WO2016063957A1 - Dérivé de décaline et procédé de production associé - Google Patents

Dérivé de décaline et procédé de production associé Download PDF

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Publication number
WO2016063957A1
WO2016063957A1 PCT/JP2015/079851 JP2015079851W WO2016063957A1 WO 2016063957 A1 WO2016063957 A1 WO 2016063957A1 JP 2015079851 W JP2015079851 W JP 2015079851W WO 2016063957 A1 WO2016063957 A1 WO 2016063957A1
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Prior art keywords
decalin
formula
group
allyloxy
bis
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PCT/JP2015/079851
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English (en)
Japanese (ja)
Inventor
健治 峯山
拓也 飯田
拓真 中村
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スガイ化学工業株式会社
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Priority to JP2016555394A priority Critical patent/JP6633537B2/ja
Publication of WO2016063957A1 publication Critical patent/WO2016063957A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/188—Unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds

Definitions

  • the present invention relates to a decalin derivative such as a decalin derivative having a glycidyloxy group or an allyloxy group.
  • the present invention also relates to a method for producing a decalin derivative such as 2,7-bis (glycidyloxy) decalin and a raw material compound used in the method. More specifically, a method for producing a decalin derivative such as 2,7-bis (glycidyloxy) decalin useful as an epoxy resin (epoxy compound) having low water absorption and hygroscopicity and excellent mechanical strength and optical properties, and It is related with the raw material compound used for the manufacturing method.
  • a compound having an epoxy group is useful as a raw material or an intermediate in the fields of chemical industry and organic synthetic chemistry because the epoxy group has high reactivity, and is also used as a final product.
  • Epoxy resin is widely known as a final product using a compound having an epoxy group. Epoxy resins are used in various fields because they are excellent in heat resistance, electrical properties, mechanical properties, adhesiveness, and the like. In recent years, particularly in the electric / electronic field, an epoxy resin that gives a cured product with low water absorption and low moisture absorption has been demanded. Moreover, when used for a light emitting diode (LED) or the like, good optical characteristics are required, and an epoxy compound composed of an alicyclic compound is suitable for such a use.
  • LED light emitting diode
  • the method for producing bis (glycidyloxy) decalin described in Patent Document 2 that is, dihydroxynaphthalene and epihalohydrin are reacted to obtain bis (glycidyloxy) naphthalene, and then subjected to a hydrogenation reaction to reduce bis (glycidyl).
  • the method for obtaining oxy) decalin is a method for efficiently producing the substance.
  • the hydrogenation reaction of bis (glycidyloxy) naphthalene needs to be performed under high pressure (usually about 8 MPa), which has led to an increase in cost due to equipment problems.
  • the present inventors examined a method for producing bis (glycidyloxy) decalin that does not involve a high-pressure hydrogenation reaction.
  • dihydroxynaphthalene is hydrogenated and the resulting decahydronaphthalenediol is reacted with epihalohydrin to produce bis (glycidyloxy) decalin.
  • epihalohydrin to produce bis (glycidyloxy) decalin.
  • the present inventors oxidized 2,7-bis (allyloxy) decalin using hydrogen peroxide from the viewpoint of the production method, and converted 2,7-bis (glycidyloxy) decalin.
  • the manufacturing method was examined.
  • a method for synthesizing a compound having a glycidyloxy group a method in which a compound having an allyloxy group is oxidized using hydrogen peroxide to convert the allyl group into an epoxy group is known (for example, Patent Document 3). .
  • the method described in Patent Document 3 is a method for obtaining a glycidyl adamantane compound by reacting an allyloxyadamantane compound, a hydrogen peroxide solution, and a nitrile in the presence of a basic substance.
  • This method has an advantage that the halogen content in the target glycidyl compound can be significantly reduced in that no halide is used.
  • the yield of the glycidyl adamantane compound by the method described in Patent Document 3 is on the order of 60%, which is inferior in yield as an industrial production method. It is enough.
  • 2,7-bis (glycidyloxy) decalin is useful as an epoxy resin (epoxy compound), but its performance as a monomer for epoxy resin varies depending on the substitution position of the glycidyloxy group on the decalin ring. Depending on the substitution position, the epoxy resin may be superior to the 2,7-isomer. Therefore, the present invention provides an epoxy resin (epoxy compound) having further excellent mechanical strength and optical properties, and further provides a decalin derivative having a glycidyloxy group as an intermediate useful in various organic synthesis. The purpose is to provide.
  • An object of the present invention is to provide a new method for producing a decalin derivative having a glycidyloxy group.
  • an object of the present invention is to provide a method capable of producing a decalin derivative having a glycidyloxy group or an allyloxy group in a high yield under mild conditions, and a novel decalin derivative obtained by such a method. is there.
  • Another object of the present invention is to provide a novel epoxy compound (decalin derivative having a glycidyloxy group) having a greatly reduced halogen content, a method for producing the same, and a novel monomer (allyloxy group) useful for producing such an epoxy compound. It is to provide a decalin derivative having the above and a method for producing the same.
  • a decalin derivative having an allyloxy group such as 2,7-bis (allyloxy) decalin
  • a decalin derivative having a glycidyloxy group A method for producing (2,7-bis (glycidyloxy) decalin, etc.) was examined, and the target product was obtained in high purity and high yield by optimizing the reaction conditions; glycidyl on the decalin ring A monomer capable of producing an epoxy compound (or epoxy resin) with excellent mechanical strength and optical properties is obtained depending on the substitution position of the oxy group.
  • the decalin derivative of the present invention can be represented by the following formula (1).
  • R is a vinyl group or an epoxy group, and n is 1 or 2)
  • n is 1 or 2
  • 2,7-bis (glycidyloxy) decalin is excluded from the decalin derivative.
  • the present invention also includes a method for producing a (glycidyloxy) decalin derivative, in which the formula (1-1)
  • 2,7-bis (allyloxy) decalin may be used as the compound represented by formula (1-1) to produce 2,7-bis (glycidyloxy) decalin.
  • the nitriles may be, for example, acetonitrile, benzonitrile and the like. Further, the reaction may be carried out while adjusting the pH of the reaction solution to 9.5 to 10.5.
  • the (allyloxy) decalin derivative represented by the formula (1-1) is, for example, the formula (2)
  • n 1 or 2
  • n 1 or 2
  • the phase transfer catalyst comprises tri C 6-18 alkyl mono C 1-2 alkyl ammonium salt, mono C 6-18 alkyl tri C 1-2 alkyl ammonium salt, and mono C 6-12 aryl C 1- 4 alkyl tri C 1-2 may be at least one selected from alkylammonium salts, e.g., trioctyl methyl ammonium salt, trilauryl methyl ammonium salts, cetyl trimethyl ammonium salts, benzyl trimethyl ammonium salts, benzyltriethylammonium salts And at least one selected from benzyltri-n-butylammonium salts.
  • alkylammonium salts e.g., trioctyl methyl ammonium salt, trilauryl methyl ammonium salts, cetyl trimethyl ammonium salts, benzyl trimethyl ammonium salts, benzyltriethylammonium salts And at least one selected from benzyl
  • the decalin derivative having a glycidyloxy group of the present invention is useful as an intermediate for various organic synthesis, and as an end product, it is useful as an epoxy resin (epoxy compound) used in the field of electronic components.
  • a decalin derivative having an allyloxy group is useful as an intermediate for various organic syntheses, and is also useful as a raw material for the above-mentioned decalin derivative having a glycidyloxy group.
  • a decalin derivative having a glycidyloxy group can be obtained in a high yield from a decalin derivative having an allyloxy group.
  • 2,7-bis (glycidyloxy) decalin can be obtained from 2,7-bis (allyloxy) decalin with high purity and high yield, and the production cost of the substance can be reduced.
  • decalin derivatives such as bis (glycidyloxy) decalin derivatives
  • having a glycidyloxy group which is a kind of product, have a low halogen content and are suitable for electronic component applications.
  • a decalin derivative having an allyloxy group can be obtained in high yield from a hydroxydecalin derivative.
  • the decalin derivative of the present invention is represented by the formula (1).
  • R is an epoxy group or a vinyl group, and n is 1 or 2.
  • These compounds (decalin derivatives) are novel compounds except for 2,7-bis (glycidyloxy) decalin.
  • the group —O—CH 2 —R may be substituted at the 1-position or 2-position of the decalin ring. In some cases, the group —O—CH 2 —R may be bonded to any position of the decalin ring, for example, to one ring of the decalin ring, or to each of the two rings.
  • the position of substitution of the group —O—CH 2 —R for the decalin ring is 1,2-position, 1,3-position, 1,4-position, 1,5-position, 1 , 6-position, 1,7-position, 1,8-position, 2,3-position, 2,4-position, 2,5-position, 2,6-position, 2,7-position, 2,8 It may be in the minus position.
  • Examples of the compound wherein R is an epoxy group (oxiranyl group or 1,2-epoxy group) and n is 1 include 1-glycidyloxydecalin and 2-glycidyloxydecalin.
  • R is an epoxy group and n is 2
  • two glycidyloxy groups may be bonded to one ring of the decalin ring, The form which couple
  • examples of the bis (glycidyloxy) decalin derivative include 2,3-bis (glycidyloxy) decalin, 2,6-bis (glycidyloxy) decalin, and 1,5-bis (glycidyloxy) decalin. 1,6-bis (glycidyloxy) decalin, 1,7-bis (glycidyloxy) decalin and the like.
  • the bis (glycidyloxy) decalin derivative may usually be 2,3-bis (glycidyloxy) decalin or 2,6-bis (glycidyloxy) decalin.
  • a compound in which R is a vinyl group is useful as a raw material for producing the glycidyloxydecalin derivative and can be used as a raw material for various organic synthesis.
  • examples of the compound in which R is a vinyl group and n is 1 include 1-allyloxydecalin and 2-allyloxydecalin.
  • examples of the compound in which R is a vinyl group and n is 2 include 1-allyloxydecalin and 2-allyloxydecalin.
  • R is a vinyl group and n is 2
  • that is, a bis (allyloxy) decalin derivative two allyloxy groups may be bonded to one ring of the decalin ring, or both rings The form which couple
  • examples of the bis (allyloxy) decalin derivative include 2,3-bis (allyloxy) decalin, 2,6-bis (allyloxy) decalin, 2,7-bis (allyloxy) decalin, 1,5 -Bis (allyloxy) decalin, 1,6-bis (allyloxy) decalin, 1,7-bis (allyloxy) decalin and the like.
  • the bis (allyloxy) decalin derivative may usually be 2,3-bis (allyloxy) decalin, 2,6-bis (allyloxy) decalin, or 2,7-bis (allyloxy) decalin.
  • the decalin derivative represented by the formula (1) includes an isomer based on the ring structure in addition to the isomer depending on the position of the substituent. All of the isomers are included within the scope of the present invention.
  • the (allyloxy) decalin derivative (2,7-bis (allyloxy) decalin etc.) used as a raw material in this method and represented by the formula (1-1) is a novel substance and can be obtained by the method described later. .
  • the hydrogen peroxide used in the method of the present invention is usually used as a hydrogen peroxide solution and can be used in various concentrations, and is 20 to 60% by mass (for example, 25 to 50% by mass), preferably 30 to 40% by mass. %, Particularly from the viewpoint of reactivity and handling, 35% by mass of hydrogen peroxide is preferably used.
  • the amount of hydrogen peroxide used is at least 1 molar equivalent (equivalent hydrogen peroxide to the allyloxy group of the (allyloxy) decalin derivative) with respect to the (allyloxy) decalin derivative represented by the formula (1-1), Simply referred to as equivalent), preferably about 1 to 5 equivalents (eg 2 to 5 equivalents), more preferably about 3 to 5 equivalents (eg 4 equivalents).
  • the amount of hydrogen peroxide used is 2 to 6 times mol (1 to 3 equivalents), preferably 3 to 4 times mol (1.5 to 1 mol) of 2,7-bis (allyloxy) decalin. 2 equivalents). If the amount is less than the equivalent (for example, less than 2 moles), the reaction is not completed, and even if it is used in excess (for example, more than 5 equivalents), there is no problem, but the reaction proceeds in the above amount.
  • R 1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group which may have a substituent.
  • the alkyl group having 1 to 6 carbon atoms may be a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. It is done.
  • the alkyl group is preferably a methyl group because of its availability.
  • R 1 may be a phenyl group which may have a substituent, and examples of the substituent include an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), a halogen group (For example, chloro group, bromo group, etc.), nitro group and the like.
  • substituents include an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), a halogen group (For example, chloro group, bromo group, etc.), nitro group and the like.
  • the phenyl group which may have a substituent include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a chlorophenyl group, a bromophenyl group, and a nitrophenyl group.
  • nitriles include acetonitrile, propionitrile, hexanenitrile, benzonitrile, o-tolunitrile, m-tolunitrile, p-tolunitrile, 2-chlorobenzonitrile, 3-chlorobenzonitrile, 4-chloro Examples include benzonitrile, 2-bromobenzonitrile, 3-bromobenzonitrile, 4-bromobenzonitrile, 4-nitrobenzonitrile and the like. These nitriles can be used alone or in combination of two or more. From the viewpoint of availability and reactivity, acetonitrile and benzonitrile are preferable.
  • the amount of the nitrile used is at least 1 equivalent, preferably 1 to 5 equivalents (eg 2 to 5 equivalents), more preferably 2 with respect to the (allyloxy) decalin derivative represented by the formula (1-1). Used in the range of 5 to 4 equivalents.
  • the amount of nitriles to be used is at least 2-fold mol (at least 1 equivalent), preferably 2-10-fold mol (1-5 equivalents), more than 2,7-bis (allyloxy) decalin. It is preferably used in the range of 3 to 8 times mol (1.5 to 4 equivalents), particularly 5 to 8 times mol (2.5 to 4 equivalents).
  • the method of the present invention can be usually carried out in the presence of a hydrophilic organic solvent inert to the reaction.
  • the hydrophilic organic solvent include alcohols, ketones (such as acetone), cyclic ethers (such as dioxane and tetrahydrofuran), sulfoxides (dimethylsulfoxide), amides (such as dimethylformamide and dimethylacetamide), and the like. . These solvents can be used alone or in combination of two or more.
  • the reaction is particularly preferably performed in the presence of alcohols.
  • alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol. These alcohols can be used alone or in combination of two or more. Methanol is preferable from the viewpoint of cost and reactivity.
  • the above-mentioned solvent can be used in an appropriate amount as necessary, and is usually 0.1 to 10 parts by mass (for example, 0. 3 to 7 parts by mass), preferably about 0.5 to 2 parts by mass, and about 5 to 10 times mol (or 2.5 to 5 equivalents) relative to the (allyloxy) decalin derivative It may be used in the ratio.
  • the method of the present invention is characterized in that the reaction is carried out using a basic substance while maintaining the pH of the reaction solution at about 9 to 11, preferably about 9.5 to 10.5. It has been clarified that when the reaction is carried out in this pH range, there are few side reactions and the target product can be obtained with high purity and high yield.
  • the basic substance examples include inorganic bases [alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate). And the like], and organic bases (for example, trimethylamine, triethylamine, N, N-dimethylaniline, etc.).
  • inorganic bases alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate). And the like]
  • organic bases for example, trimethylamine, triethylamine, N, N-dimethylaniline, etc.
  • these basic substances can be used alone or in combination of two or more.
  • an alkali metal hydroxide, particularly sodium hydroxide is preferably used.
  • these basic substances can be used as aqueous solution as needed.
  • the amount of the basic substance used may be such that the pH is adjusted to 9 to 11, preferably 9.5 to 10.5, as long as the pH of the reaction solution is monitored. -1) for the (allyloxy) decalin derivative represented by 0.01 to 0.6 equivalents (for example, 0.1 to 0.6 equivalents), preferably about 0.05 to 0.5 equivalents. it can. More specifically, the use amount of the basic substance is usually 0.1 to 0.6 times mol (for example, 0.05 to 0.3 equivalent) with respect to 2,7-bis (allyloxy) decalin. Degree.
  • the method of the present invention may be carried out by reacting the (allyloxy) decalin derivative represented by the formula (1-1) with hydrogen peroxide in the presence of nitriles while controlling the pH of the reaction solution. It can be done by the method.
  • an (allyloxy) decalin derivative represented by the formula (1-1) for example, 2,7-bis (allyloxy) decalin
  • hydrogen peroxide solution for example, 2,7-bis (allyloxy) decalin
  • nitriles for example, 2,7-bis (allyloxy) decalin
  • an organic solvent and a basic substance are added at once. When mixed, the reaction may proceed rapidly.
  • hydrogen peroxide solution is added to a mixture of (allyloxy) decalin derivative (for example, 2,7-bis (allyloxy) decalin), a nitrile and an organic solvent, and a mixture containing an appropriate amount of a basic substance as required.
  • the method of dripping is preferable.
  • a method of monitoring the pH of the reaction solution and adding a basic substance or an aqueous solution thereof so that the pH is in the range of about 9 to 11, preferably about 9.5 to 10.5 is preferable.
  • the reaction temperature is usually under cooling to about room temperature, preferably about 20 to 30 ° C., and the reaction time varies depending on the reaction temperature and may be about 1 to 10 hours, usually about 4 to 7 hours.
  • the reaction is complete.
  • the obtained (glycidyloxy) decalin (2,7-bis (glycidyloxy) decalin etc.) represented by the formula (1-2) has isomers based on the ring structure as described above. All of the isomers are included within the scope of the present invention.
  • the (allyloxy) decalin derivative (2,7-bis (allyloxy) decalin and the like) represented by the formula (1-1), which is a raw material compound of the first production method of the present invention, is a novel substance. Yes, this new material can be prepared in various ways.
  • the second production method of the present invention by reacting mono- or dihydroxydecalin (decahydronaphthalene mono or diol) represented by the above formula (2) and allyl halide (or allyl halide), the above formula ( The (allyloxy) decalin derivative represented by 1-1) is produced.
  • 2,7-bis (allyloxy) decalin can be obtained by reacting 2,7-dihydroxydecalin (decahydro-2,7-naphthalenediol) with allyl halide.
  • the hydroxyl group of hydroxynaphthalenes is a phenolic hydroxyl group, which is highly reactive, whereas the hydroxyl group of hydroxydecalins is an alcoholic hydroxyl group, which is weak in reactivity, or in the presence of a basic substance. It was difficult to obtain (allyloxy) decalins in a high yield by reaction with allyl halide. The present inventors have found that when this reaction is carried out in the presence of a phase transfer catalyst and a basic substance, an (allyloxy) decalin derivative can be obtained in high yield.
  • the amount of the allyl halide (or allyl halide) used is at least 1 equivalent, preferably 2 to 10 equivalents (for example, 3 to 10 equivalents) based on the hydroxyl group of the hydroxydecalin represented by the formula (2), More preferably 4 to 8 equivalents, especially 4 to 5 equivalents.
  • the amount of allyl halide used is at least 2-fold mol, for example, 5-20 times mol (2.5-10 equivalents), preferably 8-15 times mol, relative to 2,7-dihydroxydecalin. (4 to 7.5 equivalents), more preferably about 8 to 12 times mol (4 to 6 equivalents) (for example, 10 times mol (5 equivalents)).
  • Allyl halide (or allyl halide) may also be used as a solvent.
  • the inventors of the present invention have found that the yield of the target product is reduced when other organic solvents are used in combination, and it is preferable to use allyl halide as a reaction solvent without using other organic solvents.
  • phase transfer catalyst a conventional quaternary ammonium salt is used. More specifically, for example, trialkylammonium salt (tetramethylammonium salt, tetraethylammonium salt, tetra-n-propylammonium salt, tetra-n-butylammonium salt, trioctylmethylammonium salt, trilaurylmethylammonium salt Cetyltrimethylammonium salt, aryltrialkylammonium salt (phenyltrimethylammonium salt, etc.), aralkyltrialkylammonium salt (benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltri-n-butylammonium salt, etc.) .
  • trialkylammonium salt tetramethylammonium salt, tetraethylammonium salt, tetra-n-propylammonium salt, tetra-n-butyl
  • quaternary ammonium salts can be used alone or in combination of two or more.
  • the salt of the alkylammonium salt include halides such as chloride, bromide and iodide, hydroxides, hydrogen sulfates and the like.
  • quaternary ammonium salts which are phase transfer catalysts described above
  • the use of a quaternary ammonium salt which is a group in which at least one substituent of the organic substituent has high hydrophobicity, improves the yield of the target product.
  • a highly hydrophobic group specifically, an alkyl group or aralkyl group having 6 to 18 carbon atoms (for example, 6 to 16 carbon atoms), preferably 7 to 17 carbon atoms (C 6-12 such as a benzyl group).
  • Aryl- C1-4 alkyl group and the like.
  • phase transfer catalyst having such a hydrophobic group examples include tri-C 6-18 alkyl mono-C 1-2 alkyl ammonium salts (eg, trioctyl methyl ammonium salt, trilauryl methyl ammonium salt, etc.), mono-C 6 -18 alkyl tri-C 1-2 alkyl ammonium salt (eg cetyl trimethyl ammonium salt), mono C 6-12 aryl C 1-4 alkyl tri-C 1-2 alkyl ammonium salt (eg benzyl trimethyl ammonium salt, benzyl triethyl Ammonium salt, benzyltri-n-butylammonium salt) is preferably used.
  • tri-C 6-18 alkyl mono-C 1-2 alkyl ammonium salts eg, trioctyl methyl ammonium salt, trilauryl methyl ammonium salt, etc.
  • mono-C 6 -18 alkyl tri-C 1-2 alkyl ammonium salt eg cetyl tri
  • the amount of the phase transfer catalyst used is 0.01 to 0.5 equivalent (for example, 0.1 to 0.5 equivalent), preferably 0.03 to 0, based on the hydroxydecalin represented by the formula (2). .3 equivalents. Specifically, the amount of the phase transfer catalyst used is 0.05 to 0.2 times mol (0.025 to 0.1 equivalent), preferably 0.07 to 0, based on 2,7-dihydroxydecalin. About 15 times mole (0.035 to 0.075 equivalent) (for example, 0.1 times mole (0.05 equivalent)).
  • the basic substance (base) examples include inorganic bases [alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (eg, sodium carbonate, potassium carbonate, hydrogen carbonate). Sodium) and the like], and organic bases (eg, trimethylamine, triethylamine, N, N-dimethylaniline, etc.). These basic substances can be used alone or in combination of two or more. Of these basic substances, alkali metal hydroxides, particularly sodium hydroxide and potassium hydroxide are preferably used.
  • the amount of the basic substance used is 5 to 20 equivalents, preferably 10 to 15 equivalents, based on the hydroxydecalin represented by the formula (2). Specifically, the basic substance is used in an amount of 10 to 40 times mol (5 to 20 equivalents), preferably 20 to 35 times mol (10 to 17.5 equivalents) of 2,7-dihydroxydecalin. Degree.
  • the reaction can be carried out by various methods as long as the hydroxydecalin represented by the formula (2) is reacted with allyl halide in the presence of a phase transfer catalyst and a basic substance, and preferably the formula (2)
  • a phase transfer catalyst is added to the mixed solution, and then an aqueous solution of a basic substance (usually 50 W). / V% aqueous solution) is added dropwise under cooling (preferably 10 to 20 ° C.), and the reaction is carried out at that temperature for 5 to 24 hours, usually 6 to 12 hours.
  • an (allyloxy) decalin derivative represented by the formula (1-1) (such as 2,7-bis (allyloxy) decalin) can be obtained.
  • bis (glycidyloxy) decalin derivatives (such as 2,7-bis (glycidyloxy) decalin) Low hygroscopicity and excellent mechanical strength and optical properties. Therefore, it is useful as an epoxy resin (or an epoxy compound), and is cured using a curing agent according to a conventional method, so that a sealing agent (a sealing material such as a light emitting diode LED or a semiconductor) or an electronic component is insulated. It can be used in various fields as materials and adhesives. In addition, you may add conventional materials, such as a solvent, a coloring agent, and a filler, to an epoxy resin (or epoxy compound) as needed.
  • the (glycidyloxy) decalin derivative (2,7-bis (allyloxy) decalin etc.) represented by the formula (1-2) may be used in combination with a plurality of different (glycidyloxy) decalin derivatives.
  • One or a plurality of other epoxy compounds (or epoxy resins) may be used in combination, and a copolymer (copolymerized epoxy resin) may be formed.
  • the (glycidyloxy) decalin derivative may be cured in combination with a cationic polymerization initiator, or may be combined with a photoacid generator to form a predetermined pattern by light irradiation.
  • the decalin derivative represented by the formula (1) is also used as a raw material or an intermediate in the fields of various chemical industries and organic synthetic chemistry.
  • Example 1 In a 3 L flask of 2,7-bis (glycidyloxy) decalin , 389.4 g of methanol, 401.2 g of 2,7-bis (allyloxy) decalin (purity 98.0%, 1.57 mol), 387.1 g of acetonitrile ( 9.42 moles, 6 equivalents), cooled to 0-15 ° C., and 610.1 g of 35% hydrogen peroxide (6.28 moles, 4 equivalents) in the range of 10-15 ° C. over 5 hours. While dropping, 8% aqueous sodium hydroxide was appropriately added dropwise to adjust the pH of the reaction solution to 9.5 to 10.5. Thereafter, the temperature was adjusted to 20 to 30 ° C. and reacted for 4 hours.
  • Example 2 In a 3 L flask of 2,7-bis (glycidyloxy) decalin , 389.4 g of methanol, 401.2 g of 2,7-bis (allyloxy) decalin (purity 98.0%, 1.57 mol), 387.1 g of acetonitrile ( 9.42 mol, 6 equivalents) and 43.4 g of potassium carbonate (0.31 mol, 0.2 equivalent) were charged, cooled to 0 to 15 ° C., and 610.1 g (6.28 mol) of 35% aqueous hydrogen peroxide.
  • Example 3 In Example 1, the reaction and treatment were carried out in the same manner except that the pH of the reaction solution was maintained at about 9, to obtain 2,7-bis (diglycidyloxy) decalin (yield: 77.5%).
  • Example 4 In Example 1, the reaction and treatment were carried out in substantially the same manner except that benzonitrile was used instead of acetonitrile to obtain 2,7-bis (diglycidyloxy) decalin (yield: 81.3%). .
  • Production Example 2 In Production Example 1, reaction and treatment were conducted in the same manner except that allyl chloride was used in an amount of 10-fold mol with respect to 2,7-dihydroxydecalin to obtain 2,7-bis (allyloxy) decalin (yield: 91. 0%).
  • a 3 L flask was charged with 2720.0 g (34.0 mol, 20 equivalents) of 50% sodium hydroxide, adjusted to a temperature of 15 to 25 ° C., and then 53.0 g (0.17 mol) of benzyl-n-tributylammonium chloride. 0.1 equivalents), 520.2 g (6.8 moles, 4 equivalents) of allyl chloride, and 262.3 g (1.7 moles) of 1-hydroxydecahydronaphthalene, respectively, and then in the range of 15 to 25 ° C. React for 7 hours.
  • Example 5 2-allyloxydecalin was obtained by the same reaction and treatment except that 2-hydroxydecahydronaphthalene was used instead of 1-hydroxydecahydronaphthalene to obtain 2-allyloxydecalin (purity 98.0%, total Cl Min. 500 ppm or less, Hazen color number 30 or less, yield 94.0%).
  • Example 6 2-glycidyloxydecalin was obtained by the same reaction and treatment except that 2-allyloxydecalin was used in place of 1-allyloxydecalin to obtain 2-glycidyloxydecalin (purity 96.1%, total Cl content 500 ppm). (Hazen color number 40 or less, yield 91.5%).
  • 1 H NMR 400 MHz, CDCl 3 ) ⁇ : 1.19-1.78 (m, 16H), 2.61-2.63 (m, 1H), 2.79-2.81 (m, 1H), 3.12-3.16 (m, 1H), 3.30-3.32 (m, 1H), 3.45-3.49 (m, 1H), 3.69-3.73 (m, 1H) ) Ppm.
  • Example 5 reaction and treatment were carried out in the same manner except that 2,3-dihydroxydecahydronaphthalene was used in place of 1-hydroxydecahydronaphthalene to obtain 2,3-bis (allyloxy) decalin (purity 98 3%, total Cl content 500 ppm or less, Hazen color number 50 or less, yield 91.4%). *
  • Example 6 2,3-bis (glycidyloxy) decalin was obtained by the same reaction and treatment except that 2,3-bis (allyloxy) decalin was used instead of 1-allyloxydecalin (purity) 97.9%, total Cl content 500 ppm or less, Hazen color number 40 or less, yield 91.0%).
  • Example 5 2,6-bis (allyloxy) decalin was obtained in the same manner except that 2,6-dihydroxydecahydronaphthalene was used instead of 1-hydroxydecahydronaphthalene to obtain 2,6-bis (allyloxy) decalin (purity 96 2%, total Cl content 500 ppm or less, Hazen color number 50 or less, yield 91.0%). *
  • Example 6 2,6-bis (glycidyloxy) decalin was obtained by the same reaction and treatment except that 2,6-bis (allyloxy) decalin was used instead of 1-allyloxydecalin (purity) 96.9%, total Cl content 500 ppm or less, Hazen color number 40 or less, yield 90.0%).
  • the decalin derivative represented by the formula (1) is useful as a raw material / intermediate for various organic synthetic chemistry, etc., or as a monomer for epoxy resin, and as a sealing material for semiconductors, LEDs, etc., an insulating material for electronic parts, an adhesive, etc. Available.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un dérivé de décaline contenant un groupe glycidyloxy ou un groupe allyloxy ; ainsi qu'un procédé de production de ce dérivé de décaline. Selon l'invention, un dérivé de décaline représenté par la formule (1) est produit par : la mise en oeuvre d'un procédé consistant à mettre en réaction un composé d'hydroxydécaline de formule (2) avec un halogénure d'allyle en présence d'un catalyseur de transfert de phase et d'une substance basique pour obtenir un dérivé d'(allyloxy)décaline représenté par la formule (1-1) ; ou par la mise en oeuvre d'un procédé consistant à mettre en réaction le dérivé d'(allyloxy)décaline, du peroxyde d'hydrogène et un composé de nitrile de formule R1-C≡N (R1 représentant un groupe alkyle C1-6 ou un groupe phényle pouvant être doté d'un substituant), tout en maintenant la valeur du pH de la solution de réaction entre 9 et 11 au moyen d'une substance basique afin d'obtenir un dérivé de (glycidyloxy)décaline représenté par la formule (1-2). (Dans les formules, R représente un groupe vinyle ou un groupe époxy ; et n représente 1 ou 2). Le dérivé de décaline de formule (1) est utile en tant que matière première ou intermédiaire dans divers domaines chimiques synthétiques organiques, en tant que composé époxy ou monomère pour un composé époxy.
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