JP5453885B2 - N−モノメチル−3,5−ジブロモアニリン化合物およびその製造法 - Google Patents
N−モノメチル−3,5−ジブロモアニリン化合物およびその製造法 Download PDFInfo
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- JP5453885B2 JP5453885B2 JP2009090126A JP2009090126A JP5453885B2 JP 5453885 B2 JP5453885 B2 JP 5453885B2 JP 2009090126 A JP2009090126 A JP 2009090126A JP 2009090126 A JP2009090126 A JP 2009090126A JP 5453885 B2 JP5453885 B2 JP 5453885B2
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- compound
- dibromoaniline
- monomethyl
- methyl
- reaction
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- -1 N-monomethyl-3,5-dibromoaniline compound Chemical class 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- RVNUUWJGSOHMRR-UHFFFAOYSA-N 3,5-dibromoaniline Chemical compound NC1=CC(Br)=CC(Br)=C1 RVNUUWJGSOHMRR-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- QPERVCCWWNPWND-UHFFFAOYSA-N 3,5-dibromo-n-methylaniline Chemical class CNC1=CC(Br)=CC(Br)=C1 QPERVCCWWNPWND-UHFFFAOYSA-N 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 0 *NC(C=C(C1)Br)=CC1Br Chemical compound *NC(C=C(C1)Br)=CC1Br 0.000 description 2
- JWHARUCAPVXUMJ-UHFFFAOYSA-N 3,5-dibromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC(Br)=CC(Br)=C1 JWHARUCAPVXUMJ-UHFFFAOYSA-N 0.000 description 2
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-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
- 239000002861 polymer material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 description 1
- WPHUUIODWRNJLO-UHFFFAOYSA-N 2-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1S(Cl)(=O)=O WPHUUIODWRNJLO-UHFFFAOYSA-N 0.000 description 1
- AQQXBHBSQSSIPR-UHFFFAOYSA-N 3,3-dibromocyclohexa-1,5-dien-1-amine Chemical compound BrC1(CC=CC(N)=C1)Br AQQXBHBSQSSIPR-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ここで、R2は水素原子、炭素数1〜3のアルキル基またはフェニル基であるが、含フッ素ポリエーテル化合物を低粘度化するため、ならびにC-N結合生成を回避し、ボロン酸エステル化合物硬化剤によるC-C結合生成による硬化反応を効果的に行うために、R2を炭素数1〜3のアルキル基またはフェニル基にする必要があった。そのため、含フッ素ポリエーテル化合物〔II〕の原料としてN-モノアルキル-3,5-ジブロモアニリン化合物が必要となった。しかしながら、N-モノアルキル-モノブロモアニリン(特許文献1〜3参照)や3,5-ジブロモアニリンは公知の化合物であるが、意外にもN-モノメチル-3,5-ジブロモアニリンは知られていない化合物であった。
注) Ni(dppp)Cl2:〔1,3-ビス(ジフェニルホスフィノ)プロパン〕ジクロロニッケル
(1) 70℃で、1,2-ジメトキシエタン40ml中に3,5-ジブロモアニリン23.8g(95ミリモル)を加え、次いでジメチル硫酸14.2g(112ミリモル)を滴下し、1時間反応を行った。その後、55重量%の水酸化カリウム水溶液22.6gを加え、同温度で1時間反応させた。通常の反応後処理およびn-ヘキサン-ジメチルエーテル(7/1(v/v))混合溶媒を溶出液とするカラムクロマトグラフィー(ワコーゲルC-300)により、N,N-ジメチル-3,5-ジブロモアニリンとN-メチル-3,5-ジブロモアニリンの混合物16.5gおよび反応原料である3,5-ジブロモアニリン7.5gを回収した。
1H-NMR(CDCl3、300MHz)δ:2.79ppm (doublet、J=5.1Hz、3H、N-CH3)
3.84ppm (broad singlet、1H、N-H)
6.63ppm (doublet、J=1.6Hz、2H、Ar)
6.94ppm (triplet、J=1.6Hz、1H、Ar)
IR(neat)ν: 1,071cm-1
1,098cm-1
1,278cm-1
1,309cm-1
1,421cm-1
1,500cm-1
1,590cm-1
2,897cm-1
3,087cm-1
3,432cm-1
(1) N-メチル-3,5-ジブロモアニリン4.5g(17ミリモル)およびトリエチルアミン2.4g(24ミリモル)含む1,2-ジメトキシエタン溶液30ml中に、酸フルオリドCF3CF2CF2OCF(CF3)COF 6.9g(21ミリモル)を滴下し、室温で2時間反応を行った。通常の反応後処理を行った後、粗生成物を減圧蒸留し、次式で示されるN-メチル-3,5-ジブロモアニリド化合物を無色の液体として8.0g得た(N-メチル-3,5-ジブロモアニリンを基準とした収率80%)。
1H-NMR(CDCl3、300MHz)δ:1.35ppm (singlet、24H、CH3)
3.36ppm (singlet、3H、N-CH3)
7.68ppm (singlet、2H、Ar)
8.26ppm (singlet、1H、Ar)
IR(KBr)ν: 2,981cm-1
1,698cm-1
1,336cm-1
1,450cm-1
1,243cm-1
1,142cm-1
含フッ素ジカルボン酸フルオリド(l+m=102)
78g(約4.5ミリモル)をフッ素系溶媒(住友3M製品HFE-7100)90ml中に溶解し、トリエチルアミン2.1g(21ミリモル)およびジエチルエーテル36mlを加えた。さらにN-メチル-3,5-ジブロモアニリン3.1g(11ミリモル)を加え、30℃で2時間反応を行った。得られた反応混合物を飽和食塩水中に加え、分離した有機層を無水硫酸マグネシウムで乾燥、ろ過した。減圧下で、ろ液からフッ素系溶媒およびジエチルエーテルを留去した後、得られた粘稠な液体をジエチルエーテルで数回洗浄し、次いで減圧下でジエチルエーテルを完全に留去した。このようにして、次式で示される含フッ素ポリエーテル化合物
を、僅かに黄色味を帯びた透明な液体として68g得た。E型粘度計(東機産業製TEV-22)により粘度を測定したところ、15Pa・s(25℃)であった。
19F-NMR(neat、300MHz)δ:(ケミカルシフトはCFCl3基準)
-124ppm(Fb)
-147ppm(Fc)
1H-NMR(CDCl3、300MHz)δ:(ケミカルシフトはTMS基準)
7.6ppm(Ha)
7.3ppm(Hb)
3.2ppm(Hc)
IR(neat)ν: 1,709cm-1
1,561cm-1
1,583cm-1
Claims (2)
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JP2009090126A JP5453885B2 (ja) | 2009-04-02 | 2009-04-02 | N−モノメチル−3,5−ジブロモアニリン化合物およびその製造法 |
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JP2010241707A JP2010241707A (ja) | 2010-10-28 |
JP2010241707A5 JP2010241707A5 (ja) | 2013-05-23 |
JP5453885B2 true JP5453885B2 (ja) | 2014-03-26 |
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JP5381257B2 (ja) * | 2009-04-09 | 2014-01-08 | ユニマテック株式会社 | 含フッ素ボロン酸エステル化合物の製造方法 |
JP5446435B2 (ja) * | 2009-05-08 | 2014-03-19 | ユニマテック株式会社 | N−モノアルキル−3,5−ジブロモアニリン誘導体化合物およびその製造法 |
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US6767872B2 (en) * | 2001-05-18 | 2004-07-27 | The Charles Stark Draper Laboratory, Inc. | Elastohydrodynamic and boundary lubricant and method of lubricating |
EP2135889B1 (en) * | 2007-04-06 | 2012-12-19 | Unimatec Co., Ltd. | Fluorinated polyether compound, process for producing the same, and curable composition containing the same |
JP5098460B2 (ja) * | 2007-06-22 | 2012-12-12 | ユニマテック株式会社 | 含フッ素ポリエーテル化合物、その製造方法およびそれを含有する硬化性組成物 |
JP5098462B2 (ja) * | 2007-06-25 | 2012-12-12 | ユニマテック株式会社 | 含フッ素ポリエーテル化合物、その製造方法およびそれを含有する硬化性組成物 |
EP2280037A1 (en) * | 2008-05-19 | 2011-02-02 | Unimatec Co., Ltd. | Fluorine-containing polyether compound and method for producing the same |
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