CN111201213A - 3-乙酰氧基苯乙烯的制造方法 - Google Patents
3-乙酰氧基苯乙烯的制造方法 Download PDFInfo
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- OWTJYMHZFCHOBI-UHFFFAOYSA-N (3-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=CC(C=C)=C1 OWTJYMHZFCHOBI-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000007341 Heck reaction Methods 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 229910052763 palladium Inorganic materials 0.000 claims description 7
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- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
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- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
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- LFNXCUNDYSYVJY-UHFFFAOYSA-N tris(3-methylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 LFNXCUNDYSYVJY-UHFFFAOYSA-N 0.000 description 2
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- QJIMTLTYXBDJFC-UHFFFAOYSA-N (4-methylphenyl)-diphenylphosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJIMTLTYXBDJFC-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
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- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 description 1
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
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- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000006114 decarboxylation reaction Methods 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- LVTCZSBUROAWTE-UHFFFAOYSA-N diethyl(phenyl)phosphane Chemical compound CCP(CC)C1=CC=CC=C1 LVTCZSBUROAWTE-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- -1 palladium (II) halides Chemical class 0.000 description 1
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- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- XDASSWBZWFFNPX-UHFFFAOYSA-N palladium(ii) cyanide Chemical compound [Pd+2].N#[C-].N#[C-] XDASSWBZWFFNPX-UHFFFAOYSA-N 0.000 description 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种工业上有利的3‑乙酰氧基苯乙烯的制造方法。上述制造方法是下述式(2)所示的3‑乙酰氧基苯乙烯的制造方法,其特征为使下述式(1)所示的3‑乙酰氧基卤苯(X表示F、Cl、Br或I)进行Heck反应。
Description
技术领域
本发明涉及3-乙酰氧基苯乙烯的制造方法。
现有技术
3-乙酰氧基苯乙烯是用于医药中间体、光致抗蚀剂材料等的化合物。对于3-乙酰氧基苯乙烯的合成方法,在一些专利中有记载。Chandros等在二氯甲烷溶液中使3-羟基苯甲醛与乙酰氯进行反应,合成了3-乙酰氧基苯甲醛,然后通过与甲基三苯基溴化的Wittig反应而得到了3-乙酰氧基苯乙烯(专利文献1)。但是,该方法由于总收率低至55.0%,且在第二反应中生成作为副产物的三苯基氧化膦,因此产生大量废弃物,存在对其处理负担较大的课题。
另外,辻本等在甲苯溶液中使3-羟基苯甲醛与乙酸酐进行反应,合成了3-乙酰氧基苯甲醛,然后通过在锌金属和活性的氯化物的存在下与二溴甲烷进行反应,得到了3-乙酰氧基苯乙烯(专利文献2)。但是,这些方法的总收率也低至48.5%,存在废弃物处理的负担大的课题。
另外,河口等通过在甲酸、草酸等脂肪族羧酸的存在下使间叔丁氧基苯乙烯与乙酸酐进行反应而得到了3-乙酰氧基苯乙烯(专利文献3)。该方法虽然收率高达90%左右,但由于主原料间叔丁氧基苯乙烯价格较高,因此存在成本方面不利的课题。
此外,竹内等通过在阻聚剂的存在下使1-(3-乙酰氧基苯基)乙基羧酸酯与酸性催化剂进行反应而得到了3-乙酰氧基苯乙烯(专利文献4)。但是,该方法也以间羟基苯乙酮作为原料,经过还原、乙酰化、脱羧这3个工序来合成,因此总收率为70%左右,不能说是令人满意的结果。
另一方面,已知有通过使4-乙酰氧基卤苯进行Heck反应而制造4-乙酰氧基苯乙烯的方法(专利文献5)。在该方法中使用比较廉价的原料,以90%左右的高收率得到了4-乙酰氧基苯乙烯。但是,该文献中对于3-乙酰氧基苯乙烯的制造并无记载,尚不明确该方法是否能够适用于3-乙酰氧基苯乙烯的制造。
现有技术文献
专利文献
专利文献1:日本特开平7-181691号公报
专利文献2:日本特开平8-157410号公报
专利文献3:日本特开平10-316618号公报
专利文献4:日本特开2004-331515号公报
专利文献5:日本特开2002-179621号公报
发明内容
发明所要解决的课题
本发明的目的在于提供现有方法无法满足的工业上有利的3-乙酰氧基苯乙烯的制造方法。
解决课题的方法
本发明人等为了解决现有的问题而进行了深入研究,结果完成了本发明。即,本发明是制造下述式(2)所示的3-乙酰氧基苯乙烯的方法,其特征在于使下述式(1)所示的3-乙酰氧基卤苯进行Heck反应。根据本发明,可以廉价且高收率地制造3-乙酰氧基苯乙烯。
[化学式1]
发明的效果
如以上所述,根据本发明,能够解决目前的各种问题,而且可以以工业规模且经济性优异的方法制造3-乙酰氧基苯乙烯。
具体实施方式
接下来,列举优选的实施方式对本发明进一步详细地进行说明。
本发明中使用的3-乙酰氧基卤苯是由3-卤代苯酚合成的,3-卤代苯酚没有特别限定。即,作为3-卤代苯酚,可列举:3-氟苯酚、3-氯苯酚、3-溴苯酚、3-碘苯酚。
本发明中使用的3-乙酰氧基卤苯可以通过在三乙基胺的存在下使3-卤代苯酚与乙酸酐进行反应而容易地合成。
在本发明的Heck反应中使用下述的钯系催化剂。本发明中使用的钯系催化剂可以列举:氯化钯(II)、溴化钯(II)、碘化钯(II)等卤化钯(II)、乙酸钯(II)、丙酸钯(II)等有机酸钯(II)、乙酰丙酮钯(II)、氰化钯(II)、硝酸钯(II)、硫酸钯(II)等2价钯化合物。
相对于3-乙酰氧基卤苯1摩尔,钯催化剂的用量优选为0.001~10摩尔,更优选为0.005~2摩尔。催化剂量过少时,收率降低,另一方面,过多时,由于钯催化剂昂贵而使制造成本增加。
本发明中使用的膦配体可以列举:三苯基膦、三邻甲苯基膦、三间甲苯基膦、三对甲苯基膦、二苯基对甲苯基膦等三芳基膦、二乙基苯基膦、乙基二苯基膦、二甲基苯基膦、甲基二苯基膦等烷基芳基膦类、三丁基膦、三乙基膦等三烷基膦、1,2-双(二苯基膦基)乙烷、1,3-双(二苯基膦基)丙烷、1,4-双(二苯基膦基)丁烷等双齿配位膦等,从可以廉价使用的观点考虑,优选为三苯基膦、三磷甲苯基膦、三间甲苯基膦、三对甲苯基膦等。膦配体优选以磷/钯(原子比)成为1~50的范围、更优选以成为1~25的范围使用。
作为本发明中使用的反应溶剂,可以列举:醚类溶剂、含氧类溶剂、含氮类溶剂、芳香烃类溶剂、脂肪烃类溶剂、有机卤素类溶剂等单独的溶剂及它们的混合物,特别是从反应性的观点考虑,优选为乙腈。
在本反应中,存在用于将反应时体系内产生的卤化氢立即中和的碱物质。作为使用的碱物质,可以列举:三甲基胺、三乙基胺、三丁基胺、二乙基胺、吡啶、DBU(1,8-二氮杂二环[5,4,0]十一碳-7-烯)等有机碱、强碱性离子交换树脂等,更优选为三乙基胺、三丁基胺等三烷基胺。
本发明的方法在乙烯气体氛围中进行,乙烯气体的压力在常压以上的条件下进行,考虑到反应性及装置方面的问题,优选为0.3~3MPa的压力。另外,考虑到3-乙酰氧基苯乙烯的热稳定性,本发明的方法优选在170℃以下的温度下实施。
在反应结束后,将自然冷却至室温的反应液中的有机碱的卤化氢盐滤除,用与溶剂相同组成的液体清洗残渣。接着,合并滤液和洗液,在减压下蒸馏去除溶剂,向浓缩物加入乙酸乙酯等不与水混和的溶剂,使其溶解。滤除析出的结晶,将滤液用氯化铵水溶液清洗,接着用水清洗。用无水硫酸钠干燥有机相,向其中添加叔丁基邻苯二酚等阻聚剂进行蒸馏,由此得到作为目标的3-乙酰氧基苯乙烯。
实施例
在具备搅拌机、温度计、压力计的300mL高压反应釜加入3-乙酰氧基溴苯20.1g(0.0935摩尔)、乙酸钯0.0722g(0.322毫摩尔)、三邻甲苯基膦2.20g(7.22毫摩尔)、三乙基胺24.5g(0.242摩尔)、以及乙腈102g,用乙烯气体对体系内进行置换,在0.5MPa的加压下,一边搅拌,一边于80℃下反应6小时。反应结束后,取出反应液,滤除析出物,用乙腈25g清洗过滤残渣。合并滤液和洗液,通过蒸发馏除乙腈,将浓缩物溶解于甲苯,用1%NaOH水溶液清洗,接着用离子交换水清洗。将得到的有机层蒸发,馏除甲苯后,添加叔丁基邻苯二酚进行减压蒸馏,由此得到了3-乙酰氧基苯乙烯14.0g(收率92.4%、GC纯度99.4%)。
Claims (6)
2.根据权利要求1所述的制造方法,其中,相对于3-乙酰氧基卤苯1摩尔,使用0.001~10摩尔的钯催化剂,以磷/钯(原子比)为1~50使用膦配体。
3.根据权利要求1或2所述的制造方法,其中,使用乙腈作为反应溶剂。
4.根据权利要求1~3中任一项所述的制造方法,其中,使反应体系中存在三烷基胺。
5.根据权利要求1~4中任一项所述的制造方法,其中,在乙烯气体氛围中、于0.3~3MPa的压力下进行反应。
6.根据权利要求1~5中任一项所述的制造方法,其中,在170℃以下的温度下进行反应。
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