WO2012133108A1 - Procédé de production d'un composé 2-alcényléther - Google Patents

Procédé de production d'un composé 2-alcényléther Download PDF

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WO2012133108A1
WO2012133108A1 PCT/JP2012/057338 JP2012057338W WO2012133108A1 WO 2012133108 A1 WO2012133108 A1 WO 2012133108A1 JP 2012057338 W JP2012057338 W JP 2012057338W WO 2012133108 A1 WO2012133108 A1 WO 2012133108A1
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group
compound
carbon atoms
acetate
transition metal
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圭孝 石橋
内田　博
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昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • 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

  • the present invention relates to a method for producing a 2-alkenyl ether compound typified by allyl ether. More specifically, a 2-alkenyl ether compound can be obtained with high efficiency by reacting a compound having a hydroxyl group and a compound having a 2-alkenyl group with a specific transition metal complex in the presence of a ligand. Regarding the method.
  • Glycidyl ether compounds known as raw materials for epoxy resins are industrially produced on a large scale and are widely used in various fields.
  • Non-Patent Document 1 As a conventional reaction example of allylation of alcohol or phenols, as an example using a palladium catalyst, a method of allylating phenol, which is an active hydrogen-containing compound, with allyl acetate, which is an allylating agent, is disclosed in Non-Patent Document 1, for example.
  • Patent Document 1 US Pat. No. 4,507,492
  • Non-Patent Document 2 S. Sivaram et al., Macromolecular Reports, A32 (Suppl. 7), pp.
  • Non-Patent Document 3 (A. Mortreux et al., J. Chem. Soc., Chem. Commun., Pp. 1863-1864 (1995)) describes acetic acid as an allylating agent.
  • a method of allylating phenol, which is an active hydrogen-containing compound, with allyl is described.
  • the stoichiometric amount relative to the allylating agent is generally used for the purpose of capturing by-products derived from the allylating agent. Since a basic compound more than the stoichiometric amount is required, the production cost is increased. Moreover, it is necessary to remove these basic compounds from the target allyl ether compound.
  • the allylating agent is converted into a salt with a basic compound, for example, when allyl acetate is used as the allylating agent, the by-product acetate salt is returned to acetic acid and the allyl acetate recycling step is performed. Circulation takes time and is industrially disadvantageous.
  • Patent Document 2 Japanese Patent Publication No. 2006-501209
  • Non-Patent Document 4 F. Ozawa et al., J. Am. Chem. Soc., 124, pp. 10968-10969 (2002)
  • the former is non-uniform.
  • An example of allylation using a transition metal complex salt (palladium salt) and a phosphorus ligand as a catalyst is disclosed, but the stability of the phosphorus ligand itself to an oxidizing agent is low.
  • triphenylphosphine which is a typical example of a phosphorus-based ligand
  • phosphorus-based ligands have complicated synthesis routes and are difficult to industrialize.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-107339 discloses a method for producing allyl ethers in the presence of a Group 8-10 transition metal complex having a multidentate chelate-type phosphite ligand.
  • allyl alcohol and alcohol can be dehydrated and condensed and converted directly to allyl ether, but diallyl ether formation by homocoupling of allyl alcohols and isomerization of allyl alcohol are easy to proceed. It cannot be used effectively in the reaction system.
  • the Claisen rearrangement is caused in the produced allyl ether compound, the by-product formation of a C-allylic compound different from the target product is a cause of yield reduction.
  • Non-Patent Document 5 (Y. Ishii et al., J. Org. Chem., 69, pp. 3474-3477 (2004)) uses a carboxylic acid allyl ester as an allylating agent and a cationic iridium complex for alcohol. Discloses a method for producing allyl ethers. By this method, allyl ether can be obtained from carboxylic acid allyl ester and alcohol accompanied by elimination of carboxylic acid, but transesterification reaction between carboxylic acid allyl ester and alcohol, formation of aldehyde by Openauer oxidation of alcohol, And the Tishchenko reaction for the resulting aldehyde also competes, so the yield of the target is generally low. Attempts have been made to increase the allylation efficiency by using an excessive amount of an allylating agent, but it is necessary to add more than 10 times the amount of alcohol, which is inefficient and desirable from the environmental aspect. I can't say that.
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-289977 discloses a method for producing allyl ethers in the presence of a cyclopentadienyl ruthenium complex having an ⁇ -imino acid type ligand or an ⁇ -amino acid type ligand. is doing. According to this method, allyl ether can be produced dehydratingly from allyl alcohol and alcohol without using any additive. The co-product is only water and is a very efficient method in harmony with the environment. However, allyl alcohol, which is an allylating agent, is highly toxic and it is not preferable to use it in a large amount in view of industrial reasons. Moreover, depending on the type of alcohol, the yield of allyl ether, which is the target product, is low because of the low detachability of the water that is the coproduct.
  • An object of the present invention is to provide a method for efficiently producing a corresponding 2-alkenyl ether compound using a compound having a hydroxyl group and a 2-alkenylating agent other than allyl alcohol as starting materials.
  • the present inventors have obtained a compound having a hydroxyl group from a complexing agent and a monovalent anionic 5-membered substance using a specific 2-alkenylating agent. It has been found that 2-alkenyl ether compounds can be efficiently obtained by 2-alkenylation in the presence of a catalyst (transition metal complex) comprising a transition metal precursor stabilized by a ring conjugated diene compound. It came to complete.
  • a catalyst transition metal complex
  • X represents any substituent selected from the group consisting of NO 2 —, RO—, RS (O) 2 O—, RCOO—, and ROCOO— (where R is an organic group having 1 to 30 carbon atoms).
  • the catalyst arranges a complexing agent having a nitrogen coordination part-oxygen coordination part that is bidentate to a transition metal atom in the molecule and a monovalent anionic five-membered ring conjugated diene in the molecule.
  • the complexing agent is represented by the general formula (2): ⁇ Wherein R 6 to R 9 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a substituent.
  • R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 6 and R 8 , R 6 and R 9 , R 7 and R 9 are bonded to each other to form a saturated or unsaturated 4- An 8-membered ring may be formed.
  • the transition metal precursor contains at least one transition metal atom selected from the group consisting of transition metals belonging to Groups 8 and 9 of the periodic table
  • the manufacturing method of 2-alkenyl ether compound of description [4]
  • the monovalent anionic 5-membered ring conjugated diene is represented by the general formula (3): ⁇ Wherein R 10 to R 30 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a substituent. Represents an alkyl-substituted alkyl group having 1 to 30 carbon atoms in total or an aryl-substituted silyl group having 6 to 30 carbon atoms in total, and groups bonded to two adjacent carbon atoms on the ring are bonded to each other.
  • a saturated or unsaturated 4- to 8-membered ring may be formed with the two adjacent carbon atoms.
  • the conjugated monovalent anion structure ⁇ wherein the anion is present conjugated to the bonding carbon of R 10 to R 30 .
  • the compound represented by the general formula (1) is allyl acetate, 2-methyl-2-propenyl acetate, 2-hexenyl acetate, 2,4-hexadienyl acetate, prenyl acetate (3-methyl-2-acetate).
  • Butenyl geranyl acetate, farnesyl acetate, cinnamyl acetate, linalyl acetate, 3-buten-2-yl acetate, 2-cyclopentenyl acetate, 2-trimethylsilylmethyl-2-propenyl acetate, 2-methyl-2-cyclohexenyl acetate, 1-phenyl-1-buten-3-yl propionate, 1-cyclohexyl-2-butene butyrate, 4-cyclopentene-1,3-diol-1-acetate, and 1,4-diacetoxybutene-2,3- Carboxylic acid ester selected from the group consisting of acetoxy-4-hydroxybutene-1 or allyl methyl carbonate 4-acetoxy-2-Buarticuluechiru carbonate, Nerirumechiru carbonate, and method for producing 2-alkenyl ether compound according to any one of a carbonic ester [1] to [5], which is selected from the group consisting of
  • the compound having a hydroxyl group is a saturated aliphatic alcohol having 1 to 30 carbon atoms having one or two hydroxyl groups in the molecule, and the number of carbons having one or two hydroxyl groups in the molecule. Any one of [1] to [7], wherein is selected from the group consisting of a saturated alicyclic alcohol having 3 to 30 and an aryl compound having 1 to 10 hydroxyl groups in the molecule and having 6 to 30 carbon atoms A process for producing a 2-alkenyl ether compound as described in 1. above. [9] The method for producing a 2-alkenyl ether compound according to [8], wherein the hydroxyl group-containing compound is a primary saturated aliphatic alcohol or alicyclic alcohol.
  • the transition metal complex is added to 1 mol of the sum of the compound having a hydroxyl group and the compound having a 2-alkenyl group (molar amount of the compound having hydroxyl group + molar amount of the compound having 2-alkenyl group).
  • the method for producing a 2-alkenyl ether compound according to any one of [1] to [9], wherein 0.000001 to 10 mol is used.
  • a step of producing a transition metal precursor having a monovalent anionic 5-membered ring conjugated diene as a ligand in the molecule by reacting a compound having a monovalent anionic 5-membered ring conjugated diene skeleton with a transition metal compound.
  • an alcoholic or phenolic hydroxyl group can be formed by a compound having a 2-alkenyl group without using an additive other than a solvent that does not directly contribute to the 2-alkenylation reaction.
  • 2-alkenyl ether can be produced with a high reaction rate. Since an allylating agent (2-alkenylating agent) such as conventional allyl acetate and a salt such as palladium acetate are used as a catalyst, an additive such as a by-product neutralizing agent is not required.
  • a highly productive and environmentally harmonious method can be provided.
  • the reaction can be carried out without using a solvent.
  • the allylating agent which is a representative example of the 2-alkenylating agent, can use a carboxylic acid allyl ester that can be supplied in large quantities and is inexpensive, has higher reactivity as a 2-alkenylating agent than allylic alcohol, and is toxic. Therefore, the method for producing a 2-alkenyl ether compound according to the present invention is very useful from the viewpoint of productivity and operability.
  • the obtained 2-alkenyl ether compound can be converted into a corresponding glycidyl ether compound by an epoxidation reaction. Therefore, it is possible to produce a low chlorine content epoxy resin that is useful in various fields such as the chemical industry as a raw material for various materials such as electronic materials, adhesives, paint resins, etc. Useful for.
  • a compound having a hydroxyl group is used as a compound having a specific 2-alkenyl group, and a complexing agent and a monovalent anionic 5-membered ring conjugated diene are contained in the molecule. It is characterized by 2-alkenylation using a transition metal complex, which is a reaction product with a transition metal precursor having a ligand, as a catalyst.
  • the compound having a hydroxyl group used in the present invention may be a compound having one hydroxyl group or a compound having two or more hydroxyl groups, and is not particularly limited.
  • Examples of the compound having a hydroxyl group include a saturated aliphatic alcohol having 1 to 30 carbon atoms or an unsaturated aliphatic alcohol having 2 to 30 carbon atoms having one hydroxyl group in the molecule, and one hydroxyl group in the molecule.
  • the compound having a hydroxyl group may contain a substituent such as a halogen atom.
  • saturated aliphatic alcohol having 1 to 30 carbon atoms or the unsaturated aliphatic alcohol having 2 to 30 carbon atoms having one hydroxyl group in the molecule include methyl alcohol, ethyl alcohol, n-propyl alcohol, i -Propyl alcohol, n-butyl alcohol, neopentyl alcohol, 2-ethylhexanol, n-octanol, allyl alcohol, crotyl alcohol, saturated or unsaturated having 3 to 30 carbon atoms with one hydroxyl group in the molecule
  • Specific examples of the alicyclic alcohol include 2-methylcyclopentanol, 4-cyclohexenol, cholesterol and the like.
  • saturated aliphatic diol or polyhydric alcohol having 1 to 30 carbon atoms and having 2 or more hydroxyl groups in the molecule, or the unsaturated aliphatic diol or polyhydric alcohol having 2 to 30 carbon atoms include 1 , 2-ethanediol, 1,3-propanediol, 1,4-butanediol, 2-butene-1,4-diol, 2-chloro-1,3-propanediol, glycerin, pentaerythritol, hydroxyl in the molecule
  • saturated or unsaturated alicyclic diol or polyhydric alcohol having 3 to 30 carbon atoms having two or more groups include 1,2-cyclopentanediol, 1,4-cyclohexanedimethanol and the like. It is done.
  • the monohydroxyaryl compound having 6 to 30 carbon atoms having one hydroxyl group in the molecule include phenol, cresol, 4-nitrophenol, 2,4-di-t-butylphenol, 2,4-di -Tert-butyl-6-methylphenol, 1-naphthol, 2-naphthol, 3-tert-butyl-2-naphthol, benzyl alcohol, 2-phenylethanol and the like.
  • polyhydroxyaryl compounds having 2 to 10 hydroxyl groups in the molecule and having 6 to 30 carbon atoms include catechol, resorcinol, hydroquinone, 2,4-dihydroxyphenyl ethyl ketone, and 4-n-hexylresorcinol. 1,8-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, 1-methyl-2,3-dihydroxynaphthalene, 1,2,4-benzenetriol and the like.
  • saturated fatty alcohols having 1 to 30 carbon atoms having one or two hydroxyl groups in the molecule and saturated fats having 3 to 30 carbon atoms having one or two hydroxyl groups in the molecule. It is more preferably a cyclic alcohol or an aryl compound having 1 to 10 hydroxy groups in the molecule and having 6 to 30 carbon atoms, and is preferably a primary saturated aliphatic alcohol or alicyclic alcohol. More preferable in terms of high properties.
  • the compound having a 2-alkenyl group used in the present invention is represented by the following general formula (1) capable of reacting with a hydroxyl group of a compound having a hydroxyl group to produce a 2-alkenyl ether.
  • R 1 , R 2 , R 3 , R 4 , and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 carbon atom.
  • X represents any substituent selected from the group consisting of NO 2 —, RO—, RS (O) 2 O—, RCOO—, and ROCOO— (where R is an organic group having 1 to 30 carbon atoms). ⁇ . These Xs are easily desorbed as compared to HO— that allyl alcohol has.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and R is A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferable. More preferably, R 1 , R 2 , R 3 , R 4 , and R 5 are all hydrogen atoms.
  • Specific examples of the compound having a 2-alkenyl group in which X is NO 2 — include 1-nitro-2-butene, 1-nitro-1,3-diphenyl-2-propene, and 3-nitro-3-methoxypropene.
  • Specific examples of the compound having a 2-alkenyl group in which X is RO— include methyl allyl ether, ethyl allyl ether, diallyl ether, allyl phenyl ether and the like.
  • Specific examples of the compound having a 2-alkenyl group in which X is RS (O) 2 O— include allyl benzenesulfonate and allyl p-toluenesulfonate.
  • Specific examples of the compound having a 2-alkenyl group in which X is RCOO— include allyl acetate, 2-methyl-2-propenyl acetate, 2-hexenyl acetate, 2,4-hexadienyl acetate, prenyl acetate (3-methyl acetate -2-butenyl), geranyl acetate, farnesyl acetate, cinnamyl acetate, linalyl acetate, 3-buten-2-yl acetate, 2-cyclopentenyl acetate, 2-trimethylsilylmethyl-2-propenyl acetate, 2-methyl-2-acetate Cyclohexenyl, 1-phenyl-1-buten-3-yl propionate, 1-cyclohexyl-2-butene butyrate, 4-cyclopentene-1,3-diol-1-acetate, 1,4-diacetoxybutene-2, 3-acetoxy-4-hydroxybutene-1 and the like.
  • the compound having a 2-alkenyl group in which X is ROCOO— include allylmethyl carbonate, 4-acetoxy-2-butenylethyl carbonate, nerylmethyl carbonate, diallyl carbonate and the like. These compounds having a 2-alkenyl group can be used alone or in any combination of two or more thereof. Most preferred compounds having a 2-alkenyl group for use in the present invention are carboxylic acid esters in which X is RCOO- and X is ROCOO- because the elimination products have high stability and are easily available. It is a carbonate ester.
  • the amount of the compound having a 2-alkenyl group used relative to the compound having a hydroxyl group is such that the compound having a 2-alkenyl group is 0.1 to 500 equivalents, preferably 0.5 to 1 equivalent per hydroxyl group equivalent of the hydroxyl group-containing compound. 50 equivalents, more preferably 1 to 20 equivalents. If the equivalent of the compound having 2-alkenyl groups per equivalent of hydroxyl group of the compound having hydroxyl groups is significantly greater than 1 (equivalent ratio is 1), the compound having excess 2-alkenyl groups is In addition to being used as an agent, it is also used as a solvent.
  • the conversion to the target product may be extremely low. It becomes remarkable when the equivalent ratio is less than 0.1. If the equivalent ratio is less than 1, the compound having an excess of hydroxyl groups can be recovered as needed and recycled to this process. Since the 2-alkenylation reaction is preferably carried out in a homogeneous system, it is preferable to use a combination of a compound having a hydroxyl group and a compound having a 2-alkenyl group which are mixed to form a uniform liquid.
  • a complexing agent described in detail below reacts with a transition metal precursor obtained by complexing a transition metal compound and a monovalent anionic five-membered ring conjugated diene compound. It is a complex obtained.
  • a nitrogen coordination part-oxygen coordination part that is bidentate to the transition metal atom in the molecule. It preferably has a general formula (2): ⁇ Wherein R 6 to R 9 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a substituent. Represents an alkyl-substituted alkyl group having 1 to 30 carbon atoms in total or an aryl-substituted silyl group having 6 to 30 carbon atoms in total.
  • R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 6 and R 8 , R 6 and R 9 , R 7 and R 9 are bonded to each other to form a saturated or unsaturated 4- An 8-membered ring may be formed.
  • the ⁇ -imino acid type ligand compound is preferably used in the present invention because it exhibits high activity for the 2-alkenylation reaction. These can be used alone or in any combination.
  • the transition metal compound used in the production of the transition metal precursor useful for forming the transition metal complex used in the present invention is at least one selected from the group consisting of transition metals belonging to Groups 8 and 9 of the periodic table. A compound containing a transition metal atom is used.
  • iron compounds such as iron (III) chloride, iron (III) bromide, iron (III) nitrate, ruthenium (III) chloride, ruthenium (III) bromide, ruthenium (III) nitrate, hexaammineruthenium (II), ruthenium compounds such as hexaaquathenium (III), osmium compounds such as osmium chloride (III) and osmium oxide (VI), cobalt compounds such as cobalt chloride (III), and rhodium compounds such as rhodium chloride (III) Iridium compounds such as iridium chloride (III) and iridium acetate (II), etc., among which ruthenium compounds, rhodium compounds, and iridium compounds are preferable, and ruthenium compounds are particularly high in activity of 2-alkenylation reaction and relatively inexpensive. Therefore, it is preferable.
  • the monovalent anionic 5-membered ring conjugated diene reacts with the transition metal compound to form a complex, thereby forming a transition metal precursor in which the transition metal atom is stabilized.
  • the monovalent anionic 5-membered ring conjugated diene compound refers to a monovalent anion having a cyclopentadienyl skeleton in the molecule, and can be conjugated 1 represented by the following general formula (3).
  • a compound having a valent anion structure is preferred.
  • R 10 to R 30 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a substituent.
  • a saturated or unsaturated 4- to 8-membered ring may be formed with the two adjacent carbon atoms.
  • the anion is present conjugated to the bonded carbon of R 10 to R 30 .
  • the monovalent anionic 5-membered ring conjugated diene useful in the present invention include, for example, ⁇ 5 -cyclopentadienyl anion, ⁇ 5 -methylcyclopentadienyl anion, ⁇ 5 -dimethylcyclopentadienyl anion, ⁇ 5 -trimethylcyclopentadienyl anion, ⁇ 5 -tetramethylcyclopentadienyl anion, ⁇ 5 -pentamethylcyclopentadienyl anion, ⁇ 5 -ethylcyclopentadienyl anion, ⁇ 5 -n-propylcyclopenta dienyl anion, eta 5 - isopropyl cyclopentadienyl anion, eta 5-n-butyl cyclopentadienyl anion, eta 5-sec-butylcyclopentadienyl anion, eta 5-tert-
  • the transition metal precursor can be synthesized by a known method, and is preferably obtained by reacting the monovalent anionic 5-membered ring conjugated diene compound with a transition metal halide or the like.
  • suitable preparation methods are described, for example, in Adv. Synth. Catal, 346, pp. 901-904 (2004) and Japanese translations of PCT publication No. 2003-507387.
  • ruthenium (III) chloride with sodium ⁇ 5 -cyclopentadienyl to obtain a di ( ⁇ 5 -cyclopentadienyl) ruthenium complex
  • Adv. Synth. Catal, 346, pp. 901-904 (2004) can be converted to a cyclopentadienyl ruthenium triacetonitrile complex (transition metal precursor).
  • a catalyst composed of a transition metal complex can be obtained by dissolving the complexing agent and the transition metal precursor in a reaction solvent and reacting them.
  • the mixing ratio of the complexing agent and the transition metal precursor is 0.8 to 1.5, more preferably 0.9 to 1. 1. It can be obtained by mixing at a reaction temperature of 0 to 100 ° C., more preferably 20 to 50 ° C. Both of them are dissolved in a solvent and react quickly after mixing to form a transition metal complex. Therefore, they can be used immediately after being dissolved and mixed in the solvent, or after aging for a while after mixing.
  • the reaction time is preferably 0.01 to 10 hours, more preferably 0.2 to 1 hour.
  • the 2-alkenylation reaction is preferably carried out in a homogeneous system, and the transition metal complex is preferably dissolved in the compound having a hydroxyl group and the compound having a 2-alkenyl group.
  • the transition metal complex is dissolved in a compound having a hydroxyl group and a compound having a 2-alkenyl group
  • the transition metal complex, the compound having a hydroxyl group, and the compound having a 2-alkenyl group are simultaneously charged into a reaction vessel and used.
  • the amount of catalyst used can be adjusted as appropriate according to a number of factors, for example, the form of the catalyst, the type of reaction (batch reaction, continuous fixed bed reaction, continuous fluidized bed reaction), the amount of solvent used, and the like. It is.
  • the amount of the transition metal complex used is the sum of the compound having a hydroxyl group and the compound having a 2-alkenyl group (when the hydroxyl group is used) when used as a homogeneous catalyst (using the catalyst dissolved in the reaction system).
  • the molar amount of the compound having + the molar amount of the compound having 2-alkenyl group) is 0.000001 to 10 mol with respect to 1 mol.
  • the compound having a hydroxyl group and the compound having a 2-alkenyl group Is 0.000001 to 0.5 mol with respect to 1 mol in total.
  • a complexing agent bound to a carrier polystyrene or the like
  • a transition metal precursor can be reacted to be used as a supported catalyst (heterogeneous catalyst).
  • a supported catalyst heterogeneous catalyst
  • the amount of transition metal complex used is 0 with respect to 1 mol of the total of the compound having a hydroxyl group and the compound having a 2-alkenyl group. 0.0001 to 0.5 mole.
  • a solvent can be used as necessary for the purpose of homogenizing the reaction solution and adjusting the viscosity.
  • Solvents that can be used include water, aliphatic, alicyclic and aromatic hydrocarbons, aliphatic, alicyclic and aromatic halogenated hydrocarbons, nitroalkanes, and oxygen containing ethers, glycol ethers, esters, ketones, etc. A hydrocarbon is mentioned.
  • preferable solvents include hexane, octane as examples of aliphatic hydrocarbons, cyclohexane as examples of alicyclic hydrocarbons, toluene, xylene as examples of aromatic hydrocarbons, and examples of aliphatic halogenated hydrocarbons.
  • dichloromethane 1,2-dichloroethane, chlorobenzene as an example of aromatic halogenated hydrocarbon
  • nitromethane as an example of nitroalkane
  • tetrahydrofuran as an example of ether
  • dimethoxyethane as an example of glycol ether
  • ethyl acetate as an example of ester
  • ketone examples of the solvent include acetone and methyl ethyl ketone.
  • Cyclohexane, dichloromethane, toluene, and dimethoxyethane are particularly preferable in terms of reactivity, solubility, cost, and the like. These solvents can be used alone or in any combination.
  • the solvent is used in an amount of 1000 parts by mass or less, preferably 0.5 to 500 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the compound having a hydroxyl group.
  • the 2-alkenylation reaction is carried out at a temperature of 10 to 200 ° C., preferably 50 to 150 ° C., more preferably 60 to 90 ° C. for a time sufficient for the reaction to be essentially complete, usually 0.1 to 72 hours. , Preferably 0.1 to 48 hours, more preferably 0.1 to 24 hours.
  • the optimum 2-alkenylation reaction temperature and time for a compound having an individual hydroxyl group depends on the reactivity of the compound having a hydroxyl group used, the solvent and the catalyst.
  • the reaction is preferably carried out in the liquid phase, and therefore it is preferred to carry out the reaction under a pressure atmosphere in which the reaction system is kept in the liquid phase. For example, a pressure of about 5 to about 2000 kPa can be used.
  • Solvents added include aliphatic, alicyclic and aromatic hydrocarbons, aliphatic, alicyclic and aromatic halogenated hydrocarbons, nitroalkanes, and oxygen-containing hydrocarbons such as ethers, glycol ethers, esters and ketones. It is preferable to include at least one organic solvent selected from the group.
  • An organic solvent is mentioned.
  • release product resulting from X of General formula (1) is water-soluble
  • a strong acid such as sulfuric acid
  • the separation residue (separated aqueous layer) is washed again with the same solvent as the added solvent, and the trace amount contained in the aqueous layer is 2-
  • the product recovery rate can be increased. Washing, fractional distillation, extractive distillation, liquid-liquid extraction, solid-liquid extraction and crystallization or any combination of these methods can be used to separate and recover the 2-alkenylation reaction product from the reaction liquid.
  • a solvent and an unreacted 2-alkenylating agent are removed from the reaction mixture by distillation or evaporation.
  • the carboxylic acid byproduct can then be recovered by distillation or extraction, and the desired 2-alkenyl derivative product can be recovered as the bottom product.
  • the reaction liquid containing the 2-alkenyl ether product from which unnecessary components have been separated by the above method can be directly used as a reaction liquid in a process such as epoxidation.
  • Example 1 In a 10 mL Schlenk type reaction tube with a Youngcock, under a stream of argon, quinaldic acid (17 mg, 0.10 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) as a complexing agent, [CpRu (CH 3 CN) 3 as a transition metal precursor ] PF 6 (43mg, 0.10mmol; Aldrich Co.): was added (Cp cyclopentadienyl complexes).
  • 1,4-cyclohexanedimethanol (1.4 g, 10 mmol) and allyl acetate (3.0 g, 30 mmol) (R 1 , R 2 , R in the general formula (1)) were subjected to freeze-dry operation three times.
  • 3 , R 4 , and R 5 are all hydrogen atoms, and X is CH 3 COO—), and quinaldic acid and [CpRu (CH 3 CN) 3 ] PF 6 are dissolved and mixed. Stir at 80 ° C. for 6 hours.
  • Example 2 In Example 1, except that only the catalyst was changed to 1/10 (quinaldic acid (1.7 mg, 0.010 mmol), [CpRu (CH 3 CN) 3 ] PF 6 (4.3 mg, 0.010 mmol)). 2-Alkenylation was carried out under exactly the same conditions as in Example 1. As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion rate of 1,4-cyclohexanedimethanol> 98% and a total yield of 2-alkenylation of 95%. 23% of mono (2-alkenyl) compound (monoallyl ether) and 72% of di (2-alkenyl) compound (diallyl ether) were produced.
  • Example 3 In Example 1, 2-alkenylation was performed under exactly the same conditions as in Example 1 except that the complexing agent was changed to picolinic acid (12 mg, 0.10 mmol); manufactured by Kanto Chemical Co., Inc. As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion rate of 99% and a total yield of 2-alkenylation of 99%. 22% of mono (2-alkenyl) compound (monoallyl ether) and 77% of di (2-alkenyl) compound (diallyl ether) were produced. When quinaldic acid is used as the complexing agent rather than picolinic acid, the yield of di (2-alkenyl) compound (diallyl ether) is increased.
  • Example 4 Exactly the same as Example 1, except that the compound having a hydroxyl group instead of 1,4-cyclohexanedimethanol was changed to benzyl alcohol (1.1 g, 10 mmol); manufactured by Tokyo Chemical Industry Co., Ltd. Under conditions, 2-alkenylation occurred. As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion rate of 90% and a 2-alkenylation yield of 90%.
  • Example 5 In Example 1, 2-alkenylation was performed under exactly the same conditions as in Example 1 except that the substrate was changed to phenol (0.94 g, 10 mmol) instead of 1,4-cyclohexanedimethanol. As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion of 50% and a 2-alkenylation yield of 50%.
  • Example 6 In Example 1, allyl acetate as a 2-alkenylating agent was diallyl carbonate (4.2 g, 30 mmol); manufactured by Kanto Chemical Co., Ltd. (R 1 , R 2 , R 3 , R 4 in the general formula (1)) , And R 5 are all hydrogen atoms, and X is H 2 C ⁇ CH—CH 2 OCOO—.
  • 2- Alkenylation was performed under the same conditions as in Example 1. As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion rate of 1,4-cyclohexanedimethanol of 99% and a 2-alkenylation total yield of 99%. 8.6% of mono (2-alkenyl) compound (monoallyl ether) and 91% of di (2-alkenyl) compound (diallyl ether) were produced.
  • Example 7 In Example 1, the transition metal precursor was changed to [Cp * Ru (CH 3 CN) 3 ] PF 6 (50.4 mg, 0.10 mmol); manufactured by Aldrich) (Cp * : pentamethylcyclopentadienyl complex). Except that, 2-alkenylation was carried out under exactly the same conditions as in Example 1. As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion rate of 1,4-cyclohexanedimethanol of 95% and a total 2-alkenylation yield of 95%. 35% of mono (2-alkenyl) compound (monoallyl ether) and 60% of di (2-alkenyl) compound (diallyl ether) were produced.
  • Example 8 2-alkenylation was carried out under the same conditions as in Example 1 except that each solvent (2.0 mL) shown in Table 1 below was allowed to coexist and the amount of catalyst was changed to 1/5.
  • Table 1 The results of analyzing the solution after the reaction are summarized in Table 1.
  • Example 11 In Example 1, 2-alkenylation was carried out under exactly the same conditions as in Example 1 except that allyl acetate was changed to a double amount (6.0 g, 60 mmol). As a result of analyzing the solution after the reaction, a 2-alkenylated product was obtained with a conversion rate of 1,4-cyclohexanedimethanol> 99% and a total yield of 2-alkenylation> 99%. 7% of mono (2-alkenyl) compound (monoallyl ether) and 93% of di (2-alkenyl) compound (diallyl ether) were produced.
  • Example 12 2-alkenylation was carried out under the same conditions as in Example 1, except that allyl acetate was changed to each 2-alkenylating agent (30 mmol) shown in Table 1 below.
  • the results of analyzing the solution after the reaction are summarized in Table 2. It was confirmed that 2-alkenyl ether compounds can be obtained in the same manner, although the reactivity is lower than when allyl acetate is used.
  • Example 4 2-alkenylation was performed under exactly the same conditions as in Example 1 except that the transition metal precursor was changed to palladium acetate (22 mg, 0.10 mmol). As a result of analyzing the solution after the reaction, the 2-alkenylation reaction hardly proceeded at the conversion rate ⁇ 1% and the total yield of 2-alkenylation ⁇ 1%, and the desired product was not obtained at all.
  • an alcoholic or phenolic hydroxyl group is formed by a 2-alkenylating agent without using an additive other than a solvent that does not directly contribute to the 2-alkenylation reaction.
  • 2-alkenyl ether can be produced with a high reaction rate.
  • the 2-alkenylating agent carboxylic acid allyl ester that can be supplied in large quantities and inexpensive can be used, and has higher reactivity and lower toxicity as 2-alkenylating agent than allyl alcohol, so it is safe during industrialization. This method is also highly useful and is very beneficial from the viewpoint of productivity and operability.
  • the obtained allyl ether compound can be converted into a corresponding glycidyl ether compound by an epoxidation reaction. Therefore, it is possible to produce useful low chlorine content epoxy resins widely used in various industrial fields including chemical industry as raw materials for various materials such as electronic materials, adhesives, paint resins, etc. Useful for.

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Abstract

La présente invention concerne un procédé dans le cadre duquel un composé comportant un groupe hydroxyle et un composé comportant un groupe 2-alcényle, autre qu'un alcool allylique, sont utilisés en tant que matériaux de départ afin de produire de façon efficace et peu coûteuse un composé 2-alcényléther correspondant. Un 2-alcényléther est obtenu à l'issue d'une 2-alcénylation d'un composé comportant un groupe hydroxyle faisant appel à un composé comportant un groupe 2-alcényle particulier en présence d'un catalyseur constitué d'un agent complexant et d'un complexe d'un métal de transition stabilisé par un diène conjugué anionique monovalent à cinq chaînons.
PCT/JP2012/057338 2011-03-29 2012-03-22 Procédé de production d'un composé 2-alcényléther WO2012133108A1 (fr)

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