JPS6310140B2 - - Google Patents
Info
- Publication number
- JPS6310140B2 JPS6310140B2 JP59125297A JP12529784A JPS6310140B2 JP S6310140 B2 JPS6310140 B2 JP S6310140B2 JP 59125297 A JP59125297 A JP 59125297A JP 12529784 A JP12529784 A JP 12529784A JP S6310140 B2 JPS6310140 B2 JP S6310140B2
- Authority
- JP
- Japan
- Prior art keywords
- dimethylphenol
- acid
- parafluorobenzoyl
- reaction
- halides
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- -1 parafluorobenzoic acid 2,6-dimethylphenyl ester Chemical class 0.000 claims description 21
- ZEJARTSMPYSXPM-UHFFFAOYSA-N (4-fluorophenyl)-(4-hydroxy-3,5-dimethylphenyl)methanone Chemical compound CC1=C(O)C(C)=CC(C(=O)C=2C=CC(F)=CC=2)=C1 ZEJARTSMPYSXPM-UHFFFAOYSA-N 0.000 claims description 11
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 230000008707 rearrangement Effects 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000006462 rearrangement reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RLTYXFNYOONZGH-UHFFFAOYSA-N (4-chlorophenyl)-(4-hydroxy-3,5-dimethylphenyl)methanone Chemical compound CC1=C(O)C(C)=CC(C(=O)C=2C=CC(Cl)=CC=2)=C1 RLTYXFNYOONZGH-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBEGDBKYQGCYHC-UHFFFAOYSA-N FC1=CC=C(C(=O)C=2C(=C(C(=CC2)C)O)C)C=C1 Chemical compound FC1=CC=C(C(=O)C=2C(=C(C(=CC2)C)O)C)C=C1 FBEGDBKYQGCYHC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000005618 Fries rearrangement reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Polyethers (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規な化合物である４−（パラフルオ
ロベンゾイル）−２，６−ジメチルフエノール及
びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel compound, 4-(parafluorobenzoyl)-2,6-dimethylphenol, and a method for producing the same.
〔従来の技術〕
４−（パラクロロベンゾイル）−２，６−ジメチ
ルフエノールは、特開昭51−131843号公報（ドイ
ツ公開特許第2605382号公報）によつて新規な物
質として提案されている。しかしながら、そのフ
ツ素誘導体である４−（パラフルオロベンゾイル）
−２・６−ジメチルフエノールについては全く知
られていなかつた。[Prior Art] 4-(parachlorobenzoyl)-2,6-dimethylphenol has been proposed as a new substance in JP-A-51-131843 (German Published Patent Application No. 2605382). However, its fluorine derivative 4-(parafluorobenzoyl)
-2,6-dimethylphenol was completely unknown.
本発明は、新規な化合物である４−（パラフル
オロベンゾイル）−２，６−ジメチルフエノール
及びそれを高収率、高選択率で製造する方法を提
供することにある。すなわち、本発明は、４−
（パラフルオロベンゾイル）−２，６−ジメチルフ
エノール、及びパラフルオロ安息香酸２，６−ジ
メチルフエニルエステルを酸触媒の存在下に転位
させることから成る４−（パラフルオロベンゾイ
ル）−２，６−ジメチルフエノールの製造方法ま
たは式（）で表わされるパラフルオロ安息香酸
ハライドと２，６−ジメチルフエノールとを酸触
媒の存在下に反応させることから成る４−（パラ
フルオロベンゾイル）−２，６−ジメチルフエノ
ールの製造方法を提供することにある。
The present invention provides a novel compound, 4-(parafluorobenzoyl)-2,6-dimethylphenol, and a method for producing it with high yield and high selectivity. That is, the present invention provides 4-
4-(parafluorobenzoyl)-2,6- consisting of rearrangement of (parafluorobenzoyl)-2,6-dimethylphenol and parafluorobenzoic acid 2,6-dimethylphenyl ester in the presence of an acid catalyst. Method for producing dimethylphenol or 4-(parafluorobenzoyl)-2,6-dimethyl comprising reacting parafluorobenzoic acid halide represented by formula () with 2,6-dimethylphenol in the presence of an acid catalyst An object of the present invention is to provide a method for producing phenol.
（但し、ＸはＦ、Cl、Br、Ｉから選ばれたハロ
ゲンを表わす）
本発明の４−（パラフルオロベンゾイル）−２，
６−ジメチルフエノールは、どのような方法によ
つて製造されたものであつてもよいが、好ましい
製造方法の１つは、下記式（）で表わされるパ
ラフルオロ安息香酸２，６−ジメチルフエニルエ
ステルを酸触媒の存在下に転位させる方法であつ
て、その反応式は次のように表わされる。 (However, X represents a halogen selected from F, Cl, Br, and I) 4-(parafluorobenzoyl)-2,
6-dimethylphenol may be produced by any method, but one preferred production method is 2,6-dimethylphenyl parafluorobenzoate represented by the following formula (). This is a method of rearranging esters in the presence of an acid catalyst, and the reaction formula is expressed as follows.
この転位反応はフリース転位の応用であるが、
フエニルエステル基の酸素原子に対してオルト位
がメチル基で置換されているために、未置換のフ
エニルエステルの場合と異なり、オルト異性体が
全く存在せず、パラ体である４−（パラフルオロ
ベンゾイル）−２，６−ジメチルフエノールを選
択的に製造することができる方法である。 This rearrangement reaction is an application of Fries rearrangement,
Because the ortho position to the oxygen atom of the phenyl ester group is substituted with a methyl group, unlike the case of unsubstituted phenyl ester, there is no ortho isomer at all, and the para isomer 4-( This is a method that can selectively produce parafluorobenzoyl)-2,6-dimethylphenol.
この転位反応で用いられる酸触媒としては、硫
酸、リン酸、ポリリン酸、塩酸、フツ化水素など
の鉱酸類；ドデカモリブドリン酸、ドデカモリブ
ドケイ酸、ドデカタングストリン酸、ドデカタン
グストケイ酸などのヘテロポリ酸類；クロルスル
ホン酸、ブロムスルホン酸などのハロゲン化スル
ホン酸類；メタンスルホン酸、トリフルオロメタ
ンスルホン酸、ベンゼンスルホン酸、トルエンス
ルホン酸などの有機スルホン酸類；ハロゲン化ホ
ウ素、ハロゲン化アルミニウム、ハロゲン化ケイ
素、ハロゲン化チタン、ハロゲン化スズ、ハロゲ
ン化ジルコニウム、ハロゲン化アンチモン、ハロ
ゲン化ビスマス、ハロゲン化鉄、ハロゲン化ニツ
ケル、ハロゲン化銅、ハロゲン化亜鉛などのルイ
ス酸類；フルオロアルキルスルホン酸基を有する
陽イオン交換体などが用いられる。特に好ましい
のは無水塩化アルミニウムなどのルイス酸であ
る。 Acid catalysts used in this rearrangement reaction include mineral acids such as sulfuric acid, phosphoric acid, polyphosphoric acid, hydrochloric acid, and hydrogen fluoride; dodecamolybdophosphoric acid, dodecamolybdosilicic acid, dodecatungstophosphoric acid, dodecatungstosilicic acid, etc. heteropolyacids; halogenated sulfonic acids such as chlorosulfonic acid and bromesulfonic acid; organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid; boron halides, aluminum halides, and halogenated Lewis acids such as silicon, titanium halides, tin halides, zirconium halides, antimony halides, bismuth halides, iron halides, nickel halides, copper halides, and zinc halides; An ion exchanger or the like is used. Particularly preferred are Lewis acids such as anhydrous aluminum chloride.
また、この転位反応は無溶媒で行なつてもよい
が、反応に悪影響を及ぼさない溶媒を用いること
もできる。このような溶媒としては、二硫化炭
素；クロロホルム、塩化メチレン、四塩化炭素、
ジクロルエタン、トリクロロエタン、テトラクロ
ロエタンなどのハロゲン化炭化水素類；クロルベ
ンゼン、ジクロルベンゼン、ブロムベンゼン、ク
ロルナフタレンなどのハロゲン化芳香族炭化水素
類；ニトロベンゼン、ニトロトルエン、ニトロメ
タンなどのニトロ化合物類などが用いられる。 Further, this rearrangement reaction may be carried out without a solvent, but a solvent that does not adversely affect the reaction may also be used. Such solvents include carbon disulfide; chloroform, methylene chloride, carbon tetrachloride,
Halogenated hydrocarbons such as dichloroethane, trichloroethane, tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlornaphthalene; nitro compounds such as nitrobenzene, nitrotoluene, nitromethane, etc. are used. .
またこの転位反応を行う温度及び反応時間は用
いる触媒や溶媒の種類などの他の反応条件によつ
て異なるが、通常０〜350℃、１分〜50時間であ
り、好ましくは30〜250℃、５分〜20時間である。 The temperature and reaction time for this rearrangement reaction vary depending on other reaction conditions such as the type of catalyst and solvent used, but are usually 0 to 350°C and 1 minute to 50 hours, preferably 30 to 250°C, The duration is 5 minutes to 20 hours.
この転位反応に用いられる原料であるパラフル
オロ安息香酸２・６−ジメチルフエニルエステル
は、どのような方法によつて製造されたものであ
つてもよい。 Parafluorobenzoic acid 2,6-dimethylphenyl ester, which is a raw material used in this rearrangement reaction, may be produced by any method.
本発明の４−（パラフルオロベンゾイル）−２，
６−ジメチルフエノールを製造する他の好ましい
方法は、下記式（）で表わされるパラフルオロ
安息香酸ハライドと２，６−ジメチルフエノール
とを酸触媒の存在下に反応させる方法であつて、
その反応式は次のように表わされる。 4-(parafluorobenzoyl)-2 of the present invention,
Another preferred method for producing 6-dimethylphenol is a method in which parafluorobenzoic acid halide represented by the following formula () and 2,6-dimethylphenol are reacted in the presence of an acid catalyst,
The reaction formula is expressed as follows.
（但し、ＸはＦ、Cl、Br、Ｉから選ばれたハロ
ゲンを表わす）
この反応はフリーデル・クラフツ反応の応用で
あるが、２，６−ジメチルフエノールは水酸基に
対してオルト位がメチル基で置換されているため
に、未置換のフエノールの場合と異なり、オルト
異性体は全く存在せず、パラ体である４−（パラ
フルオロベンゾイル）−２，６−ジメチルフエノ
ールを選択的に製造することができる。この反応
に用いられる酸触媒としては前記の転位反応に用
いられると同様の物があげられる。またこの反応
も無溶媒でも実施できるが、反応に悪影響を及ぼ
さない前記のような溶媒を用いることもできる。 (However, X represents a halogen selected from F, Cl, Br, and I) This reaction is an application of the Friedel-Crafts reaction, but 2,6-dimethylphenol has a methyl group ortho to the hydroxyl group. Because of the substitution, unlike the case of unsubstituted phenol, there is no ortho isomer at all, and the para isomer 4-(parafluorobenzoyl)-2,6-dimethylphenol is selectively produced. be able to. The acid catalyst used in this reaction includes the same ones used in the rearrangement reaction described above. Although this reaction can also be carried out without a solvent, it is also possible to use the above-mentioned solvents that do not adversely affect the reaction.
また反応温度及び反応時間は用いる触媒や溶媒
の種類などの他の反応条件によつて異なるが、通
常０〜350℃、１分〜50時間であり、好ましくは
30〜250℃、５分〜30時間である。 The reaction temperature and reaction time vary depending on other reaction conditions such as the type of catalyst and solvent used, but are usually 0 to 350°C and 1 minute to 50 hours, preferably
The temperature is 30 to 250°C for 5 minutes to 30 hours.
本発明の４−（パラフルオロベンゾイル）−２，
６−ジメチルフエノールは、酸化防止剤、ポリマ
ーの安定剤、あるいは農薬や医薬の原料として用
いられ、さらには耐熱性ポリマーのモノマーとし
て使用することができる。耐熱性ポリマーとして
は、例えば本発明の化合物が自己縮合したポリエ
ーテルケトン類があげられるが、この場合、相当
するクロル化合物である４−（パラクロロベンゾ
イル）−２，６−ジメチルフエノールをモノマー
として用いると、殆んど重合しないか、低重合度
のポリマーしか与えないのと比べて、本発明のフ
ツ素化合物は、このような縮合反応に高活性であ
り高重合度のポリマーを与えることができるので
モノマーとして特に重要な化合物である。 4-(parafluorobenzoyl)-2 of the present invention,
6-Dimethylphenol is used as an antioxidant, a polymer stabilizer, or a raw material for agricultural chemicals and medicines, and can also be used as a monomer for heat-resistant polymers. Examples of heat-resistant polymers include polyetherketones in which the compound of the present invention is self-condensed; in this case, the corresponding chloro compound 4-(parachlorobenzoyl)-2,6-dimethylphenol is used as a monomer. When used, the fluorine compound of the present invention is highly active in such condensation reactions and is capable of producing polymers with a high degree of polymerization. It is a particularly important compound as a monomer.
実施例 １
パラフルオロ安息香酸２，６−ジメチルフエニ
ルエステル61ｇ（0.25モル）、無水塩化アルミニ
ウム36ｇ（0.27モル）を乾燥オルトジクロルベン
ゼン350ml中に入れ、150℃で撹拌下に４時間反応
させた。反応後、オルトジクロルベンゼンを減圧
下で留去し、残渣に塩酸水溶液を入れ撹拌した。
次いで酢酸エチルで注出を行い、抽出液から酢酸
エチルを留去することによつて黄白色結晶を得
た。この結晶をベンゼン−アセトン混合溶媒を用
いて再結晶することによつて、融点146〜147℃の
白色結晶を得た。収量57ｇ（収率93％）この白色
結晶は、次のような分析法によつて、４−（パラ
フルオロベンゾイル）−２，６−ジメチルフエノ
ールであると同定された。
Example 1 61 g (0.25 mol) of parafluorobenzoic acid 2,6-dimethylphenyl ester and 36 g (0.27 mol) of anhydrous aluminum chloride were placed in 350 ml of dry orthodichlorobenzene, and reacted at 150°C for 4 hours with stirring. Ta. After the reaction, orthodichlorobenzene was distilled off under reduced pressure, and an aqueous hydrochloric acid solution was added to the residue, followed by stirring.
Next, the extract was extracted with ethyl acetate, and the ethyl acetate was distilled off from the extract to obtain yellowish-white crystals. By recrystallizing this crystal using a benzene-acetone mixed solvent, white crystals with a melting point of 146 to 147°C were obtained. The yield was 57 g (yield 93%). The white crystals were identified as 4-(parafluorobenzoyl)-2,6-dimethylphenol by the following analytical method.
赤外線吸収スペクトル：3470cm-1（OH）、1640
cm-1及び1595cm-1（Ｃ＝Ｏ及びそれに共役する
ベンゼン環）
マススペクトル：ｍ／ｅ＝244（P+）、229、149、
123、121、77
プロトン−NMR（δ値）：2.3ppm（6H）、5.8ppm
（1H）、6.9〜8.0ppm（6H）
実施例 ２
乾燥１，１，２，２−テトラクロロエタン
（100ml）中のパラフルオロ安息香酸クロリド（16
ｇ）、２，６−ジメチルフエノール（14ｇ）の混
合溶液に、撹拌下、無水塩化アルミニウム（16
ｇ）を少量ずつ30分で加えた。混合物を還流下に
20時間反応させた後、溶媒を減圧下に留去した。
ついで塩酸水溶液を加え、酢酸エチルで抽出し
た。抽出液から酢酸エチルを留去し、得られた結
晶をベンゼン−アセトン混合溶媒で再結晶するこ
とによつて融点146〜147℃の白色結晶である４−
（パラフルオロベンゾイル）−２，６−ジメチルフ
エノール23ｇ（収率94％）を得た。 Infrared absorption spectrum: 3470cm -1 (OH), 1640
cm -1 and 1595 cm -1 (C=O and benzene ring conjugated to it) Mass spectrum: m/e = 244 (P + ), 229, 149,
123, 121, 77 Proton-NMR (δ value): 2.3ppm (6H), 5.8ppm
(1H), 6.9-8.0 ppm (6H) Example 2 Parafluorobenzoic acid chloride (16
g), 2,6-dimethylphenol (14 g), anhydrous aluminum chloride (16
g) was added little by little over 30 minutes. Bring the mixture under reflux
After reacting for 20 hours, the solvent was distilled off under reduced pressure.
Then, an aqueous hydrochloric acid solution was added, and the mixture was extracted with ethyl acetate. Ethyl acetate was distilled off from the extract, and the resulting crystals were recrystallized with a benzene-acetone mixed solvent to obtain 4-, which is a white crystal with a melting point of 146-147°C.
23 g (yield 94%) of (parafluorobenzoyl)-2,6-dimethylphenol was obtained.
４−（パラフルオロベンゾイル）−２，６−ジメ
チルフエノール6.1ｇ、無水炭酸ナトリウム1.3
ｇ、無水炭酸カリウム0.05ｇ、ジフエニルスルホ
ン40ｇから成る混合物を窒素雰囲気下で撹拌しな
がら、240℃で１時間、280℃で１時間、300℃で
１時間反応させた後、反応混合物を溶融状態で取
り出し、冷却して固化した混合物を粉砕し、アセ
トン及び水でそれぞれ数回洗浄した。得られた固
体物質を減圧下に加熱乾燥することによつて、乳
白色の粉末状ポリマーが定量的に得られた。この
ポリマーは、赤外線吸収スペクトル、NMRスペ
クトル等によつて、次のような繰返し単位を有す
る芳香族ポリエーテルケトンであることが確認さ
れた。
4-(parafluorobenzoyl)-2,6-dimethylphenol 6.1g, anhydrous sodium carbonate 1.3
g, anhydrous potassium carbonate 0.05 g, and diphenyl sulfone 40 g were reacted at 240°C for 1 hour, 280°C for 1 hour, and 300°C for 1 hour while stirring under a nitrogen atmosphere, and then the reaction mixture was melted. The mixture was taken out, cooled and solidified, and the mixture was ground and washed several times with acetone and water, respectively. By heating and drying the obtained solid substance under reduced pressure, a milky white powdery polymer was quantitatively obtained. This polymer was confirmed by infrared absorption spectrum, NMR spectrum, etc. to be an aromatic polyetherketone having the following repeating unit.
このポリマーは、98％硫酸を溶媒とし、濃度
0.1ｇ／dl、25℃で測定した還元粘度は1.35であ
つた。 This polymer was prepared using 98% sulfuric acid as a solvent and
The reduced viscosity measured at 0.1 g/dl and 25°C was 1.35.
一方、４−（パラフルオロベンゾイル）−２，６
−ジメチルフエノールの代りに、４−（パラクロ
ロベンゾイル）−２，６−ジメチルフエノール6.5
ｇを用いる以外は、全く同様な方法により重合反
応及び後処理を行い、ポリマー状物質3.8ｇ（収
率68％）を得たが、その還元粘度は0.32（98％硫
酸、濃度0.1ｇ／dl、25℃）と低かつた。このよ
うに本発明化合物は対応するクロル化合物と比べ
て、高活性であり、収率よく高重合度のポリマー
を生成することができる。 On the other hand, 4-(parafluorobenzoyl)-2,6
-4-(parachlorobenzoyl)-2,6-dimethylphenol6.5 instead of dimethylphenol
The polymerization reaction and post-treatment were carried out in exactly the same manner except that 3.8 g (yield: 68%) of a polymeric substance was obtained, but its reduced viscosity was 0.32 (98% sulfuric acid, concentration 0.1 g/dl). , 25℃). As described above, the compound of the present invention has higher activity than the corresponding chloro compound, and can produce a polymer with a high degree of polymerization in good yield.
第１図は、本発明の４−（パラフルオロベンゾ
イル）−２，６−ジメチルフエノールの赤外線吸
収スペクトル、第２図は、本発明の４−（パラフ
ルオロベンゾイル）−２，６−ジメチルフエノー
ルのプロトン−NMRである。
Figure 1 shows the infrared absorption spectrum of 4-(parafluorobenzoyl)-2,6-dimethylphenol of the present invention, and Figure 2 shows the infrared absorption spectrum of 4-(parafluorobenzoyl)-2,6-dimethylphenol of the present invention. Proton-NMR.
Claims (1)
メチルフエノール。 ２ パラフルオロ安息香酸２，６−ジメチルフエ
ニルエステルを酸触媒の存在下に転位させること
から成る４−（パラフルオロベンゾイル）−２，６
−ジメチルフエノールの製造方法。 ３ 式（）で表わされるパラフルオロ安息香酸
ハライドと２，６−ジメチルフエノールとを酸触
媒の存在下に反応させることから成る４−（パラ
フルオロベンゾイル）−２，６−ジメチルフエノ
ールの製造方法。 （但し、ＸはＦ、Cl、Br、Ｉから選ばれたハロ
ゲンを表わす）[Claims] 1 4-(parafluorobenzoyl)-2,6-dimethylphenol. 2 4-(parafluorobenzoyl)-2,6 consisting of rearrangement of parafluorobenzoic acid 2,6-dimethylphenyl ester in the presence of an acid catalyst
- A method for producing dimethylphenol. 3. A method for producing 4-(parafluorobenzoyl)-2,6-dimethylphenol, which comprises reacting parafluorobenzoic acid halide represented by formula () with 2,6-dimethylphenol in the presence of an acid catalyst. (However, X represents a halogen selected from F, Cl, Br, and I)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12529784A JPS617230A (en) | 1984-06-20 | 1984-06-20 | 4-(parafluorobenzoyl)-2,6-dimethylphenol and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12529784A JPS617230A (en) | 1984-06-20 | 1984-06-20 | 4-(parafluorobenzoyl)-2,6-dimethylphenol and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS617230A JPS617230A (en) | 1986-01-13 |
| JPS6310140B2 true JPS6310140B2 (en) | 1988-03-04 |
Family
ID=14906594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12529784A Granted JPS617230A (en) | 1984-06-20 | 1984-06-20 | 4-(parafluorobenzoyl)-2,6-dimethylphenol and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS617230A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5647456A (en) * | 1979-09-26 | 1981-04-30 | Dainippon Ink & Chem Inc | Resin composition for powder coating material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49253A (en) * | 1972-04-18 | 1974-01-05 | ||
| JPS49251A (en) * | 1972-04-17 | 1974-01-05 | ||
| JPS4948317A (en) * | 1972-03-02 | 1974-05-10 | ||
| JPS51131843A (en) * | 1975-02-12 | 1976-11-16 | Orchimed Sa | Lipidddepleted active compound |
| JPS5740128A (en) * | 1980-08-20 | 1982-03-05 | Tokico Ltd | Disc brake |
-
1984
- 1984-06-20 JP JP12529784A patent/JPS617230A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948317A (en) * | 1972-03-02 | 1974-05-10 | ||
| JPS49251A (en) * | 1972-04-17 | 1974-01-05 | ||
| JPS49253A (en) * | 1972-04-18 | 1974-01-05 | ||
| JPS51131843A (en) * | 1975-02-12 | 1976-11-16 | Orchimed Sa | Lipidddepleted active compound |
| JPS5740128A (en) * | 1980-08-20 | 1982-03-05 | Tokico Ltd | Disc brake |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS617230A (en) | 1986-01-13 |
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