Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
  • C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/48—Preparation of compounds having groups
  • C07C41/50—Preparation of compounds having groups by reactions producing groups
  • C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
  • C07D321/02—Seven-membered rings
  • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• This invention relates to a method for producing a ketal and/or acetal by oxidizing olefins with molecular oxygen .
• Corresponding aldehydes or ketones obtained by oxidizing olefins with molecular oxygen are industrially useful compounds, and their synthesis by catalytic reactions have been carried out for a long time .
• Particularly useful method among them is a reaction generally known as Wacker reaction. That is, a method in which acetaldehyde is produced from ethylene, and acetone from propylene, by molecular oxygen using an aqueous solution containing PdCl 2 and CuCl 2 as the catalyst has been employed industrially.
• Patent 4,400,544 JP-A-60-92236, JP-A-61-60621; the term “JP-A” as used herein means an "unexamined published Japanese patent application”) .
• a monohydric alcohol such as methanol or ethanol is used as the reaction medium instead of water which is used in the conventional Wacker reaction, and metal salts of Pd and Cu and/or Fe are used as the catalyst, but as a industrial process, this reaction has fatal disadvantages such as low selectivity of ketone or aldehyde as the product and precipitation of Pd metal when the reaction condition is shi ed to high temperature side .
• These documents describe that the co-catalysts Cu and Fe have equivalent effect.
• J. Org. Cheua. , vol. 34, 3949 (1969) discloses that 1 , 4-dioxospiro [4,5] decane is obtained from cyclohexene with a high yield by the use of PdCl 2 and CuCl 2 as the catalyst and a polyhydric alcohol such as ethylene glycol or glycerol as the reaction solvent, but it does not describe details such as illustrative yield.
• This document does not describe about the use of iron salt as a catalyst component and also does not disclose about a method for solving the Pd precipitation which is a fatal disadvantage as a industrial process .
• cyclohexanone useful as a precursor of caprolactam is produced by a method in which cyclohexane is oxidized in the presence, as occasion demands, of a catalyst and the cyclohexanone-cyclohexanol mixture is dehydrogenated or a method in which cyclohexanol obtained by hydrating cyclohexene is subjected to dehydrogenation reaction.
• the formed products in the former method are apt to undergo oxidation successively during the oxidation of cyclohexane, it is necessary to control the conversion to a considerably low level and to circulate large excess of unreacted cyclohexane, so that this method becomes a process having low energy efficiency as a result.
• the latter method has problems in that yield of the hydration reaction is not sufficient and a large quantity of energy is consumed when cyclohexene is extracted and separated from a benzene-cyclohexane mixture having markedly close boiling point or when cyclohexanone alone is separated from an approximately equimolar cyclohexanone-cyclohexanol mixture having high boiling point.
• the gist of the invention resides in the following aspects .
• 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.
• the catalyst of the invention is composed of components comprising (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.
• the components of (a) to (c) may be present in the reaction system in any form such as dissociated ions, salts or molecules .
• the (a) palladium may be in divalent to tetravalent form, and can be selected optionally from known and commercially available compounds . Its examples include palladium halides such as palladium chloride and palladium bromide, palladium salts of inorganic acid or organic acid, such as palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate and palladium acetylacetonate and inorganic palladium such as palladium oxide and palladium hydroxide.
• palladium halides such as palladium chloride and palladium bromide
• palladium salts of inorganic acid or organic acid such as palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate and palladium acetylacetonate
• inorganic palladium such as palladium oxide and palladium hydroxide.
• base- coordinated compounds derived from these metal salts such as [Pd(en) 2 ]Cl 2 , [Pd(phen) 2 ] Cl 2 , [Pd(CH 3 CN) 2 ]C1 2 , [Pd(C 6 H 5 CN) 2 ]Cl 2 , [Pd(C 2 0 4 )2J.2, [PdCl 2 (NH 3 ) 2 ] and [Pd(N0 2 ) 2 (NH 3 ) 2 ] though not limited thereto (wherein en represents ethylenedia ine , and phen represents 1,10- phenanthroline) .
• a divalent palladium source particularly as a chloride or a nitrile compound-coordinated compound.
• the role of palladium in the catalyst system is expressed by its mutual action with iron ion and polyhydric alcohol, but the action condition is not always clear. Since the essence is that palladium expresses its activity by constituting an active species with other catalyst components, it is enough if a palladium source sufficient for inducing the essence is present in the system.
• iron, cobalt, nickel, ruthenium and tin can be cited, of which iron is preferred.
• the catalyst compound to be used as iron source may be in a divalent or trivalent form.
• it can be used in the reaction as various salts including chlorides such as iron (II) chloride and iron (III) chloride, bromides such as iron (II) bromide and iron (III) bromide, inorganic acid salts such as iron (II) sulfate, iron (III) sulfate, iron (II) nitrate and iron (III) nitrate 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 coordination compounds thereof.
• the essence is that iron expresses its activity by constituting an active species with other catalyst components, so that it is enough if an iron source sufficient for inducing the essence is present in the system.
• the catalyst compound to be used as the source of cobalt, nickel, ruthenium or tin may be in a divalent, trivalent or tetravalent form.
• various salts including their halides such as chloride and bromide, inorganic acid salts such as sulfate and nitrate and salts such as acetate, oxalate , formate and acetylacetonate salt, or coordination compounds thereof can be used.
• the component (b) is cobalt, nickel, ruthenium or tin, it is desirable to further combine with copper.
• the main effect of the invention is that the Pd precipitation is markedly inhibited by the addition of the component (b) , but further addition of a copper compound such as CuCl or CuCl 2 thereto exerts another advantageous result as an industrial process in which the reaction rate is improved and by-products such as halides are reduced.
• the halogen (c) is chlorine (Cl) and/or bromine (Br) , but chlorine (Cl) is particularly preferable.
• the halogen may be present in the reaction system as counter anions of Pd and/or Fe. Also, it is possible to supply it to the reaction system as a halide of other catalyst component or in a certain form such as HC1 or HBr, but it is necessary that such a compound is present in the reaction system in the orm of ions in ether case .
• a ketal and/or acetal is produced by allowing olefins to react with oxygen and a polyhydric alcohol in a liquid phase in which the catalyst described above is dissolved.
• the olefins to be used in the invention are aliphatic or alicyclic organic compounds containing at least one ethylenic double bond.
• chain olefins olefins having generally 2 or more, preferably from 2 to 25, more preferably from 3 to 10 carbon atoms, such as ethylene, propylene, butene, pentene, hexene and octene, can be cited.
• the position of double bond may be either terminal or internal, and an acetal or ketal of methyl ketones is mainly formed in the case of terminal olefin, and a corresponding ketal is mainly obtained in the case of internal olefin .
• cyclic olefins include compounds having from 4 to 10 , preferably from 5 to 8 carbon atoms and containing at least one ethylenic double bond, such as cyclopentene, cyclohexene, cyclohexadiene , cycloheptene and cyclooctene, of which cyclopentene and cyclohexene are particularly useful compounds industrially.
• 1,4- dioxospiro [4 , 5] decane (to be referred to as cyclohexanone ketal hereinafter) is formed as the product.
• At least one substituent group such as alkyl group, alkoxy group, aryl group, phenyl group, carboxyl group, halogen atom or nitro group may be present on any position of the principal chain of these olefins .
• olefins having a functional group such as acrylonitrile, acrolein, acrylic acid or vinyl chloride on the 2-position, or styrene or methylstyrenes undergo the reaction suitably.
• a compound having condensed ring such as 3,4-dihydronaphthalene, can also be used if it has an ethylenic double bond. (Polyhydric alcohol)
• the polyhydric alcohol is generally divalent to tetravalent, and diols are particularly desirable.
• a diol it generally has 2 or more carbon atoms , but preferably from 2 to 10, more preferably from 3 to 8 carbon atoms when cost, stability and easy formation of acetal or ketal are taken into consideration, and preferred illustrative examples of these diols include ethylene glycol, 1,3-propanediol, 1,2-dihydroxybutane, 1,2-dihydroxypropane, 1,4-butanediol, 1,4-cyclohexane- dimethanol, 1,2-cyclohexanedimethanol, diethylene glycol, 1 , 2-trans-cyclopentanediol , 2 , 4-pentanediol , styrene glycol, 1,5-dihydroxycyclooctane, 1, 4-dihydroxycyclooctane, 2 , 5-dihydroxynorbornane
• the use of oxygen- containing gas is a necessary condition, but since there is a possibility that oxygen and an organic compound may form an explosive mixture at a certain temperature, under a certain pressure range and within a certain compositional range, it is necessary to avoid the danger.
• the reaction will proceed if the partial pressure of oxygen is 0.001 MPa or more, but the reaction rate becomes slow and the catalyst tends to be inactivated if the oxygen partial pressure is too low.
• it is pre erably rom 0.01 to 10 MPa and more pref rably from 0.05 to 5 MPa, but most preferable pressure is selected from the safety and economical points of view.
• the reaction will proceed when the reaction temperature is 0°C or more, but since temperature- dependency of the reaction of the invention is large, more higher temperature is desirable .
• the reaction temperature is selected by taking formation conditions of explosive mixtures and increase in by-products due to radical auto-oxidation into consideration, but an economically significant reaction rate can be obtained within a temperature range of generally from 20 to 200°C, preferably from 40 to 180°C.
• Total pressure of the reaction may be a liquid phase holding pressure or more, but is generally from 0.1 MPa to 20 MPa, preferably from 0.1 MPa to 15 MPa.
• the reaction time (residence time) is generally from 5 seconds to 20 hours, preferably rom 10 seconds to 10 hours .
• Concentration of the (a) palladium as a catalyst is within the range of from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, as [Pd + ] based on the total weight of reaction solution. Under high concentration condition, the reaction rate shows a different concentration-dependency from that under low concentration condition, and the catalytic efficiency tends to worsen, so that an efficient concentration is selected from the economical point of view.
• Concentration of the (b) at least one metal M other than palladium belonging to the groups 8, 9, 10 and 14 of the periodic table can be described as its relative concentration to (a) palladium. That is, it can be selected within the range of generally 0.1 ⁇ [M] / [Pd] ⁇ 100 (molar ratio), preferably 0.1 ⁇ [M] / [Pd] ⁇ 10 (molar ratio).
• concentration if lower than this would entail a tendency of reducing the reaction rate and also a tendency of reducing the Pd precipitation inhibition effect as the principal effect of the metal (b) . Also, its addition in too large amount may not inhibit the reaction itself but will cause a tendency of limiting its dissolving amount in the reaction system.
• Relative concentration of the halogen (c) to Pd is within the range of generally 1 ⁇ [C1 and/or Br]/[Pd] ⁇ 100 (molar ratio) and preferably 0.3 ⁇ [C1 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 a high halogen concentration condition, it is desirable to select concentration of the halogen in such a level that the catalyst system functions within a level as low as possible. Also, a component containing a catalyst- derived halogen may be formed in some cases as a part of by-products, and in that case, it is desirable to supply the consumed halogen continuously or periodically in the form, e.g. , of its metal salt.
• the existing amount of polyhydric alcohols in the reaction system may be the theoretical amount (1 mole) based on olefin, but according to the invention, it is desirable to use also as a reaction solvent. It is within the range of generally from 1 to 99% by volume, preferably from 5 to 99% by volume, based on the total reaction volume. Also, amount of the polyhydric alcohol is generally from 1 to 100 moles, preferably from 2 to 50 moles, based on olefin. The existing amount of olefins in the reaction system can be selected within the range of generally from 1 to 99% by volume, preferably from 1 to 50% by volume.
• concentration of polyhydric alcohols When concentration of polyhydric alcohols is relatively low, namely when relative concentration of olefins is too high, it may entail a tendency of easily causing precipitation of palladium due to distribution of a part of the catalyst components into the olefin phase . If the polyhydric alcohol concentration is too large, on the other hand, concentration of supplied olefin becomes relatively small and tends to entail low productivity and a difficulty in carrying out phase separation after the reaction. In such cases, it is possible to adjust relative concentrations of polyhydric alcohols and olefins and further improve phase separation characteristics, by adding an oxidation-inert third component to the reaction system.
• an additive agent having an effect to enhance the oxidation reaction such as a copper compound or an alkali, alkaline earth or rare earth metal, may be added.
• a method in which side reactions are inhibited by adding a radical trapping agent may be employed.
• the reaction of the invention can be carried out in accordance with the general oxidation reaction.
• the oxidation reaction can be effected using a batch reactor and by allowing olefins to contact with an oxygen-containing gas for a specified period of reaction time or using a continuous phase reactor and by continuously supplying an oxygen-containing gas and olefins .
• the liquid phase reaction can be used, or a so-called trickle bed system can be employed in which the catalyst is packed in a fixing bed and corresponding olefins and oxygen are supplied as a liquid phase .
• a technique effective for dissolving oxygen in the reaction solution system such as a technique in which the oxygen-containing gas is made into fine bubbles using mixing blades , a technique in which oxygen gas is made into fine bubbles by arranging baffle plates in the reactor or a technique in which the gas is sprayed into the system with a high linear velocity from a nozzle, can be employed.
• the reaction product solution after oxidation reaction contains the material olefin, the ketal and/or acetal as the product, the catalyst components and the polyhydric alcohol .
• the pressure may be reduced by releasing it to a certain degree .
• an extraction solvent such as an organic solvent which forms two phase with the polyhydric alcohol is added, and two phase separation is carried out by extraction to separate the extraction solvent phase containing the olefin and ketal and/or acetal from the polyhydric alcohol phase containing the catalyst components. Thereafter, the olefin and ketal and/or acetal are recovered from the extraction solvent phase, and then the ketal and/or acetal can be taken out by distillation separation.
• the polyhydric alcohol phase containing the catalyst components can be recycled to the oxidation reaction step.
• the remaining amount of catalyst components in the extraction phase can be reduced to a negligible level by carrying out extraction of the extraction solvent phase twice or more with the polyhydric alcohol solvent. Also, it is possible to employ a technique in which the olefin and ketal and/or acetal are separated from the extraction solvent phase by distillation after the first two phase separation, thereby increasing the residual catalyst concentration in the extraction solvent phase to a certain degree, and then the extraction is carried out again.
• a vessel generally used as a corrosion- resistant reactor namely a vessel made of an alloy such as a stainless alloy, particularly which is commonly called Hastelloy, an alloy containing titanium or an alloy containing zirconium, or a vessel in which these alloys are coated and adhered by compression to the surface.
• a vessel generally used as a corrosion- resistant reactor, namely a vessel made of an alloy such as a stainless alloy, particularly which is commonly called Hastelloy, an alloy containing titanium or an alloy containing zirconium, or a vessel in which these alloys are coated and adhered by compression to the surface.
• the reactor has a particularly high possibility of undergoing corrosion, when a standing vessel and separation vessel are further arranged, these parts also have a high possibility of undergoing corrosion.
• the polyhydric alcohols which are present in the reaction system as essential components are not completely inactive to the oxidation reaction. Also, though in extremely small amounts , some compounds formed by the successive oxidation of olefins have similar polarity to that of polyhydric alcohols. Thus, when a batch reaction is repeated for a prolonged period of time or in the case of a continuous reaction, certain components which are derived from the polyhydric alcohols and olefins but not necessarily desirable for the reaction are accumulated in the alcohol phase containing catalyst components . In order to operate the process stably, it is necessary to control the total material balance promptly.
• the ketal and/or acetals obtained by the invention are converted into corresponding ketones and/or aldehydes by carrying out hydrolysis in the presence of water and an acid.
• the acid which can be used in this case include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, polyacids such as a heteropolyacid, and solid acids such as an ion exchange resin, zeolite and clay.
• the aldehydes and ketones of interest can be efficiently obtained by recovering water and polyhydric alcohols from the thus obtained reaction product solution rich in aldehydes and/or ketones and then separating and purifying the aldehydes and ketones as the intended compounds .
• the ketal and/or acetals obtained by the invention can be converted efficiently into corresponding alcohols by carrying out hydrogenation in the presence of water, a hydrogen source and a hydrogenation catalyst.
• the hydrogen source include hydrogen, formalin and disodium borohydride (NaBH 4 )
• the hydrogenation catalyst include Raney Ni, Raney Co, an oxide containing Cu-Cr, a catalyst in which a group 8 metal such as Pd, Pt or Ru is carried on a carrier and a complex catalyst which uses a group 8 metal such as Ru, Pt or Pd as the central metal .
• the alcohols of interest can be efficiently obtained by recovering water and the acetal and/or ketal-formed alcohol from the reaction product solution which is obtained by hydrogenation and rich in alcohols and then separating and purifying the alcohols as the intended compounds .
• a drum-shaped Pyrex reactor of 40 mm in inner diameter and 12 mm in height equipped with a magnetic bar and a gas-introducing tube was charged with 0.1 mmol of Pd(CH 3 CN) 2 Cl 2 , 0.1 mmol of CuCl 2 , 0.1 mmol of FeCl 3 , 10 ml of ethylene glycol and 20 mmol of cyclohexene, the air was replaced with pure oxygen and then the reaction was carried out at 40°C for 5 hours under stirring.
• the product was analyzed by a gas chromatography. 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 formation rate of cyclohexanone and cyclohexanone ketal (mol) per 1 mol Pd per hour. In this case, only cyclohexanone ketal was formed. Precipitation of palladium was not found in the solution after the reaction. Also, chlorocyclohexane was not formed.
• reaction solution was turbid by fine black powder of Pd-black and precipitation of palladium was found on the bottom and the inner wall of the reactor.
• a cylinder type Teflon beaker of 40 mm in inner diameter and 15 mm in height equipped with a magnetic stirrer was inserted into a SUS-316 autoclave having a withstand pressure of 100 kG and a size just fitted to the beaker, and the reaction was carried out at a reaction temperature of 70, 80, 90 or 100°C for 1 hour under an oxygen pressure of 7 kG using the same charging composition of Example 1. Precipitation of Pd was not found in the solution after the reaction . The results are shown in Table 4. It can be seen that the reaction rate largely depends on the reaction temperature and oxygen pressure.
• Example 14 The reaction of Example 14 was carried out, except that the reaction temperature was fixed to 80°C and the charging amount of cyclohexene was changed. Precipitation of Pd was not found in the solution after the reaction. The results are shown in Table 6.
• Example 15 The reaction of Example 15 was carried out, except that the reaction temperature was fixed to 90°C and the charging amount of each of Pd, Cu and Fe was fixed to 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. Precipitation of Pd was not found in the solution after the reaction. EXAMPLE 18
• Example 7 The same oxidation reaction of Example 3 was carried out, except that FeCl 3 was changed to the co-catalysts shown in Table 7. As a result, the product was mostly cyclohexanone ketal .
• the TOF values are shown in Table 7.
• a cylinder type Teflon beaker of 40 mm in inner diameter and 15 mm in height equipped with a magnetic stirrer was inserted into a SUS-316 autoclave having a withstand pressure of 100 kG and a size just fitted to the beaker, and the reaction was carried out at a reaction temperature of 80°C under an oxygen pressure of 7 kG using the same charging composition of Example 1 and adding 20 mmol of styrene. After 1 hour of the reaction, the contents were taken out and analyzed by GC .
• a cylinder type Teflon beaker of 40 mm in inner diameter and 15 mm in height equipped with a magnetic stirrer was inserted into a SUS-316 autoclave having a withstand pressure of 100 kG and a size just fitted to the beaker and, with an assumption of the case of the coexistence of benzene, charged with 2.2 g of benzene, 2 g of cyclohexene, 0.3 mmol of Pd(CH 3 CN) 2 C1 2 , 0.3 mmol of CuCl 2 , 0.3 mmol of FeCl 3 and 6.2 g of 1 ,4-butanediol .
• the reaction was carried out at a reaction temperature of 70°C and under various oxygen pressures described in the following table .
• the main product other than cyclohexanone and cyclohexanone ketal was cyclohexenone .
• the results are shown in Table 8.
• Example 24 The same reaction apparatus of Example 24 was used and, with an assumption of the case of the coexistence of benzene, charged with 2.2 g of benzene, 2 g of cyclohexene, 0.6 mmol of Pd (CH 3 CN) 2 C1 2 , 0.6 mmol of CuCl 2 , 0.6 mmol of FeCl 3 and 6.2 g of 1,4-butanediol.
• the reaction was carried out under an oxygen pressure of 7 kG and at various reaction temperatures described in the following table .
• the main product other than cyclohexanone and cyclohexanone ketal was cyclohexenone. The results are shown in Table 9.
• Example 24 The same reaction apparatus of Example 24 was used and, with an assumption of the case of the coexistence of benzene , charged with 1.1 g of benzene , 1 g of cyclohexene , 0.3 mmol of Pd (CH 3 CN) 2 C1 2 , 0.3 mmol of CuCl 2 , 0.3 mmol of FeCl 3 and 6.2 g of 1,4-butanediol . The reaction was carried out at a reaction temperature of 80°C for 3.5 minuets under an oxygen pressure of 7 kG. As a result, conversion of cyclohexene was 92% , selectivity of cyclohexanone and cyclohexanone ketal was 70% . The main product other than cyclohexanone and cyclohexanone ketal was cyclohexenone. EXAMPLE 27

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