WO2007105665A2 - Procédé de production de composé alcane de bis-indényle - Google Patents

Procédé de production de composé alcane de bis-indényle Download PDF

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Publication number
WO2007105665A2
WO2007105665A2 PCT/JP2007/054759 JP2007054759W WO2007105665A2 WO 2007105665 A2 WO2007105665 A2 WO 2007105665A2 JP 2007054759 W JP2007054759 W JP 2007054759W WO 2007105665 A2 WO2007105665 A2 WO 2007105665A2
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WO
WIPO (PCT)
Prior art keywords
bis
indenyl
reaction
indul
ethane
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Ceased
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PCT/JP2007/054759
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English (en)
Japanese (ja)
Inventor
Tuyoshi Tagata
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Koei Chemical Co Ltd
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Koei Chemical Co Ltd
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Publication date
Application filed by Koei Chemical Co Ltd filed Critical Koei Chemical Co Ltd
Priority to JP2008505126A priority Critical patent/JPWO2007105665A1/ja
Publication of WO2007105665A2 publication Critical patent/WO2007105665A2/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
    • C07C13/465—Indenes; Completely or partially hydrogenated indenes

Definitions

  • the present invention relates to a process for producing bisdenenylalkanes.
  • Bisindulp alkanes such as 1,2-bis (3-indenole) ethane are useful as raw materials for meta-octene catalysts for olefin polymerization.
  • a disubstituted alden is added to a lithiated indene obtained by reacting an indene with an alkyllithium, and the lithiated indene is disubstituted.
  • a method of producing it by reacting with alkane is known (see Organome tallics, 10 0, 1 50 1 (1 9 9 1)).
  • Organome tallics 10 0, 1 50 1 (1 9 9 1)
  • the present invention provides a method by which bisindulalkanes can be produced at a higher yield than conventional methods.
  • Ri R 4 may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group.
  • Lithioindenes are expressed in formula (2):
  • R 5 represents a methylene group, an alkylene group having 2 to 4 carbon atoms, 1 and 2 may be the same or different, and represent a leaving group.
  • the reaction is carried out while continuously supplying the lithioindenes and the disubstituted alkane represented by the formula (2) to the reactor, and the reaction solution is appropriately extracted according to the supply rate.
  • the manufacturing method of Claim 1 characterized by these.
  • alkyl group having 1 to 4 carbon atoms represented by ⁇ 1 to! ⁇ 4 include a linear or branched alkyl group having 1 to 4 carbon atoms, specifically a methyl group or an ethyl group.
  • Examples of aryl groups include aryl groups that may be substituted with the aforementioned alkyl group having 1 to 4 carbon atoms.
  • the alkylene group having 2 to 4 carbon atoms represented by R 5 includes a linear or branched alkylene group having 2 to 4 carbon atoms. Examples include ethylene group, 1, rimethylene group, tetramethylene group, 1-methyl-trimethylene group, 2-methyl-trimethylene group and the like. Of these, an ethylene group is preferred.
  • examples of the leaving group include halogeno groups such as a black mouth group, a promo group, and a odo group, a mesylate group, a tosylate group, and a triflate group, and a halogeno group is preferable.
  • lithioindenes include, for example, endurium, 1-methylindenyllithium, 2-methylindulium, 4-methylindenyllithium, 5-methylindulium, 6-methylindulium, 7-methylindenyllithium, 1-ethynoleinde-norelethium, 2-ethylinduryllithium, 4-ethylindenyllithium, 5-ethylinduryllithium, 6-ethynindenyllithium, 7-ethylindenyllithium Propyl indenyl lithium, 2-propyl induryl lithium, 4-neck pill indenyl lithium, 5-propinolein denyl lithium, 6-propinole indur lithium, 7-propyl indenylol lithium, 1-butyl indenyl lithium, 2-Butylindulium, 4-Butylindenylolethium, 5-Petyl / Laindenyllithium, 6-Butylindenylolethium, 7-
  • R 6 represents an alkyl group having 1 to 6 carbon atoms. It can be produced by reacting with an alkyl lithium represented by:
  • the reaction liquid containing lithioindene obtained after completion of the reaction can be used as a raw material as it is.
  • disubstituted alkanes (2) include, for example, dichloromethane, dibromomethane, jodomethane, 1,2-jik mouth ethane, 1,2-dibromoethane, 1,2-jodoethane, 1-1chloro-2-bu, Lomotan, 1—Black mouth-- 2—3 1-ethane, 1-promo 2—Neo-ethane, 1, 2 1-di (methane sulphoxy) ethane, 1, 2-di (p-tonoleene sulfoxy) ethane, 1, 2-Di (trifluoromethanesulphonoxy) ethane, 1,3-Dichloropropane, 1,3-Dibromopropane, 1,3-Jodopropane, 1,3-Di (methanesulphonoxy) Propane, 1, 3 —Di (p-tonoleenesulfoxy) propane, 1,3-
  • biindenylalkanes (3) include bis (3-indenyl) methane, bis [3- (1-methyl) indenyl] methane, and bis [3 (2-methyl) indul].
  • Methane bis [3- (4-methyl) indenyl] Methane, bis [3- (5-methyl) indul] methane, bis [3- (6-methyl) indenyl] methane, bis [3 (7-methyl) Indenyl] methane, bis [3- (1-ethyl) indul] methane, bis [3- (2-ethyl) indul] methane, bis [4- (ethyl) indenyl] methane, bis [3- (5-ethynole) indenyl ] Methane, Bis [3— (6-Ethyl) indenyl] Methane, Bis [3— (7-Ethyl) Indul] Methane, Bis [3— (1-Propyl)
  • reaction is carried out while continuously supplying lithioindenes and disubstituted alkanes (2) to the reactor, and the reaction solution is appropriately extracted according to the supply rate.
  • the methods 1) and 4) are preferable.
  • the supply is usually carried out continuously with the same supply rate at the start and end of supply. If necessary, both supply start time and Z or supply end time may be shifted, or both or one of the supply speeds may be changed. It may be allowed.
  • the lithioindenes and the disubstituted alkane (2) are preferably supplied after being dissolved in a solvent.
  • the amount of the lithioindene used is usually 2.0 mol or more, preferably 2.1 to 5.0 mol, particularly preferably 2.1 to 3.0 mol, per 1 mol of the disubstituted alkane (2).
  • the 1 kill solvent be used in the reaction and raw material for dissolution, eg Jechirue Tenore, dibutyl Honoré ether Honoré, tert chromatography butyrate Honoré methylate Honoré ether Honoré, dimethyl Tokishe Tan, as tetrahydrofuran, 1, 4 ether such as one Jiokisan Examples thereof include aliphatic or alicyclic hydrocarbon solvents such as a solvent, hexane, octane, cyclohexane, and methylcyclohexane, with ether solvents being preferred, and tetrahydrofuran being particularly preferred. These may be used alone or in combination of two or more.
  • the amount of the solvent used as the reaction solvent is usually 100 parts by weight or less, preferably 50 parts by weight or less, particularly preferably 15 parts by weight or less, per 1 part by weight of the disubstituted alkane (2). .
  • the lithium indene and the disubstituted alkane (2) are supplied after being dissolved in a solvent, it is usually from 0.0 1 to 2 Ommo 1 / m 1 although it varies depending on the solvent, temperature and specific gravity.
  • the reaction temperature is usually from 78 ° C to 50 ° C, preferably from 20 ° C to 30 ° C.
  • the reaction time in the methods 1) to 3), that is, the feed time of the raw material varies depending on the raw material used, its amount, reaction temperature, etc., but is usually 1 to 48 hours, preferably 2 to 30 hours.
  • the reaction time, that is, the residence time in the method 4) varies depending on the raw materials used, the amount thereof, the reaction temperature, etc., but is usually from 0.01 minutes to 48 hours, preferably from 0.1 minutes to 24 hours.
  • the reactor is generally a tank type or tower type, and is not particularly limited. Usually, for example, a tower-type flow reaction apparatus, a tank-type flow reaction apparatus, a tank-type batch reaction apparatus, or the like can be used.
  • Indenyl alkanes (3) produced by the production method of the present invention may have tautomers, and the above compounds include tautomers.
  • aging is carried out to convert the tautomer into a thermodynamically stable bisindenylalkane (3). preferable.
  • the reaction solution may be stirred as it is for a predetermined temperature and for a predetermined time, and less than the theoretical amount of lithioindene was used.
  • a base such as butyl lithium may be added to the reaction solution and stirred at a predetermined temperature for a predetermined time.
  • the aging temperature is usually 120 ° C to 50 ° C, preferably 0 ° C to 50 ° C.
  • the aging time varies depending on the temperature and the like, but is usually 1 to 10 hours, preferably 3 to 8 hours.
  • the bisindenylalkanes (3) can be isolated by carrying out desired isolation and purification means such as extraction, concentration, distillation, recrystallization, column chromatography and the like.
  • Inden 100 ml (860 mm o 1) was dissolved in 889 g of tetrahydrofuran and cooled to 0 ° C.
  • a hexane solution of butyllithium in an amount of 540 ml 1 (concentration: 1.6 mol ZL, containing butyllithium in 864 mm o 1) was added dropwise over 1 hour and reacted at 0 ° C. for 1 hour to obtain a reaction liquid containing lithioindene.
  • reaction solution containing the resulting lithioindene was reacted dropwise with a solution of 1,2-dibromoethane (74 g, 39 4 mmo 1) in tetrahydrofuran (178 g) cooled to 0 ° C over 5 hours. Thereafter, the mixture was aged by stirring at 0 ° C for 1 hour and at 20 ° C for 4 hours.
  • 1,2-bis (3-indul) ethane and indene had a yield of 85% and a yield of 8, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production de composé alcane de bis-indényle représenté par la formule (3), dans laquelle: R1 à R4, identiques ou différents, représentent chacun hydrogène C1-4 alkyle, ou aryle; R5 représente méthylène ou alkylène C2-4, comprenant la réaction d'un composé indène qui à été soumis à une lithiation (désigné ci-après, composé indène lithiè) représenté par la formule (1), dans laquelle R1 à R4 sont tels que définis plus haut avec un alcane disubstitué représenté par la formule (2) X1-R5-X2, dans laquelle: R5 est tel que défini plus haut; et X1 et X2, identiques ou différents, représentent chacun un groupe partant. L'invention se caractérise en ce qu'au moins une réaction est effectuée lors de l'alimentation du composé indène lithià au système réactionnel.
PCT/JP2007/054759 2006-03-08 2007-03-06 Procédé de production de composé alcane de bis-indényle Ceased WO2007105665A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008505126A JPWO2007105665A1 (ja) 2006-03-08 2007-03-06 ビスインデニルアルカン類の製造法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-062920 2006-03-08
JP2006062920 2006-03-08
JP2007-041041 2007-02-21
JP2007041041 2007-02-21

Publications (1)

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WO2007105665A2 true WO2007105665A2 (fr) 2007-09-20

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PCT/JP2007/054759 Ceased WO2007105665A2 (fr) 2006-03-08 2007-03-06 Procédé de production de composé alcane de bis-indényle

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JP (1) JPWO2007105665A1 (fr)
WO (1) WO2007105665A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104370681A (zh) * 2014-09-29 2015-02-25 中国科学院上海高等研究院 一种乙烯基桥联的二烷基茚化合物的合成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104370681A (zh) * 2014-09-29 2015-02-25 中国科学院上海高等研究院 一种乙烯基桥联的二烷基茚化合物的合成方法

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