wherein the olefin is an internal olefin having 4 to 25 carbon atoms. (21) A method of producing a ketal and/or an acetal according to any one of (1) to (20) wherein the polyhydric alcohol is an aliphatic or cycloaliphatic diol. (22) A method for producing a ketal and/or a shrinkage according to any one of (1) to (21), wherein the amount of the polyhydric alcohol is from 1 to 10 Torr based on the olefin. (23) A method for producing a ketone and/or an aldehyde, which is produced by hydrolyzing a ketal and/or an acetal obtained by the method according to any one of (1) to (22) in the presence of an acid catalyst. . BEST MODE FOR CARRYING OUT THE INVENTION (Catalyst) The catalyst of the present invention comprises (a), (b) at least one metal other than I bar belonging to Groups 8, 9, 10 and 14 of the periodic table, and (c) a The composition of the teeth is composed of components. In this case, the components (a) to (c) may be in any form.

C:\2D-C0DE\90-07\90109988.ptd Page 9 1294423 V. INSTRUCTIONS (6) If dissociated ions, salts or molecular forms are present in the reaction system. (a) The palladium may be in a divalent to tetravalent form, and may be selected from known and commercially available compounds as needed. Examples thereof include palladium complexes such as palladium vapor and palladium bromide, salts of inorganic or organic acids such as nitric acid, sulfuric acid, palladium acetate, difluoroacetic acid and acetylacetate I bar, and inorganic oxidizing, for example, And palladium hydroxide. Base coordination compounds derived from these metal salts such as [Pd(en)2]Cl2, [Pd(phen)2]Cl2, [Pd(CH3CN)2]Cl2, [Pd(C6H5CN)2]Cl2, may also be used. [Pd(C2 04 )2 ]2, [PdCl2(NH3)2] and [Pd(N02)2(NH3)2]2 but not limited to this (whereen represents ethylidene diamine and phen represents 1,10 - phenanthroline). Among these palladium sources, it is necessary to use a divalent palladium source, particularly a chloride or nitrile compound-coordination compound. The role of palladium in the catalyst system is manifested by interaction with iron ions and polyhydric alcohols, but the conditions of action are not always clear. Since the focus is on the performance of palladium via the composition of active species with other catalysts, the palladium source is sufficient to induce the necessary conditions to be present in the system. As for (b) at least one metal other than palladium belonging to Groups 8, 9, 10 and 14 of the periodic table, it is worth mentioning that there are iron, inscriptions, records, and tin, of which iron is preferred. The catalyst system to be used as the iron source may be in the form of a divalent or trivalent form. For example, it can be used in various salt forms for the reaction including chlorides such as iron chloride (Π) and iron (111), bromides such as iron bromide and iron bromide, and inorganic acid salts such as Iron sulphate (11), iron sulphate (iron), iron nitrate (yttrium) and iron nitrate (111) and salts such as iron acetate (Π), iron acetate (11.1), iron oxalate (Π), iron oxalate (I π ), iron citrate and iron acetylate pyruvate, or their coordination

C:\2D-CODE\90-07\90109988.ptd Page 10 1294423 V. INSTRUCTIONS (7) Compound form. In the case of palladium-like cases, the focus is on the fact that the iron system expresses its activity by forming active species with other catalyst components, so that an iron source sufficient to induce the necessary components exists in the system. The catalyst compound to be used as a source of cobalt, nickel, ruthenium or tin may be in the form of a divalent, divalent or tetravalent form. By way of example, a variety of salts can be used including, for example, chlorides and bromides, inorganic salts such as sulfates and nitrates, and salts such as acetates, oxalates, citrates, and acetoacetates. Or its coordination compound. When the component (b) is cobalt, nickel, ruthenium or tin, it is desirable to further combine copper. The main effect of the present invention is that palladium precipitation can be significantly inhibited by the addition of component (b), but further addition of a copper compound such as CuCl or CuCl2 thereto has another advantageous effect as an industrial process in which the reaction rate is improved and by-products such as i The compound is reduced. The element (c) is chlorine (c丨) and/or bromine (Br), but is particularly excellent in gas (c i). Halogen, can, she and / or iron relative anions are present in the reaction system. Further, it may be a halide of the catalyst component or may be supplied to the reaction system in some form such as vaporized hydrogen or dehydrogenated hydroquinone, but it is required that the compound is present in the reaction system in an ionic form in either case. According to the present invention, the production of a ketal and/or an acetal is carried out in the liquid phase via an olefin with oxygen and/or oxime, and the catalyst is dissolved therein. (Olefin) The olefin is an aliphatic or ring-containing compound containing at least one ethylenic double bond. No. As for the chain hydrocarbon, it is worth mentioning that it usually contains 2 5 , and the car is preferably 2 to 25, more preferably 3 to 10. a rare hydrocarbon of carbon atoms, for example

1294423 V. Description of invention (8) If the position of π double bond of y, j, and butyl is ～: pentene, hexene and octene. In this case, it is mainly formed by the worm or the ketal of the methyl ketone. And, to form, and the corresponding ketal is mainly contained in the internal olefin case, j=including 4 to 10, preferably 5 to 8 carbon atoms and hexanyl-π^ olefinic double bond Compounds such as cyclopentene, cyclohexene, and cyclopentane; dilute and cyclodextrin; produced by cyclopentene and cyclohexene; at least two & / alkane (hereinafter referred to as cyclohexanone ketal) As a product. , the atomic biting ΐ ΐ = burnt, alkoxy, aryl, phenyl, slow or ethinyl chloride;; nitrile, propylene, acrylic. In addition, it contains ί ί 乙 乙 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可One naphthalene, one right (polyalcohol) Polyalcohol is usually bivalent, usually containing 2 or 2 =: shoulder; an alcohol is particularly good. When the diol is used for cost, stability and ease of formation, :: = 8 carbon atoms of the di- or ketal; this towering - preferably 3 2 to 1 〇 and more preferably 3 to τ butyl, the 4-alcohol Preferably, the diol, 1,2-di-butylidene, including ethylene glycol, 1,3-propane ring-diethanol 3, ρ2-/ search for propylene, 1,4-butanediol '14-τ And 1, 1,2-hexane hexane dimethanol, monocyclopentanediol, 2, 4-pentane-| 7 & 1-ethyl alcohol, 1,2-trans-^, oxime to the present ethylene glycol, 1 5 -heterocycloalkane, 1,4-dihydroxycyclooctane, 2 bis = 〗, 5 - 裱 原 冰 冰 ,, 2, 6-dihydroxy original ice page 12 \\312\2d-code \90-07\90109988.ptd 1294423 V. Description of the invention (9) by ~2,4-didecyl 1,4-alcohol, butanediol,. However, it is calcined, 1,4-dihydroxy-2,3-didecylbutane, 1,5-di-pentane, cyclobutane-L2-dimethanol, cyclohexane-[;3- Dimethanol is di- 2,3-di-butane and 2, 5-dihydroxyhexane, wherein Ethyl dipropanediol, it dihydroxybutane, 1 > 2-dihydroxypropane, 14-alcohol '14-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, diethyl L 2 -anticyclopentanediol, 2,4-pentanediol, styrenediol is more preferably two or more Can be combined. Although the reason for the need for the use of polyhydric alcohols in the present invention has not been absolutely clarified, the formation of divalent peroxyl compounds as a novel active ingredient, and the consideration of alcohols inducing such activity On the species ^ 1 effective role. In addition to this role, it reacts with the formed aldehyde or _ to form the corresponding acetal or ketal, so that the free aldehyde and ketone can be compared to the oxo, which is significantly higher stability. This becomes such that the selectivity of the product of interest is maintained at a significantly higher level. Ιι 口:: When a hydroxyl alcohol such as methanol, ethanol or propanol is used in place of a polyhydric alcohol, the product is not readily available in such a free (four) and/or _ _ _ _ or ❿ 氧化 ; Reversed, when using ethylene glycol Hg including divalent diol, this phase is obtained by the corresponding acetal or oxidized reaction product obtained by the corresponding (four) and condensed 2 ^ & . As a result of this, the former obtains * or _ by the hydrolysis of the former to carry out oxygen (reaction conditions) such as a significant increase in the yield. The use of oxygen-containing gas is essential in accordance with the present invention, but due to oxygen and organic

1294423 V. INSTRUCTION DESCRIPTION αο) A compound may form an explosive mixed character at a certain pressure range: within a certain composition range of 0.001 MPa or more. Progress: Against the cause / avoiding risks. If the partial pressure of oxygen is at a rate of U, the catalyst is tilted; ^f/i', but if the partial pressure of oxygen is too low, the back pressure is preferably from 0.01 to 10 MPa and activation. In the present invention, the oxygen content is selected by safety and economy; ❻/5 to 5 MPa, but the scent should be regarded as the best pressure. The reaction temperature is 〇〇C or μ#c; the relationship between the virtual μ and the temperature is high, so it is necessary to use hydrazine, but due to the reaction of the present invention: ί; formation conditions of the ΐ compound and the self-oxidation reaction of the group The increase in by-products is selected, but an economically significant reaction rate is usually obtained at a temperature range of from 2 Torr to 2 Torr and preferably from 40 to 180 ° C. The total reaction pressure can be maintained in the liquid phase at a higher pressure or higher, but is usually from 百万. 百万 million ψ white to 20 MPa 乂 乂 乂 〇. 1 MPa to 15 MPa. Further, the reaction time (residence time) is usually from 5 seconds to 20 hours, preferably from 1 second to 1 hour. The (a) palladium concentration as a catalyst is expressed in terms of [pd2+] based on the total weight of the reaction solution in a range of from 0.001 to 1% by weight and preferably from 0.001 to 5% by weight. Under the conditions of 7 degrees, the reaction rate shows different concentration dependence under low concentration conditions, and the catalytic efficiency tends to deteriorate. Therefore, the effective concentration should be selected from an economic point of view. (b) The concentration of at least one of the gold genus other than the group of Groups 8, 9, 10 and 14 of the periodic table can be described as its relative concentration to (a) palladium. In other words, it is usually selected to be in the range of 0.1 < [M] / [Pd] < 100 (mole ratio), preferably 〇.i < [M] / [Pd] < 1 0 (mr ratio). Concentration below this range will cause a decrease in the reaction rate, and also cause a decrease in the main effect of the metal (b).

1294423 V. INSTRUCTION OF THE INVENTION (11) The excessive amount of the effect of X is too large to suppress the reaction itself, and instead causes a tendency to limit its amount dissolved in the reaction system. The relative concentration of halogen (c) to palladium is usually at 0. 1 < [C1 and / or Br] / [Pd] < 1 〇〇 f molar ratio) and preferably 〇. 3 < [C1 and / or Br ]/[Pd]<50 (Morbi). Since the material in the reactor may be rotted due to the water in the reactor under high halogen concentration conditions, it is desirable to use a halogen-concentrating system to perform as low a function as possible. Further, the component containing the catalyst-derived element may be formed as a by-product in some cases, in which case it is desirable to continuously or periodically supply the spent polyol 0 reaction system polyhydric alcohol, for example, in the form of its metal s. The amount present may be a theoretical amount (1 mole) relative to the olefin' but is also contemplated as a reaction solvent in accordance with the present invention. Based on 'capacity', usually in the range of i to 99% by volume and preferably 5 to 'volume of two volumes' and based on olefins, the amount of polyhydric alcohol is usually from 1 to 2, preferably from 2 to 50. Moor. The amount of olefin present in the reaction system may be selected from the range of pass, 99% by volume, and preferably 1 to 5% by volume. ... When the degree of multi-alcohol is quite low, in other words, when the flue-cured tobacco is relatively, it may cause a part of the catalyst composition to be distributed in the sister-smoke hall. In terms of it, when the alcohol concentration is too high, the supply = change: the species 2 is easy to cause low productivity of t and the difficulty of phase separation after the reaction, and the oxidative inert third component VIII β 雍 system can be adjusted and adjusted. The relative concentrations of polyhydric alcohols and olefins, as well as: core separation characteristics. One step improvement phase According to the present invention, activity can be increased by further adding another component

1294423 V. Description of invention (12) # f 3 should be. Regular. Additives which enhance the oxidation reaction such as copper or alkali, alkaline earth or rare earth metals may be added. Further, a method of suppressing side reactions by using a group trapping agent can be employed. In the Dali process, especially in the reaction of the present invention, a cyclohexene is produced by a method in which the material balance of the overall process is considered, and even if there is a trace impurity of argon, it is necessary to effectively separate the impurities. For example, it is particularly difficult to separate and possibly! The formation of impurities which adversely affect the product such as cyclohexenone: decenyl alcohol, decyl hexanone and cyclohexanone ketal should be controlled to the lowest possible extent. The reaction of the present invention can be carried out in accordance with a general oxidation reaction. When the various components of the catalyst are present in a solution state, the oxidation reaction can be carried out using a batch reactor, and by subjecting the olefin to an oxygen-containing gas to undergo a specific reaction, 2, or using a (four) phase reaction n, and via continuous supply. Oxygen gas and line. In terms of the fact that when the catalyst component of the present invention is braked, a liquid phase reaction can be used or a so-called trickle bed system can be employed, in which a fixed bed is charged, and a corresponding liquid phase is supplied to the olefin and oxygen. The supply of oxygen 'can use the technique of effectively dissolving oxygen in the reaction solution system', for example, using a mixed vane to make an oxygen-containing gas into small bubbles, the technique is to form a small bubble by setting a baffle in the reactor. The technique of linear velocity spraying a gas into a system. / field (treatment after oxidation reaction) The oxidation product solution after the oxidation reaction contains a raw material olefin, a product condensed or acetal, a catalyst component, and a polyhydric alcohol. When the reaction product is taken up under pressurized conditions, the force can be lowered by depressurizing to some extent. When the olefin of the reaction product solution and the ketal and/or acetal have a low boiling point

1294423 V. INSTRUCTIONS (13) - When there is a big difference between the point and the glutinous alcohol, the low boiling point component (dilute hydrocarbon and ketal and/or acetal) can be directly separated from the reaction product solution by distillation. . The catalyst component which is obtained as a bottom fraction of the distillation is subjected to an alcohol-soluble cycle to the oxidation reaction step. / / When the olefin and the ketal and / or acetal boiling point is higher than the polyalcohol solvent point, an extraction solvent such as an organic solvent is added, the extraction solvent forms a two phase with the polyalcohol, and phase separation is carried out by extraction, The oxime is separated from the olefin containing ketal and/or acetal by the alcohol phase containing the catalyst component. The olefin and the ketal and/or acetal are then recovered from the extraction volume phase and then separated by distillation to remove the ketal and/or acetal. The portion containing the catalyst component can be recycled to the oxidation reaction step through the alcohol phase. In the two-phase separation, when the 77-containing lean > smoke and ketal and/or acetal extraction solvent side contaminates the trace catalyst component, the remaining amount of the catalyst component in the extract phase can be extracted by using a polyhydric alcohol solvent. Two or more extractions of the solvent phase are reduced to negligible privacy. Further, a technique may be employed in which after the initial two-phase separation, the olefin f ketal and/or acetal is separated from the extraction solvent by distillation, thereby increasing the residual catalyst concentration of the extraction solvent phase to a certain extent. Perform extraction. ... In addition, during the process of oxidizing to form a ketal, water is formed in the reactor but only a small amount of water is formed. It is desirable to remove the water thus formed as much as possible from the reaction system, _ but = when the _f component, such as chlorine, remains in the system, the susceptibility to corrosion of the reactor remains high. As a result, highly corrosive acids such as gasified materials must be used for the necessary parts. Materials such as glass, ceramics and Teflon can be used in areas where the reaction pressure is not too high.

(14) V. The invention field; in the case of high reaction pressure, it is necessary to use the container of the reactor. In other words, the alloy is a stainless alloy (Hastelloy), which is a titanium-containing alloy container, or the alloy thereof Coating and borrowing a '3 compressor. Although the reactor has extremely high corrosion potential, when the vertical vessel and the separation vessel are used, these components have a high therapeutic effect on the oil phase containing the product, and when the catalyst component is concentrated, it is possible to have a high-corrosion main container. And the degree of use of the pipe attached to the main vessel is determined to be economically acceptable. The use of the reaction system as a main component is not active. Further, although a very small amount is used, the olefin-forming compound has an alcohol phase which is similar to the polyhydric alcohol polarity time in the batch reaction or in the continuous alcohol and the fumigation but not the reaction. In order to stabilize the operation, it must be balanced. The results must be responsive to the rate of impurity formation and the rate of formation, by removing some of the catalyst from the system to the fresh catalyst material solution. In this case, the composition of the back j component is larger than the economic burden of the big time. The recycling method is not particularly limited, but the technique of washing and recycling metal components is useful. There are two kinds of phase separation products (ketal and/or phase). When the extraction solvent such as organic solvent is used in the steaming hall, it is usually used as an anti-corrosion and anti-corrosion, which is commonly known as Hastel or misplaced alloy. However, it is possible to further set the name of the direct rot. In addition, when the composition is divided, there may be a halogen surname. It is hoped that this anti-text material is based on the rot-resistant material. & The alcohol is not completely oxygen-carrying but some polarity of the oxidative oxidation In this way, some of the poly-alcoholic phases derived from the multi-phase accumulation in the catalyst-containing catalyst to rapidly control the oxidizing component of the oxidizing component are used to remove the catalysis by the samarium system. , the acid extraction) of the extraction solvent, in the same way 1294423 V, invention (15) impurity accumulation, in this case can also supply fresh extraction solvent by removing some of the old extraction solvent. The ketal and/or condensate obtained by the present invention is converted into a corresponding ketone and/or aldehyde by hydrolysis in the presence of water and an acid. Examples of useful acids in this case include inorganic acids such as hydrochloric acid, sulfuric acid, citric acid and scaly acid, polybasic acids such as heteropolyacids, and solid acids such as ion exchange resins, zeolites and clays. The aldehydes and ketones of interest can be recovered from the reaction product solution of the aldehydes and/or ketones thus obtained, and then the aldehydes and ketones are separated and purified as a desired product to effectively obtain the aldehyde of interest and copper. Further, the ketal and/or acetal obtained by the present invention can be efficiently converted into the corresponding alcohol by hydrogenation in the presence of water, a hydrogen source and a hydrogenation catalyst. Hydrogen sources include, for example, hydrogen, formalin, and sodium borohydride (NaBH4), and hydrogenation catalysts include, for example, nickel hydride, kononic, copper-chromium-containing oxides, in which a Group 8 metal such as palladium, platinum or rhodium is supported on a carrier. The catalyst thereon, and a complex catalyst using a Group 8 metal such as ruthenium, ruthenium or a central metal. The alcohols of interest can be efficiently obtained by recovering water from the alcohol-rich reaction product solution obtained by hydrogenation and condensing and/or condensing the alcohol formed, and then separating and purifying the alcohol as a desired compound. The invention will be further illustrated by the following examples, but the invention is not limited to the examples. EXAMPLES Example 1 A drum-shaped heat-resistant glass reactor equipped with a magnetic bellows and a gas introduction tube, having an inner diameter of mm and a height of 12 mm, was filled with 1 mm of a l ^ 1 ((;: 113 (^) 2 ( :12, 1294423 Five inventions description (16) ^^ 〇. 1亳莫耳CuCl2, 〇·i milli Mo 2. Momo earrings have #, air to: millimoles of ethylene glycol and carry out for 5 hours. After the reaction, the reaction was analyzed by gas chromatography with stirring at 40 t. The product was solidified to the reaction solution, and the product was obtained in a yield of 2.5%. T0F = 1 〇 / / ^ conversion rate of 2.5%, Cyclohexanone ketal palladium protection p 航 R π mouth. ϋ / small ^ ° TOF means that every hour and palladium % ketone and bad ketone ketal to form tacrole. No palladium precipitation in the course. The chlorocyclohexane was not formed. Example 2 2 ii was carried out according to the procedure of Example 1 but no cuc was added. The result was a fine conversion of 2.5%, and the cyclohexanone ketal was obtained at a yield of 2.5%. Uf is, η: cyclohexanone ketal is used as a reference to produce u mole % chlorocyclohexane hydrazine product. No palladium precipitation is observed in the solution after the reaction. The first embodiment should be in the same manner as in the first embodiment. Executed but not added to FeC 3. As a result, the conversion of hexene is 2.3%, the yield of cyclohexanone ketal is 2.3%, and T〇F is 〇·92/hour. After the reaction, the reaction solution is changed by fine black powder of palladium black. Turbid, the bottom of the reaction and the side walls appear to precipitate.

\\312\2d.code\9〇.〇7\9〇i〇9988.ptd Page 20 1294423 V. Description of invention (17) Table 1 Palladium compound iron compound copper compound cyclohexene conversion rate * ketal yield ** D. Remarks Example] 0.] 〇·] 〇 ] ] ] ] ] ] ] ] ] ] 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 0.1% without using 2.5% 2.5%]·〇/hour palladium is not precipitated, no chlorine cyclohexane is not formed. Comparison of 0.] No use of 〇·]mmol 2.3% 2.3% 0.92/hour palladium precipitation 1 Molmers 41 * : cyclohexene conversion rate: cyclohexanone ketal yield mother small % materol ring cyclohexan and cyclohexanone ketal production rate I by comparing the examples 1 and 2 In comparison with the comparative examples, it was found that palladium precipitation was inhibited by the addition of iron. It was found that the formation of cyclohexane was also suppressed by further addition of a copper compound. Example 3 / With a magnetic stirrer with a cylindrical diameter of 4 mm and a height of 15 mm, the fluorolong beaker is placed in a _3_316 pressure cooker, and the pressure cooker can withstand the pressure of 丨(10) kG and the size of the chisel beaker, and The same feed composition was used at an oxygen pressure of 7 kG at a reaction temperature of 8 ° C for an hour. As a result, the yield of the reaction product of cyclohexanone ketal/cyclohexanone=24·8 and cyclohexanone ketal/cyclohexene copper=26·i was obtained, and the conversion rate of the mixture was 3〇% and T〇F. It is 6 baht / hour. After the reaction was completed, Ji Shen Temple was not seen.

\\312\2d-code\90-07\90109988.ptd Page 21 1294423 V. Description of the Invention (18) Example 4 The reaction was carried out in the same manner as described in Example 3 except that CuC丨 was not used. As a result, the cyclohexene conversion was 34% and the τOF was 6 7 /hr. Chlorocyclohexane is produced in an amount of 1 mol% based on the ketal. No palladium precipitation was observed after completion of the reaction. Comparative Example 2 The reaction was carried out in the same manner as in Example 4, but without using Fec 13 and

The amount of CuCl2 or CuCl used is a predetermined amount. The results are shown in Table 2. Each case was found in Ji Shen Temple. Table 2 Conversion of copper compound cyclohexene to T0F*(/hour) CuCl (〇·1 mmol) 13.5% 27 CuCl2 (0·1 mmol) 21. 0% 42 CuCl2 (〇· 2 mmol)氺: 丄α太仁七e ·πτ 45. 〇% 90 丄乂, 6% π% hexanone and cyclohexanone ketal production rate from the results of the narration, when Jingjing six + w ^ ^ U Λ ^ P V- ^ When iron is present in the system, even if the oxygen concentration ^ 2 and % know that the conversion rate is high:: The agent can still function effectively. The above method was carried out in the same manner as described in Example 1, except that the reaction was carried out in the same manner as in the case of the reaction of the first embodiment, but the use of ethanol 5; ^ + 乙一知2·5 gram of the mixed solution to replace the 俨 广 P Guang 0 hair, ^ 22% + not \ already ^ The selectivity is MX and the TQF is 8·. After the reverse shore ^ ^ § No palladium precipitation. J 'Set solution t is carried out' but using 1,3-propanedi-/cyclohexanone = ^hexene conversion rate 16 〇 / 〇 4 / hour. After the reaction, 1294423 -----______ V. Description of the invention (19) The reaction was carried out in the same manner as described in Example 1, except that a mixed solution of methanol 5 ml of te-ethyl alcohol 1 2 3 4 · 5 g was used instead of ethylene. alcohol. As a result, a cyclohexene S-ketal and a cyclohexanone were obtained at a ratio of 17.6, and the conversion of cyclohexene was 丨〇·〇%, and the yield of (cyclohexene 0 + cyclohexanone ketal) was 10· %, TOF is 4·0/hour. No palladium precipitate was observed in the solution after the reaction. " The second reaction was carried out in the same manner as described in Example 1, except that a mixed solution of hydrazine, 4-butadiene = 7 gram 5 g + ethylene glycol 2.5 g was used instead of ethylene glycol. As a result, the ring rate was 22% and the TOF was 8.0 / hour. No solution in the solution after the reaction

The reaction was carried out in the same manner as described in Example 1, but using 2

C:\2D-CODE\90-07\90109988.ptd Page 23 1 The reaction was carried out in the same manner as described in Example 1 to replace glycol. As a result, the reaction product cyclohexyl 2·8 7 and cyclohexanone ketal/cyclohexene copper = i 6 . 1, 3 were obtained. As for the formation rate of (cyclohexanone + ketal), the TOF was 6. No precipitation was observed in the liquid. 4

Example Q The reaction was carried out in the same manner as described in Example 1, except that the alcohol was substituted for ethylene glycol. As a result, a reaction product obtained by cyclohexyl-condensation of 4-butane oxime 41 and cyclohexanone ketal/cyclohexene copper = 4.93, cyclohexanone = . (cyclohexanone + ketal) selectivity was 79% and T〇F was 8: conversion rate was 27%. hour. Reaction 5 Example 1 0 1294423 V. Description of the invention (20) Cyclohexanone ketal + ring After the reaction, the alcohol replaces ethylene glycol. As a result, the ring was diluted =:) the selectivity was 91.5% and the _ was 26/'' small. No palladium precipitation was observed. Example

The reaction was carried out in the same manner as described in Example 1 - adding the catastrophe 1 9 - τ® P diol instead of ethylene glycol. The results of the ring: the sputum, the use of the kernel, 2 - clothing pm ^0 7 ρ π hexene conversion rate of 12%, cyclohexanone ketal / 咏巳 is 3 · 7, (Yuchen hexanone Weixi Hanban class

For the 4 /5 ^ 嗣 嗣 嗣) selectivity of 90% and T0F π should not be seen in the solution after the palladium precipitation. Comparative Example ^ Further, the reaction was carried out in the same manner as in Example 1. The result was a conversion of cyclohexanone to 35; 匕: = alcohol substitution The cyclohexanone selectivity was 51%. The yield of f-hexanone in the reactor was 17%. Hexanone acetal. See palladium precipitation. Examples 5 to 11 and comparative examples are shown in Table 3 below. Alpha fruit together with the results of Example 1

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Page 24 1294423 V. INSTRUCTIONS (21) Table 3 Alcohol CHN ketal / CHN* Q * * Remarks - Example 1 Ethylene glycol (EG) 10 ml 100 I.0 / hour without palladium precipitation, no chlorine ring Hexane Example 5 1 Ethanol 5 ml + EG 2.5 g > 10 8.4 / hr without palladium precipitation Example 6 Methanol 5 ml + EG 2.5 g 17.6 4.0 / hr without palladium precipitation Example 7 1,4-butanediol ( BG) 7.5 g + EG 2.5 g > 10 8.0 / hr without palladium precipitation Example 8 1,3-propanediol 1 〇 ml 2.8 7 6.4 / hr without palladium precipitation Example 9 1,4-butanediol (BG) 10 ML 0.4 1 8.5 / hr without palladium precipitation Example 10 2,3-butanediol 1 〇 ml 5-10 2.6 / hour without palladium precipitation Example 1 1 1,2-cyclohexanediol 10 ml 3.7 4.3 / hour no Palladium precipitation comparison Example 3 Ethanol 10 ml 0 6.8 / hour without palladium precipitation, no ketal state __11丨C:\2D-CODE\90-07\90109988.ptd Page 25 1294423

Anthraquinone ketal _ /cyclohexanone = hour per cyclohexanone cyclohexanone and cyclohexyl condensed ketone, sitting by Comparative Examples 1 and 5 to 11 and Comparative Example 3, The cyclohexanone ketal is formed upon storage of the alcohol. Because cyclohexanone is more oxidized than car, there is almost no oxidization, which is 汨 反 反 Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi Hi ^ ^ ^ ^ ^ ^ ^ Γ Γ Γ Γ 择 择 择 择 择 择It is hoped that 彳 彳 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 1((:113^'〇2(:12. The result is hexene conversion of 5% and 1<1; 1 is 2/hour. No precipitation was observed in the solution after the reaction. ^ Example 1 3 The same procedure as in Example 7 was carried out except that pd C 1 was used instead of Pd(CH 3 CN) 2 Cl 2 . As a result, the conversion of the bad dilute was 4% and the concentration of t〇F was 16 6 , and no precipitation was observed in the solution after the reaction. Example 1 4 A cylindrical Teflon beaker with a diameter of 40 mm and a height of 15 mm with a magnetic stirrer is placed in SUS - 3 1 6 high-pressure steel. The high-dust steel can withstand the pressure of 1 〇〇 kG and the size fits. The beaker was reacted using the same feed composition of Example 1 at 70, 80, 90 or 100 under an oxygen pressure of 7 kG. (The reaction temperature was carried out for 1 hour. After the reaction, no palladium precipitate was observed in the solution. In Table 4. Visible The reaction rate has a great relationship with the reaction temperature and oxygen pressure. Table 4

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1294423

Reaction temperature (°c) Cyclohexene conversion TOF* ketal/cyclohexanone ketal/cyclohexenone 70 21% 42 >40 >1000 80 30% 58 24.8 26.1 90 50% 93 28.5 12.3 100 58 % 110 18.3 15.7 * ·································································· A mixture of 5 g + 1,4 - butanediol 7 · 5 g was used as a reaction solvent, and the reaction temperature was 40, 60, 80 or 90 C. No precipitate was observed in the solution after the reaction. The results are shown in Table 5 〇 Table 5 Reaction temperature (°C) Cyclohexene conversion rate TOF* ketal / cyclohexanone ketal / ring susceptibility 40 4% 8 5.3 12.5 60 13% 24 2.6 8.0 80 46% 84 2.3 7.2 90 87% 154 1.1 3.7

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It can be seen that Ik is rapidly rising in reaction rate with the reaction temperature. Example 1 6 The reaction of Example 进行 was carried out, but the reaction temperature was fixed at 80 ° C, and the feed amount of cyclohexene was changed. No palladium precipitate was observed in the solution after the reaction. The results are shown in Table 6. Table 6 Cyclohexene/palladium reaction time cyclohexene conversion TOF* (/hour) ketal / cyclohexanone / cyclohexenone 200 1.0 26% 50 24.8 26.1 3.0 7 0.5% 43 11.7 10.4 400 1.0 3 7% 47 27.6 19.0 3.0 60% 37 17.2 11.9

* : Formation rate of cyclohexanone and cyclohexanone ketal per hour per liter of palladium. Example 1 7 The reaction of Example 15 was carried out, but the reaction temperature was fixed at 90 ° C, palladium, copper and iron. The feed rate is individually fixed at 0 · 0 2 5 millimoles. As a result, the cyclohexene conversion rate was 58%, and the T 0 F value was 4 2 5 /hr. The ratio of cyclohexene S to the same / cyclohexanone ratio was 4 · 4 and the cyclohexanone ketal / cyclohexenone ratio was 8 · 5. No palladium was found in the solution after the reaction.

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Shown in Table Table 7

Acac : Acetylpyruvate Example 1 Q A round-shaped Teflon beaker with an internal diameter of 40 mm and a height of 5 mm equipped with a magnetic stirrer is placed in SUS-316 high-pressure steel, and the pressure of the pressure cooker is 1〇〇. The kG size just as a beaker's reaction was carried out using the same feed composition of Example 1 at a reaction temperature of 80 ° C under an oxygen pressure of 7 kG and adding 20 millimoles of styrene. After 1 hour of reaction, the contents were taken out and analyzed by GC. As a result, the TOF value was 154 / hr, and the selectivity of the phenyl acetal compound of phenylacetaldehyde was 54 ° /. The selectivity of the EG ketal compound of stupid ethyl ketone is 11%, and the selectivity of (phenyl acetaldehyde + acetophenone) is 25%. After the reaction, the palladium precipitated in the solution.

\\312\2d-code\90-07\90109988.ptd Page 29 1294423 V. INSTRUCTIONS (26) EXAMPLE 2 0 The reaction was carried out in the same manner as described in Example 119, but using α-mercaptobenzene Ethylene replaces styrene. As a result, the TOF value was 54 / hr, and only 2-propionic propionic acid and its E G condensed compound were formed. The acid/acid ratio is 2 · 5. No palladium precipitate was observed 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-diazepine was used instead of styrene. As a result, the TOF value was 90/hour. No palladium precipitate was observed in the solution after the reaction. Example 2 2 The reaction was carried out in the same manner as described in Example 19 except that 1-bromo was used instead. As a result, the Τ 0 F value was 4 6 /hr, the (ketal compound + condensate compound) selectivity was 70%', and the ketal compound which mainly obtained the double-bindered octyl bromide compound. No palladium was found in the solution after the reaction. Example 2 3 The reaction was carried out in the same manner as in Example 22 except that 2-octyl was used instead of octene. As a result, the TOF value was 40 /hr and the selectivity of (ketal compound + acid-reducing compound) was 84%. The distribution of the generated products is the same as in the case of Example 22. No precipitation was observed in the solution after the reaction. (Example of a mixed material using cyclohexene and benzene) Example 24 A cylindrical Teflon beaker equipped with a magnetic stirrer having an inner diameter of 40 mm and a height of 15 mm was placed in a SUS-316 pressure cooker, and the pressure cooker was subjected to a pressure of 1 Torr. 〇P kG, the size can be chiseled beaker, assuming stupid coexistence, feed 2 · 2 grams stupid, 2 grams

1294423 V. INSTRUCTIONS (27) Cyclohexene, 0·3 mM Pd(CH3CN)2Cl2, 〇·3 mM CuCl2, 〇·3 冤Moule FeClg and 6.2 g 1,4 - butyl The case of alcohol. The reaction is at 7 Torr. 〇 The reaction temperature is carried out under various oxygen pressures as described in the table below. The composition other than cyclohexanone and cyclohexanone ketal is cyclohexene copper. The results are shown in Table 8. Oxygen pressure (kG) reaction time (minutes) cyclohexene conversion (%) selectivity (%) 4 24 63 7 1 5 20 67 72 6 22 68 77 7 24 62 84 8 9 72 70 9 7=f 11 85 74 Selective = cyclohexanone + cyclohexanone ketal Example 2 5 Table 8 ---- wide - ___ ❶ The same reaction apparatus as in Example 24 was used, assuming benzene total #, feeding 2 · 2 grams of benzene , 2 g of cyclohexene, 〇 · 6 mmoles of pd (c 〇 · 6 ears of CuCl2: U millimolar FeCl3 and 6.2 butyl diol)

The oxime reaction is carried out at a temperature of 7 k G at >5 ΊΓmain V b and various reaction temperatures as described in the table below. The composition of cyclohexanone and cyclohexanone ketal, such as &, is a cyclohexene copper. The results are shown in Table 9 〇 Table 9

1294423 V. INSTRUCTIONS (28) Reaction temperature (°c) Reaction time (minutes) Conversion rate (%) selected / 70 8 80 65 11 -7 5 60 28 7 2 7 0 76 79 Selectivity = ring Cyclohexanone condensed with Example 2 6 The same reaction apparatus as in Example 24 was used, assuming a clump of 1 gram of benzene, 1 gram of cyclohexene, 〇·3 mM pd(CH3CN)2Ci, storage, CuCl2, 〇 · 3 mM FeCl3 and 6.2 gram 1,4 should be subjected to a reaction temperature of 80 ° C at an oxygen pressure of 7 kG for 3 · 5 minutes of dream feed 1 alcohol 〇 macro 3 millimoles case. The result is a cyclohexene conversion of 92%, cyclohexanone and cyclohexanol. result? The product other than cyclohexanone and cyclohexanone is cyclohexyl, and the selectivity is 7 〇 〇 / 〇 Example 2 7 岬蜩. The material and catalyst composition were divided into the corresponding apparatus described in Example 24, but using 1,2-cyclohexanedimethanol instead of hydrazine, and the method was fed to a reaction temperature of 70 C at a pressure of 7 kG for 32 minutes. The conversion of the reaction alcohol was 52%, and the cyclohexene and cyclohexanone were selected to give a cyclohexenone ketal/cyclohexanone ratio of 3. The sex is 84%. Example 2 2 The ring material and catalyst composition are divided into the apparatus described in Example 27, but using 2.3 g 丨,? - Cyclohexane Diterpene Method is fed to the reverse methanol replacement 6 · 2 ancient 1 〇 _ ϊ 。. , 々- Ρ» a 3 · 9 g 1,- 己烷 hexane dimethanol instead of 6.2 g 1,2 -cyclohexanedimethanol reaction system in 7 〇 ring

C:\2D-CODE\90-07\90109988.ptd Page 32 1294423 V. INSTRUCTIONS (29) Two degrees have been carried out at 2 ° minutes under Μ oxygen pressure. As a result, the conversion rate of cyclohexanone was 6% and the selectivity of hexanone was 63%. Cyclohexanone condensate / industrial application According to the present invention, it is possible to produce a shrinkage and/or shrinkage disk from an olefin with high conversion and high selectivity, and at the same time suppress precipitation of a palladium component, so that the industrial utilization rate is high. The details of the present invention are illustrated by those skilled in the art, and it is obvious 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 the application of Japanese Patent Application No. 20 00 - No. 25535, filed on Apr. 26, 2000, the entire contents of which is hereby incorporated by reference.

C:\2D-CQDE\90-07\90109988.ptd Page 33 1294423 Schematic description <1 C:\2D-CODE\90-07\90109988.ptd Page 34

Claims (1)

1294423 Nickname 90109988 A method for the manufacture of ketals and / or six, the scope of patent application ra 2 face change Hj—a batch reactor or a continuous reactor, such that a chain-like hydrocarbon having a carbon number of 2 to 10 and at least one ethylenic double bond is based on a total reaction volume of 丨 to 99% by volume, Or a cyclic olefin having a slave atomic number of 4 to 10 and at least one olefinic double bond, which is contacted with oxygen having a partial pressure of 0.01 to 10 MPa to produce a ketal and/or an acetal; The reaction system is a polyhydric alcohol having (a) palladium ion, (b) iron ion, (c) halogen ion, and a volume ratio of 1 to 99% based on the total reaction volume, having a carbon number of 2 -1 Torr. In the solution, the sister is carried out at a temperature of 20 to 20 ° C and a pressure of 0.1 to 20 MPa, wherein the molar ratio of iron to Ι ε in the reaction solution is 〇 1 to 10 0. 2. A method of producing a ketal and/or an acetal according to the first aspect of the invention, wherein the reaction is carried out in a liquid phase in which the catalyst is dissolved. 3. The method of producing a ketal and/or an acetal according to claim 1, wherein the copper ion is further included as a catalyst. 4. A method of producing a ketal and/or an acetal according to the third aspect of the patent application, wherein the catalyst compound to be used as a copper source is at least one of copper chloride (ruthenium) and copper chloride (11). 5. A method of producing a ketal and/or an acetal according to item 3 of the patent application, wherein the amount of copper is 0.1 to 1 mole per mole based on iron. 6. A method of producing a ketal and/or an acetal according to the first aspect of the patent application, wherein (c) i is chlorine (C1). 7. The method for producing a ketal and/or an acetal according to the first aspect of the patent application, wherein the concentration in the reaction solution is from 0 001 to 10% by weight. 8 · A method for producing a ketal and/or an acetal according to item 1 of the patent application, C:\M\90\90109988\90i09988(^)-3<ptc~ 1294423 __面901 805 巧_年月日日__ Amendment six, the patent application range '~' - where the reaction solution (C) halogen pair The molar ratio of palladium is 〇, 1 to 1 〇〇. 9. A method of producing a ketal and/or an acetal as claimed in claim 1 wherein the catalyst compound to be used as (a) is chlorinated. I 0 The method for producing a ketal and/or a condensed acid according to the first aspect of the patent application, wherein the catalyst compound to be used as the source of (a) palladium is a divalent saturated compound. II. A method for producing a ketal and/or an acetal according to claim 1 wherein the catalyst compound to be used as (a) is a nitrile compound coordination compound. 12. The method for producing a ketal and/or an acetal according to the first aspect of the patent application, wherein the catalyst compound to be used as the iron source is a chloride. 1 3 . The method for producing a ketal and/or an acetal according to the first aspect of the patent application, wherein the chlorine as the (C) halogen is used as the chloride of (3) or (1)). A method of producing a ketal and/or an acetal according to the first aspect of the invention, wherein the olefin is a cyclic olefin having 4 to 1 atomic broken atom. 1 5 A method of producing a ketal and/or an acetal according to claim 14 wherein the olefin is cyclohexene. A method of producing a ketal and/or an acid reduction according to the first aspect of the invention, wherein the olefin is a terminal olefin having 4 to 10 carbon atoms. A method of producing a ketal and/or an acetal according to the first aspect of the invention, wherein the olefin is an internal olefin having 4 to 10 carbon atoms. 18. A method of making a ketal and/or shrinking according to claim 1 wherein the polyhydric alcohol is an aliphatic or cycloaliphatic > alcohol. C:\总档\9〇\9〇1〇9988\9〇1〇9988 (replacement)-3.ptc Page 36 1294423 One nickname · 90109988 Sixth, the scope of application for patents 19 · If the scope of patent application A method for producing a ketal and/or an acetal in the first step, wherein the amount of the polyhydric alcohol is based on the olefin (1) ❻ 2 〇 · a method for producing a ketone and/or an acid, in the presence of a pulp and a mouthing agent Hydrolysis is carried out in accordance with the scope of the patent application, item X', via acid catalysis or acetal. , the ketal obtained by the formula and / C:\Total file\90\90109988\90109988 (replace)-3.ptc Page 37