WO2007049656A1 - Nouveau derive fluoroadamantane et procede pour le produire - Google Patents

Nouveau derive fluoroadamantane et procede pour le produire Download PDF

Info

Publication number
WO2007049656A1
WO2007049656A1 PCT/JP2006/321297 JP2006321297W WO2007049656A1 WO 2007049656 A1 WO2007049656 A1 WO 2007049656A1 JP 2006321297 W JP2006321297 W JP 2006321297W WO 2007049656 A1 WO2007049656 A1 WO 2007049656A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
formula
same
hydrogen atom
Prior art date
Application number
PCT/JP2006/321297
Other languages
English (en)
Japanese (ja)
Inventor
Koichi Murata
Shu-Zhong Wang
Kazuya Oharu
Original Assignee
Asahi Glass Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to JP2007542627A priority Critical patent/JPWO2007049656A1/ja
Publication of WO2007049656A1 publication Critical patent/WO2007049656A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/10—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/15—Saturated compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a novel fluoroadamantane derivative and a method for producing the same.
  • Non-Patent Document 1 discloses a perfluoroalkylcarboxylic acid having a CF COC1 group.
  • Patent Document 1 International Publication No. 04Z052832 Pamphlet
  • Non-Patent Literature 1 Synthesis of Fluoroorganic ⁇ Jompounds; Knunants, I. L., Yakobson, G. G., Eds .; Springer- Verlag: Berin, 1985; pp77-78.
  • the present inventors examined the reactivity of a fluorocarbonyl group of a fluoroadamantane compound having a fluorocarbon group at a tertiary carbon atom. As a result, it was found that the fluorocarbonyl group can be chemically converted into an isocyanato group, and the inventors succeeded in obtaining a fluoroadamantane compound having an isocyanato group at a tertiary carbon atom.
  • the present invention has the following gist.
  • a process for producing a compound represented by the following formula (2) which comprises reacting a compound represented by the following formula (1) with an azide and then heat-treating it.
  • Q A monofluoromethylene group or a difluoromethylene group, and six Qs may be the same or different.
  • X a hydrogen atom, a fluorine atom, or a fluorocarbon group, and the three Xs may be the same or different! / ⁇ .
  • Y groups corresponding to X, ⁇ corresponding to X being a hydrogen atom, hydrogen atom corresponding to X, ⁇ corresponding to X being a fluorine atom, corresponding to fluorine atom, X corresponding to fluorocarbon group ⁇ is a fluorocarbonyl group or an isocyanato group.
  • Y 3 is a hydrogen atom, a fluorine atom, or an isocyanato group, and three Y a may be the same or different.
  • Isocyanato of compound (2a) characterized by addition reaction of a compound represented by formula (2a) and a hydroxy compound represented by formula R A (—OH)
  • a method for producing a fluoradamantane derivative having an —NHC (O) 2 O bond formed by an addition reaction between a hydroxyl group and a hydroxy group of the hydroxy compound A method for producing a fluoradamantane derivative having an —NHC (O) 2 O bond formed by an addition reaction between a hydroxyl group and a hydroxy group of the hydroxy compound.
  • R A A residue obtained by removing p hydroxy groups from the hydroxy compound.
  • p An integer from 1 to 4.
  • R B a residue obtained by removing q groups — a group represented by NHR e from the amine compound.
  • R e a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • q An integer from 1 to 4.
  • Z is a group corresponding to each of Y a, and Z corresponding to Y 3 which is a hydrogen atom is a hydrogen atom
  • Z corresponding to a fluorine atom Y a corresponds to a fluorine atom, an isocyanato group Y a
  • Z is an isocyanato group or an amino group.
  • Z a a hydrogen atom, a fluorine atom, or an amino group, and the three Z a may be the same or different.
  • a novel fluoroadamantane derivative and a method for producing the same are provided.
  • the fluoroadamantane derivative of the present invention is excellent in heat resistance, releasability, chemical resistance, transparency, light resistance, water repellency, oil repellency, low refractive index and the like.
  • the present invention provides a process for producing the following compound (2) in which the following compound (1) is reacted with an azig compound and then heat-treated.
  • Six Qs in the compound of the present invention may be the same or different, and it is preferable that four or more are difluoromethylene groups. All six Qs are difluoromethylene groups. It is particularly preferable (the same applies hereinafter) o
  • three X's are each independently a fluorine atom or a fluorocarbo -It is preferred to be a group! /.
  • Specific examples of the compound (1) include the following compounds.
  • Y in the compound (2) is a group corresponding to X.
  • Isocyanato group is preferred as Y corresponding to X which is a fluorocarbonyl group. That is, in the method for producing the compound (2) of the present invention, it is preferable that all of the fluorocarbo- col groups of the compound (1) are substituted with isocyanato groups.
  • the azide is preferably sodium azide.
  • the amount of azide with respect to compound (1) having m fluorocarbon groups (1) is preferably 1 X m to 10 X m-fold mol. Xm to 2Xm times moles are particularly preferred.
  • reaction conditions temperature, pressure, time, etc.
  • known reaction conditions can be applied. For example, the reaction conditions described in Sander, M. Monatsh. Chem. 1964, 95, 608 are preferably applied.
  • the temperature in the reaction is preferably 50 to + 50 ° C, particularly preferably 20 to + 20 ° C.
  • the pressure in the reaction is not particularly limited.
  • the reaction is preferably carried out in the presence of a solvent.
  • the solvent is particularly preferably an organic solvent having a boiling point of 90 to 140 ° C., preferably an organic solvent having a boiling point of 80 to 160 ° C.
  • organic solvents include toluene, xylene, nitrobenzene, fluorinate FC-77 Examples include REM Co., Ltd. (trade name), Fluoroether E2 (Sleem KK, trade name), perfluorooctane, perfluorodecalin, and the like.
  • Y P a corresponding group X
  • the Y P is hydrogen atom corresponding to X is a hydrogen atom
  • a Upsilon [rho fluorine atom corresponding to X is a fluorine atom
  • a full O b group ⁇ ⁇ ⁇ corresponding to X is a fluorocarbonyl group or an azidocarbonyl group.
  • the compound (p2) isolated from the reaction product may be heat-treated, or the compound (p2) may be heat-treated as it is without isolating the compound (p2) from the reaction product. From the viewpoint of reaction operation, the latter heat treatment is preferred. However, when the reaction between compound (1) and azide is carried out in the presence of water, it is preferable to remove the water before the heat treatment.
  • reaction conditions can be applied to the reaction conditions (temperature, pressure, time, etc.) in the heat treatment.
  • the reaction conditions described in Sander, M. Monatsh. Chem. 1964, 95, 608 are preferably applied.
  • the temperature in the heat treatment is preferably 60 to 120 ° C, and 70 to 110 ° C is particularly preferred U.
  • the heat treatment pressure is not particularly limited.
  • One preferred embodiment of the method for producing the compound (2) of the present invention is a method for producing the following compound (21), in which the following compound (11) is reacted with azido sodium and then heat-treated. It is done. [0040] [Chemical 9]
  • a fluoroadamantane derivative having an isocyanato group bonded to a tertiary carbon atom of adamantane can be produced.
  • the present invention provides the following compound (2a).
  • the three Y 3 are preferably each independently a fluorine atom or an isocyanato group.
  • Compound (2a) is a novel compound having a characteristic structure having an isocyanato group bonded to the tertiary carbon atom of adamantane. Since the compound (2a) has a reactive isocyanato group, it can be derived into various fluoroadamantane derivatives by reacting with a compound having a group capable of reacting with the isocyanato group. [0047] Examples of the method for producing the fluoroadamantane derivative include the following production methods 1, 2, and 3.
  • a compound Also called a compound.
  • Compound (2a) and an amine compound represented by the formula R B (—NHR e ) are subjected to an addition reaction, and the isocyanate group of compound (2a) and the amine compound are combined.
  • the hydroxy compound in production method 1 has 1 to 4 hydroxy groups.
  • R A in the hydroxy compound is a group having 1 to 10 carbon atoms, and a 1 to 4 valent aliphatic hydrocarbon group, a 1 to 4 valent aromatic hydrocarbon group, and a 1 to 4 valent etheric oxygen Hydrocarbons containing atoms
  • At least one group that is also chosen for its group power is preferred.
  • carbon group 1 ⁇ : LO group, monovalent to tetravalent saturated hydrocarbon group, phenol group, phenol group, benzenetriyl group, and benzenetetrayl group force are selected.
  • At least one group, or a group having 2 to 10 carbon atoms, excluding a hydroxy group such as polyether monool, polyether diol, polyether triol, or polyether tetraol. Particularly preferred.
  • the monovalent R A is preferably an alkyl group having 1 to LO carbon atoms, an alkyl group having 2 to LO carbon atoms, an alkyl group containing an etheric oxygen atom between carbon bonds, or a phenyl group.
  • monohydroxy compounds include methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert butyl alcohol, benzyl alcohol and the like.
  • the divalent RA is preferably an alkylene group having 1 to LO carbon atoms, an alkylene group having 2 to LO carbon atoms, an ethereal oxygen atom between carbon bonds, or a phenylene group.
  • Dihydroxy compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2,2 dimethyl-1,3 propanediol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, (2 hydroxy Ethoxy) Benzene and the like.
  • Examples of the trihydroxy compound or tetrahydroxy compound include glycerin, trimethylolpropane, pentaerythritol, and diglycerin.
  • the reaction temperature in the addition reaction using the compound (2a) having one isocyanato group and the monohydroxy compound is preferably 50 to + 90 ° C. 20 ⁇ + 40 ° C. is particularly preferred.
  • the pressure in the addition reaction is not particularly limited.
  • the addition reaction is preferably performed in the presence of a solvent.
  • Solvents include jetyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorodifluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (manufactured by Slieem, trade name), fluoro ether Examples include E2 (trade name, manufactured by Lancaster), perfluorooctane, perfluorodephosphorus, etc.
  • the catalyst examples include dibutyl-tin-dilaurate, tin-otatanoate, cobalt naphthenate, vanadium-acetylacetonate, dimethyl-tin-ethylhexanoate, triethylenediamine, tetramethyldazine, or dimethyl-cyclohexamine. It is done. Further, the catalyst may be one kind of catalyst or two or more kinds of catalysts.
  • the adamantane derivative obtained by Production Method 1 is excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance, low refractive index property and the like.
  • the amine compound in production method 2 is a compound having 1 to 4 groups represented by the formula NHR e .
  • Re is preferably a hydrogen atom.
  • R B of Amin compound is a group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, and 1-4 divalent aliphatic hydrocarbon group, 1-4 monovalent aromatic hydrocarbon group, And at least one group selected from a group power consisting of a hydrocarbon group including a monovalent to tetravalent etheric oxygen atom.
  • a group having 1 to 10 carbon atoms, a monovalent to tetravalent saturated hydrocarbon group, a phenyl group, a phenyl group, a benzenetriyl group, and a benzenetetrayl group is selected. At least one group is particularly preferred.
  • the amine compound may be an aliphatic amine or an aromatic amine.
  • Aliphatic amines include methylamine, ethylamine, 1-propylamine, 2-propylamine, jetylamine, diisopropylamine, pyrrolidine, piperidine, morpholine, ethylenediamine, propylenediamine, hexamethylenediamine, isophorone diamine. And amine, 1, 4 cyclohexanediamine, piperazine and the like.
  • Aromatic amines include aline, benzylamine, 1-phenylethylamine, diaminobenzene, 2,4-diaminotoluene, 2,6 diaminotoluene, 4,4'-diaminodiphenylmethane, 3,3,1 dimethyl 4,4'-diaminodiphenylmethane, 3,3,1 jetyl-1,4,4'-diaminodiphenylmethane, 3,5 jetyl-2,4 diaminotoluene, 3,5 diethyl-2,6 diaminotoluene, m xylylenediamine Min, p-xylylenediamine and the like.
  • reaction temperature in the addition reaction with a compound having a group represented by C is preferably is 50 to + 9 0 ° C instrument. 20 to + 40 ° C is particularly preferred.
  • the pressure in the addition reaction is not particularly limited.
  • the addition reaction is preferably performed in the presence of a solvent.
  • Solvents include diethyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorotetrafluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (manufactured by Slieem, trade name), fluoroether E2 (Lancaster) Product, trade name), perfluorooctane, perfluorodecalin and the like.
  • the adamantane derivative obtained by the production method 2 is excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance, low refractive index property and the like.
  • reaction conditions temperature, pressure, time, etc.
  • the amount of water relative to the total amount of isocyanato groups of compound (2) in the hydrolysis reaction is preferably 1 to: LOO times molar amount.
  • the reaction temperature in the hydrolysis reaction is preferably 0 to 90 ° C, particularly preferably 0 to 40 ° C.
  • the reaction pressure is not particularly limited.
  • the hydrolysis reaction is preferably performed in the presence of a solvent.
  • Solvents include jetyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorodifluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (manufactured by Seriem, product name), fluoroether E2 (manufactured by Lancaster, product) Name), perfluorooctane, perfluorodecalin and the like.
  • Compound (3) is a corresponding group Y a.
  • Z corresponding to Y 3 which is an isocyanato group is preferably an amino group. That is, in the production method 3, it is preferable that all of the isocyanato groups of the compound (2a) are chemically converted to amino groups.
  • One preferred embodiment of the method for producing the compound (3) of the present invention includes a method for producing the following compound (31) in which the following compound (21) is hydrolyzed.
  • a fluoroadamantane derivative having an amino group bonded to a tertiary carbon atom of adamantane can be produced.
  • the present invention provides the following compound (3a).
  • 3 Z a in the compound (3a) are each independently preferably Ru fluorine atom or an amino group der.
  • Compound (3a) is a novel compound having a characteristic structure having an amino group bonded to the tertiary carbon atom of adamantane. Since the compound (3a) has a reactive amino group, it can be derived into various fluoroadamantane derivatives by reacting with a compound having a group capable of reacting with an amino group.
  • the adamantane derivative is excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance, low refractive index property and the like.
  • GC gas chromatography
  • IR IR spectrum
  • GC purity is determined by GC peak area ratio
  • tetramethylsilane is TMS
  • CF C1CF CHFC1 is R-225
  • FC-77 is a fluorine-containing organic solvent.
  • the following compound (2-4) is obtained by reacting under the same conditions as in Example 11 except that the compound (11) is changed to the following compound (14).
  • a novel fluoroadamantane derivative excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance and low refractive index and a method for producing the same are provided.
  • Loadamantane derivatives are composed of one optical fiber material (core material and clad material for one optical fiber), pellicle material, lens material (eyeglass lens, optical lens, optical cell, etc.), display (PDP, LCD, CRT, FED). Etc.) is useful as a surface protective film.

Landscapes

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

Abstract

L’invention a pour objet un nouveau dérivé fluoroadamantane et un procédé pour le produire. L’invention concerne spécifiquement : un procédé de production du composé (2) ci-représenté, selon lequel on fait réagir un composé (1) ci-représenté avec un azide puis on le soumet à un traitement thermique ; un composé (2a) ci-représenté ; un procédé de production d’un dérivé adamantane selon lequel on soumet le composé (2a) à une réaction d’addition avec un composé hydroxy ; un procédé de production d’un dérivé adamantane selon lequel on soumet le composé (2a) à une réaction d’addition avec un composé amine ; un procédé de production du composé (3) ci-représenté, selon lequel le composé (2a) est hydrolysé ; et un composé (3a) ci-représenté. A ce sujet, Q représente -CHF- ou -CF2- ; X représente H, F ou COF ; Y représente un groupe correspondant à X ; Ya représente H, F ou NCO ; Z représente un groupe correspondant à Ya ; enfin Za représente H, F ou NH2.
PCT/JP2006/321297 2005-10-28 2006-10-25 Nouveau derive fluoroadamantane et procede pour le produire WO2007049656A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007542627A JPWO2007049656A1 (ja) 2005-10-28 2006-10-25 新規なフルオロアダマンタン誘導体およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-314800 2005-10-28
JP2005314800 2005-10-28

Publications (1)

Publication Number Publication Date
WO2007049656A1 true WO2007049656A1 (fr) 2007-05-03

Family

ID=37967768

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/321297 WO2007049656A1 (fr) 2005-10-28 2006-10-25 Nouveau derive fluoroadamantane et procede pour le produire

Country Status (2)

Country Link
JP (1) JPWO2007049656A1 (fr)
WO (1) WO2007049656A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052832A1 (fr) * 2002-12-11 2004-06-24 Asahi Glass Company, Limited Derives fluores de l'adamantane
JP2006131879A (ja) * 2004-10-04 2006-05-25 Asahi Glass Co Ltd 含フッ素共重合体とその製造方法およびそれを含むレジスト組成物
JP2006137798A (ja) * 2004-11-10 2006-06-01 Asahi Glass Co Ltd 新規なアダマンタン反応物の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052832A1 (fr) * 2002-12-11 2004-06-24 Asahi Glass Company, Limited Derives fluores de l'adamantane
JP2006131879A (ja) * 2004-10-04 2006-05-25 Asahi Glass Co Ltd 含フッ素共重合体とその製造方法およびそれを含むレジスト組成物
JP2006137798A (ja) * 2004-11-10 2006-06-01 Asahi Glass Co Ltd 新規なアダマンタン反応物の製造方法

Also Published As

Publication number Publication date
JPWO2007049656A1 (ja) 2009-04-30

Similar Documents

Publication Publication Date Title
JP4556151B2 (ja) フッ素化合物及びそれを用いた活性エネルギー線硬化型樹脂組成物
KR101773184B1 (ko) 퍼플루오로폴리에테르기를 갖는 아크릴레이트 화합물
JP6402643B2 (ja) 含フッ素アクリル化合物及びその製造方法並びに硬化性組成物、基材
JP6784257B2 (ja) 含フッ素化合物、光硬化性組成物、コーティング液、ハードコート層形成用組成物および物品
JP6265207B2 (ja) 含フッ素エーテル化合物、ハードコート層形成用組成物およびハードコート層を有する物品
TW200819421A (en) The method of synthesizing biphenol A, BPA having di-alkoxyl group by using polycarbonate or its waste
JP6377525B2 (ja) イオン化フルオロポリマーの組成物
WO2015056731A1 (fr) Composé contenant du fluor, composition permettant d'obtenir une couche de revêtement dur et objet comportant une couche de revêtement dur
JP2008038015A (ja) 含フッ素ポリエーテル（メタ）アクリレートおよびその製造法
JPH101486A (ja) ケイ素含有イソシアネート化合物の製造方法
CN1197843C (zh) 含氟二醇及其应用
US8143359B2 (en) Organic silicone compound
US20220127418A1 (en) Fluoropolyether group-containing silane compound
JP2885872B2 (ja) 脂肪族コポリカーボネート及び該単位を含有するポリウレタン
JP4575710B2 (ja) 少なくとも１つの−ｃｈ２ｏｈまたは−ｃｈ（ｃｆ３）ｏｈ末端基を有するパーフルオロポリエーテルの製造
CA2552000A1 (fr) Procede pour preparer des monoisocyanates fluores
WO2018203491A2 (fr) Procédé de fabrication d'un composé d'éther contenant du fluor, et composé d'éther contenant du fluor
JPH0375557B2 (fr)
JP2012121876A (ja) （メタ）アクリレート化合物およびその製造方法
CN106543873B (zh) 含氟固化性组合物和物品
WO2007049656A1 (fr) Nouveau derive fluoroadamantane et procede pour le produire
JP6705557B2 (ja) 含フッ素エーテル化合物の製造方法および含フッ素エーテル化合物
JP5549054B2 (ja) 多官能アクリレート
WO2017014218A1 (fr) Composé contenant du fluor, composition photodurcissable, liquide de revêtement, composition pour la fabrication d'une couche de revêtement dure et article
JP2007131669A (ja) アダマンタンポリウレタンの製造方法

Legal Events

Date Code Title Description
DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007542627

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06822274

Country of ref document: EP

Kind code of ref document: A1