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WO2019176592A1 - Procédé de production d'un composé vinylique aromatique contenant un hétéroatome - Google Patents

Procédé de production d'un composé vinylique aromatique contenant un hétéroatome Download PDF

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Publication number
WO2019176592A1
WO2019176592A1 PCT/JP2019/008161 JP2019008161W WO2019176592A1 WO 2019176592 A1 WO2019176592 A1 WO 2019176592A1 JP 2019008161 W JP2019008161 W JP 2019008161W WO 2019176592 A1 WO2019176592 A1 WO 2019176592A1
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alkyl
formula
group
halogen
aromatic vinyl
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健介 鷲頭
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Sumitomo Rubber Industries Ltd
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Sumitomo Rubber Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages

Definitions

  • the present invention relates to a method for producing an aromatic vinyl compound having a hetero atom.
  • An aromatic vinyl compound having a substituent containing a hetero atom is an important intermediate for pharmaceuticals and electronic materials, and is also an important monomer component of a functional polymer.
  • a dihalogenated dialkylsilane is reacted with an alkyl alcohol in the presence of an organic solvent and a tertiary amine to produce a monoalkoxychlorosilane.
  • by-product hydrochloride is removed by Celite filtration or the like, and then purified by distillation and reacted with a Grignard reagent derived from halogenated styrene.
  • the obtained monoalkoxydialkylsilylstyrene is filtered from the magnesium halide salt and then purified by distillation.
  • Non-Patent Document 1 discloses that a dialkyldichlorosilane and alcohol are reacted at 0 ° C. for 5 hours in an inert gas atmosphere under a hydrocarbon solvent using amines as a deoxidizer and filtered. , A method for obtaining monoalkoxychlorosilane through solvent washing and distillation.
  • Non-Patent Document 1 a salt of hydrogen chloride and an amine is produced.
  • this salt is soluble in a hydrocarbon solvent, it is difficult to remove it by filtration, solvent washing, and distillation alone. There exists a problem of reducing the yield and purity of the target product due to the side reaction in the next step.
  • monoalkoxychlorosilane is highly reactive and easily decomposes in the air, causing a decrease in purity and yield, or reacting with moisture to generate hydrogen chloride, which is a problem in handling safety. There is. Moreover, the loss of the target product at the time of filtration separation from the produced salt and distillation purification occurs, which causes a decrease in yield. Furthermore, in the reaction with the Grignard reagent, the alkoxysilyl group of the resulting monoalkoxydialkylsilylstyrene also has reactivity with the Grignard reagent, so that there is a problem that an unintended side reaction occurs.
  • an object of the present invention is to provide a production method capable of obtaining a target heteroatom-containing aromatic vinyl compound with high purity and high yield.
  • the present inventor can obtain a heteroatom-containing aromatic vinyl compound with high purity and high yield safely by using a halogenated aromatic vinyl compound as a starting material and reacting in one pod.
  • the present inventors have found that the above problems can be solved, and have further studied to complete the present invention.
  • R 1 -R 2 -Y wherein R 1 is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent, R 2 is Si (R 10 ) (R 11 ),
  • R 10 and R 11 are each independently a group containing at least one atom selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur and oxygen atoms, Y is carbon, A functional group containing at least one atom selected from the group consisting of silicon, nitrogen, sulfur and oxygen atoms)
  • a process for producing a heteroatom-containing aromatic vinyl compound represented by formula (I) by adding a functional group Y by adding [2] (C) comprising the step of isolating the heteroatom-containing aromatic vinyl compound represented by the formula (I) obtained in the step (B) by filtration and / or vacuum distillation , [3]
  • An organometallic nucleophile is Formula (V): M 1 -Y (Wherein M 1 is an alkali metal and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms)
  • M 1 is an alkali metal
  • Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms
  • R 1 -R 2 -Y of the present invention (wherein R 1 is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent) , R 2 is Si (R 10 ) (R 11 ), wherein R 10 and R 11 are each independently selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur or oxygen atoms.
  • Y is a group containing at least one atom, and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms), Si
  • a method for producing a heteroatom-containing aromatic vinyl compound containing at least one heteroatom selected from O, N, and S wherein (A) Formula (II): R 1 -X 1 (wherein R 1 is the same as defined above, X 1 is a compound represented by a halogen)
  • An organometallic nucleophile containing a functional group Y is added to the reaction mixture containing the halogenated
  • a heteroatom-containing aromatic vinyl compound represented by the formula (I) has a high purity and a high purity. It is possible to obtain safely at a rate.
  • the present invention relates to the formula (I): R 1 —R 2 —Y (wherein R 1 is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent. , R 2 is Si (R 10 ) (R 11 ), wherein R 10 and R 11 are each independently selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur or oxygen atoms.
  • Y is a group containing at least one atom, and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms)
  • a method for producing a containing aromatic vinyl compound which is represented by (A) Formula (II): R 1 -X 1 (wherein R 1 is the same as above, and X 1 is halogen)
  • a reaction solution containing a Grignard reagent obtained by reacting magnesium with a compound is added to the formula (III : X 2 -R 2 -X 3 (wherein, X 2 and X 3 is a halogen independently, R 2 is as defined above) by reacting a halogen compound represented by the formula (IV)
  • step (A) formula (II): R 1 -X 1 (wherein R 1 is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent,
  • a reaction solution containing a Grignard reagent obtained by reacting magnesium with a compound of 1 is halogen
  • R 1 -R 2 -X 3 wherein R 1 , R 2 and X 3 are the above-mentioned groups.
  • R 1 is an aromatic group which has a vinyl group and may be substituted with a group inert to the Grignard reagent, and the vinyl group means a reactive carbon-carbon double bond.
  • the aromatic group of the “aromatic group optionally substituted with a group inert to the Grignard reagent” constitutes a ring, for example, a 5- to 14-membered aryl group, preferably a 5- to 6-membered aryl group A 5- to 14-membered heteroaryl group, preferably a 5- to 6-membered heteroaryl group containing at least one, preferably 1 to 2, heteroatoms such as nitrogen, sulfur, oxygen, etc.
  • Examples of the group inert to the Grignard reagent that may be substituted with the aromatic group of the “aromatic group optionally substituted with an inert group to the Grignard reagent” include an alkyl group (for example, 1 to 5 carbon atoms).
  • Alkyl groups specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), ether groups, silyl ether groups, and the like.
  • the group inert to the Grignard reagent may be substituted at any substitutable position of the aromatic group, but preferably has a bond to X 1 at the para position of the substitution position by the vinyl group. It is preferable to substitute at other substitutable positions. When two or more substituents are present, the substituents may be the same or different.
  • the number of substituents is preferably 1 to 3, more preferably 1.
  • X 1 is halogen, selected from a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.
  • R 1 -X 1 (wherein R 1 is an aromatic group having a vinyl group, which may be substituted with a group inert to the Grignard reagent, and X 1 is a halogen)
  • R 1 is an aromatic group having a vinyl group, which may be substituted with a group inert to the Grignard reagent, and X 1 is a halogen
  • Specific examples of the compound include 4-chlorostyrene, 4-bromostyrene, 2-vinyl-6-chloropyridine and the like.
  • X 2 and X 3 are each independently a halogen such as a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferable from the viewpoint of low cost and availability.
  • R 2 is Si (R 10 ) (R 11 ), wherein R 10 and R 11 are each independently at least one selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur and oxygen atoms. A group containing more than one kind of atom.
  • R 10 and R 11 each independently include a group containing halogen, linear or branched alkyl, linear or branched alkenyl, carbonyl, amide, amino, ether, phenol or phenyl, Specifically, halogen, C 1-10 alkyl, C 2-10 alkenyl, tri C 1-6 alkylsiloxy, C 1-6 acyl, C 1-6 acyloxy, C 1-6 acyloxy C 1-6 alkyl, C 1-6 alkoxy, C 6-12 aryl, C 6-12 aryloxy, amino, C 1-6 alkylamino, di-C 1-6 alkylamino, cyano C 1-6 alkyl, C 1-6 alkoxy C 1 -6 alkyl, C 4-10
  • the halogen is a chlorine atom, a bromine atom or an iodine atom.
  • C 1-10 alkyl is a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms, and is not particularly limited, but examples thereof include methyl, ethyl, propyl, Examples thereof include isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
  • R 10 or R 11 is more preferably methyl, ethyl, octyl or the like.
  • C 2-10 alkenyl is a hydrocarbon group having 2 to 10 carbon atoms having at least one straight-chain or branched carbon-carbon double bond, and is not particularly limited. Are, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 2-pentenyl and the like.
  • tri-C 1-6 alkylsiloxy examples include trimethylsiloxy, triethylsiloxy, tributylsiloxy, tri-iso-propylsiloxy, tri-tert-butylsiloxy and the like.
  • C 1-6 acyl means one obtained by removing an OH group from a carboxylic acid having 1 to 6 carbon atoms, and is not particularly limited. Specifically, methanoyl, Examples include ethanoyl and benzoyl.
  • C 1-6 acyloxy is not particularly limited, and examples thereof include acetoxy, propanoyloxy, acryloyloxy, methacryloyloxy, malonyloxy, benzoyloxy and the like.
  • C 1-6 acyloxy C 1-6 alkyl is not particularly limited, but “C 1-6 acyloxy” as defined herein such as acetoxyethyl is added. And an alkyl group having 1 to 6 carbon atoms as defined herein.
  • C 1-6 alkoxy means an alkyl group having 1 to 6 carbon atoms bonded to an oxygen atom, and is not particularly limited. Ethoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, propoxy, methylenedioxy and the like.
  • C 6-12 aryl means a group derived from an aromatic hydrocarbon having 6 to 12 carbon atoms, and is not particularly limited. Examples thereof include 3-phenylpropyl, tolyl, xylyl, cumenyl, benzyl, phenethyl, cinamyl, biphenyl and the like, and may have a substituent.
  • C 6-12 aryloxy is not particularly limited, and examples thereof include phenoxy and 3-phenoxypropyl, which may have a substituent.
  • C 1-6 alkylamino is not particularly limited, and specifically includes methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, tert-butyl. Examples include amino and sec-butylamino.
  • di-C 1-6 alkylamino is not particularly limited, but dimethylamino, diethylamino, ethylmethylamino, dipropylamino, diisopropylamino, dibutylamino, di-tert-butyl. Examples include amino.
  • cyano C 1-6 alkyl includes an alkyl group having 1 to 6 carbon atoms as defined herein, to which a “cyano” group is added.
  • C 1-6 alkoxy C 1-6 alkyl has 1 to 6 carbon atoms as defined in the present specification to which “C 1-6 alkoxy” as defined in the present specification is added.
  • An alkyl group is 1 to 6 carbon atoms as defined in the present specification to which “C 1-6 alkoxy” as defined in the present specification is added.
  • C 4-10 heterocyclyl is not particularly limited, but is a heterocycle having 4 to 10 carbon atoms having at least one heteroatom selected from N, O or S.
  • a group generated by removing one hydrogen atom from a ring atom and specific examples include thienyl, pyrrolidyl, pyrrolyl, pyridyl, furanyl and the like.
  • thiobenzene C 1-6 alkyl is not particularly limited, and examples thereof include an alkyl group having 1 to 6 carbon atoms as defined in the present specification to which thiobenzene is added.
  • “Amido C 1-6 alkyl” is not particularly limited, but is substituted with an alkyl group such as dimethylamide, diethylamide, dipropylamide, di-iso-propylamide, dibutylamide, di-tert-butylamide and the like. And an alkyl group having 1 to 6 carbon atoms, as defined herein, to which is added an amide group.
  • halogen compound of the above formula (III) are not particularly limited, but include dichlorodiC 1-6 alkylsilanes such as dichlorodimethylsilane, dichlorodiethylsilane or dichlorodipropylsilane, dichloroditrimethyl.
  • silane Cycloditriethylsiloxysilane, Dichlorodidimethylsiloxysilane or dichlorodialkylsiloxysilane such as dichlorodidiethylsiloxysilane, Tetrahalogenated silane such as tetrachlorosilane, Dichloro (acetoxyethyl) (methyl) silane, (Methyl) silane Dihalogen (acyloxyalkyl) (alkyl) silanes such as dichloro (acetoxymethyl) dichloro (methyl) silane or dichloro (acetoxyethyl) (ethyl) silane, dichloroditert-but Dihalogen dialkoxysilanes such as xysilane, dichloro (phenoxy) (methyl) silane, dichloro (phenyl) (methyl) silane, dichlorodidimethylaminosilane, dichlorocyanopropylmethylsilane, dichloro (ethoxy
  • an ether solvent usually used for Grignard reaction is added to metal magnesium under an inert gas atmosphere, and a catalyst amount of an initiator usually used to produce a Grignard reagent is added and stirred.
  • the compound of II) is preferably dropped and stirred to obtain a Grignard reagent, and the halogen compound of formula (III) is preferably dropped directly into the reaction solution containing the obtained Grignard reagent.
  • the inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, and helium gas. Nitrogen gas is preferable from the viewpoint of low cost and availability.
  • the amount of metal magnesium used is preferably 1.00 to 1.20 mol, more preferably 1.05 to 1.10 mol, per 1 mol of the compound of the above formula (II).
  • the ether solvent is not particularly limited, and examples thereof include diethyl ether, dimethoxyethane, diethoxymethane, t-butyl methyl ether, dibutyl ether, tetrahydrofuran (THF), diglyme and the like, and tetrahydrofuran is preferable. .
  • the initiator is not particularly limited, and examples thereof include iodine and alkyl halides such as 1,2-dibromoethane. Of these, 1,2-dibromoethane is preferable because it is inexpensive and easily available.
  • the amount of the halogen compound of the formula (III) used is preferably an equimolar amount with respect to the compound of the formula (II), and used in the range of 1.01 to 1.10 mol with respect to 1 mol of the compound of the formula (II). be able to.
  • the reaction temperature in step (A) is preferably 0 to 80 ° C, more preferably 40 to 60 ° C. Further, in the step (A), the reaction temperature when the obtained Grignard reagent is reacted with the halogen compound of the above formula (III) is preferably 0 to 80 ° C., more preferably 10 to 50 ° C., particularly in the reaction vessel. The temperature is preferably not more than 50 ° C, more preferably not more than 30 ° C.
  • the reaction time in step (A) is preferably 1.0 to 3.0 hours, more preferably 1.5 to 2.0 hours after the dropwise addition of the compound of formula (II) in the preparation reaction of the Grignard reagent.
  • the reaction of the obtained Grignard reagent with the compound of the above formula (III) is carried out by adding the compound of the above formula (III) dropwise over 1 to 8 hours, preferably 2 to 5 hours, usually at 10 to 40 ° C., preferably Is preferably carried out at 20 to 40 ° C.
  • halogenated aromatic vinyl intermediate of the above formula (IV) obtained in the step (A) is used in the next step (B) as it is without purification or isolation.
  • step (B) an organometallic nucleophile containing a functional group Y is added to the reaction mixture containing the halogenated aromatic vinyl intermediate of the above formula (IV) obtained in the step (A) to convert the functional group Y.
  • the organometallic nucleophile is not particularly limited as long as it contains a functional group Y and the functional group Y can be introduced into the halogenated aromatic vinyl intermediate of the above formula (IV).
  • V M 1 -Y (wherein M 1 is an alkali metal and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms)
  • M 2 is an alkaline earth metal
  • Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms
  • R 3 is halogen
  • a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms and may be the same as or different from Y). It is done.
  • M 1 is an alkali metal, and specific examples include lithium, sodium, potassium, cesium and the like.
  • Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, specifically, halogen, C 1-10 alkyl, C 2-10 Alkenyl, Tri C 1-6 alkylsiloxy, Silanol, C 1-6 acyl, C 1-6 acyloxy, C 1-6 acyloxy C 1-6 alkyl, C 1-6 alkoxy, C 6-12 aryl, C 6- 12 aryloxy, amino, C 1-6 alkylamino, diC 1-6 alkylamino, cyano C 1-6 alkyl, C 1-6 alkoxy C 1-6 alkyl, C 4-10 heterocyclyl, thionyl, thiobenzene C 1 -6 alkyl, C 1-6 alkylamide, amide C 1-6 alkyl and the like are preferable.
  • Y may be any functional group that forms a salt with an alkali metal, and is preferably C 1-10 alkyl, C 1-6 alkoxy, di-C 1-6 alkylamino, or the like.
  • Y may be a functional group that forms a salt with an alkaline earth metal or a group that can take a Grignard reagent with M 2 and R 3 .
  • the organometallic compound of the formula (V) is not particularly limited, and examples thereof include sodium methoxide, potassium methoxide, lithium methoxide, cesium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, Cesium ethoxide, sodium n-butoxide, potassium n-butoxide, lithium n-butoxide, cesium n-butoxide, sodium s-butoxide, potassium s-butoxide, lithium s-butoxide, cesium s-butoxide, sodium t-butoxide, potassium t-butoxide, lithium t-butoxide, cesium t-butoxide, sodium n-propoxide, potassium n-propoxide, lithium n-propoxide, cesium n-propoxide, sodium isopropoxide, potassium Metal alkoxides such as um isopropoxide, lithium isopropoxide, cesium isopropoxide, metal salts of phenols such as
  • M 2 is an alkaline earth metal, and specific examples thereof include magnesium and calcium.
  • R 3 may be any functional group that forms a salt with halogen or an alkaline earth metal, and includes at least one atom selected from the group consisting of halogen, silicon, nitrogen, sulfur, and oxygen atoms.
  • Etc. R 3 is, for example, halogen such as chlorine, bromine or iodine, or C 1-10 alkyl, C 2-10 alkenyl, tri-C 1-6 alkylsiloxy, silanol, C 1-6 acyl, C 1-6 acyloxy, C 1-6 acyloxy C 1-6 alkyl, C 1-6 alkoxy, C 6-12 aryl, C 6-12 aryloxy, amino, C 1-6 alkylamino, di-C 1-6 alkylamino, cyano C 1- Preferred are 6 alkyl, C 1-6 alkoxy C 1-6 alkyl, C 4-10 heterocyclyl, thionyl, thiobenzene C 1-6 alkyl, C 1-6 alkylamide, amide C 1-6
  • the organometallic compound of the above formula (VI) is not particularly limited.
  • M 2 is magnesium
  • R 3 is halogen
  • Y is C 1-10 alkyl, C 2-10 alkenyl, C 1-6 acyloxy C 1-6.
  • Grignard reagents which are alkyl, C 6-12 aryl, cyano C 1-6 alkyl, C 1-6 alkoxy C 1-6 alkyl, C 4-10 heterocyclyl, thiobenzene C 1-6 alkyl or amide C 1-6 alkyl; You can also
  • the vinyl aromatic peak derived from the Grignard reagent in the reaction mixture is directly applied to the reaction mixture obtained in the step (A) by gas chromatography-mass spectrometry (GC-MS) or the like.
  • GC-MS gas chromatography-mass spectrometry
  • inert gas and the ether solvent those described for the step (A) can be used similarly, and those used in the step (A) are preferably used.
  • the amount of the organometallic compound of the formula (V) or (VI) used is preferably an equimolar amount with respect to the compound of the formula (II), and 1.0 to 3.0 with respect to 1 mol of the compound of the formula (II). It can be used in a molar range.
  • the reaction temperature in step (B) is preferably 0 to 80 ° C, more preferably 10 to 60 ° C.
  • the temperature in the reaction vessel is preferably not more than 40 ° C, more preferably not more than 35 ° C.
  • the progress of the reaction in the step (B), that is, the production of the heteroatom-containing aromatic vinyl compound of the formula (I) is fast, and the reaction is completed almost simultaneously with the completion of the dropping.
  • step (C) of isolating the heteroatom-containing aromatic vinyl compound of the formula (I) obtained in the step (B) by filtration and / or vacuum distillation.
  • Filtration is performed by, for example, filtering the reaction solution obtained using a filter such as a cellulose filter and collecting the filtrate.
  • the obtained filtrate is preferably concentrated under reduced pressure, the solvent is distilled off, and further distilled under reduced pressure.
  • the filter used for filtration is not particularly limited, but a cellulose filter having a mesh of 70 mm is preferably used.
  • PTFE may be used as the material of the filter, and silica gel, alumina, celite, or the like may be used as the filter medium.
  • the vacuum concentration is preferably performed at an external temperature of 30 ° C./0.2 kPa to 60 ° C./0.2 kPa, and the vacuum distillation is preferably performed at 30 ° C./0.1 kPa to 120 ° C./0.1 kPa. It is possible to carry out by collecting the main distillation according to the boiling point of the heteroatom-containing aromatic vinyl compound.
  • tert-Butoxy potassium lithium diisopropylamide manufactured by Wako Pure Chemical Industries, Ltd .: 1.5 mol / L solution (organometallic compound of formula (VI)) manufactured by Tokyo Chemical Industry Co., Ltd. n-octylmagnesium bromide: manufactured by Tokyo Chemical Industry Co., Ltd., about 22% THF solution, about 1 mol / L Ethanol: Wako Pure Chemical Industries, Ltd. Isopropanol: Wako Pure Chemical Industries, Ltd. tert-butanol: Wako Pure Chemical Industries, Ltd. Triethylamine: Wako Pure Chemical Industries, Ltd. Hexane: Wako Pure Chemical Industries, Ltd. Magnesium: Wako Pure Chemical Industries, Ltd. Dibromoethane: Wako Pure Chemical Industries, Ltd. ( Manufactured by THF (tetrahydrofuran): manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 Synthesis of ethoxydimethyl (4-vinylphenyl) silane Under a nitrogen gas atmosphere, 13.15 g (0.54 mol) of magnesium, 33.9 g of THF, and 1.87 g (0.01 mol) of 1,2-dibromoethane were placed in a 500 mL glass four-necked flask. Stir at 26 ° C. for 30 minutes. Next, 92.00 g (0.50 mol) of 4-bromostyrene was added dropwise so that the internal temperature did not exceed 60 ° C., and the mixture was stirred at 24 to 26 ° C. for 3 hours to react with (4-vinylphenyl) magnesium bromide. 45.9 g of liquid was prepared.
  • Example 2 Synthesis of iso-propoxydimethyl (4-vinylphenyl) silane Other than using 49.06 g (0.50 mol) of iso-propoxy potassium in place of ethoxy potassium and distilling under reduced pressure at 75 ° C./0.1 kPa to collect a fraction having a boiling point of 70 ° C./0.1 kPa as the main distillation Obtained iso-propoxydimethyl (4-biphenyl) silane in the same manner as in Example 1. The total yield calculated from the molar ratio of the starting 4-bromostyrene was 72.4%. As a result of GC-MS analysis, no dimethylbis (4-vinylphenyl) silane was detected, and the purity of iso-propoxydimethyl (4-vinylphenyl) silane was 99.9%.
  • Example 3 Synthesis of tert-butoxydimethyl (4-vinylphenyl) silane Except that 56.10 g (0.50 mol) of tert-butoxy potassium was used instead of ethoxy potassium, distilled under reduced pressure at 80 ° C./0.1 kPa, and the fraction having a boiling point of 73 ° C./0.1 kPa was recovered as the main distillation Produced tert-butoxydimethyl (4-vinylphenyl) silane in the same manner as in Example 1. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 74.1%. As a result of GC-MS analysis, no dimethylbis (4-vinylphenyl) silane was detected, and the purity of tert-butoxydimethyl (4-vinylphenyl) silane was 99.9%.
  • Example 4 Synthesis of diisopropylaminodimethyl (4-vinylphenyl) silane Implemented except that lithium diisopropylamide (0.50 mol) was used instead of ethoxypotassium and distilled under reduced pressure at 130 ° C / 0.1 kPa and the fraction having a boiling point of 96 ° C / 0.1 kPa was recovered as the main distillation.
  • diisopropylamino (4-vinylphenyl) silane was obtained.
  • the overall yield calculated from the molar ratio of the starting 4-bromostyrene was 74.1%.
  • the purity of diisopropylamino (4-vinylphenyl) silane was 99.9%.
  • Example 5 Synthesis of (2-thienyl) dimethyl (4-vinylphenyl) silane A solution reacted with 2-thienylmagnesium bromide (0.50 mol) produced in Production Example 1 described later instead of ethoxypotassium was filtered through silica gel, and then the solvent was distilled off under reduced pressure. In the same manner as in 1, (2-thienyl) dimethyl (4-vinylphenyl) silane was obtained. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 80.6%. As a result of GC-MS analysis, the purity of (2-thienyl) dimethyl (4-vinylphenyl) silane was 99.7%.
  • Example 6 Synthesis of dimethyloctyl (4-vinylphenyl) silane A crude reaction solution was obtained in the same manner as in Example 1 except that n-octylmagnesium bromide (0.50 mol) was used in place of ethoxypotassium, and then obtained by filtration through silica gel instead of the cellulose filter. The solvent was distilled off to obtain dimethyl-n-octyl (4-vinylphenyl) silane. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 84%. As a result of GC-MS analysis, the purity of dimethyloctyl (4-vinylphenyl) silane was 99.0%.
  • Example 7 Synthesis of methyloctyl (2-thienyl) (4-vinylphenyl) silane Instead of dichlorodimethylsilane (0.50 mol), dichloro (2-thienyl) methylsilane (0.50 mol) was used, and n-octylmagnesium bromide (0.50 mol) was used instead of ethoxypotassium. Except for the above, a crude reaction solution was obtained in the same manner as in Example 1, and the filtrate obtained by filtration through silica gel instead of the cellulose filter was evaporated to remove methyloctyl (2-thienyl) (4-vinylphenyl). Silane was obtained.
  • the overall yield calculated from the molar ratio of the starting 4-bromostyrene was 86%.
  • the purity of methyloctyl (2-thienyl) (4-vinylphenyl) silane was 99.0%.
  • Example 8 Synthesis of methyl (2-thienyl) ethoxy (4-vinylphenyl) silane
  • the crude reaction solution was used in the same manner as in Example 1 except that dichloro (2-thienyl) methylsilane (0.50 mol) produced in Production Example 2 described later was used instead of dichlorodimethylsilane (0.50 mol).
  • the filtrate obtained by filtering with silica gel instead of the cellulose filter was evaporated to obtain methyl (2-thienyl) ethoxy (4-vinylphenyl) silane.
  • the overall yield calculated from the molar ratio of the starting 4-bromostyrene was 86%.
  • the purity of methyl (2-thienyl) ethoxy (4-vinylphenyl) silane was 99.0%.
  • Production Example 1 Production of organometallic compound of formula (VI), 2-thienylmagnesium bromide
  • 4-bromothiophene (0. 50 mol) was used to produce 2-thienylmagnesium bromide.
  • Production Example 2 Production of Halogen Compound of Formula (III), Dichloro (2-thienyl) methylsilane
  • 2-bromothiophene (0 Trichloromethylsilane was added dropwise to the solution of 2-thienylmagnesium bromide prepared using .50 mol) so that the internal temperature did not exceed 60 ° C. to prepare a THF solution of dichloro (2-thienyl) methylsilane.
  • Synthesis Example 2 Synthesis of chloroethoxydimethylsilane
  • 49.4 g (0.39 mol) of dimethyldichlorosilane and 194 g of hexane were added to a 1 L glass four-necked flask at room temperature, followed by salt / ice. While cooling to 0 ° C. in a bath, a mixed solution of 17.90 g (0.39 mol) of ethanol, 38.5 g (0.38 mol) of triethylamine, and 194 g of hexane was added for 90 minutes so that the internal temperature was 15 ° C. or less. And then stirred at 24 to 26 ° C.
  • chloroethoxydimethylsilane reaction solution is filtered through celite, concentrated at 80 ° C under atmospheric pressure to distill off the solvent, and then distilled under reduced pressure at 80 ° C / 15 kPa, with the fraction having a boiling point of 65 ° C / 15 kPa as the main fraction. Collected to obtain purified chloroethoxydimethylsilane.
  • Synthesis Example 3 Synthesis of ethoxydimethyl (4-vinylphenyl) silane Chloroethoxydimethylsilane (0.39 mol) prepared in Synthesis Example 2 was placed in a nitrogen-substituted 500 mL glass four-necked flask under an ice bath. The mixture was stirred while cooling until the internal temperature became 3-10 ° C. or lower. Thereafter, the reaction solution (0.39 mol) of (4-vinylphenyl) magnesium bromide prepared in Synthesis Example 1 was added dropwise so that the internal temperature was 15 ° C. or lower, and the mixture was stirred at 24 to 26 ° C. for 20 hours.
  • the overall yield calculated from the molar ratio of the starting dichlorodimethylsilane was 7.4%.
  • 5.0% of dimethylbis (4-vinylphenyl) silane (molecular weight: 264.13) was contained as an impurity, and the purity of ethoxydimethyl (4-vinylphenyl) silane was 95. 0.0%.
  • Comparative Example 2 Synthesis of iso-propoxydimethyl (4-vinylphenyl) silane Using 23.40 g (0.39 mol) of isopropanol instead of ethanol, distilled under reduced pressure at 85 ° C / 15 kPa, and having a boiling point of 70 ° C / 15 kPa Purified chloroisopropoxydimethylsilane was obtained in the same manner as in Synthesis Example 2 of Comparative Example 1 except that the fraction was collected as the main distillate.
  • Iso-propoxydimethyl (4-biphenyl) silane was obtained in the same manner as in Synthesis Example 3 of Comparative Example 1 except that the chloroisopropoxydimethylsilane obtained above was used instead of chloroethoxydimethylsilane.
  • the overall yield calculated from the molar ratio of the starting dichlorodimethylsilane was 8.2%.
  • dimethylbis (4-vinylphenyl) silane was contained as an impurity, and the purity of isopropoxydimethyl (4-vinylphenyl) silane was 93.8%. .
  • Comparative Example 3 Synthesis of tert-butoxydimethyl (4-vinylphenyl) silane 28.91 g (0.39 mol) of tert-butanol was used instead of ethanol and distilled under reduced pressure at 88 ° C / 15 kPa, and the boiling point was 75 ° C / Purified chloro-tert-butoxydimethylsilane was obtained in the same manner as in Synthesis Example 2 of Comparative Example 1 except that the 15 kPa fraction was collected as the main distillation.
  • Tert-butoxydimethyl (4-vinylphenyl) silane was obtained in the same manner as in Synthesis Example 3 of Comparative Example 1 except that the chloro-tert-butoxydimethylsilane obtained above was used instead of chloroethoxydimethylsilane.
  • the overall yield calculated from the molar ratio of the starting dichlorodimethylsilane was 9.1%.
  • 5.4% dimethylbis (4-vinylphenyl) silane was contained as an impurity, and the purity of tert-butoxydimethyl (4-vinylphenyl) silane was 94.6%. It was.
  • the production methods of Examples 1 to 8 via chloro (vinylphenyl) silane as an intermediate are more than the conventional methods for producing heteroatom-containing aromatic vinyl compounds via chloroalkoxysilane as an intermediate.
  • the target product can be obtained with high purity and high yield. Further, in the comparative example, since the hydrogen chloride triethylamine salt is generated, the operation is dangerous, whereas in the example, the target product can be safely taken out in one pot.

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Abstract

L'invention concerne un procédé de production d'un composé vinylique aromatique contenant un hétéroatome de formule (I) : R1-R2-Y [dans laquelle : R1 représente un groupe aromatique spécifique; R2 représente Si(R10)(R11), R10 et R11 représentant indépendamment un groupe spécifique; et Y représentant un groupe spécifique], ledit procédé comprenant : (A) une étape consistant à faire réagir une solution de réaction contenant un réactif de Grignard, qui est obtenue par réaction d'un composé spécifique de formule (II) : R1-X1 avec du magnésium, avec un composé halogéné spécifique de formule (III) : X2-R2-X3 pour donner un intermédiaire vinylique aromatique halogéné spécifique de formule (IV) : R1-R2-X3 dans un état brut purifié; et (B) une étape consistant à ajouter un agent nucléophile métallique organique contenant Y au mélange réactionnel contenant l'intermédiaire vinylique aromatique halogéné obtenu à l'étape (A) et à introduire ainsi le groupe fonctionnel Y dans celui-ci pour donner le composé vinylique aromatique contenant un hétéroatome représenté par la formule (I).
PCT/JP2019/008161 2018-03-12 2019-03-01 Procédé de production d'un composé vinylique aromatique contenant un hétéroatome Ceased WO2019176592A1 (fr)

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